NEW METHODS FOR THE PRODUCTION OF SOLAR GRADE SILICON

Zhang Taisheng Chen Mingbo

Shanghai Solar Energy Research Center Shanghai Institute of Space Power Sources
Floor 7,Building 5,No.555 Dongchuan Road No.388 CangWu Road
Shanghai 200241, China Shanghai 200233, China
tysonzju@hotmail.com chmb@netease.com

Li Hongbo
Shanghai Institute of Space Power Sources
No.388 CangWu Road
Shanghai 200233, China
viewwide@sina.com

ABSTRACT necessary in this field.

During the last few yearsˈthere has been a strong economic

growth around 30% in photovoltaic (PV) industry which
has resulted in a shortage of polysilicon feedstock. On one
hand, the supply of waste wafers from IC industry can not
meet the need of PV industry. On the other hand, silicon
feedstock made by siemens method has a much higher
price and purity than the PV industry prefers. Therefore, the
PV industry requires a new kind of silicon feedstocküsolar
grade silicon(SOG). It is well known that the price of solar
cell module is still high for mass application and the cost of
silicon wafer is about 40% of the cost of a module. Lots of
new methods for the production of Solar Grade Silicon
appeared, as it is important to reduce the cost of silicon
feedstock for further development of PV industry.
1. INTRODUCTION
The global energy consumption is predicted to grow
dramatically year by year. Higher prices of energy and
growing worry about global warming problem have open
up the market for solar cell. The PV industry has a growth
rate of about 30% as illustrated in Fig. 1.Till now ,about
90% of solar cells are made of crystalline silicon(see Fig. 2).
It will take at least a decade for other solar cell materials to
be competitive. The fast growth of PV industry has caused
a shortage of silicon feedstock. Silicon feedstock produced
by Siemens process is very expensive because of high
energy consumption during the production of silicon.

In this article, some of the recent development and
approaches that might benefit the PV industry are reviewed
and outlined. These new methods can be divided into two
kinds according to their purification process: gas
rectification methods and molten silicon purification
methods. None of the methods has absolute advantage to
the others. Each of the methods is still far from satisfaction
to mass production and hence, further research is still
Main obstacle for mass production of solar cells is high
cost of silicon material. If this cost will decrease by several
times, the cost of solar cell could decrease twice as less
than 1USD per watt. In this case cost of PV stations will be
competitive with cost of energy produced by conventional
methods.
 4 PV TECHNOLOGIES, SYSTEMS AND APPLICATIONS 1175

In order to find alternative silicon feedstock for PV industry,

a lot of research has been done in this field. There are two
kinds of method for SOG silicon production:
A. Purification of Si contained compounds and produce
silicon by chemical reactions
B. Purification of molten silicon.

2. GAS RECTIFICATION METHODS

There are two main methods for mass production of high

purity silicon feedstock:
A. use of hydrogenous reduction of trichlorsilane SiHCl3
named “Siemens process”(see Fig. 3)
B. disproportionation for producing of monosilane
SiH4,developed by Union Carbide Co.(see Fig. 4)
Fig. 1: Solar cell production 1999 to 2006. [1]

Fig. 3: A typical process flow for Siemens method. [3]

About 80% of world’s polysilicon is produced by method A,

and 20% is produced by method B. But these two methods
are complex, energy consuming, and ecologically
dangerous. High temperature, high pressure, chemically
Fig. 2: Market share of different solar cell materials. [2]
aggressive Cl compound are included in the two methods.
1176 Proceedings of ISES Solar World Congress 2007: Solar Energy and Human Settlement

(2) The disproportion of triethoxysilane in the presence of a

catalyst will lead to the production of silane and
tetraethoxysilane:

catalyst
4Si (OC2 H 5 )3 H SiH 4 + 3Si (OC2 H 5 ) 4

(3) Dry ethanol and by products as high purity SiO2 or

silica sol can be extracted by hydrolysis of
tetraethoxysilane. The alcohol will be returned to step 1.

Si (OC2 H 5 ) 4 + 2 H 2 O SiO2 + 4C2 H 5OH

(4) Silane is decomposed pyrolytically to pure silicon and

hydrogen at temperature of about 900ć.

850 − 900ć
SiH 4 Si + 2 H 2

The purity requirements for SOG silicon are not as high as

those for electronic applications. Thus, the silane will
undergo a simplified cycle of purification, and at Step 4 the
less expensive and less energy consuming process of the
Fig. 4: Process flow of Union Carbide Co. well known Siemens Process.

2.1 Low Temperature, Cl Free Process for SOG Silicon 2.2 Atmospheric Pressure Iodine Vapor Transport
Production (APVIT)

The National Renewable Energy Laboratory (NREL) and
Sandia National Laboratories (SNL),with funding from the
Initiative for Proliferation Prevention (IPP) Program, has
initiated a program to study new chlorine free methods of
producing SOG silicon. This new method uses MG Si and
absolute alcohol as the starting materials. This new method
requires only 15 to 30 kWh of energy per Kg of silicon
produced vs. about 250kWh/kg of the Siemens process.
The silicon yield is in the 80% to 95% range vs. 6% to 20%
for the Siemens process. The eventual cost goal is
USD10/kg of SOG silicon.
The process flow of this method are as following: [4]
(1) The reaction of MG silicon with absolute alcohol at 28
ć in the presence of a catalyst:
catalyst
Si + 3C2 H 5OH Si (OC2 H 5 )3 H + H 2
As illustrated in Fig. 5, T.F.Ciszek reported that in an
atmospheric pressure reactor,SiI2 transfer from a hot
(>1100ć) Si source to a cooler (>750ć) Si substrate and
decomposes easily via:
2SiI 2 → Si + SiI 4
The deposition rate is up to 5 micrometer/min. The
secondary product SiI4 will be recycled to transport more
Si. If MG silicon is used as raw material, impurities can be
effectively removed by three mechanisms:
(1) Differing free energies of formation during forming
silicon and impurity iodides;
(2) Rectification;
(3) Differing standard free energies of formation during
deposition.
 4 PV TECHNOLOGIES, SYSTEMS AND APPLICATIONS
Fig. 5: Schematic of the cyclic APVIT MG-Si purification
process. [5]
This method is attractive because of its fast deposition rate
and atmospheric operation. It also has the potential for
continuous operation with relatively easy input of raw
material and withdrawal of product.
3. MOLTEN SILICON PURIFICATION METHODS
The principle of melting silicon purification methods is
extract the impurities trough physical or chemical methods
while keep the molten silicon unchanged during the
purifying process. It is estimated that this kind of methods
will consume less energy and produce less pollution.
The segregation coefficient of most metallic impurities
such as Ag, Au, Fe, Cr, etc is very small. So it’s very
efficient to remove them by directional solidification. But
the segregation coefficient of B and P is very close to 1. So
TABLE 1: PROPERTIES OF THE TARGET, MG Si AND SOG Si TRIALLY PRODUCED
12
1177
it’s not so easy to remove B and P from silicon by this
method. The main efforts in this field are focus on the
efficient removal of B and P.
3.1 the NEDO Melt-Purification Process. [6]
The flow of the NEDO(New Energy and Industrial
Technology Development Organization) is shown in Fig. 6.
MG silicon is used as the raw material. In the first step,
phosphorus removal and an initial removal of metallic
impurities by directional solidification are carried out in
electron beam equipment. In the second step, removal of
boron and carbon is carried out through plasma melting in
an oxidizing atmosphere, and the molten silicon is directly
supplied to the final removal of metallic impurities by
directional solidification.
Fig. 6: Flow chart of NEDO purification process.
As we can see in TABLE 1, the impurities content has
achieved the target content. And solar cells using this kind
of material has a efficiency of 14.1%. But this method
includes many energy consuming steps such as Electron
Beam melting, plasma heating, and directional
solidification. And it seems not easy to scale up the output
by this method. So it’s still questionable whether this
method is energy effective and cost effective.
1178 Proceedings of ISES Solar World Congress 2007: Solar Energy and Human Settlement
3.2 Heat Exchange Method (HEM) [7]
C.P.Khattak etc reported a process to remove B and P from
MG silicon by refining in the molten state. A commercially
available HEM furnace (modified) was use to remove P and
B in MG silicon, then a directional solidification was
followed. The main refine approach in this process include:
(1) Evacuation
This simple refining step can remove volatile elements such
as P, Al, Na, Mg, S, and Cl irreversibly from the molten
MG silicon under vacuum.
(2) Formation of volatile species
Further refining can be achieved by reactions with O, H, Cl
to form volatile products of impurities.
(3) Oxidation of impurities or slagging
Fig. 7: Flow diagram of refining of MG silicon using HEM.
Impurity elements in MG silicon can be oxidized to form
other species and separated from MG silicon in a slag. The
slag can either float on the surface of molten silicon or sink
to the bottom of the crucible and can be easily removed.
(4) Gas blowing
These gases can be reactive with the impurities, or neutral
to promote the stirring of the melt.
Using this method, B has been reduced to 0.3ppma, P to
<10ppma and all other impurities to <0.1ppma using
commercially available MG silicon and HEM furnace.
4. SUMMARY AND CONCLUSIONS
An independent SOG silicon production for the PV
industry is necessary for the further development of this
industry. But it’s critical to keep balance between the purity
and the cost of the SOG silicon. It is estimated that the
SOG silicon will be competitive when its cost achieve
10-20USD/kg.
Additionally, the acceptance of SOG silicon by the market
doesn’t depends only on the production of silicon. The
solar cell process also need to adapt to SOG silicon in order
to fabricate high efficiency, low cost silicon solar cells.
Some of the methods mentioned here is very promising, but
none of these methods has realized mass production. More
efforts are needed in this field.
5. ACKNOWLEDGEMENTS
The contributions of Chen Mingbo and Li Hongbo are
gratefully acknowledged. This work has been funded by
Science and Technology Commission of Shanghai
Municipality (06DZ11101).
6. REFERENCES
(1) “Gigawatts-the measure of things to come”, PHOTO
International, March 2007, p.137
(2) “Gigawatts-the measure of things to come”, PHOTO
International, March 2007, p.148
(3) P.Woditsch, W.Koch, “Solar grade silicon feedstock
supply for PV industry”, Solar Energy Materials &
Solar cells 72, 2002, 11-26
(4) Y.S.Tsuo, J.M.Gee, “Environmentally Benign Silicon
Solar Cell Manufacturing”, 2nd World Conference and
 4 PV TECHNOLOGIES, SYSTEMS AND APPLICATIONS 1179

Exhibition on Photovoltaic Solar Energy Conversion;
6-10 July 1998; Vienna, Austria
(5) T.F.Ciszek, T.H.Wang, “Solar-Grade Silicon From
Metallurgical-Grade silicon Via Iodine Vapor Transport
Purification” Photovoltaic Specialists Conference 2000,
sept.2000, IEEE
(6) N.Yuge, M.Abe, “purification of Metallurgical-Grade
Silicon up to Solar Grade”, Progress In
Photovoltaics:Research and Applications,Appl.2001
(7) C.P.Khattak, “A simple process to remove boron from
metallurgical grade silicon”, Solar Energy Materials &
Solar Cells 74,2002,77-89