Nano

Nano
Contents
1
Nanomaterials
1.1
Natural nanomaterials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1.2
Fullerenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1.3
Nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1.4
2D Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1.5
3D Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1.6
Synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1.6.1
Bottom up methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1.6.2
Top down methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1.7
Characterization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1.8
Uniformity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1.9
Legal denition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1.10 Safety of nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1.11 Market . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1.12 See also . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1.13 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1.14 External links . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Nanoparticle
2.1
Denition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.2
Background . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.3
Uniformity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.4
Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
10
2.5
Synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
11
2.5.1
Sol-gel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
11
2.6
Colloids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
12
2.7
Morphology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
12
2.8
Characterization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
13
2.9
Functionalization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
13
2.9.1
Surface coating for biological applications . . . . . . . . . . . . . . . . . . . . . . . . . .
13
2.10 Safety . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
13
2.11 Laser applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
14
2.12 Medicinal applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
14
ii
CONTENTS
2.13 See also . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
14
2.14 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
15
2.15 Further reading . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
18
2.16 External links . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
18
Nanowire
19
3.1
Overview . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
19
3.2
Synthesis of nanowires . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
19
3.2.1
Suspension . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
20
3.2.2
VLS growth . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
20
3.2.3
Solution-phase synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
20
3.2.4
Non-catalytic growth . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
20
Physics of nanowires . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
21
3.3.1
Conductivity of nanowires . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
21
3.3.2
Welding nanowires . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
21
Applications of nanowires . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
22
3.4.1
Electronic devices . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
22
3.4.2
Sensing of proteins and chemicals using semiconductor nanowires . . . . . . . . . . . . . .
22
3.4.3
Probes for exploring cells interiors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
23
3.5
See also . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
23
3.6
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
23
3.7
External links . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
24
3.3
3.4
Nanomedicine
25
4.1
Drug delivery . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
25
4.1.1
Types of systems used . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
26
4.1.2
Applications
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
26
4.2
Visualization
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
27
4.3
Sensing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
28
4.4
Blood purication . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
28
4.5
Tissue engineering
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
29
4.6
Medical devices . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
29
4.7
See also . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
29
4.8
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
29
4.9
Further reading . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
32
Green nanotechnology
33
5.1
Goals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
33
5.2
Current research . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
33
5.2.1
Solar cells . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
33
5.2.2
Nanoremediation and water treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . .
34
5.2.3
Pollution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
34
CONTENTS
iii
5.3
See also . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
34
5.4
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
34
5.5
Further reading . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
35
5.6
External links . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
35
Carbon nanotube
6.1
6.2
6.3
6.4
36
Types of carbon nanotubes and related structures
. . . . . . . . . . . . . . . . . . . . . . . . . .
36
6.1.1
Terminology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
36
6.1.2
Single-walled . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
36
6.1.3
Multi-walled . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
37
6.1.4
Torus . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
38
6.1.5
Nanobud . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
38
6.1.6
Three-dimensional carbon nanotube architectures . . . . . . . . . . . . . . . . . . . . . .
38
6.1.7
Graphenated carbon nanotubes (g-CNTs)
. . . . . . . . . . . . . . . . . . . . . . . . . .
39
6.1.8
Nitrogen-doped carbon nanotubes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
39
6.1.9
Peapod . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
39
6.1.10 Cup-stacked carbon nanotubes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
39
6.1.11 Extreme carbon nanotubes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
40
Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
40
6.2.1
Strength
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
40
6.2.2
Hardness . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
41
6.2.3
Wettability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
41
6.2.4
Kinetic properties
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
41
6.2.5
Electrical properties
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
41
6.2.6
Optical properties
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
41
6.2.7
Thermal properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
41
6.2.8
Defects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
42
Safety and Health . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
42
6.3.1
Toxicity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
42
6.3.2
Epidemiology and Risk Management
. . . . . . . . . . . . . . . . . . . . . . . . . . . .
43
6.3.3
Safety and Exposure Prevention . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
43
Synthesis
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
43
6.4.1
Arc discharge . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
43
6.4.2
Laser ablation
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
44
6.4.3
Plasma torch . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
44
6.4.4
Chemical vapor deposition (CVD) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
45
6.4.5
Natural, incidental, and controlled ame environments
. . . . . . . . . . . . . . . . . . .
46
6.4.6
Removal of catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
46
6.4.7
Application-related issues
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
46
6.5
Chemical modication
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
47
6.6
Current applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
47
6.7
Potential applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
48
iv
CONTENTS
6.7.1
Biomedical . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
48
6.7.2
Structural . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
48
6.7.3
Electrical circuits . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
49
6.7.4
Electrical cables and wires . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
49
6.7.5
Actuators . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
50
6.7.6
Batteries . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
50
6.7.7
Solar cells . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
50
6.7.8
Hydrogen storage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
50
6.7.9
Supercapacitor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
51
6.7.10 Radar absorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
51
6.7.11 Textile . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
52
6.7.12 Optical power detectors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
52
6.7.13 Acoustics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
52
6.7.14 Environmental remediation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
52
6.7.15 Water treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
52
6.7.16 Other applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
53
6.8
Discovery . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
53
6.9
See also . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
54
6.10 References
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
55
6.11 External links . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
66
Energy applications of nanotechnology
68
7.1
Consumer products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
68
7.2
Reduction of energy consumption
69
7.3
Increasing the eciency of energy production
. . . . . . . . . . . . . . . . . . . . . . . . . . . .
69
7.4
Nuclear Accident Cleanup and Waste Storage
. . . . . . . . . . . . . . . . . . . . . . . . . . . .
69
7.5
Economic benets
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
69
7.6
Capacitors: then and now . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
70
7.6.1
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
71
7.7
See also . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
71
7.8
References
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
71
7.9
External links . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
71
Theory of capacitance
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Molecular scale electronics
72
8.1
Fundamental concepts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
72
8.2
Theoretical basis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
72
8.3
Examples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
73
8.3.1
Wires . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
73
8.3.2
Transistors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
73
8.3.3
Rectiers (diodes) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
74
Techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
74
8.4.1
74
8.4
Molecular gaps . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
CONTENTS
8.4.2
Anchoring . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
74
8.4.3
Fullerene nanoelectronics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
74
Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
75
8.5.1
Artifacts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
75
8.5.2
Commercialization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
75
8.6
History and recent progress . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
75
8.7
See also . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
76
8.8
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
76
8.9
Text and image sources, contributors, and licenses . . . . . . . . . . . . . . . . . . . . . . . . . .
78
8.9.1
Text . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
78
8.9.2
Images . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
80
8.9.3
Content license . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
82
8.5
Chapter 1
Nanomaterials
See the Nanomaterials category for an exhaustive list of
articles related to this subject. What follows is an introduction.
REM scan of a buttery wing scale ( 5000)
Nanomaterials describe, in principle, materials of which

a single unit is sized (in at least one dimension) between 1
and 1000 nanometers (109 meter) but is usually 1100
nm (the usual denition of nanoscale[1] ).
Brazilian Crystal Opal. The play of color is caused

by the interference and diraction of light between
silica spheres (150 - 300 nm in diameter).
Peacock wing (detail)
Lycurgus Cup, glass, 4th century, Roman.

Nanoparticles (70 nm) of gold and silver, dispersed
in colloidal form, are responsible for the dichroic
eect (red/green).
Nanomaterials research takes a materials science-based

approach to nanotechnology, leveraging advances in materials metrology and synthesis which have been developed in support of microfabrication research. Materials
with structure at the nanoscale often have unique optical,
electronic, or mechanical properties.
Blue hue of a species of tarantula (450 nm 20 nm)
1.2 Fullerenes
1.1 Natural nanomaterials
Main article: Fullerene

Biological systems often feature natural, functional nanomaterials. The structure of foraminifera (mainly chalk)
and viruses (protein, capsid), the wax crystals covering
a lotus or nasturtium leaf, spider and spider-mite silk,[2]
the blue hue of tarantulas,[3] the spatulae on the bottom of gecko feet, some buttery wing scales, natural colloids (milk, blood), horny materials (skin, claws, beaks,
feathers, horns, hair), paper, cotton, nacre, corals, and
even our own bone matrix are all natural organic nanomaterials.
The fullerenes are a class of allotropes of carbon which

conceptually are graphene sheets rolled into tubes or
spheres. These include the carbon nanotubes (or silicon
nanotubes) which are of interest both because of their
mechanical strength and also because of their electrical
properties.[4]
Natural inorganic nanomaterials occur through crystal

growth in the diverse chemical conditions of the earths
crust. For example, clays display complex nanostructures
due to anisotropy of their underlying crystal structure,
and volcanic activity can give rise to opals, which are
an instance of a naturally occurring photonic crystals due
to their nanoscale structure. Fires represent particularly
complex reactions and can produce pigments, cement,
fumed silica etc.
Viral capsid
Lotus eect, hydrophobic eect with self-cleaning
ability
Close-up of the underside of a geckos foot as it
Rotating view of C60 , one kind of fullerene.
walks on a glass wall. (spatula: 200 10-15 nm).
1
2
The rst fullerene molecule to be discovered, and the
familys namesake, buckminsterfullerene (C60 ), was prepared in 1985 by Richard Smalley, Robert Curl, James
Heath, Sean O'Brien, and Harold Kroto at Rice University. The name was a homage to Buckminster Fuller,
whose geodesic domes it resembles. Fullerenes have
since been found to occur in nature.[5] More recently,
fullerenes have been detected in outer space.[6]
For the past decade, the chemical and physical properties
of fullerenes have been a hot topic in the eld of research
and development, and are likely to continue to be for a
long time. In April 2003, fullerenes were under study
for potential medicinal use: binding specic antibiotics
to the structure of resistant bacteria and even target certain types of cancer cells such as melanoma. The October 2005 issue of Chemistry and Biology contains an
article describing the use of fullerenes as light-activated
antimicrobial agents. In the eld of nanotechnology, heat
resistance and superconductivity are among the properties attracting intense research.
A common method used to produce fullerenes is to send
a large current between two nearby graphite electrodes in
an inert atmosphere. The resulting carbon plasma arc between the electrodes cools into sooty residue from which
many fullerenes can be isolated.
There are many calculations that have been done using abinitio Quantum Methods applied to fullerenes. By DFT
and TDDFT methods one can obtain IR, Raman and UV
spectra. Results of such calculations can be compared
with experimental results.
CHAPTER 1. NANOMATERIALS
dots and as chemical catalysts such as nanomaterial-based
catalysts. Recently, a range of nanoparticles are extensively investigated for biomedical applications including
tissue engineering, drug delivery, biosensor.[8]
Nanoparticles are of great scientic interest as they are
eectively a bridge between bulk materials and atomic
or molecular structures. A bulk material should have
constant physical properties regardless of its size, but
at the nano-scale this is often not the case. Sizedependent properties are observed such as quantum connement in semiconductor particles, surface plasmon resonance in some metal particles and superparamagnetism
in magnetic materials.
Nanoparticles exhibit a number of special properties relative to bulk material. For example, the bending of bulk
copper (wire, ribbon, etc.) occurs with movement of
copper atoms/clusters at about the 50 nm scale. Copper
nanoparticles smaller than 50 nm are considered super
hard materials that do not exhibit the same malleability
and ductility as bulk copper. The change in properties
is not always desirable. Ferroelectric materials smaller
than 10 nm can switch their magnetisation direction using room temperature thermal energy, thus making them
useless for memory storage. Suspensions of nanoparticles
are possible because the interaction of the particle surface
with the solvent is strong enough to overcome dierences
in density, which usually result in a material either sinking or oating in a liquid. Nanoparticles often have unexpected visual properties because they are small enough to
conne their electrons and produce quantum eects. For
example, gold nanoparticles appear deep red to black in
solution.
1.3 Nanoparticles
The often very high surface area to volume ratio of

nanoparticles provides a tremendous driving force for
diusion, especially at elevated temperatures. Sintering
Main article: Nanoparticle
is possible at lower temperatures and over shorter durations than for larger particles. This theoretically does not
Inorganic nanomaterials, (e.g. quantum dots, nanowires aect the density of the nal product, though ow diand nanorods) because of their interesting optical and culties and the tendency of nanoparticles to agglomerate
electrical properties, could be used in optoelectronics.[7] do complicate matters. The surface eects of nanopartiFurthermore, the optical and electronic properties of cles also reduces the incipient melting temperature.
nanomaterials which depend on their size and shape can
be tuned via synthetic techniques. There are the possibilities to use those materials in organic material based opto1.4 2D Materials
electronic devices such as Organic solar cells, OLEDs etc.
The operating principles of such devices are governed
by photoinduced processes like electron transfer and en- 2D materials are crystalline materials consisting of a twoergy transfer. The performance of the devices depends dimensional single layer of atoms. The most important
on the eciency of the photoinduced process responsible representative graphene was discovered in 2004. Other
for their functioning. Therefore, better understanding of 2D materials based on other elements have since been
those photoinduced processes in organic/inorganic nano- reported.
material composite systems is necessary in order to use
them in organic optoelectronic devices.
Nanoparticles or nanocrystals made of metals, semicon- 1.5 3D Materials
ductors, or oxides are of particular interest for their mechanical, electrical, magnetic, optical, chemical and other Box-shaped graphene (BSG) nanostructure is an examproperties. Nanoparticles have been used as quantum ple of 3D nanomaterial.[9] BSG nanostructure has ap-
1.7. CHARACTERIZATION
peared after mechanical cleavage of pyrolytic graphite.
This nanostructure is a multilayer system of parallel hollow nanochannels located along the surface and having
quadrangular cross-section. The thickness of the channel
walls is approximately equal to 1 nm. The typical width
of channel facets makes about 25 nm.
3
Examples of controlled processes are self-limiting growth
solution, self-limited chemical vapor deposition, shaped
pulse femtosecond laser techniques, and molecular beam
epitaxy.
1.6.2 Top down methods
1.6 Synthesis
The goal of any synthetic method for nanomaterials is to
yield a material that exhibits properties that are a result
of their characteristic length scale being in the nanometer
range (~1 100 nm). Accordingly, the synthetic method
should exhibit control of size in this range so that one
property or another can be attained. Often the methods
are divided into two main types Bottom Up and Top
Down.
1.6.1
Bottom up methods
Knowledge of processes for bottom-up assembly of structures remain in their infancy in comparison to traditional
manufacturing techniques. As a result, the most mature
products of nanotechnology (such as modern CPUs) rely
heavily on top-down processes to dene structures. The
traditional example of a top-down technique for fabrication is lithography in which instruments (such as a modern stepper) are used to scale a macroscopic plan to the
nanoscale.
1.7 Characterization
Novel eects can occur in materials when structures are

formed with sizes comparable to any one of many possible length scales, such as the de Broglie wavelength
of electrons, or the optical wavelengths of high energy
photons. In these cases quantum mechanical eects can
dominate material properties. One example is quantum
connement where the electronic properties of solids are
altered with great reductions in particle size. The optical properties of nanoparticles, e.g. uorescence, also
become a function of the particle diameter. This eect
Chaotic processes
does not come into play by going from macrosocopic to
Chaotic processes involve elevating the constituent atoms micrometer dimensions, but becomes pronounced when
or molecules to a chaotic state and then suddenly changing the nanometer scale is reached.
the conditions so as to make that state unstable. Through In addition to optical and electronic properties, the novel
the clever manipulation of any number of parameters, mechanical properties of many nanomaterials is the subproducts form largely as a result of the insuring kinetics. ject of nanomechanics research. When added to a bulk
The collapse from the chaotic state can be dicult or im- material, nanoparticles can strongly inuence the mepossible to control and so ensemble statistics often govern chanical properties of the material, such as the stiness
the resulting size distribution and average size. Accord- or elasticity. For example, traditional polymers can be reingly, nanoparticle formation is controlled through ma- inforced by nanoparticles (such as carbon nanotubes) renipulation of the end state of the products.
sulting in novel materials which can be used as lightweight
Bottom up methods involve the assembly of atoms or
molecules into nanostructured arrays. In these methods
the raw material sources can be in the form of gases, liquids or solids. The latter requiring some sort of disassembly prior to their incorporation onto a nanostructure. Bottom methods generally fall into two categories: chaotic
and controlled.
Examples of Chaotic Processes are: Laser ablation, Ex- replacements for metals. Such composite materials may
ploding wire, Arc, Flame pyrolysis, Combustion, Precip- enable a weight reduction accompanied by an increase in
stability and improved functionality.[10]
itation synthesis techniques.
Finally, nanostructured materials with small particle size
such as zeolites, and asbestos, are used as catalysts in a
Controlled processes
wide range of critical industrial chemical reactions. The
Controlled Processes involve the controlled delivery of further development of such catalysts can form the bathe constituent atoms or molecules to the site(s) of sis of more ecient, environmentally friendly chemical
nanoparticle formation such that the nanoparticle can processes.
grow to a prescribed sizes in a controlled manner. Gen- The rst observations and size measurements of nanoerally the state of the constituent atoms or molecules particles were made during the rst decade of the 20th
are never far from that needed for nanoparticle forma- century. Zsigmondy made detailed studies of gold sols
tion. Accordingly, nanoparticle formation is controlled and other nanomaterials with sizes down to 10 nm and
through the control of the state of the reactants.
less. He published a book in 1914.[11] He used an
4
ultramicroscope that employs a dark eld method for seeing particles with sizes much less than light wavelength.
There are traditional techniques developed during 20th
century in Interface and Colloid Science for characterizing nanomaterials. These are widely used for rst generation passive nanomaterials specied in the next section.
It would therefore appear desirable to process a material
in such a way that it is physically uniform with regard to
the distribution of components and porosity, rather than
using particle size distributions which will maximize the
green density. The containment of a uniformly dispersed
assembly of strongly interacting particles in suspension
requires total control over particle-particle interactions.
It should be noted here that a number of dispersants such
as ammonium citrate (aqueous) and imidazoline or oleyl
alcohol (nonaqueous) are promising solutions as possible additives for enhanced dispersion and deagglomeration. Monodisperse nanoparticles and colloids provide
this potential.[18]
These methods include several dierent techniques for

characterizing particle size distribution. This characterization is imperative because many materials that are expected to be nano-sized are actually aggregated in solutions. Some of methods are based on light scattering.
Others apply ultrasound, such as ultrasound attenuation
spectroscopy for testing concentrated nano-dispersions
Monodisperse powders of colloidal silica, for example,
and microemulsions.[12]
may therefore be stabilized suciently to ensure a high
There is also a group of traditional techniques for degree of order in the colloidal crystal or polycrystalline
characterizing surface charge or zeta potential of colloidal solid which results from aggregation. The denano-particles in solutions. This information is re- gree of order appears to be limited by the time and space
quired for proper system stabilzation, preventing its allowed for longer-range correlations to be established.
aggregation or occulation. These methods include Such defective polycrystalline colloidal structures would
microelectrophoresis, electrophoretic light scattering and appear to be the basic elements of sub-micrometer colelectroacoustics. The last one, for instance colloid vibra- loidal materials science, and, therefore, provide the rst
tion current method is suitable for characterizing concen- step in developing a more rigorous understanding of the
trated systems.
mechanisms involved in microstructural evolution in high
performance materials and components. [19][20]
1.8 Uniformity
1.9 Legal denition
The chemical processing and synthesis of high performance technological components for the private, in- On 18 October 2011, the European Commission adopted
dustrial and military sectors requires the use of high the following denition of a nanomaterial:[21]
purity ceramics, polymers, glass-ceramics and material
composites. In condensed bodies formed from ne powA natural, incidental or manufactured maders, the irregular sizes and shapes of nanoparticles in a
terial
containing particles, in an unbound state
typical powder often lead to non-uniform packing moror
as
an aggregate or as an agglomerate and
phologies that result in packing density variations in the
where,
for 50% or more of the particles in the
powder compact.
number size distribution, one or more exterUncontrolled agglomeration of powders due to attractive
nal dimensions is in the size range 1 nm 100
van der Waals forces can also give rise to in microstrucnm. In specic cases and where warranted by
tural inhomogeneities. Dierential stresses that develop
concerns for the environment, health, safety or
as a result of non-uniform drying shrinkage are dicompetitiveness the number size distribution
rectly related to the rate at which the solvent can be rethreshold of 50% may be replaced by a threshmoved, and thus highly dependent upon the distribution
old between 1 and 50%.
of porosity. Such stresses have been associated with a
plastic-to-brittle transition in consolidated bodies, and
However, this diers from the denition adopted by
can yield to crack propagation in the unred body if not
the International Organization for Standardization (ISO),
relieved.[13][14] [15]
which is:[22]
In addition, any uctuations in packing density in the
compact as it is prepared for the kiln are often ampliMaterial with any external dimension in
ed during the sintering process, yielding inhomogeneous
the nanoscale or having internal structure in the
densication. Some pores and other structural defects asnanoscale.
sociated with density variations have been shown to play
a detrimental role in the sintering process by growing and
[22]
thus limiting end-point densities. Dierential stresses Nanoscale is, in turn, dened as:
arising from inhomogeneous densication have also been
Size range from approximately 1 nm to
shown to result in the propagation of internal cracks, thus
100 nm.
becoming the strength-controlling aws. [16][17]
1.11. MARKET
It is not currently known which of these, if any, will prevail in courts of law.
1.11 Market
Nanomaterials are slowly becoming commercialized[30]
and beginning to emerge as commodities.[31]
1.12 See also

1.10 Safety of nanoparticles
See also:
Regulation
Nanotoxicology
of
nanotechnology
Gradient multilayer nanolm

and
Nanoparticles behave dierently than other similarly

sized particles. It is therefore necessary to develop specialized approaches to testing and monitoring their eects
on human health and on the environment. The OECD
Chemicals Committee has established the Working Party
on Manufactured Nanomaterials to address this issue and
to study the practices of OECD member countries in regards to nanomaterial safety.[23]
While nanomaterials and nanotechnologies are expected
to yield numerous health and health care advances, such
as more targeted methods of delivering drugs, new cancer therapies, and methods of early detection of diseases,
they also may have unwanted eects.[24][25] Increased rate
of absorption is the main concern associated with manufactured nanoparticles.
List of software for nanostructures modeling

Nanobottle
Nanoceramic
Nanocomposite
Nanostructures
Nanotopography
Nanotoxicology
Nanotechnology
Platinum nanoparticles
Printed electronics
1.13 References
When materials are made into nanoparticles, their surface area to volume ratio increases. The greater specic
surface area (surface area per unit weight) may lead to increased rate of absorption through the skin, lungs, or digestive tract and may cause unwanted eects to the lungs
as well as other organs. However, the particles must be
absorbed in sucient quantities in order to pose health
risks.[25]
[1] Buzea, Cristina; Pacheco, Ivan; Robbie, Kevin (2007).

Nanomaterials and Nanoparticles:
Sources and
Toxicity.
Biointerphases 2 (4): MR17MR71.
doi:10.1116/1.2815690. PMID 20419892.
Nanoparticles created adventitiously (e.g., through the

rubbing of prostheses) have long been known to be a
health hazard,[26] but as the use of nanomaterials increases worldwide, concerns for worker and user safety
are mounting. To address such concerns, the Swedish
Karolinska Institute conducted a study in which various
nanoparticles were introduced to human lung epithelial
cells. The results, released in 2008, showed that iron
oxide nanoparticles caused little DNA damage and were
non-toxic. Zinc oxide nanoparticles were slightly worse.
Titanium dioxide caused only DNA damage. Carbon
nanotubes caused DNA damage at low levels. Copper
oxide was found to be the worst oender, and was
the only nanomaterial identied by the researchers as
a clear health risk.[27] Though nanomaterials are not
conrmed as a health risk to workers who produce
them, NIOSH recommends that exposure precautions
and personal protective equipment be used to protect
workers until the risks of nanomaterial manufacture are
better understood.[28][29]
[4] Fullerenes. Encyclopaedia Britannica.
[2] Novel natural nanomaterial spins o from spider-mite

genome sequencing. Phys.Org (May 23, 2013)
[3] Why Are Tarantulas Blue?
[5] Buseck, P.R.; Tsipursky, S.J.; Hettich, R. (1992).

Fullerenes from the Geological Environment. Science
257 (5067): 2157.
Bibcode:1992Sci...257..215B.
doi:10.1126/science.257.5067.215. PMID 17794751.
[6] Cami, J; Bernard-Salas, J.; Peeters, E.; Malek, S.
E. (2 September 2010).
Detection of C60 and
Science 329
C70 in a Young Planetary Nebula.
(5996):
11802.
Bibcode:2010Sci...329.1180C.
doi:10.1126/science.1192035. PMID 20651118.
[7] Zeng, S.; Baillargeat, Dominique; Ho, Ho-Pui; Yong,
Ken-Tye (2014). Nanomaterials enhanced surface plasmon resonance for biological and chemical sensing applications. Chemical Society Reviews 43 (10): 34263452.
doi:10.1039/C3CS60479A. PMID 24549396.
[8] Kerativitayanan, P; Carrow, JK; Gaharwar, AK (26 May
2015). Nanomaterials for Engineering Stem Cell Responses.. Advanced healthcare materials 4: 160027.
doi:10.1002/adhm.201500272. PMID 26010739.
[9] R. V. Lapshin (2016). STM observation of a boxshaped graphene nanostructure appeared after mechanical cleavage of pyrolytic graphite (PDF). Applied Surface Science (Netherlands: Elsevier B. V.) 360: 451460.
doi:10.1016/j.apsusc.2015.09.222. ISSN 0169-4332.
[24] Kerativitayanan, Punyavee; Carrow, James K.; Gaharwar,

Akhilesh K. (May 2015). Nanomaterials for Engineering Stem Cell Responses. Advanced Healthcare Materials 4: n/an/a. doi:10.1002/adhm.201500272. PMID
26010739.
[10] Ramsden, J.J. (2011) Nanotechnology: An Introduction,

Elsevier, Amsterdam
[25] Lauterwasser, C. (18 July 2007). Opportunities and risks

of Nanotechnologies (PDF). OECD.org.
[11] Zsigmondy, R. (1914) Colloids and the Ultramicroscope, J. Wiley and Sons, NY
[26] Revell, P.A. (2006). The biological eects of nanoparticles. Nanotechnology Perceptions 2 (3): 283298. ISSN
1660-6795.
[12] Dukhin, A.S. & Goetz, P.J. (2002). Ultrasound for characterizing colloids. Elsevier.
[13] Onoda, G.Y., Jr.; Hench, L.L., eds. (1979). Ceramic Processing Before Firing. New York: Wiley & Sons. ISBN
0-471-65410-8.
[14] Aksay, I.A.; Lange, F.F.; Davis, B.I. (1983). Uniformity
of Al2 O3 -ZrO2 Composites by Colloidal Filtration. J.
Am. Ceram. Soc. 66 (10): C190. doi:10.1111/j.11512916.1983.tb10550.x.
[15] Franks, G.V. & Lange, F.F. (1996).
Plastic-toBrittle Transition of Saturated, Alumina Powder Compacts. J. Am. Ceram. Soc. 79 (12): 31613168.
doi:10.1111/j.1151-2916.1996.tb08091.x.
[16] Evans, A.G.; Davidge, R.W. (1969).
The
strength and fracture of fully dense polycrystalline magnesium oxide.
Phil.
Mag.
20
(164):
373388.
Bibcode:1969PMag...20..373E.
doi:10.1080/14786436908228708.
[17] Lange, F.F. & Metcalf, M. (1983). Processing-Related
Fracture Origins: II, Agglomerate Motion and Cracklike
Internal Surfaces Caused by Dierential Sintering. J.
Am. Ceram. Soc. 66 (6): 398406. doi:10.1111/j.11512916.1983.tb10069.x.
[18] Evans, A.G. (1987). Considerations of Inhomogeneity
Eects in Sintering. J. Am. Ceram. Soc. 65 (10): 497
501. doi:10.1111/j.1151-2916.1982.tb10340.x.
[19] Whitesides, George M.; et al. (1991). Molecular Self-Assembly and Nanochemistry: A Chemical
Strategy for the Synthesis of Nanostructures. Science
254 (5036): 13129. Bibcode:1991Sci...254.1312W.
doi:10.1126/science.1962191. PMID 1962191.
[20] Dubbs D. M; Aksay I.A. (2000).
SelfAssembled Ceramics Produced by ComplexFluid Templation. Annu. Rev. Phys. Chem.
Bibcode:2000ARPC...51..601D.
51:
60122.
doi:10.1146/annurev.physchem.51.1.601.
PMID
11031294.
[21] Nanomaterials. European Commission. Last updated 18
October 2011
[22] ISO/TS 800004-1 NanotechnologiesVocabularyPart
1: Core terms. Geneva: 2011.
[23] Safety of Manufactured Nanomaterials: About, OECD
Environment Directorate. OECD.org. 18 July 2007.
[27] Study Sizes up Nanomaterial Toxicity. Chemical & Engineering News 86 (35): 44. 2008.
[28] Topmiller, Jennifer L.; Dunn, Kevin H. (9 December
2013). Controlling Exposures to Workers Who Make or
Use Nanomaterials. National Institute of Occupational
Safety and Health. Retrieved 6 January 2015.
[29] Current Strategies for Engineering Controls in Nanomaterial Production and Downstream Handling Processes
(PDF). National Institute of Occupational Safety and
Health. November 2013. Retrieved 6 January 2015.
[30] Eldridge, T. (8 January 2014). Achieving industry integration with nanomaterials through nancial markets.
Nanotechnology_Now.
[31] McGovern, C. (2010). Commoditization of nanomaterials. Nanotechnol. Perceptions 6 (3): 155178.
doi:10.4024/N15GO10A.ntp.06.03.
1.14 External links

Acquisition, evaluation and public orientated presentation of societal relevant data and ndings for
nanomaterials (DaNa)
Safety of Manufactured Nanomaterials: OECD Environment Directorate
Assessing health risks of nanomaterials summary by GreenFacts of the European Commission
SCENIHR assessment
International Liposome Society
Textiles Nanotechnology Laboratory at Cornell University
IOP.org Article
Nano Structured Material
Online course MSE 376-Nanomaterials by Mark C.
Hersam (2006)
Nanomaterials: Quantum Dots, Nanowires and
Nanotubes online presentation by Dr Sands
Lecture Videos for the Second International Symposium on the Risk Assessment of Manufactured
Nanomaterials, NEDO 2012
1.14. EXTERNAL LINKS

Nader Engheta: Wave interaction with metamaterials, SPIE Newsroom 2016
Chapter 2
Nanoparticle
Note 1: Modied from denitions of nanoparticle and
nanogel in [refs.,[7][8] ].
Note 2: The basis of the 100-nm limit is the fact that novel
properties that
dierentiate particles from the bulk material typically develop at a critical
length scale of under 100 nm.
Note 3: Because other phenomena (transparency or turbidity, ultraltration,
stable dispersion, etc.) that extend the upper limit are occasionally considered,
the use of the prex nano is accepted for dimensions
smaller than 500 nm,
provided reference to the denition is indicated.
Note 4: Tubes and bers with only two dimensions below
100 nm are also
nanoparticles.[9]
TEM (a, b, and c) images of prepared mesoporous silica

nanoparticles with mean outer diameter: (a) 20nm, (b) 45nm,
and (c) 80nm. SEM (d) image corresponding to (b). The insets
are a high magnication of mesoporous silica particle.
The reason for the synonymous denition of nanoparticles and ultrane particles is that, during the 197080s, when the rst thorough fundamental studies with
nanoparticles were underway in the USA (by Granqvist
and Buhrman)[10] and Japan, (within an ERATO
Project)[11] they were called ultrane particles (UFP).
However, during the 1990s before the National Nanotechnology Initiative was launched in the USA, the new
name, nanoparticle, had become fashionable (see, for
example the same senior authors paper 20 years later addressing the same issue, lognormal distribution of sizes
[12]
). Nanoparticles may or may not exhibit size-related
properties that dier signicantly from those observed in
ne particles or bulk materials.[13][14] Although the size of
most molecules would t into the above outline, individual molecules are usually not referred to as nanoparticles.
Nanoparticles are particles between 1 and 100 nanometers in size. In nanotechnology, a particle is dened as a
small object that behaves as a whole unit with respect to
its transport and properties. Particles are further classied according to diameter.[1] Ultrane particles are the
same as nanoparticles and between 1 and 100 nanometers in size, ne particles are sized between 100 and 2,500
nanometers, and coarse particles cover a range between
2,500 and 10,000 nanometers. Nanoparticle research is
currently an area of intense scientic interest due to a
wide variety of potential applications in biomedical, optical and electronic elds.[2][3][4][5] The National Nanotechnology Initiative has led to generous public funding for
nanoparticle research in the United States.
Nanoclusters have at least one dimension between 1

and 10 nanometers and a narrow size distribution.
Nanopowders[15] are agglomerates of ultrane particles,
nanoparticles, or nanoclusters. Nanometer-sized single
crystals, or single-domain ultrane particles, are often referred to as nanocrystals.
2.1 Denition
IUPAC denition
Particle of any shape with dimensions in the 1 109 and
1 107 m range.
8
2.3. UNIFORMITY
2.2 Background
morphologies that result in packing density variations in

the powder compact.
Although, in general, nanoparticles are considered a discovery of modern science, they actually have a long history. Nanoparticles were used by artisans as far back
as the ninth century in Mesopotamia for generating a
glittering eect on the surface of pots.[16][17]
Uncontrolled agglomeration of powders due to attractive

van der Waals forces can also give rise to in microstructural heterogeneity. Dierential stresses that develop as
a result of non-uniform drying shrinkage are directly related to the rate at which the solvent can be removed, and
thus highly dependent upon the distribution of porosity.
Such stresses have been associated with a plastic-tobrittle transition in consolidated bodies, and can yield
to crack propagation in the unred body if not relieved.
Even these days, pottery from the Middle Ages and

Renaissance often retain a distinct gold- or coppercolored metallic glitter. This luster is caused by a metallic lm that was applied to the transparent surface of a [22][23][24]
glazing. The luster can still be visible if the lm has resisted atmospheric oxidation and other weathering.[16][17] In addition, any uctuations in packing density in the
The luster originated within the lm itself, which con- compact as it is prepared for the kiln are often amplitained silver and copper nanoparticles dispersed homoge- ed during the sintering process, yielding inhomogeneous
neously in the glassy matrix of the ceramic glaze. These densication. Some pores and other structural defects asnanoparticles were created by the artisans by adding sociated with density variations have been shown to play
copper and silver salts and oxides together with vinegar, a detrimental role in the sintering process by growing and
ochre, and clay on the surface of previously-glazed pot- thus limiting end-point densities. Dierential stresses
tery. The object was then placed into a kiln and heated arising from inhomogeneous densication have also been
shown to result in the propagation of internal cracks, thus
to about 600 C in a reducing atmosphere.[17]
becoming the strength-controlling aws. [25][26] [27]
In the heat the glaze would soften, causing the copper and
[10][11]
are
silver ions to migrate into the outer layers of the glaze. Inert gas evaporation and inert gas deposition
free
many
of
these
defects
due
to
the
distillation
(cf.
There the reducing atmosphere reduced the ions back to
metals, which then came together forming the nanoparti- purication) nature of the process and having enough
time to form single crystal particles, however even their
cles that give the colour and optical eects.[17]
non-aggreated deposits have lognormal size distribution,
Luster technique showed that ancient craftsmen had a which is typical with nanoparticles.[11] The reason why
rather sophisticated empirical knowledge of materials. modern gas evaporation techniques can produce a relThe technique originated in the Muslim world. As Mus- atively narrow size distribution is that aggregation can
lims were not allowed to use gold in artistic representa- be avoided.[11] However, even in this case, random restions, they sought a way to create a similar eect with- idence times in the growth zone, due to the combination
out using real gold. The solution they found was using of drift and diusion, result in a size distribution appearluster.[17][18]
ing lognormal.[12]
Michael Faraday provided the rst description, in scien- It would, therefore, appear desirable to process a matetic terms, of the optical properties of nanometer-scale rial in such a way that it is physically uniform with regard
metals in his classic 1857 paper. In a subsequent paper, to the distribution of components and porosity, rather
the author (Turner) points out that: It is well known that than using particle size distributions that will maximize
when thin leaves of gold or silver are mounted upon glass the green density. The containment of a uniformly disand heated to a temperature that is well below a red heat persed assembly of strongly interacting particles in sus(~500 C), a remarkable change of properties takes place, pension requires total control over interparticle forces.
whereby the continuity of the metallic lm is destroyed. Monodisperse nanoparticles and colloids provide this poThe result is that white light is now freely transmitted, tential. [28]
reection is correspondingly diminished, while the elecMonodisperse powders of colloidal silica, for example,
trical resistivity is enormously increased. [19][20][21]
may therefore be stabilized suciently to ensure a high
degree of order in the colloidal crystal or polycrystalline
colloidal solid that results from aggregation. The degree
of order appears to be limited by the time and space
2.3 Uniformity
allowed for longer-range correlations to be established.
Such defective polycrystalline colloidal structures would
The chemical processing and synthesis of highappear to be the basic elements of submicrometer colperformance technological components for the private,
loidal materials science and, therefore, provide the rst
industrial, and military sectors requires the use of
step in developing a more rigorous understanding of the
high-purity ceramics, polymers, glass-ceramics, and
mechanisms involved in microstructural evolution in high
composite materials. In condensed bodies formed from
performance materials and components. [29][30]
ne powders, the irregular particle sizes and shapes in
a typical powder often lead to non-uniform packing
10
2.4 Properties
CHAPTER 2. NANOPARTICLE
lar thermal applications, controlling the size, shape, and
material of the particles, it is possible to control solar
absorption.[3][5][32]
Other size-dependent property changes include quantum
connement in semiconductor particles, surface
plasmon resonance[4] in some metal particles and
superparamagnetism in magnetic materials. What would
appear ironic is that the changes in physical properties are
not always desirable. Ferromagnetic materials smaller
than 10 nm can switch their magnetisation direction
using room temperature thermal energy, thus making
them unsuitable for memory storage.[33]
Suspensions of nanoparticles are possible since the interaction of the particle surface with the solvent is strong
enough to overcome density dierences, which otherwise
usually result in a material either sinking or oating in a
liquid.
Silicon nanopowder
The high surface area to volume ratio of nanoparticles

provides a tremendous driving force for diusion, especially at elevated temperatures. Sintering can take place
at lower temperatures, over shorter time scales than for
larger particles. In theory, this does not aect the density
of the nal product, though ow diculties and the tendency of nanoparticles to agglomerate complicates matters. Moreover, nanoparticles have been found to impart
some extra properties to various day to day products. For
example, the presence of titanium dioxide nanoparticles
imparts what we call the self-cleaning eect, and, the
size being nano-range, the particles cannot be observed.
1 kg of particles of 1 mm3 has the same surface area as 1 mg of Zinc oxide particles have been found to have superior UV
particles of 1 nm3
blocking properties compared to its bulk substitute. This
is one of the reasons why it is often used in the preparaNanoparticles are of great scientic interest as they are, tion of sunscreen lotions,[34] is completely photostable[35]
in eect, a bridge between bulk materials and atomic or and toxic.[36] [37] [38] [39] [40] [41]
molecular structures. A bulk material should have conClay nanoparticles when incorporated into polymer mastant physical properties regardless of its size, but at the
trices increase reinforcement, leading to stronger plasnano-scale size-dependent properties are often observed.
tics, veriable by a higher glass transition temperature
Thus, the properties of materials change as their size apand other mechanical property tests. These nanopartiproaches the nanoscale and as the percentage of atoms at
cles are hard, and impart their properties to the polymer
the surface of a material becomes signicant. For bulk
(plastic). Nanoparticles have also been attached to textile
materials larger than one micrometer (or micron), the
bers in order to create smart and functional clothing.[42]
percentage of atoms at the surface is insignicant in relation to the number of atoms in the bulk of the mate- Metal, dielectric, and semiconductor nanoparticles have
rial. The interesting and sometimes unexpected properties been formed, as well as hybrid structures (e.g., coreshell
of nanoparticles are therefore largely due to the large sur- nanoparticles).[2] Nanoparticles made of semiconducting
face area of the material, which dominates the contribu- material may also be labeled quantum dots if they are
small enough (typically sub 10 nm) that quantization of
tions made by the small bulk of the material.
electronic energy levels occurs. Such nanoscale particles
Nanoparticles often possess unexpected optical properare used in biomedical applications as drug carriers or
ties as they are small enough to conne their electrons and
imaging agents.
[4]
produce quantum eects. For example, gold nanoparticles appear deep-red to black in solution. Nanoparticles Semi-solid and soft nanoparticles have been manufacof yellow gold and grey silicon are red in color. Gold tured. A prototype nanoparticle of semi-solid nature is
nanoparticles melt at much lower temperatures (~300 C the liposome. Various types of liposome nanoparticles
for 2.5 nm size) than the gold slabs (1064 C);.[31] Ab- are currently used clinically as delivery systems for antisorption of solar radiation is much higher in materials cancer drugs and vaccines.
composed of nanoparticles than it is in thin lms of con- Nanoparticles with one half hydrophilic and the other half
tinuous sheets of material. In both solar PV and so-
2.5. SYNTHESIS
11
of plasma gas and silica vapour can be rapidly cooled by
quenching with oxygen, thus ensuring the quality of the
fumed silica produced.
In RF induction plasma torches, energy coupling to the

plasma is accomplished through the electromagnetic eld
generated by the induction coil. The plasma gas does not
come in contact with electrodes, thus eliminating possible sources of contamination and allowing the operation
of such plasma torches with a wide range of gases including inert, reducing, oxidizing, and other corrosive atmospheres. The working frequency is typically between 200
kHz and 40 MHz. Laboratory units run at power levels
in the order of 3050 kW, whereas the large-scale industrial units have been tested at power levels up to 1 MW.
As the residence time of the injected feed droplets in the
plasma is very short, it is important that the droplet sizes
are small enough in order to obtain complete evaporaSemiconductor nanoparticle (quantum dot) of lead sulde with
tion. The RF plasma method has been used to synthecomplete passivation by oleic acid, oleyl and hydroxyl (size
size dierent nanoparticle materials, for example synthe~5nm)
sis of various ceramic nanoparticles such as oxides, carbours/carbides, and nitrides of Ti and Si (see Induction
hydrophobic are termed Janus particles and are particu- plasma technology).
larly eective for stabilizing emulsions. They can self- Inert-gas condensation is frequently used to make
assemble at water/oil interfaces and act as solid surfac- nanoparticles from metals with low melting points. The
tants.
metal is vaporized in a vacuum chamber and then super-
2.5 Synthesis
There are several methods for creating nanoparticles, including attrition, pyrolysis and hydrothermal synthesis. In
attrition, macro- or micro-scale particles are ground in
a ball mill, a planetary ball mill, or other size-reducing
mechanism. The resulting particles are air classied to
recover nanoparticles. In pyrolysis, a vaporous precursor (liquid or gas) is forced through an orice at high
pressure and burned. The resulting solid (a version of
soot) is air classied to recover oxide particles from byproduct gases. Traditional pyrolysis often results in aggregates and agglomerates rather than single primary particles. Ultrasonic nozzle spray pyrolysis (USP) on the
other hand aids in preventing agglomerates from forming.
A thermal plasma can also deliver the energy necessary to cause vaporization of small micrometer-size particles. The thermal plasma temperatures are in the order of 10,000 K, so that solid powder easily evaporates.
Nanoparticles are formed upon cooling while exiting the
plasma region. The main types of the thermal plasma
torches used to produce nanoparticles are dc plasma jet,
dc arc plasma, and radio frequency (RF) induction plasmas. In the arc plasma reactors, the energy necessary for
evaporation and reaction is provided by an electric arc
formed between the anode and the cathode. For example, silica sand can be vaporized with an arc plasma at
atmospheric pressure, or thin aluminum wires can be vaporized by exploding wire method. The resulting mixture
cooled with an inert gas stream. The supercooled metal

vapor condenses into nanometer-size particles, which can
be entrained in the inert gas stream and deposited on a
substrate or studied in situ.
Nanoparticles can also be formed using radiation chemistry. Radiolysis from gamma rays can create strongly active free radicals in solution. This relatively simple technique uses a minimum number of chemicals. These including water, a soluble metallic salt, a radical scavenger
(often a secondary alcohol), and a surfactant (organic
capping agent). High gamma doses on the order of 104
Gray are required. In this process, reducing radicals will
drop metallic ions down to the zero-valence state. A scavenger chemical will preferentially interact with oxidizing
radicals to prevent the re-oxidation of the metal. Once in
the zero-valence state, metal atoms begin to coalesce into
particles. A chemical surfactant surrounds the particle
during formation and regulates its growth. In sucient
concentrations, the surfactant molecules stay attached to
the particle. This prevents it from dissociating or forming
clusters with other particles. Formation of nanoparticles
using the radiolysis method allows for tailoring of particle size and shape by adjusting precursor concentrations
and gamma dose.[43]
2.5.1 Sol-gel
The sol-gel process is a wet-chemical technique (also
known as chemical solution deposition) widely used recently in the elds of materials science and ceramic engineering. Such methods are used primarily for the
12
fabrication of materials (typically a metal oxide) starting medicine (e.g., controlled drug release) and separation
from a chemical solution (sol, short for solution), which (e.g., chromatography) technology.[46][47]
acts as the precursor for an integrated network (or gel) of
either discrete particles or network polymers. [44]
Typical precursors are metal alkoxides and metal
chlorides, which undergo hydrolysis and polycondensation reactions to form either a network elastic solid or a
colloidal suspension (or dispersion) a system composed
of discrete (often amorphous) submicrometer particles
dispersed to various degrees in a host uid. Formation of
a metal oxide involves connecting the metal centers with
oxo (M-O-M) or hydroxo (M-OH-M) bridges, therefore
generating metal-oxo or metal-hydroxo polymers in solution. Thus, the sol evolves toward the formation of a
gel-like diphasic system containing both a liquid phase
and solid phase whose morphologies range from discrete
particles to continuous polymer networks.[45]
In the case of the colloid, the volume fraction of particles (or particle density) may be so low that a signicant
amount of uid may need to be removed initially for the
gel-like properties to be recognized. This can be accomplished in a number of ways. The most simple method is
to allow time for sedimentation to occur, and then pour
o the remaining liquid. Centrifugation can also be used
to accelerate the process of phase separation.
Removal of the remaining liquid (solvent) phase requires
a drying process, which is typically accompanied by a signicant amount of shrinkage and densication. The rate
at which the solvent can be removed is ultimately determined by the distribution of porosity in the gel. The ultimate microstructure of the nal component will clearly
be strongly inuenced by changes implemented during
this phase of processing. Afterward, a thermal treatment,
or ring process, is often necessary in order to favor further polycondensation and enhance mechanical properties and structural stability via nal sintering, densication, and grain growth. One of the distinct advantages
of using this methodology as opposed to the more traditional processing techniques is that densication is often
achieved at a much lower temperature.
The precursor sol can be either deposited on a substrate
to form a lm (e.g., by dip-coating or spin-coating),
cast into a suitable container with the desired shape
(e.g., to obtain a monolithic ceramics, glasses, bers,
membranes, aerogels), or used to synthesize powders
(e.g., microspheres, nanospheres). The sol-gel approach
is a cheap and low-temperature technique that allows for
the ne control of the products chemical composition.
Even small quantities of dopants, such as organic dyes
and rare earth metals, can be introduced in the sol and
end up uniformly dispersed in the nal product. It can
be used in ceramics processing and manufacturing as
an investment casting material, or as a means of producing very thin lms of metal oxides for various purposes. Sol-gel derived materials have diverse applications in optics, electronics, energy, space, (bio)sensors,
2.6 Colloids
The term colloid is used primarily to describe a broad
range of solidliquid (and/or liquidliquid) mixtures, all
of which containing distinct solid (and/or liquid) particles
that are dispersed to various degrees in a liquid medium.
The term is specic to the size of the individual particles, which are larger than atomic dimensions but small
enough to exhibit Brownian motion. If the particles are
large enough then their dynamic behavior in any given period of time in suspension would be governed by forces of
gravity and sedimentation. But, if they are small enough
to be colloids, then their irregular motion in suspension
can be attributed to the collective bombardment of a myriad of thermally agitated molecules in the liquid suspending medium, as described originally by Albert Einstein
in his dissertation. Einstein proved the existence of water
molecules by concluding that this erratic particle behavior
could adequately be described using the theory of Brownian motion, with sedimentation being a possible longterm result. This critical size range (or particle diameter)
typically ranges from nanometers (109 m) to micrometers (106 m).[48]
2.7 Morphology
Nanostars of vanadium(IV) oxide
Scientists have taken to naming their particles after the real-world shapes that they might represent.
Nanospheres,[49] nanoreefs,[50] nanoboxes [51] and more
have appeared in the literature. These morphologies
sometimes arise spontaneously as an eect of a templating or directing agent present in the synthesis such as miscellar emulsions or anodized alumina pores, or from the
innate crystallographic growth patterns of the materials
2.10. SAFETY
13
themselves.[52] Some of these morphologies may serve a

purpose, such as long carbon nanotubes used to bridge an
electrical junction, or just a scientic curiosity like the
stars shown at right.
be present in a controlled number per nanoparticle. Multivalent nanoparticles, bearing multiple targeting groups,
can cluster receptors, which can activate cellular signaling pathways, and give stronger anchoring. Monova[59][60][61]
Amorphous particles usually adopt a spherical shape (due lent nanoparticles, bearing a single binding site,
to their microstructural isotropy), whereas the shape avoid clustering and so are preferable for tracking the beof anisotropic microcrystalline whiskers corresponds to havior of individual proteins.
their particular crystal habit. At the small end of the Red blood cell coatings can help nanoparticles evade the
size range, nanoparticles are often referred to as clusters. immune system.[62]
Spheres, rods, bers, and cups are just a few of the shapes
that have been grown. The study of ne particles is called
micromeritics.
2.10 Safety
2.8 Characterization
The majority of nanoparticle characterization techniques
are light-based, but a non-optical nanoparticle characterization technique called Tunable Resistive Pulse Sensing (TRPS) has been developed that enables the simultaneous measurement of size, concentration and surface
charge for a wide variety of nanoparticles.[53] This technique, which applies the Coulter Principle, allows for
particle-by-particle quantication of these three nanoparticle characteristics with high resolution.
2.9 Functionalization
The surface coating of nanoparticles is crucial to determining their properties. In particular, the surface coating
can regulate stability, solubility, and targeting. A coating that is multivalent or polymeric confers high stability.
Functionalized nanomaterial-based catalysts can be used
for catalysis of many known organic reactions.
See also: Nanotoxicology, Fine particles and Regulation

of nanotechnology
Nanoparticles present possible dangers, both medically
and environmentally.[63][64] Most of these are due to
the high surface to volume ratio, which can make the
particles very reactive or catalytic.[65] They are also
able to pass through cell membranes in organisms, and
their interactions with biological systems are relatively
unknown.[66] However, it is unlikely the particles would
enter the cell nucleus, Golgi complex, endoplasmic reticulum or other internal cellular components due to the
particle size and intercellular agglomeration.[67] A recent
study looking at the eects of ZnO nanoparticles on human immune cells has found varying levels of susceptibility to cytotoxicity.[68] There are concerns that pharmaceutical companies, seeking regulatory approval for
nano-reformulations of existing medicines, are relying on
safety data produced during clinical studies of the earlier,
pre-reformulation version of the medicine. This could result in regulatory bodies, such as the FDA, missing new
side eects that are specic to the nano-reformulation.[69]
Whether cosmetics and sunscreens containing nanomaterials pose health risks remains largely unknown at
2.9.1 Surface coating for biological appli- this stage.[70] However considerable research has demonstrated that zinc nanoparticles are not absorbed into the
cations
bloodstream in vivo.[71] Diesel nanoparticles have been
found to damage the cardiovascular system in a mouse
Main article: Nanoparticlebiomolecule conjugate
model.[72]
For biological applications, the surface coating should
be polar to give high aqueous solubility and prevent
nanoparticle aggregation. In serum or on the cell surface,
highly charged coatings promote non-specic binding,
whereas polyethylene glycol linked to terminal hydroxyl
or methoxy groups repel non-specic interactions.[54][55]
Nanoparticles can be linked to biological molecules that
can act as address tags, to direct the nanoparticles to specic sites within the body,[56] specic organelles within
the cell,[57] or to follow specically the movement of individual protein or RNA molecules in living cells.[58] Common address tags are monoclonal antibodies, aptamers,
streptavidin or peptides. These targeting agents should
ideally be covalently linked to the nanoparticle and should
Concern has also been raised over the health eects

of respirable nanoparticles from certain combustion
processes.[73] As of 2013 the Environmental Protection
Agency was investigating the safety of the following
nanoparticles:[74]
Carbon Nanotubes: Carbon materials have a wide
range of uses, ranging from composites for use
in vehicles and sports equipment to integrated circuits for electronic components. The interactions
between nanomaterials such as carbon nanotubes
and natural organic matter strongly inuence both
their aggregation and deposition, which strongly affects their transport, transformation, and exposure
14
in aquatic environments. In past research, carbon organic-inorganic dye-doped nanocomposite. The optinanotubes exhibited some toxicological impacts that mum composition reported by these researchers is 30%
will be evaluated in various environmental settings w/w of SiO2 (~ 12 nm) in dye-doped PMMA.
in current EPA chemical safety research. EPA research will provide data, models, test methods, and
best practices to discover the acute health eects of 2.12 Medicinal applications
carbon nanotubes and identify methods to predict
them.[74]
Liposome
Cerium oxide: Nanoscale cerium oxide is used

in electronics, biomedical supplies, energy, and
fuel additives. Many applications of engineered
cerium oxide nanoparticles naturally disperse themselves into the environment, which increases the
risk of exposure. There is ongoing exposure to
new diesel emissions using fuel additives containing CeO2 nanoparticles, and the environmental and
public health impacts of this new technology are
unknown. EPAs chemical safety research is assessing the environmental, ecological, and health
implications of nanotechnology-enabled diesel fuel
additives.[74]
Dendrimer
Iron oxide nanoparticles
Nanomedicine
Polymer-drug conjugate
Polymeric nanoparticle
2.13 See also

Ceramic engineering
Titanium dioxide: Nano titanium dioxide is currently used in many products. Depending on the
type of particle, it may be found in sunscreens, cosmetics, and paints and coatings. It is also being investigated for use in removing contaminants from
drinking water.[74]
Coating
Nano Silver: Nano silver is being incorporated into

textiles and other materials to eliminate bacteria and
odor from clothing, food packaging, and other items
where antimicrobial properties are desirable. In collaboration with the U.S. Consumer Product Safety
Commission, EPA is studying certain products to
see whether they transfer nano-size silver particles in
real-world scenarios. EPA is researching this topic
to better understand how much nano-silver children
come in contact with in their environments.[74]
Colloidal gold
Iron: While nano-scale iron is being investigated for

many uses, including smart uids for uses such as
optics polishing and as a better-absorbed iron nutrient supplement, one of its more prominent current
uses is to remove contamination from groundwater.
This use, supported by EPA research, is being piloted at a number of sites across the country.[74]
Liposome
2.11 Laser applications

The use of nanoparticles in laser dye-doped poly(methyl
methacrylate) (PMMA) laser gain media was demonstrated in 2003 and it has been shown to improve
conversion eciencies and to decrease laser beam
divergence.[75] Researchers attribute the reduction in
beam divergence to improved dn/dT characteristics of the
Colloid
Colloid-facilitated transport
Colloidal crystal
Eigencolloid
Fullerenes
Fungal-derived nanoparticles
Gallium selenide
Icosahedral twins
Indium selenide
Magnetic immunoassay
Magnetic nanoparticles
Micromeritics
Nanobiotechnology
Nanocrystalline silicon
Nanogeoscience
Nanomaterials
Nanomedicine
Nanoparticle Tracking Analysis
Nanotechnology
2.14. REFERENCES
15
Photonic crystal
[9] Vert, Michel; Doi, Yoshiharu; Hellwich, Karl-Heinz;

Hess, Michael; Hodge, Philip; Kubisa, Przemyslaw; Rinaudo, Marguerite; Schu, Franois (2012). Terminology
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(2): 377410. doi:10.1351/PAC-REC-10-12-04.
Plasmon
Platinum nanoparticles
Quantum dot
Silicon
Silver Nano
Sol-gel
Transparent materials
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[12] Kiss, L. B.; Sderlund, J.; Niklasson, G. A.; Granqvist,
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[16] Reiss, Gunter; Hutten, Andreas (2010). Magnetic
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[18] Rawson, Philip S. (1984). Ceramics. University of Pennsylvania Press. ISBN 0-8122-1156-1.
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2.15 Further reading

Jackie Y. Ying (2001). Nanostructured Materials.
Academic Press. pp. 5. ISBN 978-0-12-7444512.
Salata, OV (2004). Applications of nanoparticles
in biology and medicine. Journal of Nanobiotechnology 2 (1): 3. doi:10.1186/1477-3155-2-3. ISSN
1477-3155. PMC 419715. PMID 15119954.
Nanoparticles Used In Solar Energy Conversion
(ScienceDaily).
Nanoparticles: An occupational hygiene review by
RJ Aitken and others. Health and Safety Executive
Research Report 274/2004
EMERGNANO: A review of completed and near
completed environment, health and safety research
on nanomaterials and nanotechnology by RJ Aitken
and others.
High transmission Tandem DMA for nanoparticle
studies by SEADM, 2014.
2.16 External links

Nanohedron.com images of nanoparticles
Lectures on All Phases of Nanoparticle Science and
Technology
ENPRA Risk Assessment of Engineered
NanoParticles EC FP7 Project led by the Institute
of Occupational Medicine
Chapter 3
Nanowire
A nanowire is a nanostructure, with the diameter of the
order of a nanometer (109 meters). It can also be dened as the ratio of the length to width being greater than
1000. Alternatively, nanowires can be dened as structures that have a thickness or diameter constrained to tens
of nanometers or less and an unconstrained length. At
these scales, quantum mechanical eects are important
which coined the term "quantum wires". Many dierent types of nanowires exist, including superconducting
(e.g., YBCO[1] ), metallic (e.g., Ni, Pt, Au), semiconducting (e.g., Si, InP, GaN, etc.), and insulating (e.g., SiO2 ,
TiO2 ). Molecular nanowires are composed of repeating
molecular units either organic (e.g. DNA) or inorganic
(e.g. Mo6 S-I).
ues of the electrical conductance. Such discrete values

arise from a quantum mechanical restraint on the number of electrons that can travel through the wire at the
nanometer scale. These discrete values are often referred
to as the quantum of conductance and are integer multiples of
3.1 Overview
Examples of nanowires include inorganic molecular

nanowires (Mo6 S-I, Li2 Mo6 Se6 ), which can have a diameter of 0.9 nm and be hundreds of micrometers long.
Other important examples are based on semiconductors
such as InP, Si, GaN, etc., dielectrics (e.g. SiO2 ,TiO2 ),
or metals (e.g. Ni, Pt).
Crystalline 22-atom tin selenide nanowire grown inside a

single-wall carbon nanotube (tube diameter ~1 nm).[2]
2e2
77.41 S
h
They are inverse of the well-known resistance unit h/e2 ,
which is roughly equal to 25812.8 ohms, and referred to
as the von Klitzing constant RK (after Klaus von Klitzing,
the discoverer of exact quantization). Since 1990, a xed
conventional value RK- is accepted.[4]
There are many applications where nanowires may become important in electronic, opto-electronic and nanoelectromechanical devices, as additives in advanced composites, for metallic interconnects in nanoscale quantum
devices, as eld-emitters and as leads for biomolecular
nanosensors.
A noise-ltered HRTEM image of a HgTe extreme nanowire embedded down the central pore of a SWCNT. The image is also
accompanied by a simulation of the crystal structure.[3]
3.2 Synthesis of nanowires
Typical nanowires exhibit aspect ratios (length-to-width

ratio) of 1000 or more. As such they are often referred to as one-dimensional (1-D) materials. Nanowires
have many interesting properties that are not seen in bulk
or 3-D (three-dimensional) materials. This is because
electrons in nanowires are quantum conned laterally and
thus occupy energy levels that are dierent from the traditional continuum of energy levels or bands found in bulk
materials.
There are two basic approaches to synthesizing

nanowires: top-down and bottom-up. A top-down
approach reduces a large piece of material to small
pieces, by various means such as lithography or
electrophoresis. A bottom-up approach synthesizes
the nanowire by combining constituent adatoms. Most
synthesis techniques use a bottom-up approach.
Nanowire production uses several common laboratory

techniques, including suspension, electrochemical deposition, vapor deposition, and VLS growth. Ion track techPeculiar features of this quantum connement exhibited nology enables growing homogeneous and segmented
by certain nanowires manifest themselves in discrete val- nanowires down to 8 nm diameter.
19
20
CHAPTER 3. NANOWIRE
3.2.3 Solution-phase synthesis

Solution-phase synthesis refers to techniques that grow
nanowires in solution. They can produce nanowires of
many types of materials. Solution-phase synthesis has
the advantage that it can produce very large quantities,
compared to other methods. In one technique, the polyol
synthesis, ethylene glycol is both solvent and reducing
agent. This technique is particularly versatile at producing nanowires of lead, platinum, and silver.
The supercritical uid-liquid-solid growth method[5][6]
can be used to synthesize semiconductor nanowires, e.g.,
Si and Ge. By using metal nanocrystals as seeds,[7] Si
and Ge organometallic precursors are fed into a reacAn SEM image of epitaxial nanowire heterostructures grown tor lled with a supercritical organic solvent, such as
from catalytic gold nanoparticles.
toluene. Thermolysis results in degradation of the precursor, allowing release of Si or Ge, and dissolution into
the metal nanocrystals. As more of the semiconductor
3.2.1 Suspension
solute is added from the supercritical phase (due to a concentration gradient), a solid crystallite precipitates, and a
A suspended nanowire is a wire produced in a highnanowire grows uniaxially from the nanocrystal seed.
vacuum chamber held at the longitudinal extremities.
Suspended nanowires can be produced by:
The chemical etching of a larger wire
The bombardment of a larger wire, typically with
highly energetic ions
Indenting the tip of a STM in the surface of a metal
near its melting point, and then retracting it
3.2.2
VLS growth
A common technique for creating a nanowire is vaporliquid-solid method (VLS). This process can produce
crystalline nanowires of some semiconductor materials.
It uses a source material from either laser ablated particles or a feed gas such as silane.
VLS synthesis requires a catalyst. For nanowires, the
best catalysts are liquid metal (such as gold) nanoclusters,
which can either be self-assembled from a thin lm by
In situ observation of CuO nanowire growth
dewetting, or purchased in colloidal form and deposited
on a substrate.
The source enters these nanoclusters and begins to saturate them. On reaching supersaturation, the source solidies and grows outward from the nanocluster. Simply turning o the source can adjust the nal length of
the nanowire. Switching sources while still in the growth
phase can create compound nanowires with super-lattices
of alternating materials.
3.2.4 Non-catalytic growth
Nanowires can be also grown without the help of catalysts, which gives an advantage of pure nanowires and
minimizes the number of technological steps. The simplest methods to obtain metal oxide nanowires use ordinary heating of the metals, e.g. metal wire heated
A single-step vapour phase reaction at elevated temper- with battery, by Joule heating in air[8] can be easily
ature synthesises inorganic nanowires such as Mo6 S-I. done at home. The vast majority of nanowire-formation
From another point of view, such nanowires are cluster mechanisms are explained through the use of catalytic
polymers.
nanoparticles, which drive the nanowire growth and are
3.3. PHYSICS OF NANOWIRES

either added intentionally or generated during the growth.
However the mechanisms for catalyst-free growth of
nanowires (or whiskers) were known from 1950s.[9]
Spontaneous nanowire formation by non-catalytic methods were explained by the dislocation present in specic directions[10][11] or the growth anisotropy of various crystal faces. More recently, after microscopy advancement, the nanowire growth driven by screw dislocations[12][13] or twin boundaries[14] were demonstrated.
The picture on the right shows a single atomic layer
growth on the tip of CuO nanowire, observed by in situ
TEM microscopy during the non-catalytic synthesis of
nanowire.
3.3 Physics of nanowires

3.3.1
Conductivity of nanowires
21
the atoms within the nanowire, and edge eects become
more important.
Furthermore, the conductivity can undergo a quantization
in energy: i.e. the energy of the electrons going through
a nanowire can assume only discrete values, which are
multiples of the conductance quantum G = 2e2 /h (where
e is the charge of the electron and h is the Planck constant.
See also the Quantum Hall eect).
The conductivity is hence described as the sum of the
transport by separate channels of dierent quantized energy levels. The thinner the wire is, the smaller the number of channels available to the transport of electrons.
This quantization has been demonstrated by measuring the conductivity of a nanowire suspended between
two electrodes while pulling it: as its diameter reduces,
its conductivity decreases in a stepwise fashion and the
plateaus correspond to multiples of G.
The quantization of conductivity is more pronounced in
semiconductors like Si or GaAs than in metals, due to
their lower electron density and lower eective mass. It
can be observed in 25 nm wide silicon ns, and results
in increased threshold voltage. In practical terms, this
means that a MOSFET with such nanoscale silicon ns,
when used in digital applications, will need a higher gate
(control) voltage to switch the transistor on.[15]
3.3.2 Welding nanowires

To incorporate nanowire technology into industrial applications, researchers in 2008 developed a method of welding nanowires together: a sacricial metal nanowire is
placed adjacent to the ends of the pieces to be joined (usAn SEM image of a 15 micrometer nickel wire.
ing the manipulators of a scanning electron microscope);
then an electric current is applied, which fuses the wire
Several physical reasons predict that the conductivity of ends. The technique fuses wires as small as 10 nm.[16]
a nanowire will be much less than that of the correspond- For nanowires with diameters less than 10 nm, exing bulk material. First, there is scattering from the wire isting welding techniques, which require precise conboundaries, whose eect will be very signicant when- trol of the heating mechanism and which may introever the wire width is below the free electron mean free duce the possibility of damage, will not be practical.
path of the bulk material. In copper, for example, the Recently scientists discovered that single-crystalline ulmean free path is 40 nm. Copper nanowires less than 40 trathin gold nanowires with diameters ~310 nm can
nm wide will shorten the mean free path to the wire width. be cold-welded together within seconds by mechanNanowires also show other peculiar electrical properties
due to their size. Unlike single wall carbon nanotubes,
whose motion of electrons can fall under the regime of
ballistic transport (meaning the electrons can travel freely
from one electrode to the other), nanowire conductivity
is strongly inuenced by edge eects. The edge eects
come from atoms that lay at the nanowire surface and
are not fully bonded to neighboring atoms like the atoms
within the bulk of the nanowire. The unbonded atoms are
often a source of defects within the nanowire, and may
cause the nanowire to conduct electricity more poorly
than the bulk material. As a nanowire shrinks in size,
the surface atoms become more numerous compared to
ical contact alone, and under remarkably low applied

pressures (unlike macro- and micro-scale cold welding
process).[17] High-resolution transmission electron microscopy and in situ measurements reveal that the welds
are nearly perfect, with the same crystal orientation,
strength and electrical conductivity as the rest of the
nanowire. The high quality of the welds is attributed
to the nanoscale sample dimensions, oriented-attachment
mechanisms and mechanically assisted fast surface diusion. Nanowire welds were also demonstrated between
gold and silver, and silver nanowires (with diameters ~5
15 nm) at near room temperature, indicating that this
technique may be generally applicable for ultrathin metal-
22
CHAPTER 3. NANOWIRE
lic nanowires. Combined with other nano- and microfabrication technologies,[18][19] cold welding is anticipated to
have potential applications in the future bottom-up assembly of metallic one-dimensional nanostructures.
3.4 Applications of nanowires

3.4.1
Electronic devices
resistance contacts by placing a silicide layer in the metalsilicon interface.[20]

It is possible that semiconductor nanowire crossings will
be important to the future of digital computing. Though
there are other uses for nanowires beyond these, the
only ones that actually take advantage of physics in the
nanometer regime are electronic.[21]
In addition, nanowires are also being studied for use as
photon ballistic waveguides as interconnects in quantum
dot/quantum eect well photon logic arrays. Photons
travel inside the tube, electrons travel on the outside shell.
When two nanowires acting as photon waveguides cross
each other the juncture acts as a quantum dot.
Conducting nanowires oer the possibility of connecting
molecular-scale entities in a molecular computer. Dispersions of conducting nanowires in dierent polymers
are being investigated for use as transparent electrodes
for exible at-screen displays.
Atomistic simulation result for formation of inversion channel

(electron density) and attainment of threshold voltage (IV) in a
nanowire MOSFET. Note that the threshold voltage for this device
lies around 0.45V.
Nanowires can be used for transistors. Transistors are

used widely as fundamental building element in todays
electronic circuits. As predicted by Moores law, the dimension of transistors is shrinking smaller and smaller
into nanoscale. One of the key challenges of building future nanoscale transistors is ensuring good gate control
over the channel. Due to the high aspect ratio, if the
gate dielectric is wrapped around the nanowire channel,
we can get good control of channel electrostatic potential,
thereby turning the transistor on and o eciently.
Because of their high Youngs moduli, their use in mechanically enhancing composites is being investigated.
Because nanowires appear in bundles, they may be used
as tribological additives to improve friction characteristics and reliability of electronic transducers and actuators.
Because of their high aspect ratio, nanowires
are also uniquely suited to dielectrophoretic
manipulation,[22][23][24] which oers a low-cost,
bottom-up approach to integrating suspended dielectric
metal oxide nanowires in electronic devices such as UV,
water vapor, and ethanol sensors.[25]
3.4.2 Sensing of proteins and chemicals

using semiconductor nanowires
To create active electronic elements, the rst key step was
to chemically dope a semiconductor nanowire. This has
already been done to individual nanowires to create p- In an analogous way to FET devices in which the modulation of conductance (ow of electrons/holes) in the
type and n-type semiconductors.
semiconductor, between the input (source) and the outThe next step was to nd a way to create a pn junction, put (drain) terminals, is controlled by electrostatic poone of the simplest electronic devices. This was achieved
tential variation (gate-electrode) of the charge carriers
in two ways. The rst way was to physically cross a p-type in the device conduction channel, the methodology of
wire over an n-type wire. The second method involved
a Bio/Chem-FET is based on the detection of the lochemically doping a single wire with dierent dopants cal change in charge density, or so-called eld eect,
along the length. This method created a p-n junction with that characterizes the recognition event between a target
only one wire.
molecule and the surface receptor.
After p-n junctions were built with nanowires, the next This change in the surface potential inuences the Chemlogical step was to build logic gates. By connecting sev- FET device exactly as a gate voltage does, leading to
eral p-n junctions together, researchers have been able a detectable and measurable change in the device conto create the basis of all logic circuits: the AND, OR, duction. When these devices are fabricated using semiand NOT gates have all been built from semiconductor conductor nanowires as the transistor element the bindnanowire crossings.
ing of a chemical or biological species to the surface of
In August 2012, researchers reported constructing the
rst NAND gate from undoped silicon nanowires. This
avoids the problem of how to achieve precision doping
of complementary nanocircuits, which is unsolved. They
were able to control the Schottky barrier to achieve low-
the sensor can lead to the depletion or accumulation of

charge carriers in the bulk of the nanometer diameter
nanowire i.e. (small cross section available for conduction channels). Moreover, the wire, which serves as a
tunable conducting channel, is in close contact with the
3.6. REFERENCES
sensing environment of the target, leading to a short response time, along with orders of magnitude increase in
the sensitivity of the device as a result of the huge S/V
ratio of the nanowires.
While several inorganic semiconducting materials such
as Si, Ge, or metal oxides (e.g. In2O3, SnO2, ZnO, etc.)
have been used for the preparation of nanowires. Silicon
nanowires are usually the material of choice when fabricating nanowire FET-based chemo/biosensors.
Several examples of the use of silicon nanowire sensing
devices include the ultra sensitive, real-time sensing of
biomarker proteins for cancer, detection of single virus
particles, and the detection of nitro-aromatic explosive
materials such as 2,4,6 Tri-nitrotoluene (TNT) in sensitives superior to these of canines.[26] Silicon nanowires
could also be used in their twisted form, as electromechanical devices, to measure intermolecular forces with
great precision.[27]
Limitations of sensing with Silicon nanowire FET devices
Generally, the charges on dissolved molecules and macromolecules are screened by dissolved counterions, since
in most cases molecules bound to the devices are separated from the sensor surface by approximately 212
nm (the size of the receptor proteins or DNA linkers
bound to the sensor surface). As a result of the screening,
the electrostatic potential that arises from charges on the
analyte molecule decays exponentially toward zero with
distance. Thus, for optimal sensing, the Debye length
must be carefully selected for nanowire FET measurements. One approach of overcoming this limitation employs fragmentation of the antibody-capturing units and
control over surface receptor density, allowing more intimate binding to the nanowire of the target protein. This
approach proved useful for dramatically enhancing the
sensitivity of cardiac biomarkers (e.g. Troponin) detection directly from serum for the diagnosis of acute myocardial infarction.[28]
3.4.3
Probes for exploring cells interiors
3.5 See also

Inorganic nanotubes
Molecular nanowires
Nanoantenna
Nanorods
Nanowire battery
Solar cell
23
3.6 References
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[3] Spencer, Joseph; Nesbitt, John; Trewhitt, Harrison;
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Eric; Smith, David (2014). Raman Spectroscopy of Optical Transitions and Vibrational Energies of ~1 nm HgTe
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[4] von Klitzing constant. physics.nist.gov
[5] Holmes, J. D.; Johnston, K. P.; Doty, R. C.; Korgel, B. A. (2000). Control of thickness and orientation of solution-grown silicon nanowires. Science
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[6] Heitsch, Andrew T.; Akhavan, Vahid A.; Korgel,
Brian A. (2011).
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[7] Hanrath, T.; Korgel, B.A. (2003). Supercritical Fluid
LiquidSolid (SFLS) Synthesis of Si and Ge Nanowires
Seeded by Colloidal Metal Nanocrystals. Advanced Materials 15 (5): 437. doi:10.1002/adma.200390101.
[8] Rackauskas, S.; Nasibulin, A. G.; Jiang, H.; Tian, Y.;
Kleshch, V. I.; Sainio, J.; Obraztsova, E. D.; Bokova,
S. N.; Obraztsov, A. N.; Kauppinen, E. I. A Novel
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[9] Sears, G.W.; A Growth Mechanism for Mercury
Whiskers. Acta Metall. 1955, 3, 361366. http://dx.doi.
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[10] Frank, F. C. The Inuence of Dislocations on Crystal
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//dx.doi.org/10.1039/df9490500048
[11] Burton, W. K.; Cabrera, N.; Frank, F. C. The Growth of
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Philos. Trans. R. Soc. London. Ser. A, Math. Phys.
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[12] Morin, S. A.; Bierman, M. J.; Tong, J.; Jin, S. Mechanism

and Kinetics of Spontaneous Nanotube Growth Driven by
Screw Dislocations. Science 2010, 328, 476480. http:
//dx.doi.org/10.1126/science.1182977
[13] Bierman, M. J.; Lau, Y. K. A.; Kvit, A. V; Schmitt, A. L.;
Jin, S. Dislocation-Driven Nanowire Growth and Eshelby
Twist. Science 2008, 320, 10601063. http://dx.doi.org/
10.1126/science.1157131
[14] Rackauskas, S.; Jiang, H.; Wagner, J. B.; Shandakov,
S. D.; Hansen, T. W.; Kauppinen, E. I.; Nasibulin, A.
G. In Situ Study of Noncatalytic Metal Oxide Nanowire
Growth. Nano Lett. 2014, 14, 58105813. http://dx.doi.
org/10.1021/nl502687s
[15] Tilke, A. T.; Simmel, F. C.; Lorenz, H.; Blick, R.
H.; Kotthaus, J. P. (2003). Quantum interference
in a one-dimensional silicon nanowire. Physical Rev.
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doi:10.1103/PhysRevB.68.075311.
[16] Halford, Bethany (2008). Wee Welding with Nanosolder. Chemical & Engineering News 86 (51): 35.
[17] Lu, Yang; Huang, Jian Yu; Wang, Chao; Sun,
Shouheng; Lou, Jun (2010).
Cold welding of
ultrathin gold nanowires.
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[18] Zhong, Z.; Wang, D; Cui, Y; Bockrath, M. W.; Lieber,
C. M. (2003). Nanowire Crossbar Arrays as Address Decoders for Integrated Nanosystems. Science
302 (5649): 13779. Bibcode:2003Sci...302.1377Z.
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[19] Huo, F.; Zheng, Z.; Zheng, G.; Giam, L. R.; Zhang, H.;
Mirkin, C. A. (2008). Polymer Pen Lithography. Science 321 (5896): 1658. Bibcode:2008Sci...321.1658H.
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[20] Mongillo, Massimo; Spathis, Panayotis; Katsaros, Georgios; Gentile, Pascal; De Franceschi, Silvano (2012).
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PMID
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[21] Appenzeller, Joerg;
Knoch, Joachim;
Bjork,
Mikael T.; Riel, Heike; Schmid, Heinz; Riess,
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ics.
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[22] Wissner-Gross, A. D. (2006).
Dielectrophoretic
reconguration
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(PDF). Nanotechnology 17 (19):
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[23] Nanowires get recongured. nanotechweb.org. October
19, 2006.
CHAPTER 3. NANOWIRE
[24] Grange, R.; Choi, J.W.; Hsieh, C.L.; Pu, Y.; Magrez, A.; Smajda, R.; Forro, L.; Psaltis, D. (2009).
Lithium niobate nanowires: synthesis, optical properties and manipulation.
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doi:10.1063/1.3236777.
[25] Vizcano, J. L. P.; Nez, C. G. A. (2013). Fast, eective
manipulation of nanowires for electronic devices. SPIE
Newsroom. doi:10.1117/2.1201312.005260.
[26] Engel, Yoni; Elnathan, R.; Pevzner, A.;, Davidi G.;
Flaxer E.; Patolsky F.; (2010). Supersensitive Detection of Explosives by Silicon Nanowire Arrays. Angewandte Chemie International Edition 49 (38): 68306835.
doi:10.1002/anie.201000847. Cite uses deprecated parameter |coauthors= (help)
[27] Garcia, J. C.; Justo, J. F. (2014). Twisted ultrathin
silicon nanowires: A possible torsion electromechanical nanodevice. Europhys. Lett. 108 (3): 36006.
Bibcode:2014EL....10836006G.
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[28] Elnathan, Roey; Kwiat, M.; Pevzner, A.; Engel, Y.;
Burstein, L.; Khatchtourints, A.; Lichtenstein, A.; Kantaev, R.; Patolsky, F. (10 September 2012). Biorecognition Layer Engineering: Overcoming Screening Limitations of Nanowire-Based FET Devices. Nano Letters
12 (10): 52455254. Bibcode:2012NanoL..12.5245E.
doi:10.1021/nl302434w. PMID 22963381.
3.7 External links

Nanohedron.com | Nano Image Gallery several images of nanowires are included in the galleries.
Stanfords nanowire battery holds 10 times the
charge of existing ones
Original article on the Quantum Hall Eect: K. v.
Klitzing, G. Dorda, and M. Pepper; Phys. Rev. Lett.
45, 494497 (1980).
Strongest theoretical nanowire produced at Australias University of Melbourne.
Penn Engineers Design Electronic Computer Memory in Nanoscale Form That Retrieves Data 1,000
Times Faster.
One atom thick, hundreds of nanometers long Ptnanowires are one of the best examples of selfassembly. (University of Twente)
Chapter 4
Nanomedicine
Nanotherapeutics redirects here. For the company, see
Nanotherapeutics (company).
4.1 Drug delivery

Antigen detection
Nanomedicine is the medical application of

nanotechnology.[1] Nanomedicine ranges from the
medical applications of nanomaterials and biological
devices, to nanoelectronic biosensors, and even possible
future applications of molecular nanotechnology such as
biological machines. Current problems for nanomedicine
involve understanding the issues related to toxicity and
environmental impact of nanoscale materials (materials
whose structure is on the scale of nanometers, i.e.
billionths of a meter).
Linkers
Functional
layers
Protective
layer
Fluorescent
signalling
Biocompatibility
Shape
recognition
Functionalities can be added to nanomaterials by interfacing them with biological molecules or structures. The
size of nanomaterials is similar to that of most biological
molecules and structures; therefore, nanomaterials can be
useful for both in vivo and in vitro biomedical research
and applications. Thus far, the integration of nanomaterials with biology has led to the development of diagnostic
devices, contrast agents, analytical tools, physical therapy
applications, and drug delivery vehicles.
Nanomedicine seeks to deliver a valuable set of research
tools and clinically useful devices in the near future.[2][3]
The National Nanotechnology Initiative expects new
commercial applications in the pharmaceutical industry
that may include advanced drug delivery systems, new
therapies, and in vivo imaging.[4] Nanomedicine research
is receiving funding from the US National Institutes of
Health, including the funding in 2005 of a ve-year plan
Nanoparticles (top), liposomes (middle), and dendrimers
to set up four nanomedicine centers.
(bottom) are some nanomaterials being investigated for
Nanomedicine is a large industry, with nanomedicine use in nanomedicine.
sales reaching $6.8 billion in 2004, and with over 200
companies and 38 products worldwide, a minimum of
Nanotechnology has provided the possibility of delivering
$3.8 billion in nanotechnology R&D is being invested
drugs to specic cells using nanoparticles.
[5]
every year. In April 2006, the journal Nature Materials estimated that 130 nanotech-based drugs and deliv- The overall drug consumption and side-eects may be
ery systems were being developed worldwide.[6] As the lowered signicantly by depositing the active agent in the
nanomedicine industry continues to grow, it is expected morbid region only and in no higher dose than needed.
Targeted drug delivery is intended to reduce the side efto have a signicant impact on the economy.
fects of drugs with concomitant decreases in consumption and treatment expenses. Drug delivery focuses
on maximizing bioavailability both at specic places in
the body and over a period of time. This can poten25
26
CHAPTER 4. NANOMEDICINE
tially be achieved by molecular targeting by nanoengineered devices.[7][8] More than $65 billion are wasted
each year due to poor bioavailability. A benet of using
nanoscale for medical technologies is that smaller devices
are less invasive and can possibly be implanted inside the
body, plus biochemical reaction times are much shorter.
These devices are faster and more sensitive than typical
drug delivery.[9] The ecacy of drug delivery through
nanomedicine is largely based upon: a) ecient encapsulation of the drugs, b) successful delivery of drug to the
targeted region of the body, and c) successful release of
the drug.
Drug delivery systems, lipid- [10] or polymer-based
nanoparticles,[11] can be designed to improve
the pharmacokinetics and biodistribution of the
drug.[12][13][14] However, the pharmacokinetics and
pharmacodynamics of nanomedicine is highly variable
among dierent patients.[15] When designed to avoid
the bodys defence mechanisms,[16] nanoparticles have
benecial properties that can be used to improve drug
delivery. Complex drug delivery mechanisms are being
developed, including the ability to get drugs through cell
membranes and into cell cytoplasm. Triggered response
is one way for drug molecules to be used more eciently.
Drugs are placed in the body and only activate on encountering a particular signal. For example, a drug with
poor solubility will be replaced by a drug delivery system
where both hydrophilic and hydrophobic environments
exist, improving the solubility.[17] Drug delivery systems
may also be able to prevent tissue damage through
regulated drug release; reduce drug clearance rates; or
lower the volume of distribution and reduce the eect
on non-target tissue. However, the biodistribution of
these nanoparticles is still imperfect due to the complex
hosts reactions to nano- and microsized materials[16]
and the diculty in targeting specic organs in the body.
Nevertheless, a lot of work is still ongoing to optimize
and better understand the potential and limitations of
nanoparticulate systems. While advancement of research
proves that targeting and distribution can be augmented
by nanoparticles, the dangers of nanotoxicity become
an important next step in further understanding of their
medical uses.[18]
nology was also instrumental in engineering medical nanodevices and novel drug delivery systems as well as in developing sensing applications.[27] Another example can
be found in dendrimers and nanoporous materials. Another example is to use block co-polymers, which form
micelles for drug encapsulation.[11]
Polymeric nano-particles are a competing technology to
lipidic (based mainly on Phospholipids) nano-particles.
There is an additional risk of toxicity associated with
polymers not widely studied or understood. The major
advantages of polymers is stability, lower cost and predictable characterisation. However, in the patients body
this very stability (slow degradation) is a negative factor. Phospholipids on the other hand are membrane lipids
(already present in the body and surrounding each cell),
have a GRAS (Generally Recognised As Safe) status from
FDA and are derived from natural sources without any
complex chemistry involved. They are not metabolised
but rather absorbed by the body and the degradation products are themselves nutrients (fats or micronutrients).
Protein and peptides exert multiple biological actions
in the human body and they have been identied as
showing great promise for treatment of various diseases and disorders. These macromolecules are called
biopharmaceuticals. Targeted and/or controlled delivery of these biopharmaceuticals using nanomaterials like
nanoparticles and Dendrimers is an emerging eld called
nanobiopharmaceutics, and these products are called
nanobiopharmaceuticals.
Another highly ecient system for microRNA delivery for example are nanoparticles formed by the selfassembly of two dierent microRNAs deregulated in
cancer.[28]
Another vision is based on small electromechanical systems; nanoelectromechanical systems are being investigated for the active release of drugs. Some potentially
important applications include cancer treatment with iron
nanoparticles or gold shells.Nanotechnology is also opening up new opportunities in implantable delivery systems,
which are often preferable to the use of injectable drugs,
because the latter frequently display rst-order kinetics
(the blood concentration goes up rapidly, but drops expoNanoparticles can be used in combination therapy for de- nentially over time). This rapid rise may cause diculties
creasing antibiotic resistance or for their antimicrobial with toxicity, and drug ecacy can diminish as the drug
properties.[19][20][21] Nanoparticles might also used to cir- concentration falls below the targeted range.
cumvent multidrug resistance (MDR) mechanisms.[22]
4.1.2 Applications
4.1.1
Types of systems used
Some nanotechnology-based drugs that are commercially

Two forms of nanomedicine that have already been tested available or in human clinical trials include:
in mice and are awaiting human trials that will be using
gold nanoshells to help diagnose and treat cancer,[23] and
Abraxane, approved by the U.S. Food and Drug Adusing liposomes as vaccine adjuvants and as vehicles for
ministration (FDA) to treat breast cancer,[29] non[24][25]
drug transport.
Similarly, drug detoxication is also
small- cell lung cancer (NSCLC)[30] and pancreatic
another application for nanomedicine which has shown
cancer,[31] is the nanoparticle albumin bound pacli[26]
taxel.
promising results in rats. Advances in Lipid nanotech-
4.2. VISUALIZATION
Doxil was originally approved by the FDA for the
use on HIV-related Kaposis sarcoma. It is now being used to also treat ovarian cancer and multiple
myeloma. The drug is encased in liposomes, which
helps to extend the life of the drug that is being distributed. Liposomes are self-assembling, spherical,
closed colloidal structures that are composed of lipid
bilayers that surround an aqueous space. The liposomes also help to increase the functionality and it
helps to decrease the damage that the drug does to
the heart muscles specically.[32]
27
Cancer
Existing and potential drug nanocarriers have been
reviewed.[39][40][41][42]
Nanoparticles have high surface area to volume ratio.

This allows for many functional groups to be attached to
a nanoparticle, which can seek out and bind to certain
tumor cells. Additionally, the small size of nanoparticles
(10 to 100 nanometers), allows them to preferentially accumulate at tumor sites (because tumors lack an eective lymphatic drainage system).[43] Limitations to conventional cancer chemotherapy include drug resistance,
Onivyde, liposome encapsulated irinotecan to treat lack of selectivity, and lack of solubility. Nanoparticles
metastatic pancreatic cancer, was approved by FDA have the potential to overcome these problems.[44]
in October 2015.[33]
In photodynamic therapy, a particle is placed within the
body and is illuminated with light from the outside. The
C-dots (Cornell dots) are the smallest silica-based light gets absorbed by the particle and if the particle is
nanoparticles with the size <10 nm. The particles metal, energy from the light will heat the particle and
are infused with organic dye which will light up with surrounding tissue. Light may also be used to produce
uorescence. Clinical trial is underway since 2011 high energy oxygen molecules which will chemically reto use the C-dots as diagnostic tool to assist surgeons act with and destroy most organic molecules that are next
to identify the location of tumor cells.[34]
to them (like tumors). This therapy is appealing for
many reasons. It does not leave a toxic trail of reactive
An early phase clinical trial using the platform of molecules throughout the body (chemotherapy) because it
Minicell nanoparticle for drug delivery have been is directed where only the light is shined and the particles
tested on patients with advanced and untreatable exist. Photodynamic therapy has potential for a noninvacancer. Built from the membranes of mutant bac- sive procedure for dealing with diseases, growth and tuteria, the minicells were loaded with paclitaxel and mors. Kanzius RF therapy is one example of such therapy
coated with cetuximab, antibodies that bind the (nanoparticle hyperthermia) . Also, gold nanoparticles
epidermal growth factor receptor (EGFR) which is have the potential to join numerous therapeutic functions
by targeting specic tumor cells,
often overexpressed in a number of cancers, as a into a single platform,
[45][46]
tissues
and
organs.
'homing' device to the tumor cells. The tumor cells
recognize the bacteria from which the minicells have
been derived, regard it as invading microorganism
and engulf it. Once inside, the payload of anticancer drug kills the tumor cells. Measured at
400 nanometers, the minicell is bigger than synthetic particles developed for drug delivery. The
researchers indicated that this larger size gives the
minicells a better prole in side-eects because the
minicells will preferentially leak out of the porous
blood vessels around the tumor cells and do not
reach the liver, digestive system and skin. This
Phase 1 clinical trial demonstrated that this treatment is well tolerated by the patients. As a platform
technology, the minicell drug delivery system can
be used to treat a number of dierent cancers with Algorithm Cancer Magnetic Nanotherapy
dierent anti-cancer drugs with the benet of lower
dose and less side-eects.[35][36]
In 2014, a Phase 3 clinical trial for treating inammation and pain after cataract surgery, and a Phase
2 trial for treating dry eye disease were initiated using nanoparticle loteprednol etabonate.[37] In 2015,
the product, KPI-121 was found to produce statistically signicant positive results for the post-surgery
treatment.[38]
4.2 Visualization
In vivo imaging is another area where tools and devices
are being developed. Using nanoparticle contrast agents,
images such as ultrasound and MRI have a favorable distribution and improved contrast. This might be accomplished by self assembled biocompatible nanodevices that
28
will detect, evaluate, treat and report to the clinical doctor tures.
automatically.
Sensor test chips containing thousands of nanowires, able
The small size of nanoparticles endows them with prop- to detect proteins and other biomarkers left behind by
erties that can be very useful in oncology, particularly cancer cells, could enable the detection and diagnosis of
in imaging. Quantum dots (nanoparticles with quantum cancer in the early stages from a few drops of a patients
connement properties, such as size-tunable light emis- blood.[49] Nanotechnology is helping to advance the use
sion), when used in conjunction with MRI (magnetic res- of arthroscopes, which are pencil-sized devices that are
onance imaging), can produce exceptional images of tu- used in surgeries with lights and cameras so surgeons can
mor sites. Nanoparticles of cadmium selenide (quantum do the surgeries with smaller incisions. The smaller the
dots) glow when exposed to ultraviolet light. When in- incisions the faster the healing time which is better for
jected, they seep into cancer tumors. The surgeon can the patients. It is also helping to nd a way to make an
see the glowing tumor, and use it as a guide for more arthroscope smaller than a strand of hair.[50]
accurate tumor removal.These nanoparticles are much
brighter than organic dyes and only need one light source
for excitation. This means that the use of uorescent
4.4 Blood purication
quantum dots could produce a higher contrast image and
at a lower cost than todays organic dyes used as contrast
media. The downside, however, is that quantum dots are Magnetic micro particles are proven research instruments
for the separation of cells and proteins from complex
usually made of quite toxic elements.
media. The technology is available under the name
Tracking movement can help determine how well drugs
Magnetic-activated cell sorting or Dynabeads among othare being distributed or how substances are metabolized.
ers. More recently it was shown in animal models that
It is dicult to track a small group of cells throughout
magnetic nanoparticles can be used for the removal of
the body, so scientists used to dye the cells. These dyes
various noxious compounds including toxins, pathogens,
needed to be excited by light of a certain wavelength in
and proteins from whole blood in an extracorporeal cirorder for them to light up. While dierent color dyes abcuit similar to dialysis.[51][52] In contrast to dialysis, which
sorb dierent frequencies of light, there was a need for as
works on the principle of the size related diusion of somany light sources as cells. A way around this problem
lutes and ultraltration of uid across a semi-permeable
is with luminescent tags. These tags are quantum dots
membrane, the purication with nanoparticles allows speattached to proteins that penetrate cell membranes. The
cic targeting of substances. Additionally larger comdots can be random in size, can be made of bio-inert mapounds which are commonly not dialyzable can be reterial, and they demonstrate the nanoscale property that
moved.
color is size-dependent. As a result, sizes are selected so
that the frequency of light used to make a group of quan- The purication process is based on functionalized
tum dots uoresce is an even multiple of the frequency iron oxide or carbon coated metal nanoparticles with
[53]
required to make another group incandesce. Then both ferromagnetic or superparamagnetic properties.
[52]
antibodies,[51]
groups can be lit with a single light source. They have Binding agents such as proteins,
[54]
[55]
[47]
or synthetic ligands
are covalently
also found a way to insert nanoparticles
into the af- antibiotics,
fected parts of the body so that those parts of the body linked to the particle surface. These binding agents are
will glow showing the tumor growth or shrinkage or also able to interact with target species forming an agglomerate. Applying an external magnetic eld gradient allows
organ trouble.[48]
exerting a force on the nanoparticles. Hence the particles
can be separated from the bulk uid, thereby cleaning it
from the contaminants.[56][57]
4.3 Sensing
Main article: Nanosensor

Nanotechnology-on-a-chip is one more dimension of labon-a-chip technology. Magnetic nanoparticles, bound to
a suitable antibody, are used to label specic molecules,
structures or microorganisms. Gold nanoparticles tagged
with short segments of DNA can be used for detection
of genetic sequence in a sample. Multicolor optical coding for biological assays has been achieved by embedding
dierent-sized quantum dots into polymeric microbeads.
Nanopore technology for analysis of nucleic acids converts strings of nucleotides directly into electronic signa-
The small size (< 100 nm) and large surface area of functionalized nanomagnets leads to advantageous properties
compared to hemoperfusion, which is a clinically used
technique for the purication of blood and is based on
surface adsorption. These advantages are high loading
and accessibility of the binding agents, high selectivity
towards the target compound, fast diusion, small hydrodynamic resistance, and low dosage.[58]
This approach oers new therapeutic possibilities for the
treatment of systemic infections such as sepsis by directly
removing the pathogen. It can also be used to selectively
remove cytokines or endotoxins[54] or for the dialysis of
compounds which are not accessible by traditional dialysis methods. However the technology is still in a preclin-
4.7. SEE ALSO
29
ical phase and rst clinical trials are not expected before would make use of these nanorobots, introduced into the
2017.[59]
body, to repair or detect damages and infections. Molecular nanotechnology is highly theoretical, seeking to anticipate what inventions nanotechnology might yield and
to propose an agenda for future inquiry. The proposed
4.5 Tissue engineering
elements of molecular nanotechnology, such as molecular assemblers and nanorobots are far beyond current
Nanotechnology may be used as part of tissue engineer- capabilities.[1][64][65][66]
ing to help reproduce or repair damaged tissue using
suitable nanomaterial-based scaolds and growth factors. Tissue engineering if successful may replace con- 4.7 See also
ventional treatments like organ transplants or articial
implants. Nanoparticles such as graphene, carbon nan Nanoparticlebiomolecule conjugate
otubes, molybdenum disulde and tungsten disulde are
being used as reinforcing agents to fabricate mechani Nanobiotechnology
cally strong biodegradable polymeric nanocomposites for
Nanotechnology in ction
bone tissue engineering applications. The addition of
these nanoparticles in the polymer matrix at low con Colloidal gold
centrations (~0.2 weight %) leads to signicant improve gold nanobeacons
ments in the compressive and exural mechanical properties of polymeric nanocomposites.[60][61] Potentially,
Top-down and bottom-up design
these nanocomposites may be used as a novel, mechanically strong, light weight composite as bone implants.
Nanosensor
For example, a esh welder was demonstrated to fuse
two pieces of chicken meat into a single piece using a
suspension of gold-coated nanoshells activated by an infrared laser. This could be used to weld arteries during
surgery.[62] Another example is nanonephrology, the use
of nanomedicine on the kidney.
4.6 Medical devices

Neuro-electronic interfacing is a visionary goal dealing
with the construction of nanodevices that will permit
computers to be joined and linked to the nervous system. This idea requires the building of a molecular structure that will permit control and detection of nerve impulses by an external computer. A refuelable strategy implies energy is relled continuously or periodically with
external sonic, chemical, tethered, magnetic, or biological electrical sources, while a nonrefuelable strategy implies that all power is drawn from internal energy storage
which would stop when all energy is drained. A nanoscale
enzymatic biofuel cell for self-powered nanodevices have
been developed that uses glucose from biouids including
human blood and watermelons.[63] One limitation to this
innovation is the fact that electrical interference or leakage or overheating from power consumption is possible.
The wiring of the structure is extremely dicult because
they must be positioned precisely in the nervous system.
The structures that will provide the interface must also be
compatible with the bodys immune system.[64]
Molecular nanotechnology is a speculative subeld of
nanotechnology regarding the possibility of engineering
molecular assemblers, machines which could re-order
matter at a molecular or atomic scale. Nanomedicine
Photodynamic therapy
Impalefection
Nanobiopharmaceutics
Monitoring (medicine)
IEEE P1906.1 Recommended Practice for
Nanoscale and Molecular Communication Framework
4.8 References
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[4] Nanotechnology in Medicine and the Biosciences, by
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[11] University of Waterloo, Nanotechnology in Targeted
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[12] Allen TM; Cullis PR (2004). Drug Delivery Systems: Entering the Mainstream.
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[22] Conde, J.; de la Fuente, JM; Baptista, PV. "Nanomaterials
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[17] Nagy ZK, Zsombor K.; Balogh A; Vajna B; Farkas A;

Patyi G; Kramarics A; Marosi G (2011). Comparison of
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[31] FDA Press Announcements (6 September 2013). FDA

approves Abraxane for late-stage pancreatic cancer.
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D. (January 2012). Nanotechnology based devices and
applications in medicine: An overview. Chronicles
of Young Scientists 3 (1): 6873. doi:10.4103/22295186.94320.
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KP, Ibarra MR, Baptista PV, Stoeger T, de la Fuente JM.
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[47] Yasitha L Hewakuruppu et al., Plasmonic " pump probe "

method to study semi-transparent nanouids, Applied Optics, 52(24) 6041-6050.
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[48] Coey, Rebecca (August 2010). 20 Things You Didn't

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[37] Press Release (19 June 2014). Kala Pharmaceuticals Initiates Phase3 Clinical Trial for Treatment of Post-Surgical
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(2005). Multiplexed electrical detection of cancer markers with nanowire sensor arrays. Nat. Biotechnol.
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[38] Press Release (1 April 2015). Kala Pharmaceuticals Announces Positive Results from Phase 3 Trial of KPI-121
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[40] Prez-Herrero E, Fernndez-Medarde A (2015). Advanced targeted therapies in cancer: Drug nanocarriers,
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[41] Nguyen-Ngoc T, Raymond E (2015).
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[42] Ghaz-Jahanian MA, Abbaspour-Aghdam F, Anarjan N,
Berenjian A, Jafarizadeh-Malmiri H (2015). Application of chitosan-based nanocarriers in tumor-targeted
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[43] Nie, Shuming; Yun Xing; Gloria J. Kim & Jonathan W.
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[44] Chidambaram, M.; Manavalan, R.; Kathiresan, K.
(2011). Nanotherapeutics to overcome conventional
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21501554.
[45] Loo C; Lin A; Hirsch L; Lee MH; Barton J; Halas N; West
J; Drezek R. (2004). Nanoshell-enabled photonics-based
imaging and therapy of cancer. Technol Cancer Res
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PMID 14750891.
[50] Hall, J. Storrs (2005). Nanofuture : whats next for nanotechnology. Amherst, NY: Prometheus Books. ISBN
978-1591022879.
[51] Herrmann, I. K. et al. Nanomagnet-based removal of lead
and digoxin from living rats. Nanoscale 5, 87188723
(2013).
[52] Kang J. H.; et al. (2014). An extracorporeal bloodcleansing device for sepsis therapy. Nat. Med 20: 1211
1216. doi:10.1038/nm.3640.
[53] Berry C. C., Curtis A. S. G. (2003). Functionalisation of
magnetic nanoparticles for applications in biomedicine.
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[54] Herrmann I. K.; et al. (2013). Endotoxin Removal
by Magnetic Separation-Based Blood Purication. Adv.
Healthc. Mater 2: 829835.
[55] Lee J.-J.; et al.
(2014).
Synthetic LigandCoated Magnetic Nanoparticles for Microuidic Bacterial Separation from Blood. Nano Lett. 14: 15.
doi:10.1021/nl3047305.
[56] Schumacher C. M.; et al. (2013). Quantitative Recovery
of Magnetic Nanoparticles from Flowing Blood: Trace
Analysis and the Role of Magnetization. Adv. Funct.
Mater 23: 48884896. doi:10.1002/adfm.201300696.
[57] Yung C. W., Fiering J., Mueller A. J., Ingber D. E.
(2009). Micromagneticmicrouidic blood cleansing
device. Lab. Chip 9: 11717. doi:10.1039/b816986a.
PMID 19370233.
[58] Herrmann, I. K., Grass, R. N. & Stark, W. J. Highstrength metal nanomagnets for diagnostics and medicine:
carbon shells allow long-term stability and reliable linker
chemistry. Nanomed. 4, 787798 (2009).
[59] Stacy Shepherd,Harvard Engineers Invented an Articial
Spleen to Treat Sepsis, Boston Magazine. Retrieved on
20 April 2015.
32
[60] Lalwani Gaurav; Henslee Allan M.; Farshid Behzad;

Lin Liangjun; Kasper F. Kurtis, Yi-; Qin Xian;
Mikos Antonios G.; Sitharaman Balaji; et al. (2013).
Two-dimensional nanostructure-reinforced biodegradable polymeric nanocomposites for bone tissue engineering.
Biomacromolecules 14 (3): 900909.
doi:10.1021/bm301995s.
PMC 3601907.
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23405887.
[61] Lalwani, Gaurav (September 2013). Tungsten disulde nanotubes reinforced biodegradable polymers for
bone tissue engineering. Acta Biomaterialia 9 (9):
83658373. doi:10.1016/j.actbio.2013.05.018. PMC
3732565. PMID 23727293.
[62] Gobin AM; O'Neal DP; Watkins DM; Halas NJ; Drezek
RA; West JL (2005). Near infrared laser-tissue welding using nanoshells as an exogenous absorber. Lasers
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16047329.
[63] http://www.nanowerk.com/spotlight/spotid=19573.php
[64] Nanomedicine, Volume IIA: Biocompatibility, by Robert
A. Freitas Jr. 2003, ISBN 1-57059-700-6
[65] Freitas, Robert A., Jr.; Havukkala, Ilkka (2005). Current
Status of Nanomedicine and Medical Nanorobotics
(PDF). Journal of Computational and Theoretical
Nanoscience 2 (4): 125. doi:10.1166/jctn.2005.001.
[66] Nanofactory Collaboration
4.9 Further reading

Institute of Medicine, United States (2011).
Nanotechnology and Oncology: Workshop Summary. Washington, DC: The National Academies
Press. ISBN 978-0-309-16321-7. Retrieved 16
August 2014.
Chapter 5
Green nanotechnology
Green nanotechnology refers to the use of
nanotechnology to enhance the environmental sustainability of processes producing negative externalities.
It also refers to the use of the products of nanotechnology to enhance sustainability. It includes making green
nano-products and using nano-products in support of
sustainability.
Green nanotechnology has been described as the development of clean technologies, to minimize potential environmental and human health risks associated with the
manufacture and use of nanotechnology products, and
to encourage replacement of existing products with new
nano-products that are more environmentally friendly
throughout their lifecycle.[1]
5.1 Goals
directly or indirectly. Nanomaterials or products directly can clean hazardous waste sites, desalinate water, treat pollutants, or sense and monitor environmental pollutants. Indirectly, lightweight nanocomposites
for automobiles and other means of transportation
could save fuel and reduce materials used for production; nanotechnology-enabled fuel cells and lightemitting diodes (LEDs) could reduce pollution from
energy generation and help conserve fossil fuels; selfcleaning nanoscale surface coatings could reduce or eliminate many cleaning chemicals used in regular maintenance routines;[3] and enhanced battery life could lead to
less material use and less waste. Green Nanotechnology
takes a broad systems view of nanomaterials and products, ensuring that unforeseen consequences are minimized and that impacts are anticipated throughout the full
life cycle.[4]
Green nanotechnology has two goals: producing

nanomaterials and products without harming the environment or human health, and producing nano-products
that provide solutions to environmental problems. It
uses existing principles of green chemistry and green
engineering[2] to make nanomaterials and nano-products 5.2
without toxic ingredients, at low temperatures using
less energy and renewable inputs wherever possible, and
using lifecycle thinking in all design and engineering 5.2.1
stages.
In addition to making nanomaterials and products with
less impact to the environment, green nanotechnology
also means using nanotechnology to make current manufacturing processes for non-nano materials and products
more environmentally friendly. For example, nanoscale
membranes can help separate desired chemical reaction
products from waste materials. Nanoscale catalysts can
make chemical reactions more ecient and less wasteful. Sensors at the nanoscale can form a part of process
control systems, working with nano-enabled information
systems. Using alternative energy systems, made possible
by nanotechnology, is another way to green manufacturing processes.
Current research
Solar cells
Main article: Energy applications of nanotechnology

One major project that is being worked on is the development of nanotechnology in solar cells.[5] Solar cells
are more ecient as they get tinier and solar energy is
a renewable resource. The price per watt of solar energy
is lower than one dollar.
Nanotechnology is already used to provide improved performance coatings for photovoltaic (PV) and solar thermal panels. Hydrophobic and self-cleaning properties
combine to create more ecient solar panels, especially
during inclement weather. PV covered with nanotechnolThe second goal of green nanotechnology involves de- ogy coatings are said to stay cleaner for longer to ensure
veloping products that benet the environment either maximum energy eciency is maintained.[6]
33
34
5.2.2
CHAPTER 5. GREEN NANOTECHNOLOGY
Nanoremediation and water treat- 5.3

ment
See also
Green chemistry
Main articles: Nanoltration and Nanoremediation
Nanotechnology oers the potential of novel
nanomaterials for the treatment of surface water,
groundwater, wastewater, and other environmental
materials contaminated by toxic metal ions, organic and
inorganic solutes, and microorganisms. Due to their
unique activity toward recalcitrant contaminants, many
nanomaterials are under active research and development for use in the treatment of water and contaminated
sites.[7][8]
The present market of nanotech-based technologies applied in water treatment consists of reverse osmosis,
nanoltration, ultraltration membranes. Indeed, among
emerging products one can name nanober lters, carbon
nanotubes and various nanoparticles.[9] Nanotechnology
is expected to deal more eciently with contaminants
which convectional water treatment systems struggle to
treat, including bacteria, viruses and heavy metals. This
eciency generally stems from the very high specic surface area of nanomaterials which increases dissolution,
reactivity and sorption of contaminants.[10][11]
Some potential applications include:
Clean technology
NBI Knowledgebase
Bioremediation
Environmental microbiology
Industrial microbiology
Tata Swach
LifeSaver bottle
5.4 References
[1] Environment and Green Nano - Topics - Nanotechnology
Project. Retrieved 11 September 2011.
[2] What is Green Engineering, US Environmental Protection
Agency
[3] Sustainable Nano Coatings. nanoShell Ltd. Retrieved 3
January 2013.
[4] Nanotechnology and Life Cycle Assessment
To maintain public health, pathogens in water need

to be identied rapidly and reliably. Unfortunately,
traditional laboratory culture tests take days to complete. Faster methods involving enzymes, immunological or genetic tests are under development.[7]
Water ltration may be improved with the use of
nanober membranes and the use of nanobiocides,
which appear promisingly eective.[12]
Biolms are mats of bacteria wrapped in natural polymers. These can be dicult to treat with
antimicrobials or other chemicals. They can be
cleaned up mechanically, but at the cost of substantial down-time and labour. Work is in progress
to develop enzyme treatments that may be able to
break down such biolms.[7]
5.2.3
Pollution
[5] Nano Flake Technology A Cheaper Way to Produce Solar Cells

[6] Improved Performance Coatings. nanoShell Ltd. Retrieved 3 January 2013.
[7] Cloete, TE et al (editor) (2010). Nanotechnology in Water
Treatment Applications. Caister Academic Press. ISBN
978-1-904455-66-0.
[8] Karn, Barbara; Todd Kuiken; Martha Otto (2009-1201). Nanotechnology and in Situ Remediation: A
Review of the Benets and Potential Risks. Environmental Health Perspectives 117 (12): 18231831.
doi:10.1289/ehp.0900793. ISSN 0091-6765. JSTOR
30249860. Retrieved 2013-11-18.
[9] Hanft, Susan (2011). Market Research Report Nanotechnology in water treatment. Wellesley, MA USA: BCC Research. p. 16. ISBN 1596237090.
[10] Nanotechnology in water treatment.
November 2013.
Retrieved 3
[11] Qu, Xiaolei; Alvarez, Pedro J J; Li, Qilin (2013).

Applications of nanotechnology in water and wastewScientists have been researching the capabilities of
ater treatment. Water research 47 (12): 393146.
buckminsterfullerene in controlling pollution, as it may
doi:10.1016/j.watres.2012.09.058. PMID 23571110.
be able to control certain chemical reactions. BuckminRetrieved 21 September 2013.
sterfullerene has been demonstrated as having the ability
of inducing the protection of reactive oxygen species and [12] Critical Reviews in Microbiology, 2010; 36(1): 6881
causing lipid peroxidation. This material may allow for
The potential of nanobers and nanobiocides in water purication Marelize Botes, and Thomas Eugene Cloete
hydrogen fuel to be more accessible to consumers.
5.6. EXTERNAL LINKS
5.5 Further reading

Evaluation of 'green' nanotechnology requires a full
life cycle assessment
Nano Flakes May Revolutionize Solar Cells
5.6 External links

Safer Nanomaterials and Nanomanufacturing Initiative
Clean Tech Law & Business
Project on Emerging Nanotechnologies
Nanotechnology Lab
National Nanotechnology Initiative
The Berkeley Nanosciences and Nanoengineering
Institute
Nanotechnology: Green Manufacturing
Nanotechnology Now
Can nanotechnology be green?
35
Chapter 6
Carbon nanotube
Not to be confused with Carbon ber.
walled nanotubes (MWNTs). Individual nanotubes natCarbon nanotubes (CNTs) are allotropes of car- urally align themselves into ropes held together by van
der Waals forces, more specically, pi-stacking.
Applied quantum chemistry, specically, orbital hybridization best describes chemical bonding in nanotubes.
The chemical bonding of nanotubes is composed entirely of sp2 bonds, similar to those of graphite. These
bonds, which are stronger than the sp3 bonds found
in alkanes and diamond, provide nanotubes with their
unique strength.
6.1 Types of carbon nanotubes and

related structures
6.1.1 Terminology
There is no consensus on some terms describing carbon nanotubes in scientic literature: both "-wall and
"-walled are being used in combination with single,
Rotating single-walled zigzag carbon nanotube
double, triple or multi, and the letter C is often
bon with a cylindrical nanostructure. Nanotubes have omitted in the abbreviation; for example, multi-walled
been constructed with length-to-diameter ratio of up to carbon nanotube (MWNT).
132,000,000:1,[1] signicantly larger than for any other
material. These cylindrical carbon molecules have unusual properties, which are valuable for nanotechnology, 6.1.2 Single-walled
electronics, optics and other elds of materials science
Armchair (n,n) i.e.: m=n
and technology. In particular, owing to their extraordinary thermal conductivity and mechanical and electrical
The translation vector is bent, while the chiral vector
properties, carbon nanotubes nd applications as addistays straight
tives to various structural materials. For instance, nanotubes form a tiny portion of the material(s) in some (pri Graphene nanoribbon
marily carbon ber) baseball bats, golf clubs, car parts or
[2][3]
damascus steel.
The chiral vector is bent, while the translation vector
Nanotubes are members of the fullerene structural famstays straight
ily. Their name is derived from their long, hollow structure with the walls formed by one-atom-thick sheets of
Zigzag (n,0)
carbon, called graphene. These sheets are rolled at specic and discrete ("chiral") angles, and the combina Chiral (n,m)
tion of the rolling angle and radius decides the nanotube
properties; for example, whether the individual nanotube
n and m can be counted at the end of the tube
shell is a metal or semiconductor. Nanotubes are categorized as single-walled nanotubes (SWNTs) and multi Graphene nanoribbon
36
6.1. TYPES OF CARBON NANOTUBES AND RELATED STRUCTURES
37
lattice of graphene. If m = 0, the nanotubes are called

zigzag nanotubes, and if n = m, the nanotubes are called
armchair nanotubes. Otherwise, they are called chiral.
The diameter of an ideal nanotube can be calculated from
its (n,m) indices as follows
d=
a 2
(n + nm + m2 ) = 78.3 ((n + m)2 nm)pm,
where a = 0.246 nm.
The (n,m) nanotube naming scheme can be thought of as a vector

(Ch) in an innite graphene sheet that describes how to roll up
the graphene sheet to make the nanotube. T denotes the tube axis,
and a1 and a2 are the unit vectors of graphene in real space.
A scanning tunneling microscopy image of single-walled carbon

nanotube
SWNTs are an important variety of carbon nanotube because most of their properties change signicantly with
the (n,m) values, and this dependence is non-monotonic
(see Kataura plot). In particular, their band gap can vary
from zero to about 2 eV and their electrical conductivity
can show metallic or semiconducting behavior. Singlewalled nanotubes are likely candidates for miniaturizing
electronics. The most basic building block of these systems is the electric wire, and SWNTs with diameters of
an order of a nanometer can be excellent conductors.[4][5]
One useful application of SWNTs is in the development
of the rst intermolecular eld-eect transistors (FET).
The rst intermolecular logic gate using SWCNT FETs
was made in 2001.[6] A logic gate requires both a p-FET
and an n-FET. Because SWNTs are p-FETs when exposed to oxygen and n-FETs otherwise, it is possible to
protect half of an SWNT from oxygen exposure, while
exposing the other half to oxygen. This results in a single
SWNT that acts as a not logic gate with both p and n-type
FETs within the same molecule.
Single-walled nanotubes are dropping precipitously in
price, from around $1500 per gram as of 2000 to retail
prices of around $50 per gram of as-produced 4060%
by weight SWNTs as of March 2010.
SWNTs have been viewed as too expensive for
widespread application but are forecast to make a large
impact in electronics applications by 2020 according to
The Global Market for Carbon Nanotubes report.
6.1.3 Multi-walled
A transmission electron microscopy image of a single-walled carbon nanotube
Most single-walled nanotubes (SWNTs) have a diameter of close to 1 nanometer, and can be many millions of
times longer. The structure of a SWNT can be conceptualized by wrapping a one-atom-thick layer of graphite
called graphene into a seamless cylinder. The way the
graphene sheet is wrapped is represented by a pair of indices (n,m). The integers n and m denote the number of
unit vectors along two directions in the honeycomb crystal
Multi-walled nanotubes (MWNTs) consist of multiple

rolled layers (concentric tubes) of graphene. There are
two models that can be used to describe the structures
of multi-walled nanotubes. In the Russian Doll model,
sheets of graphite are arranged in concentric cylinders,
e.g., a (0,8) single-walled nanotube (SWNT) within a
larger (0,17) single-walled nanotube. In the Parchment
model, a single sheet of graphite is rolled in around itself, resembling a scroll of parchment or a rolled newspaper. The interlayer distance in multi-walled nanotubes is
close to the distance between graphene layers in graphite,
approximately 3.4 . The Russian Doll structure is observed more commonly. Its individual shells can be described as SWNTs, which can be metallic or semiconducting. Because of statistical probability and restrictions
38
CHAPTER 6. CARBON NANOTUBE

telescopic motion caused by the Lennard-Jones interaction between shells and its value is about 1.5 nN.[10]
6.1.4 Torus
In theory, a nanotorus is a carbon nanotube bent into a
torus (doughnut shape). Nanotori are predicted to have
many unique properties, such as magnetic moments 1000
times larger than previously expected for certain specic
radii.[11] Properties such as magnetic moment, thermal
stability, etc. vary widely depending on radius of the torus
and radius of the tube.[11][12]
A scanning electron microscopy image of carbon nanotubes bundles
6.1.5 Nanobud
Triple-walled armchair carbon nanotube

A stable nanobud structure
on the relative diameters of the individual tubes, one of

the shells, and thus the whole MWNT, is usually a zero- Carbon nanobuds are a newly created material combining
two previously discovered allotropes of carbon: carbon
gap metal.
nanotubes and fullerenes. In this new material, fullereneDouble-walled carbon nanotubes (DWNTs) form a spe- like buds are covalently bonded to the outer sidewalls of
cial class of nanotubes because their morphology and the underlying carbon nanotube. This hybrid material has
properties are similar to those of SWNTs but their re- useful properties of both fullerenes and carbon nanotubes.
sistance to chemicals is signicantly improved. This is In particular, they have been found to be exceptionally
especially important when functionalization is required good eld emitters. In composite materials, the attached
(this means grafting of chemical functions at the surface fullerene molecules may function as molecular anchors
of the nanotubes) to add new properties to the CNT. In preventing slipping of the nanotubes, thus improving the
the case of SWNTs, covalent functionalization will break composites mechanical properties.
some C=C double bonds, leaving holes in the structure
on the nanotube and, thus, modifying both its mechanical and electrical properties. In the case of DWNTs, only 6.1.6 Three-dimensional carbon nanotube
the outer wall is modied. DWNT synthesis on the gramarchitectures
scale was rst proposed in 2003[7] by the CCVD technique, from the selective reduction of oxide solutions in Recently, several studies have highlighted the prospect
methane and hydrogen.
of using carbon nanotubes as building blocks to fabriThe telescopic motion ability of inner shells[8] and their
unique mechanical properties[9] will permit the use of
multi-walled nanotubes as main movable arms in coming
nanomechanical devices. Retraction force that occurs to
cate three-dimensional macroscopic (>100 nm in all three

dimensions) all-carbon devices. Lalwani et al. have
reported a novel radical initiated thermal crosslinking
method to fabricate macroscopic, free-standing, porous,
6.1. TYPES OF CARBON NANOTUBES AND RELATED STRUCTURES
3D carbon scaolds
all-carbon scaolds using single- and multi-walled carbon nanotubes as building blocks.[13] These scaolds possess macro-, micro-, and nanostructured pores and the
porosity can be tailored for specic applications. These
3D all-carbon scaolds/architectures may be used for
the fabrication of the next generation of energy storage, supercapacitors, eld emission transistors, highperformance catalysis, photovoltaics, and biomedical devices and implants.[14]
6.1.7
39
higher charge density and reactivity than the basal plane,

but they are dicult to arrange in a three-dimensional,
high volume-density geometry. CNTs are readily aligned
in a high density geometry (i.e., a vertically aligned
forest)[21] but lack high charge density surfacesthe sidewalls of the CNTs are similar to the basal plane of
graphene and exhibit low charge density except where
edge defects exist. Depositing a high density of graphene
foliates along the length of aligned CNTs can signicantly increase the total charge capacity per unit of nominal area as compared to other carbon nanostructures.[22]
6.1.8 Nitrogen-doped carbon nanotubes

Nitrogen doped carbon nanotubes (N-CNTs) can be produced through ve main methods, chemical vapor deposition,[23][24] high-temperature and high-pressure reactions, gas-solid reaction of amorphous carbon with NH3
at high temperature,[25] solid reaction,[26] and solvothermal synthesis.[27]
N-CNTs can also be prepared by a CVD method of py-
Graphenated carbon nanotubes (g- rolyzing melamine under Ar at elevated temperatures of

CNTs)
800980 C. However synthesis by CVD of melamine
results in the formation of bamboo-structured CNTs.
XPS spectra of grown N-CNTs reveal nitrogen in ve
main components, pyridinic nitrogen, pyrrolic nitrogen, quaternary nitrogen, and nitrogen oxides. Furthermore, synthesis temperature aects the type of nitrogen
conguration.[24]
SEM series of graphenated CNTs with varying foliate density
Graphenated CNTs are a relatively new hybrid that combines graphitic foliates grown along the sidewalls of multiwalled or bamboo style CNTs. Yu et al.[15] reported on
chemically bonded graphene leaves growing along the
sidewalls of CNTs. Stoner et al.[16] described these structures as graphenated CNTs and reported in their use for
enhanced supercapacitor performance. Hsu et al. further
reported on similar structures formed on carbon ber paper, also for use in supercapacitor applications.[17] Pham
et al. [18][19] also reported a similar structure, namely
graphene-carbon nanotube hybrids, grown directly onto
carbon ber paper to form an integrated, binder free, high
surface area conductive catalyst support for Proton Exchange Membrane Fuel Cells electrode applications with
enhanced performance and durability. The foliate density can vary as a function of deposition conditions (e.g.
temperature and time) with their structure ranging from
few layers of graphene (< 10) to thicker, more graphitelike.[20]
The fundamental advantage of an integrated grapheneCNT structure is the high surface area three-dimensional
framework of the CNTs coupled with the high edge density of graphene. Graphene edges provide signicantly
Nitrogen doping plays a pivotal role in lithium storage,

as it creates defects in the CNT walls allowing for Li
ions to diuse into interwall space. It also increases
capacity by providing more favorable bind of N-doped
sites. N-CNTs are also much more reactive to metal oxide nanoparticle deposition which can further enhance
storage capacity, especially in anode materials for Li-ion
batteries.[28] However boron-doped nanotubes have been
shown to make batteries with triple capacity.[29]
6.1.9 Peapod
A carbon peapod[30][31] is a novel hybrid carbon material
which traps fullerene inside a carbon nanotube. It can
possess interesting magnetic properties with heating and
irradiation. It can also be applied as an oscillator during
theoretical investigations and predictions.[32][33]
6.1.10 Cup-stacked carbon nanotubes

Cup-stacked carbon nanotubes (CSCNTs) dier from
other quasi-1D carbon structures, which normally behave
as quasi-metallic conductors of electrons. CSCNTs exhibit semiconducting behaviors due to the stacking microstructure of graphene layers.[34]
40
6.1.11
Extreme carbon nanotubes
als yet discovered in terms of tensile strength and elastic

modulus respectively. This strength results from the
covalent sp2 bonds formed between the individual carbon atoms. In 2000, a multi-walled carbon nanotube
was tested to have a tensile strength of 63 gigapascals
(9,100,000 psi).[43] (For illustration, this translates into
the ability to endure tension of a weight equivalent to
6,422 kilograms-force (62,980 N; 14,160 lbf) on a cable with cross-section of 1 square millimetre (0.0016 sq
in).) Further studies, such as one conducted in 2008, revealed that individual CNT shells have strengths of up
to ~100 gigapascals (15,000,000 psi), which is in agreement with quantum/atomistic models.[44] Since carbon
nanotubes have a low density for a solid of 1.3 to 1.4
Cycloparaphenylene
g/cm3 ,[45] its specic strength of up to 48,000 kNmkg1
is the best of known materials, compared to high-carbon
The observation of the longest carbon nanotubes grown steels 154 kNmkg1 .
so far are over 1/2 m (550 mm long) was reported
in 2013.[35] These nanotubes were grown on Si sub- Under excessive tensile strain, the tubes will undergo
strates using an improved chemical vapor deposition plastic deformation, which means the deformation is per(CVD) method and represent electrically uniform arrays manent. This deformation begins at strains of approximately 5% and can increase the maximum strain the tubes
of single-walled carbon nanotubes.[1]
undergo before fracture by releasing strain energy.
The shortest carbon nanotube is the organic compound
cycloparaphenylene, which was synthesized in early Although the strength of individual CNT shells is extremely high, weak shear interactions between adjacent
2009.[36][37]
shells and tubes lead to signicant reduction in the efThe thinnest carbon nanotube is the armchair (2,2) CNT fective strength of multi-walled carbon nanotubes and
with a diameter of 0.3 nm. This nanotube was grown carbon nanotube bundles down to only a few GPa.[46]
inside a multi-walled carbon nanotube. Assigning of car- This limitation has been recently addressed by applying
bon nanotube type was done by a combination of high- high-energy electron irradiation, which crosslinks inner
resolution transmission electron microscopy (HRTEM), shells and tubes, and eectively increases the strength
Raman spectroscopy and density functional theory (DFT) of these materials to ~60 GPa for multi-walled carbon
calculations.[38]
nanotubes[44] and ~17 GPa for double-walled carbon nan[46]
The thinnest freestanding single-walled carbon nanotube otube bundles.
is about 0.43 nm in diameter. Researchers suggested CNTs are not nearly as strong under compression. Bethat it can be either (5,1) or (4,2) SWCNT, but the ex- cause of their hollow structure and high aspect ratio, they
act type of carbon nanotube remains questionable.[39] tend to undergo buckling when placed under compres(3,3), (4,3) and (5,1) carbon nanotubes (all about 0.4 sive, torsional, or bending stress.[47]
nm in diameter) were unambiguously identied using E
T
aberration-corrected high-resolution transmission elec- Experimental observation; Theoretical prediction
tron microscopy inside double-walled CNTs.[40]
The highest density of CNTs was achieved in 2013, grown
on a conductive titanium-coated copper surface that was
coated with co-catalysts cobalt and molybdenum at lower
than typical temperatures of 450 C. The tubes averaged
a height of 380 nm and a mass density of 1.6 g cm3 .
The material showed ohmic conductivity (lowest resistance 22 k).[41][42]
6.2 Properties
6.2.1
Strength
See also: Mechanical properties of carbon nanotubes

Carbon nanotubes are the strongest and stiest materi-
The above discussion referred to axial properties of

the nanotube, whereas simple geometrical considerations
suggest that carbon nanotubes should be much softer
in the radial direction than along the tube axis. Indeed, TEM observation of radial elasticity suggested
that even the van der Waals forces can deform two
adjacent nanotubes.[56] Nanoindentation experiments,
performed by several groups on multiwalled carbon
nanotubes[57][58] and tapping/contact mode atomic force
microscope measurements performed on single-walled
carbon nanotubes,[59] indicated a Youngs modulus of the
order of several GPa, conrming that CNTs are indeed
rather soft in the radial direction.
6.2. PROPERTIES
6.2.2
41
Hardness
Standard single-walled carbon nanotubes can withstand

a pressure up to 25 GPa without [plastic/permanent] deformation. They then undergo a transformation to superhard phase nanotubes. Maximum pressures measured using current experimental techniques are around 55 GPa.
However, these new superhard phase nanotubes collapse
at an even higher, albeit unknown, pressure.
The bulk modulus of superhard phase nanotubes is 462
to 546 GPa, even higher than that of diamond (420 GPa
for single diamond crystal).[60]
6.2.3
Wettability
The surface wettability of CNT is of importance for its

applications in various settings. Although the intrinsic
contact angle of graphite is around 90, the contact angles of most as-synthesized CNT arrays are over 160,
exhibiting a superhydrophobic property. By applying a
low voltage as low as 1.3V, the extreme water repellant
surface can be switched into superhydrophilic.[61]
6.2.4
Kinetic properties
Multi-walled nanotubes are multiple concentric nanotubes precisely nested within one another. These exhibit a striking telescoping property whereby an inner
nanotube core may slide, almost without friction, within
its outer nanotube shell, thus creating an atomically perfect linear or rotational bearing. This is one of the rst
true examples of molecular nanotechnology, the precise
positioning of atoms to create useful machines. Already,
this property has been utilized to create the worlds smallest rotational motor.[62] Future applications such as a gigahertz mechanical oscillator are also envisioned.
6.2.5
Band structures computed using tight binding approximation for

(6,0) CNT (zigzag, metallic), (10,2) CNT (semiconducting) and
(10,10) CNT (armchair, metallic).
nanotubes can carry an electric current density of 4 109

A/cm2 , which is more than 1,000 times greater than those
of metals such as copper,[64] where for copper interconnects current densities are limited by electromigration.
Because of its nanoscale cross-section, electrons propagate only along the tubes axis. As a result, carbon
nanotubes are frequently referred to as one-dimensional
conductors. The maximum electrical conductance of a
single-walled carbon nanotube is 2G0 , where G0 = 2e2 /h
is the conductance of a single ballistic quantum channel.[65]
Electrical properties
Intrinsic superconductivity has been reported,[66] although other experiments found no evidence of this, leavBecause of the symmetry and unique electronic struc- ing the claim a subject of debate.[67]
ture of graphene, the structure of a nanotube strongly
aects its electrical properties. For a given (n,m) nanotube, if n = m, the nanotube is metallic; if n m is a 6.2.6 Optical properties
multiple of 3, then the nanotube is semiconducting with
a very small band gap, otherwise the nanotube is a mod- Main article: Optical properties of carbon nanotubes
erate semiconductor. Thus all armchair (n = m) nanotubes are metallic, and nanotubes (6,4), (9,1), etc. are
semiconducting.[63]
However, this rule has exceptions, because curvature effects in small diameter tubes can strongly inuence electrical properties. Thus, a (5,0) SWCNT that should be
semiconducting in fact is metallic according to the calculations. Likewise, zigzag and chiral SWCNTs with small
diameters that should be metallic have a nite gap (armchair nanotubes remain metallic).[63] In theory, metallic
6.2.7 Thermal properties

Main article: Thermal properties of nanostructures
All nanotubes are expected to be very good thermal conductors along the tube, exhibiting a property known as
"ballistic conduction", but good insulators laterally to the
42
tube axis. Measurements show that a SWNT has a roomtemperature thermal conductivity along its axis of about
3500 Wm1 K1 ;[68] compare this to copper, a metal well
known for its good thermal conductivity, which transmits
385 Wm1 K1 . A SWNT has a room-temperature thermal conductivity across its axis (in the radial direction)
of about 1.52 Wm1 K1 ,[69] which is about as thermally
conductive as soil. The temperature stability of carbon
nanotubes is estimated to be up to 2800 C in vacuum
and about 750 C in air.[70]
heterogeneous material. Parameters such as structure,

size distribution, surface area, surface chemistry, surface
charge, and agglomeration state as well as purity of the
samples, have considerable impact on the reactivity of
carbon nanotubes. However, available data clearly show
that, under some conditions, nanotubes can cross membrane barriers, which suggests that, if raw materials reach
the organs, they can induce harmful eects such as inammatory and brotic reactions.[73][74]
6.2.8
Results of rodent studies collectively show that regardless

of the process by which CNTs were synthesized and the
types and amounts of metals they contained, CNTs were
capable of producing inammation, epithelioid granulomas (microscopic nodules), brosis, and biochemical/toxicological changes in the lungs.[76] Comparative
toxicity studies in which mice were given equal weights
of test materials showed that SWCNTs were more toxic
than quartz, which is considered a serious occupational
health hazard when chronically inhaled. As a control, ultrane carbon black was shown to produce minimal lung
responses.[77]
Defects
Under certain conditions CNTs can enter human cells and

accumulate in the cytoplasm, causing cell death.[75]
As with any material, the existence of a crystallographic

defect aects the material properties. Defects can occur
in the form of atomic vacancies. High levels of such defects can lower the tensile strength by up to 85%. An
important example is the Stone Wales defect, which creates a pentagon and heptagon pair by rearrangement of
the bonds. Because of the very small structure of CNTs,
the tensile strength of the tube is dependent on its weakest
segment in a similar manner to a chain, where the strength
of the weakest link becomes the maximum strength of the
chain.
Carbon nanotubes deposit in the alveolar ducts by alignthe nanotubes will ofCrystallographic defects also aect the tubes electrical ing lengthwise with the airways;
[78]
ten
combine
with
metals.
The
needle-like
ber shape
properties. A common result is lowered conductivity
of
CNTs
is
similar
to
asbestos
bers.
This
raises the
through the defective region of the tube. A defect in
idea
that
widespread
use
of
carbon
nanotubes
may
lead to
armchair-type tubes (which can conduct electricity) can
pleural
mesothelioma,
a
cancer
of
the
lining
of
the
lungs,
cause the surrounding region to become semiconductor
peritoneal
mesothelioma,
a
cancer
of
the
lining
of
the
ing, and single monatomic vacancies induce magnetic
abdomen
(both
caused
by
exposure
to
asbestos).
A
reproperties.[71]
cently published pilot study supports this prediction.[79]
Crystallographic defects strongly aect the tubes ther- Scientists exposed the mesothelial lining of the body cavmal properties. Such defects lead to phonon scattering, ity of mice to long multiwalled carbon nanotubes and
which in turn increases the relaxation rate of the phonons. observed asbestos-like, length-dependent, pathogenic beThis reduces the mean free path and reduces the ther- havior that included inammation and formation of lemal conductivity of nanotube structures. Phonon trans- sions known as granulomas. Authors of the study conport simulations indicate that substitutional defects such clude:
as nitrogen or boron will primarily lead to scattering of
high-frequency optical phonons. However, larger-scale
This is of considerable importance, bedefects such as Stone Wales defects cause phonon scattercause
research and business communities coning over a wide range of frequencies, leading to a greater
[72]
tinue
to invest heavily in carbon nanotubes
reduction in thermal conductivity.
for a wide range of products under the assumption that they are no more hazardous than
graphite. Our results suggest the need for fur6.3 Safety and Health
ther research and great caution before introducing such products into the market if longterm harm is to be avoided.[79]
6.3.1 Toxicity
See also: Fullerene Safety and toxicity
Although further research is required, the available data

suggest that under certain conditions, especially those innanotubes can pose a
The toxicity of carbon nanotubes has been an impor- volving chronic exposure, carbon
[73][75][77][79]
serious
risk
to
human
health.
tant question in nanotechnology. As of 2007, such
research had just begun. The data is still fragmen- In 2014, experts from the International Agency for Retary and subject to criticism. Preliminary results high- search on Cancer (IARC) assessed the carcinogenicity of
light the diculties in evaluating the toxicity of this CNTs, including SWCNTs and MWCNTs. No human
6.4. SYNTHESIS
43
epidemiologic or cancer data was available to the IARC

Working Group at the time, so the evaluation focused on
the results of in vivo animal studies assessing the carcinogenicity of SWCNTs and MWCNTs in rodents.
to various CNT preparations such as the mixing or sonication of CNT in liquids as well as processes that cut
or drill into CNT based composites in downstream products. These types of high-energy processes will aerosolize
The Working Group concluded that there was sucient CNT which can then be inhaled.
evidence for the specic MWCNT type MWCNT-7, Guidance for minimizing exposure and risk to CNT have
limited evidence for the two other types of MWCNTs been published by several international agencies which
with dimensions similar to MWCNT-7, and inadequate includes several documents from the British Health and
evidence for SWCNTs. Therefore, it was agreed to Safety Executive titled Using nanomaterials at work Inspecically classify MWCNT-7 as possibly carcinogenic cluding carbon nanotubes and other bio-persistent high
to humans (Group 2B) while the other forms of CNT, aspect ratio nanomaterials and the Risk Management of
namely SWCNT and other types of MWCNT, excluding Carbon Nanotubes[87][88] Safe Work Australia has also
MWCNT-7, were considered not classiable as to their published guidance titled Safe Handling and use of Carcarcinogenicity to humans (Group 3) due to a lack of co- bon Nanotubes which describes two approaches to manherent evidence.[80]
aging the risks that include risk management with detailed
hazard analysis and exposure assessment as well as risk
management by using Control Banding.[89] The National
6.3.2 Epidemiology and Risk Management Institute for Occupational Safety and Health has also
published a document titled Current Intelligence BulCurrently, there is a lack of epidemiological evidence letin 65: Occupational Exposure to Carbon Nanotubes
linking exposure to CNT to human health eects. To and Nanobers describes strategies for controlling workdate, there have been only a handful of published epi- place exposures and implementing a medical surveillance
demiological studies that have solely examined the health program.[90]
eects related to the exposure of CNT, while sevThese guidance documents generally advocate instituting
eral other studies are currently underway and yet to be
the principles of the Hierarchy of Hazard Control which
published.[81][82][83] With the limited amount of human
is a system used in industry to minimize or eliminate exdata, scientists are more reliant on the results of current
posure to hazards. The hazard controls in the hierarchy
animal toxicity studies to predict adverse health eects,
are, in order of decreasing eectiveness:
as well as applying what is already known about exposures to other brous materials such as asbestos or ne
Elimination
and ultra-ne particulates. This limitation of human data
has lead to the use of the precautionary principal, which
Substitution
urges workplaces to limit exposure levels to CNT as low
Engineering Controls
as possibly achievable in the absence of known health effects data.[84]
Administration
To date, several international government agencies, as
Personal Protective Equipment
well as individual authors, have developed occupational
exposure limits (OEL) to reduce the risk of any possible human health eects associated with workplace exposures to CNT. The National Institute for Occupational 6.4 Synthesis
Safety and Health (NIOSH) conducted a risk assessment
using animal and other toxicological data relevant to as- Techniques have been developed to produce nanotubes
sessing the potential non-malignant adverse respiratory in sizable quantities, including arc discharge, laser ablaeects of CNT and proposed an OEL of 1 g/m3 ele- tion, high-pressure carbon monoxide disproportionation,
mental carbon as a respirable mass 8-hour time-weighted and chemical vapor deposition (CVD). Most of these
average (TWA) concentration.[85] Several individual au- processes take place in a vacuum or with process gases.
thors have also performed similar risk assessments using CVD growth of CNTs can occur in vacuum or at atmoanimal toxicity data and have established inhalation ex- spheric pressure. Large quantities of nanotubes can be
posure limits ranging from 2.5 to 50 ug/m3 .[86]
synthesized by these methods; advances in catalysis and
continuous growth are making CNTs more commercially
viable.[91]
6.3.3
Safety and Exposure Prevention
Occupational exposures that could potentially allow the

inhalation of CNT is of the greatest concern, especially
in situations where the CNT is handled in powder form
which can easily be aerosolized and inhaled. Also of
concern are any high-energy processes that are applied
6.4.1 Arc discharge

Nanotubes were observed in 1991 in the carbon soot
of graphite electrodes during an arc discharge, by using a current of 100 amps, that was intended to produce
44

from a cobalt and nickel mixture) to synthesize singlewalled carbon nanotubes.[96]
The laser ablation method yields around 70% and produces primarily single-walled carbon nanotubes with
a controllable diameter determined by the reaction
temperature. However, it is more expensive than either
arc discharge or chemical vapor deposition.[45]
The eective equation for few cycle optical pulse dynamics was obtained by virtue of the Boltzmann collision-less
equation solution for conduction band electrons of semiconductor carbon nanotubes in the case when medium
with carbon nanotubes has spatially-modulated refractive
index.[97]
6.4.3 Plasma torch
powder of carbon nanotubes
fullerenes.[92] However the rst macroscopic production

of carbon nanotubes was made in 1992 by two researchers
at NEC's Fundamental Research Laboratory.[93] The
method used was the same as in 1991. During this process, the carbon contained in the negative electrode sublimates because of the high-discharge temperatures.
The yield for this method is up to 30% by weight and it
produces both single- and multi-walled nanotubes with
lengths of up to 50 micrometers with few structural
defects.[45] Arc-discharge technique uses higher temperatures (above 1,700 C) for CNT synthesis which typically
causes the expansion of CNTs with fewer structural defects in comparison with other methods.[94]
6.4.2
Laser ablation
In laser ablation, a pulsed laser vaporizes a graphite target in a high-temperature reactor while an inert gas is bled
into the chamber. Nanotubes develop on the cooler surfaces of the reactor as the vaporized carbon condenses.
A water-cooled surface may be included in the system to
collect the nanotubes.
Single-walled carbon nanotubes can also be synthesized

by a thermal plasma method. It was rst invented in 2000
at INRS (Institut National de la Recherche Scientique in
Varennes, Canada), by Olivier Smiljanic. In this method,
the aim is to reproduce the conditions prevailing in the
arc discharge and laser ablation approaches, but a carboncontaining gas is used instead of graphite vapors to supply
the carbon necessary for the production of SWNT. Doing so, the growth of SWNT is more ecient (decomposing a carbon containing gas can be 10 times less energyconsuming than graphite vaporization). It is also continuous and occurs at low cost. To produce a continuous
process, a gas mixture composed of argon, ethylene and
ferrocene is introduced into a microwave plasma torch,
where it is atomized by the atmospheric pressure plasma,
which has the form of an intense 'ame'. The fumes created by the ame are found to contain SWNT, metallic
and carbon nanoparticles and amorphous carbon.[98][99]
Another way to produce single-walled carbon nanotubes
with a plasma torch, is to use the induction thermal
plasma method, implemented in 2005 by groups from
the University of Sherbrooke and the National Research
Council of Canada.[100] The method is similar to arcdischarge in that both use ionized gas to reach the high
temperature necessary to vaporize carbon-containing
substances and the metal catalysts necessary for the ensuing nanotube growth. The thermal plasma is induced
by high frequency oscillating currents in a coil, and is
maintained in owing inert gas. Typically, a feedstock
of carbon black and metal catalyst particles is fed into
the plasma, and then cooled down to form single-walled
carbon nanotubes. Dierent single-wall carbon nanotube
diameter distributions can be synthesized.
This process was developed by Dr. Richard Smalley

and co-workers at Rice University, who at the time of
the discovery of carbon nanotubes, were blasting metals
with a laser to produce various metal molecules. When
they heard of the existence of nanotubes they replaced
the metals with graphite to create multi-walled carbon The induction thermal plasma method can produce up to
nanotubes.[95] Later that year the team used a composite 2 grams of nanotube material per minute, which is higher
of graphite and metal catalyst particles (the best yield was than the arc-discharge or the laser ablation methods.
6.4. SYNTHESIS
45
the substrate.[108] Thermal catalytic decomposition of hydrocarbon has become an active area of research and can
be a promising route for the bulk production of CNTs.
Fluidised bed reactor is the most widely used reactor for
CNT preparation. Scale-up of the reactor is the major
challenge.[109][110]
CVD is the most widely used method for the production of carbon nanotubes.[111] For this purpose, the metal
nanoparticles are mixed with a catalyst support such as
MgO or Al2 O3 to increase the surface area for higher
yield of the catalytic reaction of the carbon feedstock with
the metal particles. One issue in this synthesis route is
the removal of the catalyst support via an acid treatment,
which sometimes could destroy the original structure of
the carbon nanotubes. However, alternative catalyst supports that are soluble in water have proven eective for
nanotube growth.[112]
If a plasma is generated by the application of a strong

electric eld during growth (plasma-enhanced chemical
vapor deposition), then the nanotube growth will follow
the direction of the electric eld.[113] By adjusting the
geometry of the reactor it is possible to synthesize vertically aligned carbon nanotubes[114] (i.e., perpendicular
to the substrate), a morphology that has been of interest
nanotubes being grown by plasma enhanced chemical vapor deto researchers interested in electron emission from nanposition
otubes. Without the plasma, the resulting nanotubes are
often randomly oriented. Under certain reaction conditions, even in the absence of a plasma, closely spaced nan6.4.4 Chemical vapor deposition (CVD)
otubes will maintain a vertical growth direction resulting
The catalytic vapor phase deposition of carbon was re- in a dense array of tubes resembling a carpet or forest.
ported in 1952[101] and 1959,[102] but it was not until Of the various means for nanotube synthesis, CVD shows
1993[103] that carbon nanotubes were formed by this pro- the most promise for industrial-scale deposition, becess. In 2007, researchers at the University of Cincinnati cause of its price/unit ratio, and because CVD is ca(UC) developed a process to grow aligned carbon nan- pable of growing nanotubes directly on a desired subotube arrays of length 18 mm on a FirstNano ET3000 strate, whereas the nanotubes must be collected in the
carbon nanotube growth system.[104]
other growth techniques. The growth sites are control[115]
In 2007,
During CVD, a substrate is prepared with a layer of metal lable by careful deposition of the catalyst.
[105]
a
team
from
Meijo
University
demonstrated
a highcatalyst particles, most commonly nickel, cobalt,
iron,
[106]
eciency
CVD
technique
for
growing
carbon
nanotubes
or a combination.
The metal nanoparticles can also
[116]
Researchers at Rice University, unbe produced by other ways, including reduction of ox- from camphor.
til
recently
led
by
the
late Richard Smalley, have conides or oxides solid solutions. The diameters of the nancentrated
upon
nding
methods to produce large, pure
otubes that are to be grown are related to the size of
amounts
of
particular
types
of nanotubes. Their apthe metal particles. This can be controlled by patterned
proach
grows
long
bers
from
many small seeds cut from
(or masked) deposition of the metal, annealing, or by
a
single
nanotube;
all
of
the
resulting
bers were found
plasma etching of a metal layer. The substrate is heated
to
be
of
the
same
diameter
as
the
original
nanotube
to approximately 700 C. To initiate the growth of nanand
are
expected
to
be
of
the
same
type
as
the
original
otubes, two gases are bled into the reactor: a process gas
[117]
nanotube.
(such as ammonia, nitrogen or hydrogen) and a carboncontaining gas (such as acetylene, ethylene, ethanol or
methane). Nanotubes grow at the sites of the metal catalyst; the carbon-containing gas is broken apart at the
surface of the catalyst particle, and the carbon is transported to the edges of the particle, where it forms the
nanotubes. This mechanism is still being studied.[107] The
catalyst particles can stay at the tips of the growing nanotube during growth, or remain at the nanotube base, depending on the adhesion between the catalyst particle and
Super-growth CVD
Super-growth CVD (water-assisted chemical vapor deposition) was developed by Kenji Hata, Sumio Iijima and
co-workers at AIST, Japan.[118] In this process, the activity and lifetime of the catalyst are enhanced by addition of water into the CVD reactor. Dense millimeter-tall
46
nanotube forests, aligned normal to the substrate, were ity because the environment in which they are produced
produced. The forests height could be expressed, as
is often highly uncontrolled. Thus, although they can be
used in some applications, they can lack in the high degree of uniformity necessary to satisfy the many needs of
both research and industry. Recent eorts have focused
H(t) = o (1 et/o ).
on producing more uniform carbon nanotubes in conIn this equation, is the initial growth rate and o is the trolled ame environments.[131][132][133][134] Such methcharacteristic catalyst lifetime.[119]
ods have promise for large-scale, low-cost nanotube syn[135]
though they must
2
Their specic surface exceeds 1,000 m /g (capped) or thesis based on theoretical models,
compete
with
rapidly
developing
large
scale CVD pro2
[120]
2,200 m /g (uncapped),
surpassing the value of 400
duction.
2
1,000 m /g for HiPco samples. The synthesis eciency
is about 100 times higher than for the laser ablation
method. The time required to make SWNT forests of
the height of 2.5 mm by this method was 10 minutes
in 2004. Those SWNT forests can be easily separated
from the catalyst, yielding clean SWNT material (purity >99.98%) without further purication. For comparison, the as-grown HiPco CNTs contain about 535%[121]
of metal impurities; it is therefore puried through dispersion and centrifugation that damages the nanotubes.
Super-growth avoids this problem. Patterned highly organized single-walled nanotube structures were successfully
fabricated using the super-growth technique.
The mass density of super-growth CNTs is about 0.037
g/cm3 .[122][123] It is much lower than that of conventional
CNT powders (~1.34 g/cm3 ), probably because the latter
contain metals and amorphous carbon.
The super-growth method is basically a variation of CVD.
Therefore, it is possible to grow material containing
SWNT, DWNTs and MWNTs, and to alter their ratios
by tuning the growth conditions.[124] Their ratios change
by the thinness of the catalyst. Many MWNTs are included so that the diameter of the tube is wide.[123]
The vertically aligned nanotube forests originate from a
zipping eect when they are immersed in a solvent and
dried. The zipping eect is caused by the surface tension
of the solvent and the van der Waals forces between the
carbon nanotubes. It aligns the nanotubes into a dense
material, which can be formed in various shapes, such as
sheets and bars, by applying weak compression during the
process. Densication increases the Vickers hardness by
about 70 times and density is 0.55 g/cm3 . The packed
carbon nanotubes are more than 1 mm long and have a
carbon purity of 99.9% or higher; they also retain the desirable alignment properties of the nanotubes forest.[125]
6.4.5
Natural, incidental, and controlled

ame environments
Fullerenes and carbon nanotubes are not necessarily

products of high-tech laboratories; they are commonly
formed in such mundane places as ordinary ames,[126]
produced by burning methane,[127] ethylene,[128] and
benzene,[129] and they have been found in soot from both
indoor and outdoor air.[130] However, these naturally occurring varieties can be highly irregular in size and qual-
6.4.6 Removal of catalysts

Nanoscale metal catalysts are important ingredients for
xed- and uidized-bed CVD synthesis of CNTs. They
allow increasing the growth eciency of CNTs and may
give control over their structure and chirality.[136] During synthesis, catalysts can convert carbon precursors into
tubular carbon structures but can also form encapsulating carbon overcoats. Together with metal oxide supports they may therefore attach to or become incorporated into the CNT product.[137] The presence of metal
impurities can be problematic for many applications. Especially catalyst metals like nickel, cobalt or yttrium may
be of toxicological concern.[138] While unencapsulated
catalyst metals may be readily removable by acid washing,
encapsulated ones require oxidative treatment for opening their carbon shell.[139] The eective removal of catalysts, especially of encapsulated ones, while preserving
the CNT structure is a challenge and has been addressed
in many studies.[140][141] A new approach to break carbonaceaous catalyst encapsulations is based on rapid thermal annealing.[142]
6.4.7 Application-related issues

Many electronic applications of carbon nanotubes crucially rely on techniques of selectively producing either
semiconducting or metallic CNTs, preferably of a certain
chirality. Several methods of separating semiconducting
and metallic CNTs are known, but most of them are not
yet suitable for large-scale technological processes. The
most ecient method relies on density-gradient ultracentrifugation, which separates surfactant-wrapped nanotubes by the minute dierence in their density. This
density dierence often translates into dierence in the
nanotube diameter and (semi)conducting properties.[143]
Another method of separation uses a sequence of freezing, thawing, and compression of SWNTs embedded
in agarose gel. This process results in a solution containing 70% metallic SWNTs and leaves a gel containing 95% semiconducting SWNTs. The diluted solutions
separated by this method show various colors.[144][145]
The separated carbon nanotubes using this method have
been applied to electrodes, e.g. electric double-layer
capacitor.[146] Moreover, SWNTs can be separated by
6.5. CHEMICAL MODIFICATION
47
izontally aligned arrays of 9598% semiconducting nanotubes was announced.[153]
Nanotubes are usually grown on nanoparticles of magnetic metal (Fe, Co), which facilitates production of
electronic (spintronic) devices. In particular, control
of current through a eld-eect transistor by magnetic eld has been demonstrated in such a single-tube
nanostructure.[154]
6.5 Chemical modication

Main articles: Carbon nanotube chemistry and Selective
chemistry of single-walled nanotubes
Centrifuge tube with a solution of carbon nanotubes,

which were sorted by diameter using density-gradient
ultracentrifugation.[143]
Carbon nanotubes can be functionalized to attain desired

properties that can be used in a wide variety of applications. The two main methods of carbon nanotube functionalization are covalent and non-covalent modications.
Because of their hydrophobic nature, carbon nanotubes
tend to agglomerate hindering their dispersion is solvents
or viscous polymer melts. The resulting nanotube bundles
or aggregates reduce the mechanical performance of the
nal composite. The surface of the carbon nanotubes can
be modied to reduce the hydrophobicity and improve
interfacial adhesion to a bulk polymer through chemical
attachment.[155]
6.6 Current applications
the column chromatography method. Yield is 95% in Current use and application of nanotubes has mostly been
semiconductor type SWNT and 90% in metallic type limited to the use of bulk nanotubes, which is a mass of
SWNT.[147]
rather unorganized fragments of nanotubes. Bulk nanIn addition to separation of semiconducting and metallic otube materials may never achieve a tensile strength simSWNTs, it is possible to sort SWNTs by length, diam- ilar to that of individual tubes, but such composites may,
eter, and chirality. The highest resolution length sort- nevertheless, yield strengths sucient for many applicaing, with length variation of <10%, has thus far been tions. Bulk carbon nanotubes have already been used as
achieved by size exclusion chromatography (SEC) of composite bers in polymers to improve the mechanical,
DNA-dispersed carbon nanotubes (DNA-SWNT).[148] thermal and electrical properties of the bulk product.
SWNT diameter separation has been achieved by densitygradient ultracentrifugation (DGU)[149] using surfactant Easton-Bell Sports, Inc. have been in partnerdispersed SWNTs and by ion-exchange chromatography
ship with Zyvex Performance Materials, using
(IEC) for DNA-SWNT.[150] Purication of individual
CNT technology in a number of their bicycle
chiralities has also been demonstrated with IEC of DNAcomponentsincluding at and riser handlebars,
SWNT: specic short DNA oligomers can be used to
cranks, forks, seatposts, stems and aero bars.
isolate individual SWNT chiralities. Thus far, 12 chi Zyvex Technologies has also built a 54' maritime
ralities have been isolated at purities ranging from 70%
vessel, the Piranha Unmanned Surface Vessel, as a
for (8,3) and (9,5) SWNTs to 90% for (6,5), (7,5) and
[151]
technology demonstrator for what is possible using
There have been successful eorts to
(10,5)SWNTs.
CNT technology. CNTs help improve the structural
integrate these puried nanotubes into devices, e. g.
[152]
performance of the vessel, resulting in a lightweight
FETs.
8,000 lb boat that can carry a payload of 15,000 lb
An alternative to separation is development of a selective
over a range of 2,500 miles.[156]
growth of semiconducting or metallic CNTs. Recently, a
Amroy Europe Oy manufactures Hybtonite carnew CVD recipe that involves a combination of ethanol
bon nanoepoxy resins where carbon nanotubes have
and methanol gases and quartz substrates resulting in hor-
48

been chemically activated to bond to epoxy, resulting in a composite material that is 20% to 30%
stronger than other composite materials. It has been
used for wind turbines, marine paints and variety of
sports gear such as skis, ice hockey sticks, baseball
bats, hunting arrows, and surfboards.[157]
Other current applications include:

tips for atomic force microscope probes
[158]
in tissue engineering, carbon nanotubes can act as

scaolding for bone growth[159]
sults in signicant increases in compressive and exural mechanical properties of polymeric nanocomposites.
Researchers at Rice University, Stony Brook University,
Radboud University Nijmegen Medical Centre and University of California, Riverside have shown that carbon
nanotubes and their polymer nanocomposites are suitable
scaold materials for bone tissue engineering [14][159][169]
and bone formation.[170][171]
In November 2012 researchers at the American National
Institute of Standards and Technology (NIST) proved
that single-wall carbon nanotubes may help protect DNA
molecules from damage by oxidation.[172]
A highly eective method of delivering carbon nanotubes

into cells is Cell squeezing, a high-throughput vector-free
There is also ongoing research in using carbon nanotubes microuidic platform for intracellular delivery developed
as a scaold for diverse microfabrication techniques.[160] at the Massachusetts Institute of Technology in the labs
of Robert S. Langer.[173]
Carbon nanotubes have furthermore been grown inside
microuidic channels for chemical analysis, based on
electrochromatography. Here, the high surface-area-toMain article: Potential applications of carbon nanotubes volume ratio and high hydrophobicity of CNTs are used
in order to greatly decrease the analysis time of small
that typically require large bulky equipThe strength and exibility of carbon nanotubes makes neutral molecules [174][175]
ment
for
analysis.
them of potential use in controlling other nanoscale structures, which suggests they will have an important role in
nanotechnology engineering. The highest tensile strength 6.7.2 Structural
of an individual multi-walled carbon nanotube has been
tested to be 63 GPa.[43] Carbon nanotubes were found Because of the carbon nanotubes superior mechanical
in Damascus steel from the 17th century, possibly help- properties, many structures have been proposed ranging
ing to account for the legendary strength of the swords from everyday items like clothes and sports gear to commade of it.[161][162] Recently, several studies have high- bat jackets and space elevators.[176] However, the space
lighted the prospect of using carbon nanotubes as build- elevator will require further eorts in rening carbon
ing blocks to fabricate three-dimensional macroscopic nanotube technology, as the practical tensile strength of
(>1mm in all three dimensions) all-carbon devices. Lal- carbon nanotubes must be greatly improved.[45]
wani et al. have reported a novel radical initiated thermal crosslinking method to fabricated macroscopic, free- For perspective, outstanding breakthroughs have already
standing, porous, all-carbon scaolds using single- and been made. Pioneering work led by Ray H. Baughman at
multi-walled carbon nanotubes as building blocks.[13] the NanoTech Institute has shown that single and multiThese scaolds possess macro-, micro-, and nano- struc- walled nanotubes can produce materials with toughness
[177][178]
tured pores and the porosity can be tailored for specic unmatched in the man-made and natural worlds.
applications. These 3D all-carbon scaolds/architectures
maybe used for the fabrication of the next generation
of energy storage, supercapacitors, eld emission transistors, high-performance catalysis, photovoltaics, and
biomedical devices and implants.
6.7 Potential applications
6.7.1
Biomedical
Researchers from Rice University and State University

of New York - Stony Brook have shown that the addition of low weight % of carbon nanotubes can lead to
signicant improvements in the mechanical properties
of biodegradable polymeric nanocomposites for applications in tissue engineering including bone,[163][164][165] Carbon nanotubes being spun to form a yarn, CSIRO
cartilage,[166] muscle[167] and nerve tissue.[164][168] Dispersion of low weight % of graphene (~0.02 wt.%) re- Carbon nanotubes are also a promising material as build-
6.7. POTENTIAL APPLICATIONS
49
ing blocks in hierarchical composite materials given their

exceptional mechanical properties (~1 TPa in modulus,
and ~100 GPa in strength). Initial attempts to incorporate CNTs into hierarchical structures (such as yarns or
bres) has led to mechanical properties that were significantly lower than these potential limits. Windle et al.
have used an in situ chemical vapor deposition (CVD)
spinning method to produce continuous CNT yarns from
CVD-grown CNT aerogels.[179][180] CNT yarns can also
be manufactured by drawing out CNT bundles from a
CNT forest and subsequently twisting to form the bre
(draw-twist method, see picture on right). The Windle group have fabricated CNT yarns with strengths as
high as ~9 GPa at small gage lengths of ~1 mm, however, strengths of only about ~1 GPa were reported at the
longer gage length of 20 mm.[181][182] The reason why bre strengths have been low compared to the strength of
individual CNTs is due to a failure to eectively transfer load to the constituent (discontinuous) CNTs within
the bre. One potential route for alleviating this problem is via irradiation (or deposition) induced covalent
inter-bundle and inter-CNT cross-linking to eectively
'join up' the CNTs.[183] Espinosa et al. developed high
performance DWNT-polymer composite yarns by twisting and stretching ribbons of randomly oriented bundles
of DWNTs thinly coated with polymeric organic compounds. These DWNT-polymer yarns exhibited an unusually high energy to failure of ~100 Jg1 (comparable
to one of the toughest natural materials spider silk[184] ),
and strength as high as ~1.4 GPa.[185] Eort is ongoing to
produce CNT composites that incorporate tougher matrix
materials, such as Kevlar, to further improve on the mechanical properties toward those of individual CNTs.
ohmic metal contacts and high-k gate dielectric were reported, showing 2030x higher ON current than stateof-the-art Si MOSFETs. This presented an important advance in the eld as CNT was shown to potentially outperform Si. At the time, a major challenge was ohmic metal
contact formation. In this regard, palladium, which is a
high-work function metal was shown to exhibit Schottky
barrier-free contacts to semiconducting nanotubes with
diameters >1.7 nm.[189][190]
6.7.3
6.7.4 Electrical cables and wires
The rst nanotube integrated memory circuit was made in

2004. One of the main challenges has been regulating the
conductivity of nanotubes. Depending on subtle surface
features a nanotube may act as a plain conductor or as a
semiconductor. A fully automated method has however
been developed to remove non-semiconductor tubes.[191]
Another way to make carbon nanotube transistors has
been to use random networks of them.[192] By doing so
one averages all of their electrical dierences and one
can produce devices in large scale at the wafer level.[193]
This approach was rst patented by Nanomix Inc.[194]
(date of original application June 2002[195] ). It was rst
published in the academic literature by the United States
Naval Research Laboratory in 2003 through independent
research work. This approach also enabled Nanomix
to make the rst transistor on a exible and transparent
substrate.[196][197]
Large structures of carbon nanotubes can be used for

thermal management of electronic circuits. An approximately 1 mmthick carbon nanotube layer was used as
a special material to fabricate coolers, this material has
very low density, ~20 times lower weight than a similar
copper structure, while the cooling properties are similar
[198]
Because of the high mechanical strength of carbon nan- for the two materials.
otubes, research is being made into weaving them into In 2013, researchers demonstrated a Turing-complete
clothes to create stab-proof and bulletproof clothing. The prototype micrometer-scale computer.[199][200][201]
nanotubes would eectively stop the bullet from penetrat- Carbon nanotube transistors as logic-gate circuits with
ing the body, although the bullets kinetic energy would densities comparable to modern CMOS technology has
likely cause broken bones and internal bleeding.[186]
not yet been demonstrated.
Electrical circuits
Nanotube-based transistors, also known as carbon nanotube eld-eect transistors (CNTFETs), have been
made that operate at room temperature and that are capable of digital switching using a single electron.[187] However, one major obstacle to realization of nanotubes has
been the lack of technology for mass production. In 2001
IBM researchers demonstrated how metallic nanotubes
can be destroyed, leaving semiconducting ones behind for
use as transistors. Their process is called constructive
destruction, which includes the automatic destruction of
defective nanotubes on the wafer.[188] This process, however, only gives control over the electrical properties on a
statistical scale.
Wires for carrying electric current may be fabricated

from pure nanotubes and nanotube-polymer composites. It has already been demonstrated that carbon nanotube wires can successfully be used for power or data
transmission.[202] Recently small wires have been fabricated with specic conductivity exceeding copper and
aluminum;[203][204] these cables are the highest conductivity carbon nanotube and also highest conductivity nonmetal cables. Recently, composite of carbon nanotube
and copper have been shown to exhibit nearly one hundred times higher current-carrying-capacity than pure
copper or gold.[205] Signicantly, the electrical conductivity of such a composite is similar to pure Cu. Thus, this
The potential of carbon nanotubes was demonstrated in Carbon nanotube-copper (CNT-Cu) composite possesses
2003 when room-temperature ballistic transistors with the highest observed current-carrying capacity among
50
electrical conductors. Thus for a given cross-section of

electrical conductor, the CNT-Cu composite can withstand and transport one hundred times higher current
compared to metals such as copper and gold.
vices), the power source must be equally thin, thus indicating the need for paper batteries. Recently, it has been
shown that surfaces coated with CNTs can be used to replace heavy metals in batteries.[209] More recently, functional paper batteries have been demonstrated, where a
lithium-ion battery is integrated on a single sheet of pa6.7.5 Actuators
per through a lamination process as a composite with
Li4Ti5O12 (LTO) or LiCoO2 (LCO). The paper subMain article: Carbon nanotube actuators
strate would function well as the separator for the battery,
where the CNT lms function as the current collectors
The exceptional electrical and mechanical properties of for both the anode and the cathode. These rechargeable
carbon nanotubes have made them alternatives to the energy devices show potential in RFID tags, functional
[210]
traditional electrical actuators for both microscopic and packaging, or new disposable electronic applications.
macroscopic applications. Carbon nanotubes are very
good conductors of both electricity and heat, and they
6.7.7 Solar cells
are also very strong and elastic molecules in certain directions.
One of the promising applications of single-walled carbon nanotubes (SWNTs) is their use in solar panels,
due to their strong UV/Vis-NIR absorption characteris6.7.6 Batteries
tics. Research has shown that they can provide a sizable increase in eciency, even at their current unopCarbon nanotubes (CNTs) exciting electronic propertimized state. Solar cells developed at the New Jersey
ties have shown promise in the eld of batteries, where
Institute of Technology use a carbon nanotube complex,
typically they are being experimented as a new elecformed by a mixture of carbon nanotubes and carbon
trode material, particularly the anode for lithium ion batbuckyballs (known as fullerenes) to form snake-like structeries. This is due to the fact that the anode requires
tures. Buckyballs trap electrons, but they can't make eleca relatively high reversible capacity at a potential close
trons ow.[211] Add sunlight to excite the polymers, and
to metallic lithium, and a moderate irreversible capacthe buckyballs will grab the electrons. Nanotubes, beity, observed thus far only by graphite-based composites,
having like copper wires, will then be able to make the
such as CNTs. They have shown to greatly improve caelectrons or current ow.[212]
pacity and cyclability of lithium-ion batteries, as well as
the capability to be very eective buering components, Additional research has been conducted on creating
alleviating the degradation of the batteries that is typi- SWNT hybrid solar panels to increase the eciency furcally due to repeated charging and discharging. Further, ther. These hybrids are created by combining SWNTs
electronic transport in the anode can be greatly improved with photo-excitable electron donors to increase the number of electrons generated. It has been found that
using highly metallic CNTs.[206]
the interaction between the photo-excited porphyrin and
More specically, CNTs have shown reversible capacSWNT generates electro-hole pairs at the SWNT surities from 300 to 600 mAhg1 , with some treatments
faces. This phenomenon has been observed experimento them showing these numbers rise to up to 1000
tally, and contributes practically to an increase in emAhg1 .[207] Meanwhile, graphite, which is most widely
ciency up to 8.5%.[213]
used as an anode material for these lithium batteries, has
shown capacities of only 320 mAhg1 . By creating com- Further information: Carbon nanotubes in photovoltaics
posites out of the CNTs, scientists see much potential in
taking advantage of these exceptional capacities, as well
as their excellent mechanical strength, conductivities, and
6.7.8 Hydrogen storage
low densities.[206]
Paper batteries
A paper battery is a battery engineered to use a paperthin sheet of cellulose (which is the major constituent of
regular paper, among other things) infused with aligned
carbon nanotubes.[208] The potential for these devices is
great, as they may be manufactured via a roll-to-roll process, which would make it very low-cost, and they would
be lightweight, exible, and thin. In order to productively use paper electronics (or any thin electronic de-
In addition to being able to store electrical energy, there

has been some research in using carbon nanotubes to
store hydrogen to be used as a fuel source. By taking advantage of the capillary eects of the small carbon nanotubes, it is possible to condense gases in high density inside single-walled nanotubes. This allows for gases, most
notably hydrogen (H2 ), to be stored at high densities without being condensed into a liquid. Potentially, this storage method could be used on vehicles in place of gas fuel
tanks for a hydrogen-powered car. A current issue regarding hydrogen-powered vehicles is the on-board stor-
6.7. POTENTIAL APPLICATIONS
51
age of the fuel. Current storage methods involve cooling

and condensing the H2 gas to a liquid state for storage
which causes a loss of potential energy (2545%) when
compared to the energy associated with the gaseous state.
Storage using SWNTs would allow one to keep the H2 in
its gaseous state, thereby increasing the storage eciency.
This method allows for a volume to energy ratio slightly
smaller to that of current gas powered vehicles, allowing
for a slightly lower but comparable range.[214]
Limitations on ecient hydrogen adsorption
In another experiment,[218] CNTs were synthesized via

CVD and their structure was characterized using Raman
spectroscopy. Utilizing microwave digestion, the samples were exposed to dierent acid concentrations and
dierent temperatures for various amounts of time in
an attempt to nd the optimum purication method for
SWNTs of the diameter determined earlier. The puried samples were then exposed to hydrogen gas at various
high pressures, and their adsorption by weight percent was
plotted. The data showed that hydrogen adsorption levels
of up to 3.7% are possible with a very pure sample and
under the proper conditions. It is thought that microwave
digestion helps improve the hydrogen adsorption capacity of the CNTs by opening up the ends, allowing access
to the inner cavities of the nanotubes.
such application could be to paint the nanotubes onto the

plane. Recently there has been some work done at the
University of Michigan regarding carbon nanotubes usefulness as stealth technology on aircraft. It has been found
that in addition to the radar absorbing properties, the nanotubes neither reect nor scatter visible light, making it
essentially invisible at night, much like painting current
stealth aircraft black except much more eective. Current limitations in manufacturing, however, mean that
current production of nanotube-coated aircraft is not possible. One theory to overcome these current limitations
is to cover small particles with the nanotubes and suspend the nanotube-covered particles in a medium such
as paint, which can then be applied to a surface, like a
stealth aircraft.[220]
The biggest obstacle to ecient hydrogen storage using CNTs is the purity of the nanotubes. To achieve
maximum hydrogen adsorption, there must be minimum
graphene, amorphous carbon, and metallic deposits in the
nanotube sample. Current methods of CNT synthesis require a purication step. However, even with pure nanotubes, the absorption capacity is only maximized under
An area of controversy and frequent experimentation re- high pressures, which are undesirable in commercial fuel
garding the storage of hydrogen by adsorption in carbon tanks.
nanotubes is the eciency by which this process occurs.
The eectiveness of hydrogen storage is integral to its
use as a primary fuel source since hydrogen only contains
about one fourth the energy per unit volume as gasoline. 6.7.9 Supercapacitor
Studies however show that what is the most important is
the surface area of the materials used. Hence activated Main article: Supercapacitor
carbon with surface area of 2600 m2/g can store up to
5,8% w/w. In all these carbonaceous materials, hydroMIT Research Laboratory of Electronics uses nanotubes
gen is stored by physisorption at 70-90K.[215]
to improve supercapacitors. The activated charcoal used
in conventional ultracapacitors has many small hollow
spaces of various size, which create together a large surface to store electric charge. But as charge is quantized into elementary charges, i.e. electrons, and each
Experimental capacity
such elementary charge needs a minimum space, a signicant fraction of the electrode surface is not available
[216]
One experiment
sought to determine the amount of for storage because the hollow spaces are not compatible
hydrogen stored in CNTs by utilizing elastic recoil detec- with the charges requirements. With a nanotube election analysis (ERDA). CNTs (primarily SWNTs) were trode the spaces may be tailored to sizefew too large
synthesized via chemical vapor disposition (CVD) and or too smalland consequently the capacity should be
[219]
subjected to a two-stage purication process including increased considerably.
air oxidation and acid treatment, then formed into at,
uniform discs and exposed to pure, pressurized hydrogen
at various temperatures. When the data was analyzed, it
was found that the ability of CNTs to store hydrogen de- 6.7.10 Radar absorption
creased as temperature increased. Moreover, the highest
hydrogen concentration measured was ~0.18%; signi- Main article: Radar-absorbent material
cantly lower than commercially viable hydrogen storage
needs to be. A separate experimental work performed Radars work in the microwave frequency range, which
by using a gravimetric method also revealed the maxi- can be absorbed by MWNTs. Applying the MWNTs
mum hydrogen uptake capacity of CNTs to be as low as to the aircraft would cause the radar to be absorbed and
0.2%.[217]
therefore seem to have a smaller radar cross-section. One
52
6.7.11
Textile
The previous studies on the use of CNTs for textile functionalization were focused on ber spinning for improving physical and mechanical properties.[221][222][223] Recently a great deal of attention has been focused on coating CNTs on textile fabrics. Various methods have been
employed for modifying fabrics using CNTs. Shim et
al. produced intelligent e-textiles for Human Biomonitoring using a polyelectrolyte-based coating with CNTs.[224]
Additionally, Panhuis et al. dyed textile material by immersion in either a poly (2-methoxy aniline-5-sulfonic
acid) PMAS polymer solution or PMAS-SWNT dispersion with enhanced conductivity and capacitance with a
durable behavior.[225] In another study, Hu and coworkers coated single-walled carbon nanotubes with a simple dipping and drying process for wearable electronics
and energy storage applications.[226] In the recent study,
Li and coworkers using elastomeric separator and almost achieved a fully stretchable supercapacitor based on
buckled single-walled carbon nanotube macrolms. The
electrospun polyurethane was used and provided sound
mechanical stretchability and the whole cell achieve excellent charge-discharge cycling stability.[227] CNTs have
an aligned nanotube structure and a negative surface
charge. Therefore, they have similar structures to direct
dyes, so the exhaustion method is applied for coating and
absorbing CNTs on the ber surface for preparing multifunctional fabric including antibacterial, electric conductive, ame retardant and electromagnetic absorbance
properties.[228][229][230]
6.7.12
Optical power detectors
A spray-on mixture of carbon nanotubes and ceramic

demonstrates unprecedented ability to resist damage
while absorbing laser light. Such coatings that absorb as
the energy of high-powered lasers without breaking down
are essential for optical power detectors that measure the
output of such lasers. These are used, for example, in
military equipment for defusing unexploded mines. The
composite consists of multiwall carbon nanotubes and a
ceramic made of silicon, carbon and nitrogen. Including boron boosts the breakdown temperature. The nanotubes and graphene-like carbon transmit heat well, while
the oxidation-resistant ceramic boosts damage resistance.
Creating the coating involves dispersing the nanotubes in
toluene, to which a clear liquid polymer containing boron
was added. The mixture was heated to 1,100 C (2,010
F). The result is crushed into a ne powder, dispersed
again in toluene and sprayed in a thin coat on a copper
surface. The coating absorbed 97.5 percent of the light
from a far-infrared laser and tolerated 15 kilowatts per
square centimeter for 10 seconds. Damage tolerance is
about 50 percent higher than for similar coatings, e.g.,
nanotubes alone and carbon paint.[231][232]
6.7.13 Acoustics
Carbon nanotubes have also been applied in the acoustics(such as loudspeaker and earphone).
In 2008
it was shown that a sheet of nanotubes can operate as a loudspeaker if an alternating current is applied. The sound is not produced through vibration but
thermoacoustically.[233][234] In 2013, a carbon nanotube
(CNT) thin yarn thermoacoustic earphone together with
CNT thin yarn thermoacoustic chip was demonstrated
by a research group of Tsinghua-Foxconn Nanotechnology Research Center in Tsinghua University,[235] using a
Si-based semi-conducting technology compatible fabrication process.
6.7.14 Environmental remediation

A CNT nano-structured sponge (nanosponge) containing
sulfur and iron is more eective at soaking up water contaminants such as oil, fertilizers, pesticides and pharmaceuticals. Their magnetic properties make them easier to
retrieve once the clean-up job is done. The sulfur and iron
increases sponge size to around 2 centimetres (0.79 in). It
also increases porosity due to benecial defects, creating
buoyancy and reusability. Iron, in the form of ferrocene
makes the structure easier to control and enables recovery
using magnets. Such nanosponges increase the absorption of the toxic organic solvent dichlorobenzene from
water by 3.5 times. The sponges can absorb vegetable oil
up to 150 times their initial weight and can absorb engine
oil as well.[236][237]
Earlier, a magnetic boron-doped MWNT nanosponge
that could absorb oil from water. The sponge was
grown as a forest on a substrate via chemical vapor disposition. Boron puts kinks and elbows into the tubes
as they grow and promotes the formation of covalent
bonds. The nanosponges retain their elastic property after 10,000 compressions in the lab. The sponges are both
superhydrophobic, forcing them to remain at the waters
surface and oleophilic, drawing oil to them.[238][239]
6.7.15 Water treatment

It has been shown that carbon nanotubes exhibit strong
adsorption anities to a wide range of aromatic and
aliphatic contaminants in water,[240][241][242] due to their
large and hydrophobic surface areas. They also showed
similar adsorption capacities as activated carbons in the
presence of natural organic matter.[243] As a result, they
have been suggested as promising adsorbents for removal
of contaminant in water and wastewater treatment systems.
Moreover, membranes made out of carbon nanotube arrays have been suggested as switchable molecular sieves,
with sieving and permeation features that can be dynamically activated/deactivated by either pore size distribu-
6.8. DISCOVERY
53
tion (passive control) or external electrostatic elds (ac- Carbon nanotubes provide a certain potential for metaltive control).[244]
free catalysis of inorganic and organic reactions. For
instance, oxygen groups attached to the surface of carbon nanotubes have the potential to catalyze oxidative dehydrogenations[248] or selective oxidations.[249]
6.7.16 Other applications
Nitrogen-doped carbon nanotubes may replace platinum
catalysts used to reduce oxygen in fuel cells. A forest of
Carbon nanotubes have been implemented in nanoelec- vertically aligned nanotubes can reduce oxygen in alkatromechanical systems, including mechanical memory el- line solution more eectively than platinum, which has
ements (NRAM being developed by Nantero Inc.) and been used in such applications since the 1960s. Here, the
nanoscale electric motors (see Nanomotor or Nanotube nanotubes have the added benet of not being subject to
carbon monoxide poisoning.[250]
nanomotor).
Carboxyl-modied single-walled carbon nanotubes (so
called zig-zag, armchair type) can act as sensors of atoms
and ions of alkali metals Na, Li, K.[245] In May 2005,
Nanomix Inc. placed on the market a hydrogen sensor
that integrated carbon nanotubes on a silicon platform.
Since then, Nanomix has been patenting many such sensor applications, such as in the eld of carbon dioxide, nitrous oxide, glucose, DNA detection, etc. End of 2014,
Tulane University researchers have tested Nanomixs fast
and fully automated point of care diagnostic system in
Sierra Leone to help for rapid testing for Ebola. Nanomix
announced that a product could be launched within three
to six months.
Wake Forest University engineers are using multiwalled

carbon nanotubes to enhance the brightness of eldinduced polymer electroluminescent technology, potentially oering a step forward in the search for safe, pleasing, high-eciency lighting. In this technology, moldable
polymer matrix emits light when exposed to an electric
current. It could eventually yield high-eciency lights
without the mercury vapor of compact uorescent lamps
or the bluish tint of some uorescents and LEDs, which
has been linked with circadian rhythm disruption.[251]
Candida albicans has been used in combination with carbon nanotubes (CNT) to produce stable electrically conductive bio-nano-composite tissue materials that have
Eikos Inc of Franklin, Massachusetts and Unidym Inc. been used as temperature sensing elements.[252]
of Silicon Valley, California are developing transparent, The SWNT production company OCSiAl developed a
electrically conductive lms of carbon nanotubes to re- series of masterbatches for industrial use of single-wall
place indium tin oxide (ITO). Carbon nanotube lms are CNTs in multiple types of rubber blends and tires, with
substantially more mechanically robust than ITO lms, initial trials showing increases in hardness, viscosity, tenmaking them ideal for high-reliability touchscreens and sile strain resistance and resistance to abrasion while reexible displays. Printable water-based inks of carbon ducing elongation and compression[253] In tires the three
nanotubes are desired to enable the production of these primary characteristics of durability, fuel eciency and
lms to replace ITO.[246] Nanotube lms show promise traction were improved using SWNTs. The developfor use in displays for computers, cell phones, PDAs, and ment of rubber masterbatches built on earlier work by the
ATMs.
Japanese National Institute of Advanced Industrial SciA nanoradio, a radio receiver consisting of a single nan- ence & Technology showing rubber to be a viable candidate for improvement with SWNTs.[254]
otube, was demonstrated in 2007.
A ywheel made of carbon nanotubes could be spun at extremely high velocity on a oating magnetic axis in a vacuum, and potentially store energy at a density approaching that of conventional fossil fuels. Since energy can be
added to and removed from ywheels very eciently in
the form of electricity, this might oer a way of storing
electricity, making the electrical grid more ecient and
variable power suppliers (like wind turbines) more useful
in meeting energy needs. The practicality of this depends
heavily upon the cost of making massive, unbroken nanotube structures, and their failure rate under stress.
Carbon nanotube springs have the potential to indenitely
store elastic potential energy at ten times the density of
lithium-ion batteries with exible charge and discharge
rates and extremely high cycling durability.
Introducing MWNTs to polymers can improve ame retardancy and retard thermal degradation of polymer.[255]
The results conrmed that combination of MWNTs and
ammonium polyphosphates show a synergistic eect for
improving ame retardancy.[256]
6.8 Discovery
See also: Timeline of carbon nanotubes
The true identity of the discoverers of carbon nanotubes

is a subject of some controversy.[257] For years, scientists
assumed that Sumio Iijima of NEC had discovered carbon nanotubes in 1991. He published a paper describUltra-short SWNTs (US-tubes) have been used as ing his discovery which initiated a urry of excitement
nanoscaled capsules for delivering MRI contrast agents and could be credited by inspiring the many scientists
now studying applications of carbon nanotubes. Though
in vivo.[247]
54
Iijima has been given much of the credit for discovering
carbon nanotubes, it turns out that the timeline of carbon nanotubes goes back much further than 1991.[257]
In 1952 L. V. Radushkevich and V. M. Lukyanovich
published clear images of 50 nanometer diameter tubes
made of carbon in the Soviet Journal of Physical Chemistry.[101] This discovery was largely unnoticed, as the article was published in Russian, and Western scientists
access to Soviet press was limited during the Cold War.
Before they came to be known as carbon nanotubes, in
1976, Morinobu Endo of CNRS observed hollow tubes
of rolled up graphite sheets synthesised by a chemical
vapour-growth technique.[258] The rst specimens observed would later come to be known as single-walled carbon nanotubes (SWNTs).[259] The three scientists have
been the rst ones to show images of a nanotube with a
solitary graphene wall.[257]
Endo, in his early review of vapor-phase-grown carbon
bers (VPCF), also reminded us that he had observed a
hollow tube, linearly extended with parallel carbon layer
faces near the ber core.[260] This appears to be the observation of multi-walled carbon nanotubes at the center
of the ber.[259] The mass-produced MWCNTs today are
strongly related to the VPGCF developed by Endo.[259] In
fact, they call it the Endo-process, out of respect for his
early work and patents.[259][261]

dent prediction that if single-walled carbon nanotubes
could be made, then they would exhibit remarkable conducting properties[266] helped create the initial buzz that
is now associated with carbon nanotubes. Nanotube
research accelerated greatly following the independent
discoveries[267][268] by Bethune at IBM and Iijima at NEC
of single-walled carbon nanotubes and methods to specifically produce them by adding transition-metal catalysts
to the carbon in an arc discharge. The arc discharge technique was well-known to produce the famed Buckminster
fullerene on a preparative scale,[269] and these results appeared to extend the run of accidental discoveries relating
to fullerenes. The discovery of nanotubes remains a contentious issue. Many believe that Iijimas report in 1991 is
of particular importance because it brought carbon nanotubes into the awareness of the scientic community as
a whole.[257][259]
6.9 See also

Boron nitride nanotube
Buckypaper
Carbide-derived carbon
In 1979, John Abrahamson presented evidence of carbon nanotubes at the 14th Biennial Conference of Carbon at Pennsylvania State University. The conference
paper described carbon nanotubes as carbon bers that
were produced on carbon anodes during arc discharge. A
characterization of these bers was given as well as hypotheses for their growth in a nitrogen atmosphere at low
pressures.[262]
Carbon nanocone
In 1981, a group of Soviet scientists published the results of chemical and structural characterization of carbon nanoparticles produced by a thermocatalytical disproportionation of carbon monoxide. Using TEM images
and XRD patterns, the authors suggested that their carbon multi-layer tubular crystals were formed by rolling
graphene layers into cylinders. They speculated that by
rolling graphene layers into a cylinder, many dierent
arrangements of graphene hexagonal nets are possible.
They suggested two possibilities of such arrangements:
circular arrangement (armchair nanotube) and a spiral,
helical arrangement (chiral tube).[263]
Colossal carbon tube
In 1987, Howard G. Tennent of Hyperion Catalysis was

issued a U.S. patent for the production of cylindrical discrete carbon brils with a constant diameter between
about 3.5 and about 70 nanometers..., length 102 times
the diameter, and an outer region of multiple essentially
continuous layers of ordered carbon atoms and a distinct
inner core....[264]
Ninithi (nanotube modelling software)
Iijimas discovery of multi-walled carbon nanotubes in

the insoluble material of arc-burned graphite rods in
1991[265] and Mintmire, Dunlap, and Whites indepen-
Timeline of carbon nanotubes
Carbon nanobers
Carbon nanoparticles
Carbon nanoscrolls
Carbon nanotube chemistry
Diamond nanothread
Filamentous carbon
Graphene oxide paper
List of software for nanostructures modeling
Molecular modelling
Nanoower
Organic semiconductor
Selective chemistry of single-walled nanotubes
Silicon nanotubes
Vantablack, a substance produced in 2014; the

blackest substance known
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Nanohedron.com image gallery with carbon nan-
6.11 External links
[257] Pacios Pujad, Merc (2012).

Carbon Nanotubes
as Platforms for Biosensors with Electrochemical and
Electronic Transduction. Springer Heidelberg. pp.
XX,208. doi:10.1007/978-3-642-31421-6. ISBN 978-3642-31421-6. ISSN 2190-5053.
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[259] Peter C. Eklund(Panel Chair) (2007). WTEC Panel Report on INTERNATIONAL ASSESSMENT OF RESEARCH AND DEVELOPMENT OF CARBON NANOTUBE MANUFACTURING AND APPLICATIONS
FINAL REPORT (pdf) (Report). World Technology
Evaluation Center(WTEC).
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Japanese Patent, 1982-58, 966.
[262] Abrahamson, John; Wiles, Peter G.; Rhoades, Brian
L. (1999). Structure of Carbon Fibers Found on
Carbon Arc Anodes. Carbon 37 (11): 18731874.
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otubes
The Nanotube site. Last updated 2009.05.03
EU Marie Curie Network CARBIO: Multifunctional carbon nanotubes for biomedical applications
Carbon nanotube on arxiv.org
C60 and Carbon Nanotubes a short video explaining
how nanotubes can be made from modied graphite
sheets and the three dierent types of nanotubes that
are formed
Carbon Nanotubes & Buckyballs.
The Wondrous World of Carbon Nanotubes
Learning module for Bandstructure of Carbon Nanotubes and Nanoribbons
Durability of carbon nanotubes and their potential to
cause inammation by Dr Megan Osmond and others. (SafeWork Australia, May 2011). This was a
collaboration between the Institute of Occupational
Medicine, Edinburgh University and CSIRO in Australia.
NT06 Seventh International Conference on the Science and Application of Nanotubes
6.11. EXTERNAL LINKS

NT05 Sixth International Conference on the Science
and Application of Nanotubes
Selection of free-download articles on carbon nanotubes
First computer made of carbon nanotubes is unveiled (BBC News) 2013-09-25
Research using carbon nanotubes for microfabrication and in other applications
67
Chapter 7
Energy applications of nanotechnology

Main article: List of nanotechnology applications
Over the past few decades, the elds of science and
engineering have been seeking to develop new and improved types of energy technologies that have the capability of improving life all over the world. In order to make the next leap forward from the current
generation of technology, scientists and engineers have
been developing energy applications of nanotechnology. Nanotechnology, a new eld in science, is any
technology that contains components smaller than 100
nanometers. For scale, a single virus particle is about 100
nanometers in width.
An important subeld of nanotechnology related to energy is nanofabrication. Nanofabrication is the process
of designing and creating devices on the nanoscale. Creating devices smaller than 100 nanometers opens many
doors for the development of new ways to capture, store,
and transfer energy. The inherent level of control that
nanofabrication could give scientists and engineers would
be critical in providing the capability of solving many of
the problems that the world is facing today related to the
current generation of energy technologies.[1]
People in the elds of science and engineering have already begun developing ways of utilizing nanotechnology for the development of consumer products. Benets
already observed from the design of these products are
an increased eciency of lighting and heating, increased
electrical storage capacity, and a decrease in the amount
of pollution from the use of energy. Benets such as these
make the investment of capital in the research and development of nanotechnology a top priority.
7.1 Consumer products

Recently, previously established and entirely new companies such as BetaBatt, Inc. and Oxane Materials are focusing on nanomaterials as a way to develop and improve
upon older methods for the capture, transfer, and storage
of energy for the development of consumer products.
ConsERV, a product developed by the Dais Analytic Corporation, uses nanoscale polymer membranes to increase
the eciency of heating and cooling systems and has already proven to be a lucrative design. The polymer membrane was specically congured for this application by
selectively engineering the size of the pores in the membrane to prevent air from passing, while allowing moisture to pass through the membrane. ConsERVs value is
demonstrated in the form of an energy recovery a device
which pretreats the incoming fresh air to a building using the energy found in the exhaust air steam using no
moving parts to lower the energy and carbon footprint of
existing forms of heating and cooling equipment Polymer
membranes can be designed to selectively allow particles
of one size and shape to pass through while preventing
other. This makes for a powerful tool that can be used
in all markets - consumer, commercial, industrial, and
government products from biological weapons protection
to industrial chemical separations. Daiss near term uses
of this 'family' of selectively engineered nanotechnology
materials, aside from ConsERV, include (a.) a completely new cooling cycle capable of replacing the refrigerant based cooling cycle the world has known for the
past 100 plus years. This product, under development, is
named NanoAir. NanoAir uses only water and this selectively engineered membrane material to cool (or heat)
and dehumidify (or humidify) air. There are no uorocarbon producing gasses used, and the energy required
to cool a space drops as thermodynamics does the actual
cooling. The company was awarded an Advanced Research Program Administration - Energy award in 2010,
and a United States Department of Defense (DoD) grant
in 2011 both designed to accelerate this newer, energy efcient technology closer to commercialization, and (b.) a
novel way to clean most all contaminated forms of water called NanoClear. By using the selectivity of this
hermetic, engineered composite material it can transfer
only a water molecule from one face of the membrane
to the other leaving behind the contaminants. It should
also be noted Dais received a US Patent (Patent Number
7,990,679) in October 2011 titled Nanoparticle Ultracapacitor. This patented item again uses the selectively
engineered material to create an energy storage mechanism projected to have performance and cost advantages
over existing storage technologies. The company has used
this patents concepts to create a functional energy storage
prototype device named NanoCap. NanoCap is a form of
68
7.3. INCREASING THE EFFICIENCY OF ENERGY PRODUCTION
69
ultra-capacitor potentially useful to power a broad range proaches like or quantum caged atoms (QCAs) could lead
of applications including most forms of transportation, to a strong reduction of energy consumption for illuminaenergy storage (especially useful as a storage media for re- tion.
newable energy technologies), telecommunication infrastructure, transistor gate dielectrics, and consumer battery
applications (cell phones, computers, etc.).[2]
7.3 Increasing the eciency of enA New York based company called Applied NanoWorks,
Inc. has been developing a consumer product that utilizes LED technology to generate light. Light-emitting
diodes or LEDs, use only about 10% of the energy that
a typical incandescent or uorescent light bulb uses and
typically last much longer, which makes them a viable
alternative to traditional light bulbs. While LEDs have
been around for decades, this company and others like
it have been developing a special variant of LED called
the white LED. White LEDs consist of semi-conducting
organic layers that are only about 100 nanometers in distance from each other and are placed between two electrodes, which create an anode, and a cathode. When
voltage is applied to the system, light is generated when
electricity passes through the two organic layers. This is
called electroluminescence. The semiconductor properties of the organic layers are what allow for the minimal
amount of energy necessary to generate light. In traditional light bulbs, a metal lament is used to generate light
when electricity is run through the lament. Using metal
generates a great deal of heat and therefore lowers eciency.
Research for longer lasting batteries has been an ongoing process for years. Researchers have now begun to
utilize nanotechnology for battery technology. mPhase
Technologies in conglomeration with Rutgers University
and Bell Laboratories have utilized nanomaterials to alter
the wetting behavior of the surface where the liquid in the
battery lies to spread the liquid droplets over a greater area
on the surface and therefore have greater control over the
movement of the droplets. This gives more control to the
designer of the battery. This control prevents reactions in
the battery by separating the electrolytic liquid from the
anode and the cathode when the battery is not in use and
joining them when the battery is in need of use.
ergy production
Todays best solar cells have layers of several dierent
semiconductors stacked together to absorb light at dierent energies but they still only manage to use 40 percent
of the Suns energy. Commercially available solar cells
have much lower eciencies (15-20%). Nanotechnology could help increase the eciency of light conversion
by using nanostructures with a continuum of bandgaps.
The degree of eciency of the internal combustion
engine is about 30-40% at present. Nanotechnology
could improve combustion by designing specic catalysts
with maximized surface area. In 2005, scientists at the
University of Toronto developed a spray-on nanoparticle
substance that, when applied to a surface, instantly transforms it into a solar collector.[3]
7.4 Nuclear Accident Cleanup and

Waste Storage
Nanomaterials deployed by swarm robotics may be helpful for decontaminating a site of a nuclear accident which
poses hazards to humans because of high levels of radiation and radioactive particles. Hot nuclear compounds
such as corium or melting fuel rods may be contained in
bubbles made from nanomaterials that are designed to
isolate the harmful eects of nuclear activity occurring
inside of them from the outside environment that organisms inhabit.
7.5 Economic benets
Thermal applications also are a future applications of

nanothechonlogy creating low cost system of heating, The relatively recent shift toward using nanotechnology
ventilation, and air conditioning, changing molecular with respect to the capture, transfer, and storage of energy has and will continue to have many positive ecostructure for better management of temperature
nomic impacts on society. The control of materials that
nanotechnology oers to scientists and engineers of conproducts is one of the most important aspects of
7.2 Reduction of energy consump- sumer
nanotechnology. This allows for an improved eciency
of products across the board.
tion
A reduction of energy consumption can be reached by
better insulation systems, by the use of more ecient
lighting or combustion systems, and by use of lighter
and stronger materials in the transportation sector. Currently used light bulbs only convert approximately 5% of
the electrical energy into light. Nanotechnological ap-
A major issue with current energy generation is the loss of

eciency from the generation of heat as a by-product of
the process. A common example of this is the heat generated by the internal combustion engine. The internal
combustion engine loses about 64% of the energy from
gasoline as heat and an improvement of this alone could
have a signicant economic impact. However, improving
70
CHAPTER 7. ENERGY APPLICATIONS OF NANOTECHNOLOGY
the internal combustion engine in this respect has proven

to be extremely dicult without sacricing performance.
Improving the eciency of fuel cells through the use of
nanotechnology appears to be more plausible by using
molecularly tailored catalysts, polymer membranes, and
improved fuel storage.
Traditional or foil capacitors are composed of thin metal

conducting plates separated by an electrical insulator,
which are then stacked or rolled and placed in a casing.
The problem with a traditional capacitor such as this is
that they limit how small an engineer can design a computer. Scientists and engineers have since turned to nanIn order for a fuel cell to operate, particularly of otechnology for a solution to the problem.
the hydrogen variant, a noble-metal catalyst (usually Using nanotechnology, researchers developed what they
platinum, which is very expensive) is needed to separate call ultracapacitors. An ultracapacitor is a general term
the electrons from the protons of the hydrogen atoms. that describes a capacitor that contains nanocomponents.
However, catalysts of this type are extremely sensitive Ultracapacitors are being researched heavily because of
to carbon monoxide reactions. In order to combat this, their high density interior, compact size, reliability, and
alcohols or hydrocarbons compounds are used to lower high capacitance. This decrease in size makes it increasthe carbon monoxide concentration in the system. This ingly possible to develop much smaller circuits and comadds an additional cost to the device. Using nanotech- puters. Ultracapacitors also have the capability to supnology, catalysts can be designed through nanofabrication plement batteries in hybrid vehicles by providing a large
that are much more resistant to carbon monoxide reac- amount of energy during peak acceleration and allowing
tions, which improves the eciency of the process and the battery to supply energy over longer periods of time,
may be designed with cheaper materials to additionally such as during a constant driving speed. This could decrease the size and weight of the large batteries needed
lower costs.
Fuel cells that are currently designed for transportation in hybrid vehicles as well as take additional stress o the
need rapid start-up periods for the practicality of con- battery. However, the combination of ultracapacitors and
sumer use. This process puts a lot of strain on the tradi- a battery is not cost eective due to the need of additional
tional polymer electrolyte membranes, which decreases DC/DC electronics to coordinate the two.
the life of the membrane requiring frequent replacement.
Using nanotechnology, engineers have the ability to create a much more durable polymer membrane, which addresses this problem. Nanoscale polymer membranes are
also much more ecient in ionic conductivity. This improves the eciency of the system and decreases the time
between replacements, which lowers costs.
Another problem with contemporary fuel cells is the storage of the fuel. In the case of hydrogen fuel cells, storing
the hydrogen in gaseous rather than liquid form improves
the eciency by 5%. However, the materials that we
currently have available to us signicantly limit fuel storage due to low stress tolerance and costs. Scientists have
come up with an answer to this by using a nanoporous
styrene material (which is a relatively inexpensive material) that when super-cooled to around 196o C, naturally
holds on to hydrogen atoms and when heated again releases the hydrogen for use.
7.6 Capacitors: then and now

For decades, scientists and engineers have been attempting to make computers smaller and more ecient. A crucial component of computers are capacitors. A capacitor
is a device that is made of a pair of electrodes separated
by an insulator that each stores an opposite charge. A
capacitor stores a charge when it is removed from the circuit that it is connected to; the charge is released when
it is replaced back into the circuit. Capacitors have an
advantage over batteries in that they release their charge
much more quickly than a battery.
Nanoporous carbon aerogel is one type of material that

is being utilized for the design of ultracapacitors. These
aerogels have a very large interior surface area and can
have its properties altered by changing the pore diameter
and distribution along with adding nanosized alkali metals
to alter its conductivity.
Carbon nanotubes are another possible material for use
in an ultracapacitor. Carbon nanotubes are created by
vaporizing carbon and allowing it to condense on a surface. When the carbon condenses, it forms a nanosized
tube composed of carbon atoms. This tube has a high
surface area, which increases the amount of charge that
can be stored. The low reliability and high cost of using
carbon nanotubes for ultracapacitors is currently an issue
of research.
In a study concerning ultracapacitors or supercapacitors, researchers at the Sungkyunkwan University in the
Republic of Korea explored the possibility of increasing the capacitance of electrodes through the addition
of uorine atoms to the walls of carbon nanotubes. As
briey mentioned before, carbon nanotubes are an increasing form of capacitors due to their superb chemical stability, high conductivity, light mass, and their large
surface area. These researchers uorinated single-walled
carbon nanotubes (SWCNTs) at high temperatures to
bind uorine atoms to the walls. The attached uorine
atoms changed the non-polar nanotubes to become polar molecules. This can be attributed to the charge transfer from the uorine. This created dipole-dipole layers
along the carbon nanotube walls. Testing of these uorinated SWCNTs against normal state SWCNTs showed a
dierence in capacitance. It was determined that the u-
7.9. EXTERNAL LINKS

orinated SWCNTs are advantageous in fabricating electrodes for capacitors and improve the wettability with
aqueous electrolytes, which promotes the overall performance of supercapacitors. While this study brought to
knowledge a more ecient example of capacitors, little is
known about this new supercapacitor, large scale synthesis is lacking and is necessary for any massive production,
and preparation conditions are quite tedious in achieving
the nal product.[4]
7.6.1
Theory of capacitance
Understanding the concept of capacitance can be helpful

in understanding why nanotechnology is such a powerful
tool for the design of higher energy storing capacitors. A
capacitors capacitance (C) or amount of energy stored is
equal to the amount of charge (Q) stored on each plate divided by the voltage (V) between the plates. Another representation of capacitance is that capacitance (C) is approximately equal to the permittivity () of the dielectric
times the area (A) of the plates divided by the distance
(d) between them. Therefore, capacitance is proportional
to the surface area of the conducting plate and inversely
proportional to the distance between the plates.
Using carbon nanotubes as an example, a property of
carbon nanotubes is that they have a very high surface
area to store a charge. Using the above proportionality
that capacitance (C) is proportional to the surface area
(A) of the conducting plate; it becomes obvious that using nanoscaled materials with high surface area would be
great for increasing capacitance. The other proportionality described above is that capacitance (C) is inversely
proportional to the distance (d) between the plates. Using
nanoscaled plates such as carbon nanotubes with nanofabrication techniques, gives the capability of decreasing the
space between plates which again increases capacitance.
7.7 See also

Nanotechnology
Energy
Capacitor
Fuel Cell
7.8 References
[1] http://www.crnano.org/whatis
[2] Dais Analytic Corporation.
[3]
[4] Lee et al. Fabrication of Supercapacitor Electrodes
Using Fluorinated Single-Walled Carbon Nanotubes.
American Chemical Society. May 2003: Volume 103.
71
7.9 External links

http://www.conserv.com/
http://www.daisanalytic.com
http://www.appliednanoworks.com/
http://www.mphasetech.com/
http://www.azonano.com/details.asp?ArticleID=
1123
http://www.doc.ic.ac.uk/~{}matti/ise2grp/
energystorage_report/node9.html Archived
April 2007 at the Wayback Machine
http://www.wifinotes.com/nanotechnology/
energy-applications-of-nanotechnology.html
Chapter 8
Molecular scale electronics

Molecular scale electronics, also called singlemolecule electronics, is a branch of nanotechnology
that uses single molecules, or nanoscale collections of
single molecules, as electronic components. Because
single molecules constitute the smallest stable structures
imaginable this miniaturization is the ultimate goal for
shrinking electrical circuits.
The eld is often referred to as simply "molecular electronics", but this term is also used to refer to the distantly
related eld of conductive polymers and organic electronics, which uses the properties of molecules to aect the
bulk properties of a material. A nomenclature distinction has been suggested so that molecular materials for
electronics refers to this latter eld of bulk applications,
while molecular scale electronics refers to the nanoscale
single-molecule applications discussed here.[1][2]
made at once) while the composition of molecules are

controlled down to the last atom. The molecules utilized
have properties that resemble traditional electronic components such as a wire, transistor or rectier.
Single-molecule electronics is an emerging eld, and entire electronic circuits consisting exclusively of molecular sized compounds are still very far from being realized. However, the continuous demand for more computing power together with the inherent limitations of
the present day lithographic methods make the transition
seem unavoidable. Currently, the focus is on discovering
molecules with interesting properties and on nding ways
to obtaining reliable and reproducible contacts between
the molecular components and the bulk material of the
electrodes.
8.2 Theoretical basis
8.1 Fundamental concepts

Conventional electronics have traditionally been made
from bulk materials. Ever since its invention in 1958
the performance and complexity of integrated circuits
has been growing exponentially (a trend also known as
Moores law) and has forced the feature sizes of the embedded components to shrink accordingly. As the structures become smaller, the sensitivity for deviations increases and in a few generations, when the minimum feature sizes reaches 13 nm, the composition of the devices
must be controlled to a precision of a few atoms [3] for the
devices to work. With the bulk approach having inherent
limitations in addition to becoming increasingly demanding and expensive, the idea was born that the components
could instead be built up atom for atom in a chemistry lab
(bottom up) as opposed to carving them out of bulk material (top down). This idea is the reasoning behind molecular electronics with the ultimate miniaturization being
components contained in single molecules.
In single-molecule electronics, the bulk material is replaced by single molecules. That is, instead of creating
structures by removing or applying material after a pattern scaold, the atoms are put together in a chemistry
lab. This way billions of billions of copies are made simultaneously (typically more than 10 20 molecules are
Molecular electronics operates in the quantum realm of

distances less than 100 nanometers. The miniaturization down to single molecules brings the scale down to
a regime where quantum eects are important. As opposed to the case in conventional electronic components,
where electrons can be lled in or drawn out more or less
like a continuous ow of charge, the transfer of a single
electron alters the system signicantly. This means that
when an electron has been transferred from the source
electrode to the molecule, the molecule gets charged up
and makes it much harder for the next one to transfer (see
also Coulomb blockade). The signicant amount of energy due to charging must be taken into account when
making calculations about the electronic properties of the
setup and is highly sensitive to distances to conducting
surfaces nearby.
The theory of single-molecule devices is particularly interesting since the system under consideration is an open
quantum system in nonequilibrium (driven by voltage). In
the low bias voltage regime, the nonequilibrium nature of
the molecular junction can be ignored, and the currentvoltage characteristics of the device can be calculated using the equilibrium electronic structure of the system.
However, in stronger bias regimes a more sophisticated
treatment is required, as there is no longer a variational
72
8.3. EXAMPLES
principle. In the elastic tunneling case (where the passing electron does not exchange energy with the system),
the formalism of Rolf Landauer can be used to calculate the transmission through the system as a function of
bias voltage, and hence the current. In inelastic tunneling, an elegant formalism based on the non-equilibrium
Greens functions of Leo Kadano and Gordon Baym,
and independently by Leonid Keldysh was put forth by
Ned Wingreen and Yigal Meir. This Meir-Wingreen formulation has been used to great success in the molecular
electronics community to examine the more dicult and
interesting cases where the transient electron exchanges
energy with the molecular system (for example through
electron-phonon coupling or electronic excitations).
73
in single-molecule electronics is primarily on the functionalized molecules: molecular wires are characterized
by containing no functional groups and are hence composed of plain repetitions of a conjugated building block.
Among these are the carbon nanotubes that are quite large
compared to the other suggestions but have shown very
promising electrical properties.
The main problem with the molecular wires is to obtain good electrical contact with the electrodes so that the
electrons can move freely in and out of the wire.
8.3.2 Transistors
Further, connecting single molecules reliably to a larger Single-molecule transistors are fundamentally dierent
scale circuit has proven a great challenge, and constitutes from the ones known from bulk electronics. The gate
a signicant hindrance to commercialization.
in a conventional (eld-eect) transistor determines the
conductance between the source and drain electrode by
controlling the density of charge carriers between them,
whereas the gate in a single-molecule transistor controls
8.3 Examples
the feasibility of a single electron to jump on and o the
molecule by modifying the energy of the molecular orCommon for molecules utilized in molecular electronics bitals. One of the eects of this dierence is that the
is that the structures contain a lot of alternating double single-molecule transistor is almost binary: it is either ON
and single bonds (see also Conjugated system). The rea- or OFF. This opposes its bulk counterparts, which have
son for this is that such a pattern delocalizes the molecu- quadratic responses to gate voltage.
lar orbitals making it possible for electrons to move freely
It is the quantization of charge into electrons that is reover the conjugated area.
sponsible for the markedly dierent behavior compared
to bulk electronics. Because of the size of a single
molecule, the charging due to a single electron is signi8.3.1 Wires
cant and provides a mean to turn the transistor ON or OFF
(see Coulomb blockade). For this to work, the electronic
orbitals on the transistor molecule cannot be too well integrated with the orbitals on the electrodes. If they are,
an electron cannot be said to be located on the molecule
or the electrodes and the molecule will function as a wire.
A popular group of molecules, that can work as the
semiconducting channel material in a molecular transistor, is the oligopolyphenylenevinylenes (OPVs) that
works by the Coulomb blockade mechanism when placed
between the source and drain electrode in an appropriate
way.[4] Fullerenes work by the same mechanism and have
also been commonly utilized.
Semiconducting carbon nanotubes have also been demonstrated to work as channel material but although molecular, these molecules are suciently large to behave almost
as bulk semiconductors.
The size of the molecules and the low temperature the
measurements are being conducted at makes the quanThis animation of a rotating carbon nanotube shows its 3D struc- tum mechanical states well dened. It is therefore being
researched if the quantum mechanical properties can be
ture.
used for more advanced purposes than simple transistors
The sole purpose of molecular wires is to electrically con- (e.g. spintronics).
nect dierent parts of a molecular electrical circuit. As Physicists at the University of Arizona, in collaboration
the assembly of these and their connection to a macro- with chemists from the University of Madrid, have descopic circuit is still not mastered, the focus of research signed a single-molecule transistor using a ring-shaped
74
CHAPTER 8. MOLECULAR SCALE ELECTRONICS
molecule similar to benzene. Physicists at Canadas

National Institute for Nanotechnology have designed a
single-molecule transistor using styrene. Both groups expect (their designs have yet to be experimentally veried)
their respective devices to function at room temperature,
and to be controlled by a single electron. [5]
8.3.3
Rectiers (diodes)
8.4.1 Molecular gaps

One way to produce electrodes with a molecular sized gap
between them is break junctions, in which a thin electrode
is stretched until it breaks. Another is electromigration.
Here a current is led through a thin wire until it melts
and the atoms migrate to produce the gap. Further, the
reach of conventional photolithography can be enhanced
by chemically etching or depositing metal on the electrodes.
Probably the easiest way to conduct measurements on
several molecules is to use the tip of a scanning tunneling
microscope (STM) to contact molecules adhered at the
other end to a metal substrate.[7]
8.4.2 Anchoring
Hydrogen can be removed from individual H2 TPP molecules by

applying excess voltage to the tip of a scanning tunneling microscope (STAM, a); this removal alters the current-voltage (I-V)
curves of TPP molecules, measured using the same STM tip, from
diode-like (red curve in b) to resistor-like (green curve). Image
(c) shows a row of TPP, H2 TPP and TPP molecules. While scanning image (d), excess voltage was applied to H2 TPP at the black
dot, which instantly removed hydrogen, as shown in the bottom
part of (d) and in the re-scan image (e). Such manipulations can
be used in single-molecule electronics.[6]
Molecular rectiers are mimics of their bulk counterparts

and have an asymmetric construction so that the molecule
can accept electrons in one end but not the other. The
molecules have an electron donor (D) in one end and an
electron acceptor (A) in the other. This way, the unstable
state D+ A will be more readily made than D A+ .
The result is that an electric current can be drawn through
the molecule if the electrons are added through the acceptor end, but not so easily if the reverse is attempted.
A popular way to anchor molecules to the electrodes is

to make use of sulfurs high anity to gold. In these setups, the molecules are synthesized so that sulfur atoms
are placed strategically to function as crocodile clips connecting the molecules to the gold electrodes. Though
useful, the anchoring is non-specic and thus anchors
the molecules randomly to all gold surfaces. Further,
the contact resistance is highly dependent on the precise
atomic geometry around the site of anchoring and thereby
inherently compromises the reproducibility of the connection.
To circumvent the latter issue, experiments has shown
that fullerenes could be a good candidate for use instead
of sulfur because of the large conjugated -system that
can electrically contact many more atoms at once than a
single atom of sulfur.[8]
8.4.3 Fullerene nanoelectronics
In polymers, classical organic molecules are composed

of both carbon and hydrogen (and sometimes additional
compounds such as nitrogen, chlorine or sulphur). They
are obtained from petrol and can often be synthesized in
large amounts. Most of these molecules are insulating
when their length exceeds a few nanometers. However,
naturally occurring carbon is conducting. In particular,
graphite (recovered from coal or encountered naturally)
is conducting. From a theoretical point of view, graphite
8.4 Techniques
is a semi-metal, a category in between metals and semiconductors. It has a layered structure, each sheet being
One of the biggest problems with measuring on single one atom thick. Between each sheet, the interactions are
molecules is to establish reproducible electrical contact weak enough to allow an easy manual cleavage.
with only one molecule and doing so without shortcutting Tailoring the graphite sheet to obtain well dened
the electrodes. Because the current photolithographic nanometer-sized objects remains a challenge. However,
technology is unable to produce electrode gaps small by the close of the twentieth century, chemists were exenough to contact both ends of the molecules tested (in ploring methods to fabricate extremely small graphitic
the order of nanometers) alternative strategies are put into objects that could be considered single molecules. After
use.
studying the interstellar conditions under which carbon
8.6. HISTORY AND RECENT PROGRESS

is known to form clusters, Richard Smalleys group (Rice
University, Texas) set up an experiment in which graphite
was vaporized using laser irradiation. Mass spectrometry revealed that clusters containing specic magic numbers of atoms were stable, in particular those clusters
of 60 atoms. Harry Kroto, an English chemist who assisted in the experiment, suggested a possible geometry for these clusters atoms covalently bound with the
exact symmetry of a soccer ball. Coined buckminsterfullerenes, buckyballs or C60 , the clusters retained some
properties of graphite, such as conductivity. These objects were rapidly envisioned as possible building blocks
for molecular electronics.
75
single molecules are carried out in cryogenic temperatures (close to absolute zero), which is very energy consuming. This is done to reduce signal noise enough to
measure the faint currents of single molecules.
8.6 History and recent progress
8.5 Problems
8.5.1
Artifacts
When trying to measure electronic characteristics of

molecules, articial phenomena can occur that can be
hard to distinguish from truly molecular behavior.[9] Before they were discovered these artifacts have mistakenly been published as being features pertaining to the
molecules in question.
Applying a voltage drop in the order of volts across a
nanometer sized junction results in a very strong electrical eld. The eld can cause metal atoms to migrate and
eventually close the gap by a thin lament, which can be
broken again when carrying a current. The two levels of
conductance imitate molecular switching between a conductive and an isolating state of a molecule.
Another encountered artifact is when the electrodes undergo chemical reactions due to the high eld strength in
the gap. When the bias is reversed the reaction will cause
hysteresis in the measurements that can be interpreted as
being of molecular origin.
A metallic grain between the electrodes can act as a single electron transistor by the mechanism described above
thus resembling the characteristics of a molecular transistor. This artifact is especially common with nanogaps
produced by the electromigration technique.
8.5.2
Commercialization
One of the biggest hindrances for single-molecule electronics to be commercially exploited is the lack of techniques to connect a molecular sized circuit to bulk electrodes in a way that gives reproducible results. At the
current state, the diculty of connecting single molecules
vastly outweighs any possible performance increase that
could be gained from such shrinkage. The picture becomes even worse if the molecules are to have a certain
spatial orientation and/or have multiple poles to connect.
Graphical representation of a rotaxane, useful as a molecular

switch.
In their discussion of so-called donor-acceptor complexes in the 1940s, Robert Mulliken and Albert SzentGyorgi advanced the concept of charge transfer in
molecules. They subsequently further rened the study
of both charge transfer and energy transfer in molecules.
Likewise, a 1974 paper from Mark Ratner and Ari Aviram illustrated a theoretical molecular rectier.[10] In
1988, Aviram described in detail a theoretical singlemolecule eld-eect transistor. Further concepts were
proposed by Forrest Carter of the Naval Research Laboratory, including single-molecule logic gates. A wide
range of ideas were presented, under his aegis, at a conference entitled Molecular Electronic Devices in 1988.[11]
These were all theoretical constructs and not concrete devices. The direct measurement of the electronic characteristics of individual molecules awaited the development
of methods for making molecular-scale electrical contacts. This was no easy task. Thus, the rst experiment
directly-measuring the conductance of a single molecule
was only reported in 1995 on a single C60 molecule by C.
Joachim and J. K. Gimzewsky in their seminal Physical
Revie Letter paper and later in 1997 by Mark Reed and
co-workers on a few hundred molecules. Since then, this
branch of the eld has progressed rapidly. Likewise, as it
has become possible to measure such properties directly,
the theoretical predictions of the early workers have been
substantially conrmed.
Recent progress in nanotechnology and nanoscience has

facilitated both experimental and theoretical study of
molecular electronics. In particular, the development of
the scanning tunneling microscope (STM) and later the
atomic force microscope (AFM) have facilitated manipulation of single-molecule electronics. In addition, theoAlso problematic is the fact that some measurements on retical advances in molecular electronics have facilitated
76
further understanding of non-adiabatic charge transfer Supramolecular electronics is a new eld that tackles elecevents at electrode-electrolyte interfaces.[12][13]
tronics at a supramolecular level.
The concept of molecular electronics was rst published
in 1974 when Aviram and Ratner suggested an organic
molecule that could work as a rectier.[14] Having both
huge commercial and fundamental interest much eort
was put into proving its feasibility and 16 years later in
1990 the rst demonstration of an intrinsic molecular rectier was realized by Ashwell and coworkers for a thin
lm of molecules.
An important issue in molecular electronics is the determination of the resistance of a single molecule (both theoretical and experimental). For example, Bumm, et al.
used STM to analyze a single molecular switch in a selfassembled monolayer to determine how conductive such a
molecule can be.[20] Another problem faced by this eld is
the diculty of performing direct characterization since
imaging at the molecular scale is often dicult in many
The rst measurement of the conductance of a single experimental devices.
molecule was realised in 1994 by C. Joachim and J. K.
Gimzewski and published in 1995 (see the corresponding Phys. Rev. Lett. paper). This was the conclusion of 8.7 See also
10 years of research started at IBM TJ Watson, using the
scanning tunnelling microscope tip apex to switch a single
Molecular electronics
molecule as already explored by A. Aviram, C. Joachim
Single-molecule magnet
and M. Pomerantz at the end of the 80s (see their seminal Chem. Phys. Lett. paper during this period). The
Stereoelectronics
trick was to use an UHV Scanning Tunneling microscope
to allow the tip apex to gently touch the top of a single C
Organic Semiconductors
60 molecule adsorbed on an Au(110) surface. A resistance of 55 MOhms was recorded together with a low
Conductive polymers
voltage linear I-V. The contact was certied by recording
Molecular conductance
the I-z current distance characteristic, which allows the
measurement of the deformation of the C
Software for molecular modeling
60 cage under contact. This rst experiment was followed
by the reported result using a mechanical break junction approach to connect two gold electrodes to a sulfurterminated molecular wire by Mark Reed and James Tour 8.8 References
in 1997.[15]
A single-molecule amplier was implemented by C.
Joachim and J.K. Gimzewski in IBM Zurich. This experiment involving a single C
60 molecule demonstrated that a single C
60 molecule can provide gain in a circuit just by playing
with through C
60 intramolecular quantum interference eects.
A collaboration of researchers at HP and UCLA, led by
James Heath, Fraser Stoddart, R. Stanley Williams, and
Philip Kuekes, has developed molecular electronics based
on rotaxanes and catenanes.
Work is also being done on the use of single-wall carbon
nanotubes as eld-eect transistors. Most of this work is
being done by IBM.
Some specic reports of a eld-eect transistor based on
molecular self-assembled monolayers were shown to be
fraudulent in 2002 as part of the Schn scandal.[16]
Until recently entirely theoretical, the AviramRatner model for a unimolecular rectier has been
unambiguously-conrmed in experiments by a group
led by Georey J. Ashwell at Bangor University,
UK.[17][18][19] Many rectifying molecules have so far
been identied, and the number and eciency of these
systems is expanding rapidly.
[1] Petty, M.C.; Bryce, M.R. & Bloor, D. (1995). Introduction to Molecular Electronics. New York: Oxford University Press. pp. 125. ISBN 0-19-521156-1.
[2] Tour, James M.; et al. (1998). Recent advances
in molecular scale electronics.
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New York Academy of Sciences 852:
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[3] Waser, Rainer; Lssem, B. & Bjrnholm, T. (2008).
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Nanotechnology. Volume 4: Information Technology II.
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[4] Kubatkin, S.; et al.
(2003).
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transistor of a single organic molecule with
access to several redox states.
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doi:10.1038/nature02010. PMID 14562098.
[5] Anderson, Mark (2005-06-09) Honey, I Shrunk the PC.
Wired.com
[6] Zoldan, Vincius Claudio; Faccio, Ricardo and Pasa,
Andr Avelino (2015).
N and p type character of single molecule diodes. Scientic Reports 5:
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[7] Gimzewski, J.K.; Joachim, C. (1999). Nanoscale science of single molecules using local probes. Science
283 (5408): 16831688. Bibcode:1999Sci...283.1683G.
doi:10.1126/science.283.5408.1683. PMID 10073926.
[8] Srensen, J.K.. (2006). Synthesis of new components,
functionalized with (60)fullerene, for molecular electronics. 4th Annual meeting CONT 2006, University of
Copenhagen.
[9] Service, R.F. (2003). Molecular electronics Nextgeneration technology hits an early midlife crisis. Science
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[10] Aviram, Arieh; Ratner, Mark A. (1974). Molecular rectiers.
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[11] Carter, F. L.; Siatkowski, R. E. and Wohltjen, H. (eds.)
(1988) Molecular Electronic Devices, pp. 229244, North
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[12] Gupta, Chaitanya; Shannon, Mark A.; Kenis, Paul
J. A. (2009).
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8.9 Text and image sources, contributors, and licenses

8.9.1
Text
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Top down methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

1.10 Safety of nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

1.12 See also . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

1.14 External links . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Surface coating for biological applications . . . . . . . . . . . . . . . . . . . . . . . . . .

2.11 Laser applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

2.12 Medicinal applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

2.15 Further reading . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

2.16 External links . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Sensing of proteins and chemicals using semiconductor nanowires . . . . . . . . . . . . . .

Probes for exploring cells interiors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Types of systems used . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Nanoremediation and water treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Types of carbon nanotubes and related structures

Three-dimensional carbon nanotube architectures . . . . . . . . . . . . . . . . . . . . . .

Graphenated carbon nanotubes (g-CNTs)

Nitrogen-doped carbon nanotubes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

6.1.10 Cup-stacked carbon nanotubes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

6.1.11 Extreme carbon nanotubes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Safety and Health . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Epidemiology and Risk Management

Safety and Exposure Prevention . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Chemical vapor deposition (CVD) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Natural, incidental, and controlled ame environments

Electrical cables and wires . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

6.7.10 Radar absorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

6.7.12 Optical power detectors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

6.7.14 Environmental remediation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

6.7.15 Water treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

6.7.16 Other applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

6.11 External links . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Energy applications of nanotechnology

Reduction of energy consumption

Increasing the eciency of energy production

Nuclear Accident Cleanup and Waste Storage

Capacitors: then and now . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Molecular scale electronics

History and recent progress . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Text and image sources, contributors, and licenses . . . . . . . . . . . . . . . . . . . . . . . . . .

REM scan of a buttery wing scale ( 5000)

Nanomaterials describe, in principle, materials of which

Brazilian Crystal Opal. The play of color is caused

Peacock wing (detail)

Lycurgus Cup, glass, 4th century, Roman.

Nanomaterials research takes a materials science-based

Blue hue of a species of tarantula (450 nm 20 nm)

1.1 Natural nanomaterials

Main article: Fullerene

The fullerenes are a class of allotropes of carbon which

Natural inorganic nanomaterials occur through crystal

The often very high surface area to volume ratio of

1.6.2 Top down methods

Novel eects can occur in materials when structures are

These methods include several dierent techniques for

1.12 See also

Gradient multilayer nanolm

Nanoparticles behave dierently than other similarly

List of software for nanostructures modeling

[1] Buzea, Cristina; Pacheco, Ivan; Robbie, Kevin (2007).

Nanoparticles created adventitiously (e.g., through the

[4] Fullerenes. Encyclopaedia Britannica.

[2] Novel natural nanomaterial spins o from spider-mite

[5] Buseck, P.R.; Tsipursky, S.J.; Hettich, R. (1992).