The 3rd Workshop on Reactive Metal Processing

Thermodynamics on SOG-Si Refining Processes

Institute of Industrial Science, The University of Tokyo

Kazuki Morita
1

Materials Production and Recycling Engineering Lab.

(Formerly Ferrous Metallurgy Lab.)

Recent Research Fields

Physical Chemistry of High Temperature Processing (Steelmaking and Waste Management) Microwave Processing for Recycling and Waste Treatment

Thermodynamics and Processing on Solar Grade

Silicon (SOG-Si) Production
2

Contents
1. Introduction 2. Metallurgical refining for SOG-Si
- Thermodynamic properties of impurities in molten Si alloys - Optimized Process Combined with Leaching Treatment -

3. Solidification refining of Si with Si-Al metls

- Segregation ratios of impurities between solid Si and Si-Al melt -

4. Conclusions and Future Work

3

Increase in solar cell production

1200 Total 1100 1000 900 800 700 Poly Crystalline 600 500 400 Single Crystalline 300 200 Amorphous 100 Ribbon 0 00 01 02 03 04 90 91 92 93 94 95 96 97 98 99 100101102103104 Year Fig. Amount of solar cell production by various processes. Amount of production (MW)

Depending on off-grade Si for semiconductor

Requirement for metallurgical refining process for SOG-Si

4

Possibility of Low Cost SOG-Si Production

Can we remove impurities from MG-silicon by metallurgical refining processes ?
New Refining Process?

MG-Si

SOG -Si

Impurities and solar cell efficiency

Fe, Ti, Al, P, B
Table 1 Impurity contents in MG-Si.
Impurtiry Fe Content(ppma) 1300 220 3300 30 30

Fe Ti

Al

Ti Al P B

Fig. Solar-cell efficiency versus impurity concentration for 4-cm p-base devices.
6

0
Gibbs energy of formation for oxides(kJ/mol O2)
+

4 Cu

O 2 Cu 2 = O2
= 2 Fe + O 2 2 FeO

-400

C + O2 = CO2

-800

-1200

e O4 2C+ 1/2 F 3 = O = O 2 + O e 2 n 2 CO M 2 3/2 F = O 2 n+ 2M O l 2O 3 = Si 2 2/3 A O 2 = + O 3 l + O2 Si-SiO2 Si O = 2/3 Ti 2 A 3 / 4 Mg-MgO i+ 2 4/3 T O Mg Ca-CaO 2 = Al-Al2O3 2 O g+ CaO 2M =2 O2 a+ C 2

Fe-FeO

Strong Affinity of Silicon for Oxygen

Difficulty in Oxidation Treatment

2500

-1600 0 500 1000 1500 2000

Temperature(K)

Fig. Ellingham diagram for some representative elements.

Most metallic impurities

T=T1 Si Standard : solid

P, B, C, etc.
T=T1 Si standard : solid

GM solid 0liquid

GM 0-

liquid solid

Si

Component X

Si

Component X

T1
S+L Si

T1
S+L S Si
Component X

Component X

(a) Small segregation coefficient

(b) Large segregation coefficient

Fig. Relationship between Gibbs free energy and phase diagram below melting point of silicon.

104 103 Fe Al 2 Ti 10 P B after first solidification 101 V Cr 100 Ni -1 after second 10 solidification -2 10 10-3 10-4 10-5 10-6 10-7 10-8 10-9 10-10 10-11 -6 10 10-5 10-4 10-3 10-2 10-1 100 segregation coefficient
9

Impurity content of MG-Si Required impurity content for SOG-Si

Fig. Removal of impurity in silicon by solidification refining.

impurity content (ppmw)

Thermodynamic properties of impurities in molten silicon alloys

Phosphorous

Equilibrated in a controlled phosphorous partial pressure

Titanium

and Iron

Equilibrated with lead

Aluminum,

Calcium and Magnesium

10

Equilibrated with Oxides

Thermodynamics of P in Molten Silicon

To Ribbon Heater Temperature Controller Thermocouple

Gas Inlet Tube

Ar

Silicone Plug

Mullite Tube

Ar+P4

Red Phosphorus

Ribbon Heater

Graphite Holder

Red Phosphorus Temperature Argon Flow Rate

398-461K 190cc/min

Fig. Schematic cross section of the phosphorus vapor generator.

Ar+P4 (P2+P)

Graphite or Alumina Crucible

Molten Si-P Alloy

Porous Alumina Block

Fig. Schematic Cross Section of Experimental Apparatus.

11

1/2 P2(g)=P(mass%, in Si) G= -139,000+43.4T (J/mol) Free energy change (kJ/mol)

0.05 [mass%P] 0.1

0.002 PP21/2(atm1/2)

-50 -60 -70 -80

0.001

1750

1800 T(K)

1850

Fig. Relationship between equilibrium phosphorous partial pressure and phosphorous concentration of silicon at 1823K.

Fig. Temperature dependence of free energy change of phosphorous dissolution into silicon.

12

Hertz-Knudsen equation
Mi dy 0 = i pi X i 2RT dt
1823K 1867K estimated Ikeda et al.

10-4 10-5 10-6 10-7 10-8 10-9 10-10 10-11 10-12 10-13 10-14 10-15 10-16 -6 10

(V/A)log([mass%P]0/[mass%P]t)(m)

0.03

estimated Suzuki et al. Yuge et al.

PP ,PP2 (atm)

PP PP2

0.02

0.01

10-5

10-4 10-3 [mass%P]

10-2

10-1

Fig. Relationship between equilibrium partial pressure of P, P2 and phosphorous content of silicon at 1823K.

2 3 4 Time (ks) Fig. Relationship between time for vacuum treatment and (V/A) log([mass%P]0/[mass%P]t). 13

Thermodynamics of Ti and Fe in Molten Silicon

Gas Inlet Tube Mullite Tube

Graphite Holder Graphite Lid Graphite Crucible Molten Si-M (M:Fe,Ti) Molten Lead Porous Alumina Block

Si

Fig. Phase diagram of Si-Pb system.

Pb

Fig. Schematic Cross Section of Experimental Apparatus.

14

lnXTi in Pb-lnXTi in Si-13.2XPb in Si -10.8XSi in Pb-1.74

Ti(l) in Si=4.4810-4
Ti Ti in Si=3.97

lnXFe in Pb-lnXFe in Si-14.1XPb in Si -23.8XSi in Pb+4.91

-6

-1 -2 -3 -4 -5 -6 0

Fe(l) in Si=2.8510 Fe in Si=3.17

Fe

-2

-7

-8
lnXTi in Pb-lnXTi in Si-13.2XPb in Si -10.8XSi in Pb-1.74 = -7.71+3.97XTi in Si

-9 0

lnXFe in Pb-lnXFe in Si-14.1XPb in Si -23.8XSi in Pb+4.91 =-3.56(0.40)+3.17(5.46)XFe in Si

0.025 0.05 0.075 XTi in Si

0.1

0.02

0.04

0.06

XFe in Si

Fig. Relationsip between XTi in Si and ln XPb in Pb ln XPb in Si at 1723K.

Fig. Relationsip between XFe in Si and ln XPb in Pb ln XPb in Si at 1723K.

15

Ti and Fe are stable in molten silicon.

Removal of Ti and Fe by chemical reaction (i.e. oxidation, chlorination) is considered to be impossible.

Double solidification process is required.

16

Thermodynamics of Al, Ca and Mg in Molten Silicon

Graphite Holder

Al

Al2O3-Al6Si2O13 Crucible

Molten Si-Al Alloy

Ca

SiO2 Crucible Molten SiO2 satd. CaO-SiO2 Slag Molten Si-Ca Alloy SiO2 Crucible MgSiO3, SiO2 pellet

Mg

Molten MgSiO3, SiO2 satd.MgO-SiO2-Al2O3 Slag Molten Si-Mg Alloy

Fig. Schematic Cross Section of Experimental Apparatus.

17

0 log Al(l), log Mg(l) -0.2 -0.4 -0.6 -0.8 -1 5.4

1823

T(K) 1773 Ca Al

1723 -2.6 -2.8 -3 -3.2 Mg -3.4 -3.6 log Ca(l)

3610 + 0.452 T 14300 ln Ca = + 1.55 T 11300 ln Mg = + 4.51 T ln Al =

5.6 5.8 4 -1 10 /T(K )

Fig. Temperature dependence of the activity coefficient of aluminum, calcium, and magnesium in molten silicon relative to pure liquid.
18

P, Al, Ca and Mg can be removed by vacuum melting.

mass of Si : 1000kg 2 40.3m surface area 0.739m
2

20
Ca

2000

10
Al

1000

Mg

3 4 5 Time(ks) Fig. Relationship between vacuum time and impurity content of silicon at 1823K.

0 6

mass ppm Al, mass ppm Ca

30

3000

mass ppm P

19

NEDO SOG-Si Manufacturing Process (Operated in JFE Steel Co.)

MG-Si
First step purification Second step purification

Vacuum melting by electron beam Removal of P, (Al, Ca) Directional solidification Removal of Fe,Ti,Al
Vacuum

Plasma melting with water vapor Removal of B, C Directional solidification Removal of Fe,Ti,Al
Argon

SOG-Si

Lower cost refining process is desired to be developed

20

Is there any way to reduce the times of solidification refining? If the treatment of MG-Si can remove 90% of Ti and Fe,

Possibility of Acid Leaching

21

Acid Leaching Test with Ca Addition

Si-Ca-Fe or Ti dissolved at 1723K Cooling to 1300K (CaSi2 formation)
Graphite Holder

Ar
Graphite Crucible

Acid leaching with aqua regia

Porous Alumina Block

Chemical analysis
22

Removal Fraction of Fe

23

Consideration of Removal Behavior of Fe with the Ca-Fe-Si Phase Diagram

Eutectic Point XCa/XFe6.4 Secondary Phase CaSi2 or FeSi2 ?

Fig. Phase Diagram of the Si rich corner for the Ca-Fe-Si System [calculated by Thermo-Calc]
24

Si-3.26%Ca-0.424%Fe, 4.4K/min

Fig. (a) SEM micrograph of Si-Ca-Fe alloy. (b) Microstructure of Si-Ca-Fe alloy. (c) Concentration profile by EPMA line analysis.

25

Si-2.41%Ca-0.685%Fe, 4.4K/min

Fig. (a) SEM micrograph of Si-Ca-Fe alloy. (b) Microstructure of Si-Ca-Fe alloy. (c) Concentration profile by EPMA line analysis.

26

Acid leaching treatment with Ca addition NEDO SOG-Si Manufacturing Process Removal Fe and Ti Co.) (Operated inof JFE Steel
MG-Si
First step purification Second step purification

Vacuum melting by electron beam Removal of P, (Al, Ca)

Plasma melting with water vapor Removal of B, C, (Al, Ca)

P : 30 < 0.1ppmw
Directional solidification Removal of Fe,Ti,Al
Vacuum

B : 5-10 0.1-0.3 ppmw

Directional solidification Removal of Fe,Ti,Al
Argon

SOG-Si

27

Acid leaching treatment with Ca addition NEDO SOG-Si Manufacturing Process Removal of Ti, P and B (Operated inFe, JFE Steel Co.)
MG-Si
First step purification Second step purification

Vacuum melting by electron beam Removal of P, (Al, Ca)

Plasma melting with water vapor Removal of B, C, (Al, Ca)

P : 30 < 0.1ppmw
Directional solidification Removal of Fe,Ti,Al
Vacuum

B : 5-10 0.1-0.3 ppmw

Directional solidification Removal of Fe,Ti,Al
Argon

Reduction of processing time

SOG-Si

28

Phase diagrams for the Si-Al system

Pure Al MG-Si (98-99%)
X i in solid

Segregation ratio k i =

Si

X i in Si Al melt

Fig. Phase diagram of Si-Al system.

Low eutectic temperature

Removal of impurities by use of enhanced segregation at low temperature

Solidification refining of Si with Si-Al melt at low temperature.

29

Segregation ratios of impurities between solid Si and Si-Al melt

Thermodynamics of impurity elements in solid Si

Evaluation of low temperature Si refining process

Segregation ratios of impurities between Si-Al melt and solid Si

Al, B, P Fe,Ti, etc.

Experimentally determined Theoretically determined

30

Determination for segregation ratios of P and B

Diffusion coefficient of impurity elements in solid Si

Al, P, B Considerably small diffusion coefficient in solid Si

Solidification method to attain the equilibrium

Fig. Diffusion coefficient of impurity elements in solid silicon.

31

Determination for segregation ratios of P and B

Temperature Gradient Zone Melting(TGZM) method

a) L S L+S
C1l C2l C1s C2s T1 A Distance 1 2

Temp.

Tm,A T2

b)

Component B

c)
Solid Si

Solid Si

Precipitated Si Si-Al melt

Fig. Schematic diagrams of the temperature gradient zone melting. (a) Portion of phase diagram. (b) Temperature gradient in system. (c) Physical system comprising (A+B)molten zone traveling through solid A.
32

Determination for segregation ratios of P and B

Experimental method
Temperature Gradient Zone Melting Method
Al and P contents in solid silicon EPMA analysis
5 4 6 7 8 9 10

Ar atmosphere 24-72h Temperature Gradient 10-40K/cm

Distribution of P (and Al) between solid Si and Si-Al-P alloy - Red phosphorus stuck Al foil Distribution of B (and Al) between solid Si and Si-Al-B alloy

2 1

11 12

- Prepared Al-B foil

Fig. 1. Schematic diagram of an experimental apparatus: 1-SiC heating element; 2-thermocouple connected to PID controller; 3-gas outlet tube; 4-stainless steel holder; 5-single crystalline silicon; 6aluminum foil; 7-mullite tube; 8-thermocouple for measuring temperature of molten zone; 9-porous alumina boat 10-gas inlet tube; 11-alumina plate; 12-Sponge titanium 33

Determination for segregation ratios of P and B

Sample after TGZM experiment

B A

Segregation ratio
400 Intensities of K radiation of aluminum and phosphorus P Al 300

200
(b) Migrated region (c) Si-Al zone (a) Single crystalline Si (d) Single crystalline Si

100

10mm

Fig. Photo of a TGZM specimen after the experiment.

200 300 400 500 600 Distance ( m) Fig. Intensity profiles of Ka radiation of aluminum and phosphorus of the sample (accelerating voltage of 15kV, sample current of 200nA, sampling step of 10m).
34

100

Segregation ratios of P and B

5 P B

Segregation coefficient between solid/liquid Si.

Segregation ratio

1 0.5

0.1 0.05

Segregation ratio between solid Si and Si-Al melt

0.01 1200 1400 Temperature (K) 1600

Segregation ratios are smaller at low temperature. Low temperature refining is effective.
35

Derivation of segregation ratio of impurity elements between solid Si and Si-Al melt
Equality in chemical potential of impurity between solid Si and Si-Al melt

Gi + RT ln ai = Gi
l0 l

s0

+ RT ln ai
l0

1)

ln k i = ln

Xi Xi

s l

Gi i = + ln s 0 RT i
fus

2)

Activity coefficients in solid Si and Si-Al melt

Based on the reported thermodynamic data
36

Segregation ratios between solid Si and Si-Al melt

<

Segregation coefficients between solid/liquid Si

Segregation ratio betw een Si-Al m elt E lem ent 1073K Fe Ti Cr Mn Ni Cu Zn Ag Au Ga In Sb Pb Bi P B Al 1.710 -11 3.810 -9 4.910 -10 3.410 -10 1.310 -9 9.210 -8 2.210 -9 1.910 -8 1.510 -11 2.110 -4 1.110 -5 3.410 -3 9.710 -5 1.310 -6 4.010 -2 7.610 -2 1.410 -4 and solid Si 1273K 5.910 -9 1.610 -7 2.510 -8 4.510 -8 1.610 -7 4.410 -6 1.210 -7 1.710 -6 6.110 -9 8.910 -4 4.910 -5 3.710 -3 2.910 -4 2.110 -5 8.510 -2 2.210 -1 4.910 -4 1473K 3.010 -7 9.610 -7 2.510 -7 9.910 -7 4.510 -6 2.510 -5 2.110 -6 6.610 -6 3.610 -7 2.410 -3 1.510 -4 8.210 -3 1.010 -3 1.710 -4 1.610 -1 4.910 -1 1.210 -3 Segregation coefficient betw een solid/liquid Si at m .p. of Si (6-3) 6.410 -6 2.010 -6 1.110 -5 1.310 -5 1.310 -4 4.010 -4 1.010 -5 5.010 -5 2.510 -5 8.010 -3 4.010 -4 2.310 -2 2.010 -3 7.010 -4 3.510 -1 8.010 -1 2.810 -3

37

Impurity contents of Si after low temperature solidification refining with Si-Al melt at 1273K and ordinary Si solidification refining of MG-Si.
Contents after purification; Ci = ki Ciini
Contents of MG-Si Contents after solidification refining with Si-Al melt at 1273K Contents after ordinary solidification refining

Initial content (MG-Si) Allowable contents for SOG-S Si

103 102 101 100 10-1 10-2 10-3 10-4 10-5 10-6

Impurity content (ppmw)

Fe

Ti

38

Viewing the development of the solidification refining of Si with Si-Al melt at low temperature

Discussion of the Si solidification method

from Si-Al melt Refining test
Si bath Al bath

Si-Al melt

Fig. Phase diagram of Si-Al system.

Poly or Single Crystalline ?

39

Discussion for separating of solid Si from Si-Al melt by flotation

(solid Si < 2.33g/cm3, Al-25.8%Si 2.45g/cm3) Holding Si-55.3at%Al alloy (liquidus temp. 1273K) at 1173K for 12h Si saturated, solid fraction = 0.168

Needle like Si grains

Preparation Melting in the induction furnace and rapid cooling

40

Separation of solidified Si from Si-Al melt using electromagnetic force Induction furnace
3 1 4 5 6

Si-55.3at%Al alloy (liquidus, 1273K) was melted and held at 1323K in the induction furnace

8 9 10 11 12

Measuring the surface temp. of the melt by the infrared pyrometer Cooling and Solidifying the sample by lowering from the position of induction coil
41

Solidified Si-Al alloy using induction furnace

Bottom 1cm

Agglomeration of solidified Si by electromagnetic stirring

42

Agglomeration mechanism of Si under the fixed alternative magnetic field

Difference in induced swirl current to the perpendicular direction
Induction coil B J F J

Solidification of Si at lower position Downward bulk flow Agglomeration of Si grains to the bottom of the sample

B Induced flow

Si-Al melt

Solidified Si

Solidification refining test

43

Experimental method
Prism Gas inlet tube

Synthesized MG-Si was alloyed to Si55.3at%Al(liquidus, 1273K) or Si-64.6 at%Al(liquidus, 1173K) with pure Al

Melting and holding at 1323K or 1223K

Measuring the surface temp. by infrared pyrometer

Quartz tube

Graphite crucible Induction coil Molten alloy Alumina block

Cooling and solidifying the sample by lowering from the coil Crashing the Si agglomerated part (> 840m), then acid cleaning
Sample No. PrSi-1 Fe 4500 2160 Ti 691 248 Al 1280 1560 B 56 36 P 36 19

Fig. Schematic cross section of experimental apparatus.

PrSi-2

44

Impurity contents of refined Si in the test run (ppmw)

Sample No
SR-1 SR-2 SR-3 SR-4 SR-5 SR-6

Source
PrSi-1 PrSi-1 PrSi-2 PrSi-2 PrSi-1 PrSi-1 13 13 20 27 47 36

Fe
(99.7%) (99.7%) (99.1%) (98.8%) (99.0%) (99.2%)

Ti
5.2 (99.2%) 2.7 (99.6%) 2.8 (98.9%) 4.5 (98.2%) 7.7 (98.9%) 5.6 (99.2%)

B 0.81 (98.6%) 0.88 (98.4%) 0.71 (98.1%) 1.90 (94.8%) 0.98 (98.3%) 0.99 (98.2%)

P
0.93 (97.4%) 1.2 (96.7%) 0.72 (96.3%) 1.0 (95.1%) 0.42 (98.8%) 0.66 (98.2%)

Al
599 (53.1%) 534 (58.1%) 575 (63.1%) 602 (61.3%) 538 (57.8%) 453 (64.5%)

Fe, Ti Well reduced but not as well as predicted values B, P Effectively removed

High ability for purification was confirmed.

45

Proposal of refining process for SOG-Si

Reduction of SiO2 in arc furnace Alloying of silicon with Al

Solidification refining with Si-Al melts

Acid cleaning Pre-refined Si (5N except Al)
Vacuum melting by electron beam Removal of P, (Al, Ca) Directional solidification Removal of Fe,Ti,Al

SOG-Si

46

Conclusions and Future Work

The optimum metallurgical refining process for SOG-Si was thermodynamically assessed. Possibility of solidification refining of Si with Si-Al melt was clarified. Solidification and separation of Si from the melt is the major problem to solve for the practical process.
47

Acknowledgments
Present data are based on two Doctoral Dissertations by Takahiro Miki (1999), now a research associate of Tohoku University, and Takeshi Yoshikawa (2005), now an assistant professor of Osaka University.

48

Periodical Journal Publication List 1

Metallurgical Refining
T.Miki, K.Morita and N.Sano :Metallurgical and Materials Transactions B, 27B(1996), 937-942, Thermodynamics of Phosphorus in Molten Silicon T.Miki, K.Morita and N.Sano :Metallurgical and Materials Transactions B, 28B(1997), 861-867, Thermodynamic Properties of Titanium and Iron in Molten Silicon T.Miki, K.Morita and N.Sano :Metallurgical and Materials Transactions B, 28B(1997), 861-867, Thermodynamic Properties of Titanium and Iron in Molten Silicon T.Miki, K.Morita and M.Yamawaki :Journal of the Mass Spectrometry Society of Japan47(1999), 72-75, Measurements of Thermodynamic Properties of Iron in Molten Silicon by Knudsen Effusion Method T.Miki, K.Morita and N.Sano :Materials Transactions, JIM, 40 (1999), 1108-1116, Thermodynamic Properties of Si-Al, -Ca, -Mg Binary and Si-Ca-Al, -Ti, -Fe Ternary Alloys 66(2002), 459-465, K.Morita and T.Miki :Intermetallics, 11(2003), 1111-1117, Thermodynamics on SolarGrade-Silicon Refining G.Inoue, T.Yoshikawa and K.Morita :High Temperature Materials and Processes, 22(2003), 221-226, Effect of Calcium on Thermodynamic Properties of Boron in Molten Silicon T.Shinpo, T.Yoshikawa and K.Morita :Metallurgical and Materials Transactions B, 35B(2004), 277-284, Thermodynamic Study of the Effect of Calcium on Removal of Phosphorus from Silicon by Acid Leaching Treatment
49

Periodical Journal Publication List 2

Solidification Refining
T.Yoshikawa and K.Morita :J.Electrochem. Soc., 150(2003), G465-G468, Solid Solubilities and Thermodynamic Properties of Aluminum in Solid Silicon T.Yoshikawa and K.Morita :Science and Technology of Advanced Materials, 4(2003), 531537, Removal of Phosphorus by the Solidification Refining with SiAl Melts T.Yoshikawa and K.Morita :Journal of Physics and Chemistry of Solids, 66(2005), 261-265, Thermodynamics of Solid Silicon Equilibrated with Si-Al-Cu Liquid Alloys T.Yoshikawa and K.Morita :Materials Transaction, 46(2005), 1335-1340, Thermodynamic Property of B in Molten Si and Phase Relations for the Si-Al-B System T.Yoshikawa and K.Morita :ISIJ International, 45(2005), 967-971, Refining of Si by the Solidification of Si-Al Melt with Electromagnetic Force T.Yoshikawa and K.Morita :Metallurgical and Materirals Transactions B, 36B(2005), 731736, Removal of B from Si by the Solidification Refining with SiAl Melts T.Yoshikawa, K.Arimura and K.Morita :Metallurgical and Materirals Transactions B, 36B(2005), 837-842, B Removal by Ti Addition in the Solidification Refining of Si with Si Al Melts T.Yoshikawa and K.Morita :Journal of Alloys and Compounds, 420(2006), 136-144 Activity Measurements of Al and Cu in Si-Al-Cu Melt at 1273 and 1373 K by the Equilibration with Molten Pb
50