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Abstract
CdS quantum dot (QD) solar concentrators were prepared by a solgel spin coating method. Thin lms were prepared at dierent
annealing temperatures and characterized by X-ray diraction and spectroscopic techniques. The eect of temperature on the optical
properties of CdS QDs embedded in silica matrix was assessed before and after exposure of the samples to sunlight for up to 4 weeks.
The results show that as the annealing temperature increases, the uorescent intensity and Stokes shift decrease. Therefore lower temperatures are preferable for the preparation of highly ecient QD solar concentrator systems.
2007 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
Keywords: CdS; Luminescent solar collector; Solgel; Stokes shift
1. Introduction
An interesting approach for conversion of light to electricity is the luminescent at plate concentrator [1]. The
plate contains luminescent particles that absorb the light
and emit part of the absorbed light diusely at a longer
wavelength. The light emitted by the particles is guided
through the plate by total internal reection to a solar cell
tted at the edge (Fig. 1). A fundamental dierence
between the luminescent concentrator compared to other
concentrators is that it concentrates diuse light as well
as direct light, and tracking of the sun is not necessary.
However, the development of such concentrators has been
limited by the performance of luminescent dyes. Recently,
novel luminescent quantum dots (QDs) have been
exploited in an unconventional solar concentrator in which
the dyes are replaced by QDs [2]. QDs have the following
advantages over dyes: (i) it is possible to tune the absorption threshold by choice of dot diameter; (ii) they can provide high luminescence quantum eciency; and (iii) they
should be inherently more stable than dyes. Moreover,
(iv) the red-shift between absorption and luminescence is
quantitatively related to the spread of QD sizes, which
can be determined during the growth process and allows
losses due to reabsorption to be minimized [2]. QDs in
transparent media, especially in solgel glasses, have
recently received much attention due to their promising
applications in several elds [3]. The solgel process is
based on hydrolysis and condensation reactions of organometallic compounds in alcoholic solutions. The most
widely investigated system involves silica-based glasses
which are prepared by polymerization of a silica alkoxide,
Si(OR)4. The doped SiO2 matrix proved to an excellent
matrix, providing good mechanical and optical properties
and conferring a high kinetic stability on nanometer-size
semiconductor crystallites [4,5]. Among the QDs, cadmium
sulphide (CdS) is an important member of the luminescent
1359-6454/$30.00 2007 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.actamat.2007.09.017
260
Solar radiation
Matrix
material
The nanocrystalline CdS-doped silica gels were characterized using X-ray diraction and UVvisible spectroscopic
methods. Optical absorption spectra were recorded using a
PerkinElmer Lambda 40 spectrophotometer. X-ray diraction (XRD) studies were carried out on a Diano Corporation
USA diractometer using Co radiation (k = 0.179 nm).
3. Results and discussion
Quantum dot
Total internal
reflection
3.1. Characterization
XRD measurements of nanocrystalline CdS-doped silica
were taken by varying the annealing temperature from 373
to 673 K. Fig. 2 shows that as the annealing temperature
increases, the intensity of the peaks increases and the width
of the peaks decreases. Peaks were obtained at 2h values of
24, 26.5, 28, 44, 48 and 52, corresponding to the
(1 0 0), (0 0 2), (1 0 1), (1 1 0), (1 0 3) and (1 1 2) planes, respectively. By comparing the peak proles with standard
ASTM data, the crystal structure was found to be hexagonal wurtzite. The CdS crystallite sizes were determined
from the width of the XRD peak at a 2h value of 44 using
Scherrers equation [4] and are listed in Table 1. It was
found that the crystallite size of CdS increased from 3.5
to 6.5 nm as the annealing temperature increased from
373 to 673 K. This can be attributed to the quantum connement eects of the SiO2 network. When the temperature
increases, the connement eects of the SiO2 network are
weakened, and the CdS crystallites continue to grow.
Optical absorption spectra for the lms of CdS embedded in SiO2 glass at dierent annealing temperatures are
shown in Fig. 3; it can be seen that the lms annealed at
373, 473, 573 and 673 K showed peaks at 405, 450, 470
and 490 nm, respectively. This gradual shift towards longer
wavelengths (red-shift) indicates the growth of the particles
at higher temperatures [7].
The optical band gaps (Eg) of the CdS lms prepared at
dierent annealing temperatures were calculated using the
relation:
373 K
473 K
573 K
Intensity (a.u)
Photovoltaic
cell
673 K
20
30
40
50
60
70
80
2
Fig. 2. X-ray patterns of CdS crystalline-doped silica at dierent
annealing temperatures.
261
Table 1
Comparison between particle sizes obtained from XRD and blue-shift of optical band gap (Eg) for CdS lms annealed at dierent temperatures for 30 min
Annealing temperature (K)
Eg (eV)
373
473
573
673
4.6
3.8
3.2
2.6
3.3
4.2
5.4
6.2
3.5
4.0
5.1
6.5
0.5
573 K
473 K
0.4
Absorbance
373 K
673 K
0.3
0.2
0.1
0
350
400
450
500
550
600
650
700
Wavelength, (nm)
Fig. 3. The change in the absorption peak maxima of nanocrystalline
CdS-doped solgel glass lm with annealing temperatures.
2
ahm Ahm Eg ;
14
373 K
10
473 K
573 K
673 K
8
6
4
2
0
2.2
2.7
373 K
(h)2x103 (eV/cm)2
12
3.2
3.7
4.2
4.7
h, (eV)
Fig. 4. The change in the optical band gap energy of nanocrystalline CdSdoped solgel glass lm with annealing temperatures.
400
473 K
573 K
673 K
450
500
550
600
650
700
Wavelength, nm
Fig. 5. The change in the emission peak maxima of nanocrystalline CdSdoped solgel glass lm with annealing temperature.
262
373 K before
0.36
373 K after
0.27
0.27
0.18
0.18
Absorbance
0.09
0
300
473 K after
0.36
0.09
400
500
600
700
0.45
0
300
400
600
700
0.45
673 K before
573 K before
573 K after
673 K after
0.36
0.36
0.27
0.27
0.18
0.18
0.09
0.09
0
300
500
400
500
600
700
0
400
500
600
700
Wavelength, nm
Fig. 6. Absorption spectra for nanocrystalline CdS-doped solgel glass before and after exposure to sunlight for 4 weeks.
400
373 K
473 K
573 K
673 K
450
500
550
600
650
Wavelength, nm
Fig. 7. The change in the emission peak maxima of nanocrystalline CdSdoped solgel glass lm with annealing temperature after exposure to
sunlight for 4 weeks.
263
473 K before
373 K before
373 K after
400
400
450
450
500
500
550
550
600
473 K after
650
400
450
500
550
600
650
573 K before
673 K before
573 K after
673 K after
600
650
400
500
600
700
Wavelength, nm
Fig. 8. Emission spectra for nanocrystalline CdS-doped solgel glass before and after exposure to sunlight for 4 weeks.
Table 2
Spectra characteristics of CdS thin lms annealed at dierent temperatures before and after exposure to sunlight.
Annealing temperature (K)
kabs (nm)
kem (nm)
Dk (nm)
373
0
4
0
4
0
4
0
4
408
390
452
438
471
460
493
483
513
500
522
511
534
526
551
543
105
110
70
73
63
66
58
60
473
573
673
4. Conclusions
We have developed a simple and eective way to fabricate stable, highly luminescent QD solar concentrators.
The solgel process has been applied successfully for preparing thin lms containing CdS nanoparticles in silica
glasses. It was found from XRD that the CdS crystallite
structure in a SiO2 matrix is hexagonal and that the size
of the CdS crystallites increases with increasing annealing
264