ARTICLE IN PRESS

Solar Energy Materials & Solar Cells 92 (2008) 418–424

www.elsevier.com/locate/solmat

New processes for the production of solar-grade

polycrystalline silicon: A review
A.F.B. Braga, S.P. Moreira, P.R. Zampieri, J.M.G. Bacchin, P.R. Mei
Faculdade de Engenharia Mecânica, Departamento de Materiais, UNICAMP—Universidade Estadual de Campinas, C.P. 6122,
CEP 13083-970, Campinas, SP, Brazil
Received 12 June 2007; received in revised form 27 September 2007; accepted 15 October 2007
Available online 26 November 2007

Abstract

The global energy consumption is predicted to grow dramatically every year. Higher energy prices and public awareness for the global
warming problem have opened up the market for solar cells. The generation of electricity with solar cells is considered to be one of the
key technologies of the new century. The impressive growth is mainly based on solar cells made from polycrystalline silicon. This paper
reviews the recent advances in chemical and metallurgical routes for photovoltaic (PV) silicon production.
r 2007 Elsevier B.V. All rights reserved.

Keywords: Silicon purification, solar-grade silicon

1. Introduction
The photovoltaic (PV) industry was limited to aerospace
applications up to the early 1970s, at the time of the first oil
crisis, when a more in-depth investigation began for
terrestrial applications [1]. One of the alternatives proposed
was the development of low-cost polycrystalline silicon
cells. However, the advance of this technology was
inhibited by the low efficiency of conversion of polycrystal-
line silicon.
 In 1980, the efficiency of conversion in 100 cm2 cells was
of the order of 8%.
 The year 1984 saw a 4% increment, with the conversion
efficiency rising to 12%.
 In 1985, this efficiency had risen to 13% in laboratory
cells (2 cm2) [2].
Although this advance was not enough to drive
investments in this type of cell, it encouraged some groups
to remain in this area. During this period, the greatest
interest focused on monocrystalline silicon, amorphous
silicon and other semiconductor materials. It was only in
Corresponding author. Tel.: +55 19 3521 3334; fax: +55 19 3289 3722.
E-mail address: spmoreira@fem.unicamp.br (S.P. Moreira).
1990, with the announcement of the results of a laboratory-
scale cell with a conversion efficiency of 35% (in areas of
5 mm2), that the polycrystalline silicon cell manufacturing
technology became really interesting. This advance led to
renewed investments in research to produce low-cost
polycrystalline silicon [3]. The consequences of these
research efforts are illustrated in Fig. 1, which shows that,
up to 1996, the market was dominated by the production of
monocrystalline silicon panels. The advances in polycrys-
talline silicon cell technology resulted in an inversion in the
tendency of the curve in 1997, led, for example, by the 1996
publication presenting a panel with 15% conversion
efficiency [4].
Basically, until 1997, the silicon employed in the
production of polycrystalline solar cells originated mostly
from waste produced by the microelectronics industry.
Considering the magnitude-scale differences, differences in
silicon specification requirements for application in micro-
electronics and in the area of PV, and the costs involved in
the process, special interest has focused on the search for
more economic routes for the production of PV silicon.
Moreover, in the last 5 years, largely due to the rising price
of crude oil and to growing awareness of the need to
protect the environment, major investments began to be
made in this technology [6].

0927-0248/$ - see front matter r 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.solmat.2007.10.003
 ARTICLE IN PRESS
A.F.B. Braga et al. / Solar Energy Materials & Solar Cells 92 (2008) 418–424
Fig. 1. Production of cells by type [5].
In 2004, the PV market showed a 62% growth over 2003.
The offer of PV energy in 2004 was 927 MW. Of the total
installed PV industry, the two largest markets are Germany
and Japan, which together account for 69% of the world
market.
The consolidated production of solar cells increased to
1146 MW in 2004, with the Japanese contribution repre-
senting 48%. The lack of silicon substrate to supply this
market is well known, and this lack presages restricted
growth in coming years [7].
The demand for solar-grade silicon has grown rapidly
and an average growth of 30% per year is estimated for the
next 10 years [8].
Table 1 presents the worldwide polycrystalline silicon
production capacity and the projected growth in offer for
2010 [9]. Table 2 shows the relation between production
and demand for polycrystalline silicon between 2003 and
2010 [10]. These estimates reinforce the concern of the
international market to meet the demand for this
SiðsÞ þ 3HClðgÞ ) HSiCl3 ðgÞ
2HSiCl3 ðgÞ þ H2 ðgÞ ) Si þ SiCl4 þ 2HCl
important technology over the next four decades. Much
effort has focused on expanding silicon production plants,
as well as on investing in new low-cost routes for the
production of polycrystalline silicon.
For Brazil, the mastery of a PV silicon production route
may represent an important advance in the export segment of
products with high added value. Moreover, several factors ren-
der the mastery of a technology of this type highly attractive.
1. Brazil has the largest worldwide reserve of quartz (the
raw material for producing metallurgical silicon).
2. Brazil is the world’s fifth largest manufacturer of
metallurgical silicon [11], preceded only by China,
419
Russia, Norway and the USA. Brazil’s production of
metallurgical silicon in 2005 was 230,000 metric tons. Its
production volume in 2004 was the same, and in this
year it exported 200 thousand tons of metallic silicon at
approximately US $1.19 kg1 [12].
Considering the current picture, this paper reviews the
recent advances in the chemical and metallurgical routes
for the production of PV silicon.
2. New routes for solar-grade polycrystalline silicon
production
Metallurgical-grade silicon is obtained from the reduc-
tion of silicon in the presence of carbon [13]:
SiO2 þ 2C ! Si þ 2CO
Demand for silicon metal comes primarily from the
aluminum and chemical industries. The quantity of silicon
metal that is refined into semiconductor-grade metal is less
than 5% of total silicon metal demand [14].
In Brazil, the process for obtaining metallurgical silicon
uses not only high-quality quartz but also charcoal as a
reducing agent. This is reflected in the quality of Brazilian
metallurgical silicon, which, under well-controlled proces-
sing conditions and raw material, can reach a purity of up
to 99.88% [15].
2.1. Obtaining polycrystalline solar-grade silicon: chemical
versus metallurgical routes
Currently, the process for obtaining polycrystalline
solar-grade silicon is divided into two categories. The first,
called the chemical route, is related to the purification of
silicon by means of the Siemens process, consisting of
decomposing trichlorosilane by CVD on inverse U-shape
hot filament [16]:
)
ðHot filamentFCVD 1000  CÞ
The alternative route, known as the metallurgical route,
involves obtaining solar-grade silicon directly from metal-
lurgical silicon. This route for production can be five times
more energy efficient than the conventional Siemens
process that uses more than 200 kWh/kg [8].
Researches involving the chemical route (associated with
the Siemens process) are more advanced and are already
operating on a pilot scale. The so-called metallurgical route,
which proposes the purification of metallurgical silicon
without the stages that involve the formation of chlorosilanes,
is still in the research phase. However, Elkem of Norway
developed a process for polycrystalline solar-grade silicon
production and is building a 5000 metric tons plant [9].
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Table 1 Fig. 2 shows a general scheme of the two routes,

Worldwide PV silicon production capacity from 2004 to 2010 (in metric identifying the suppression of the use of hydrochloric acid
tons) [9]
in the metallurgical route, with the resulting reduction of
Company 2004 2005 2006 2007 2008 2009 2010 one phase of environmental control.
Another attractive aspect of the metallurgical route is
Hemlock 7000 7500 10,000 10,500 14,500 19,000 27,000 that the total consumption of energy in this process is
MEMC 2550 3700 4400 6500 8000 8400 8820
lower; indeed, the consumption of energy is estimated to be
Mitsubishi Mat 2200 2800 2800 2800 3200 3360 3528
Wacker 5200 5200 6500 7500 9000 13,500 14,175 25% lower than that of the Siemens process [20].
Tokuyama 4800 5200 5400 5940 6500 7500 8400 The metallurgical route also makes more sense from the
REC 5300 5300 5500 5500 8125 13,000 13,650 environmental standpoint, since the high growth of the PV
DeGussa/ 100 200 850 850 industry is related directly to the quest for renewable and
SolarWorld
Sumitomo 700 700 750 800 840 882
clean forms of generating energy. The production of solar
China 400 800 1600 2700 3800 cells by the chemical route also requires considerable
Endesa/Isofoton 2500 2625 consumption of energy and the handling and emission of
Elkem 1250 5000 10,000 toxic chemical compounds, leading to the need for coherent
Korea 1000 2500 3000 and responsible research for solutions enabling the energy
Other 1300 1300 1400 1500 2000 3000 4250
generated to be really clean and low cost [20].
Total (tons) 28,350 31,700 37,100 41,390 56,175 82,150 100,980 The following sections discuss the state of the art in the
development of silicon purification technologies to obtain
low-cost material.
Table 2
Analysis of silicon production and demand from 2003 to 2010 (in metric 2.2. Chemical routes
tons) [10]

Year Poly-Si Poly-Si demand Poly-Si Available Poly- 2.2.1. Wacker Chemie AG
capacity (CI- demand PV poly- Si This German company foresees an expansion of its
semiconductor) (PV) Si stocka polycrystalline solar-grade silicon production in Burghau-
2003 26,700 17,000 9000 9700 +700
sen, Germany, where its production capacity was increased
2004 28,800 19,350 14,032 9450 4582 in two stages: in 2006, the annual production will be
2005 30,200 20,085 18,181 10,115 8066 increased by 500 metric tons and in 2007 by 1000 metric
2006 34,500 21,166 16,705 13,334 3371 tons. After this expansion, its annual polycrystalline
2007 38,050 23,071 17,435 14,979 2456 production capacity will be 6500 metric tons/year. The
2008 48,550 26,301 24,089 22,249 1840
investments for this expansion lie in the order of 75 million
2009 53,800 26,837 28,233 26,973 1260
2010 58,800 27,632 32,108 31,168 940 euros [21].
The traditional Siemens process is employed to supply
a
Lack () or excess (+) of polycrystalline silicon in the worldwide the microelectronics industry, as briefly mentioned earlier.
market.
The process developed for the production of low-cost
silicon in Burghausen involves deposition in fluid-bed
reactor, which offers the following advantages: shorter
The major problem of the chemical route is that it deposition time; does not involve etching; and growth of
involves the production of chlorosilanes and reactions with polycrystalline silicon in Sio300 mm grains (seeds).
hydrochloric acid. In addition to being toxic, these This process begins with a gaseous mixture of trichlor-
compounds are corrosive, causing irritations of the skin osilane and hydrogen, which flows through a bed contain-
and mucous membranes [17]. Two silane compounds ing silicon seed grains (with sizes of less than 300 mm).
(trichlorosilane and silicon tetrachloride) are intermediates A constant flow of hydrogen is fed from the lower to the
in the solar-grade silicon production process via the upper portion of the tube. The hydrogen flow agitate the
chemical route. Not only are they highly volatile, corrosive silicon seeds, leaving them in suspension and favoring
and toxic but their handling also requires the utmost care, the deposition of polycrystalline silicon on the surface of
since they are explosive in the presence of water and the grains, thereby increasing their size, as illustrated in
hydrochloric acid [18]. Chlorine emissions in polycrystal- Fig. 3. This process is continuous and presents zones with
line silicon production by the chemical route are estimated distinct temperatures, allowing the material to be packaged
to amount to 0.002 kg of chlorine per square meter of immediately for use [21].
cell. Controlling this emission is important because
chlorine is denser than air, which accelerates the poisoning 2.2.2. Tokuyama Corporation
process. Its odor can be perceived at atmospheric The Japanese company, Tokuyama Corporation, is the
concentrations of 0.3–0.5 ppm, but the symptoms of one of the largest worldwide manufacturers of solar-grade
chlorine poisoning often appear before we become aware silicon, with an annual production of 5940 metric tons/
of the contamination [19]. year. Actually, Hemlock Semiconductor Corporation
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A.F.B. Braga et al. / Solar Energy Materials & Solar Cells 92 (2008) 418–424 421

CHEMICAL ROUTE METALLURGICAL ROUTE

Quartz Quartz

Emission of CO and silica

Reduction in the presence Reduction in the presence
of carbon REQUIRES CONTROL of carbon

Si - Metallurgical Si - Mettalurgical

Emission of Cl2 and

Purification: reactions with production of Purification: controlled fusion,
HC1 and H2 chlorosilanes refusion and solidification
REQUIRES CONTROL

Production of solar cells Handling of toxic elements Production of solar cells

REQUIRES CONTROL

Use of toxic compounds in

Solar Panels and Modules the manufacture of panels, Solar Panels and Modules
Environmental policy for
discarding batteries,

Fig. 2. Stages of the production of solar cells and panels that require research in the area of environmental control [20].

The process is based on the production of trichlorosilane

from metallurgical-grade silicon in a VLD reactor, where
the liquid silicon is produced and deposited at much higher
rates than in the conventional process [22].

2.2.3. REC Group—REC silicon

Fig. 3. Silicon seeds: (a) grains grown in the process and (b) of silicon
purified by Wacker’s new process (these photographs are illustrative and
are not on the same scale [21]).
produces 10,000 metric tons/year, Wacker produces 7500
metric tons/year, MEMC Electronic Material 6500 metric
tons/year and REC 5500 metric tons/year [9].
This company uses the Siemens process, but in 2006 it
began activities in a new production plant using an
alternative route called VLD (vapor-to-liquid deposition),
which is based on the chlorosilane decomposition on a
silicon liquid film and allows a 10-fold higher deposition
rate than in the Siemens process, generating the product at
a lower production cost. This project was financed by
Japan’s New Energy and Industrial Technology Develop-
ment Organization (NEDO), and US $28.5 million were
invested in the construction of the new plant.
The company proposes an alternative to the Siemens
process, whereby solar-grade silicon is produced in an
inverse U-shape hot filament CVD reactor from thermal
decomposition of SiH4. This proposal involves a contin-
uous process, which recycles chlorides and hydrogen.
Similarly to the aforementioned companies, the proposed
cost reduction is based on the increase of the solar-grade
polycrystalline silicon production rate.
This company is currently producing solar-grade and
electronic-grade silicon with annual production capacity
currently amounting to approximately 6000 metric tons
[23]. At the plant in Moses Lake REC has increased the
production capacity by approximately 6500 metric tons,
only solar-grade silicon qualities are produced here [23,24].
Moreover, this company is also introducing the fluidized
bed reactor process based on silane (SiH4) [23].
2.2.4. Chisso Corporation—Chisso solar-grade silicon
(CSS)
CSS transacts business in chlorination, reduction and
electrolytic reaction. In this technology, silicon tetrachlor-
ide produced by the chlorination reaction of metal silicon is
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reduced by zinc to produce 6N grade polysilicon
(99.9999%). The polysilicon specified for the PV genera-
tion purpose is used as the raw material of crystalline
silicon solar cells.
Chisso Corporation and NEDO have been engaged with
the research and development of CSS since 2002. Upgrade
from the bench-scale laboratory to a pilot plant is currently
scheduled at Minamata Research Center, Minamata City,
Kumamoto.
The chlorosilane production technology that is applied
in the chloridation process is currently operated by Chisso.
It follows the legacy of Japan’s first high-purity silicon
technology for the semiconductor purpose that was offered
by Chisso in the 1960s. The core technology developed by
Chisso will be fused with the electrolytic technology for the
metal titanium production that Toho Titanium has
accumulated over the years and the high-purity metal
technology of Nippon Mining Holdings Group.
CSS also employs a closed loop system. It cyclically
utilizes zinc chloride, which is a side effect of the reduction
process, to reduce costs and to enhance the production of
high-quality polysilicon while greatly reducing the by-
products [25].
2.3. Metallurgical routes
2.3.1. SOLSILC project
In Europe, the SOLSILC and SPURT projects propose
the development of solar-grade silicon by carbothermal
reduction of silicon, based on the use of very pure raw
materials. The project is the result of a partnership between
the SINTEF Materials and Chemistry, ECN—Energy
research Centre of the Netherlands, ScanArc Plasma
Technologies AB and Sunergy Investco BV. This proposal
can be classified as a metallurgical route to produce silicon
and foresees the use of plasma as the heating source to
reduce the silicon, followed by a unidirectional solidifica-
tion process [26].
The raw materials for this process are ultrapure quartz
and carbon black. On the one hand, this differential favors
the production of a product with low boron content
(controlled in the selection of the quartz) and a low
concentration of phosphorus (the phosphorus may come
from charcoal, depending on the cultivation process of the
wood). On the other hand, however, it may be limited due
to the exhaustion of quartz with this characteristic.
A limitation of the process is the residual carbon
originating from the reduction process.
An investment of 1.1 million euros was made and solar-
grade polycrystalline silicon cells with 10% conversion
efficiency were obtained. The advantage of the proposal is
that it reduces the consumption of energy to 25–30 kWh/kg
of product obtained. The Siemens process uses four times
more energy (120 kWh/kg of product). A pilot-scale plant
is already operating with a production capacity of 100
tons/year. This process is expected to reduce the cost of
silicon to 15h/kg.
There is a group in Kazakhstan, at the Kazakh National
Technical University, which is also working on the
carbothermal reduction of quartz using deposits of
ultrapure quartz in this country. Their results are promis-
ing and the best material obtained presents a purity of
99.96% in mass [27].
2.3.2. Elkem ASA
This company of Norwegian capital is today the largest
worldwide manufacturer of metallurgical-grade silicon. In
view of its technological vocation, Elkem opted for the
development of a metallurgical route based on pyrome-
tallurgical refinement [28] and on chemical treatment using
acid solutions [29]. The consumption of energy by this
process is similar to the SOLSILC route (25–30 kWh/kg),
which is still at laboratory level. Solar cells with efficiencies
of 15–16% have been obtained [30]. Elkem Solar has
commenced construction of the first industrial-scale
metallurgical solar silicon plant scheduled to start mid-
2008. The investment is 2.5 billions Norwegian crowns
(300 million euros) and will produce 2500 metric tons and
will be doubled to 5000 metric tons by 2010 [31].
2.3.3. Kawasaki Steel Corporation
The Japanese corporation Kawasaki uses the smelting
technique in an electron beam furnace allied to plasma
fusion with the objective of eliminating P and B,
respectively.
The starting material utilized is metallurgical-grade
silicon. The first stage foresees the use of an electron beam
to eliminate impurities. This is followed by the plasma
process. The results of Kawasaki’s purification process are
given in Table 3.
The plasma process for the purification of silicon has
been known for over 10 years. It has been stated [33] that
boron can be reduced from 35.7 ppm in mass to 0.4 ppm in
mass. Boron oxides (BO, B2O, B2O3, etc.) can be formed at
temperatures exceeding 2027 1C. These oxides present a
relatively high vapor pressure. For example, the estimated
vapor pressure of BO at 2000 1C is 74 Pa, while that of BO2
is 0.15 Pa and that of B2O3 is 0.056 Pa, and B in its
elemental form is 104 Pa at this temperature. Therefore,
Kawasaki’s process proposes the removal of boron from
the cast silicon matrix at 2027 1C (the boiling point of
silicon is 2355 1C) in the form of BO, using oxidizing
conditions for the plasma. The plasma torch is composed
of a mixture of argon and water [33].
Table 3
Behavior of P, Al and Ca in the process developed by Hazanawa [32]
Impurity Concentration (ppmw)
P 0.05
Al 18
Ca o0.1
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2.3.4. Apollon Solar—PHOTOSIL project Table 4

PHOTOSIL is a project which includes partners from Chemical analysis before and after silicon melting, final purity and
efficiency of extraction [15]
industry, R&D institutes and equipment manufacturers.
The objectives of this project are the production of solar- Impurities Before melting After melting Efficiency of
grade silicon at costs o15h/kg and of multi-crystalline (ppmw) (ppmw) extraction (%)
ingots at costs o35h/kg, starting with metallurgical silicon
Al 110.00 0.44 99.60
and using a combination of innovative up-grading and
Ba 0.04 o0.01 75.61
purification techniques. On the basis of encouraging results B 10.00 7.3 27.00
on laboratory level, the PHOTOSIL consortium has Ca 26.00 0.31 98.81
obtained the funding for the construction of an indus- Cu 6.50 0.29 95.54
trial-scale pilot line. This line became fully operational in Fe 790.00 0.70 99.91
K 0.10 0.10 0.00
October 2006 and serves to demonstrate the industrial Mg 4.20 0.02 99.50
viability of the PHOTOSIL technology by up-scaling the Mn 75.00 0.027 99.96
different laboratory-scale processes to an industrial level. Na 0.33 0.05 83.94
In the first stage, the pilot line operates with batch sizes of P 38.00 0.39 98.97
60 kg which will be doubled to 120 kg in the second stage, Ti 42.00 0.087 99.80
Others 16.32 2.74 83.21
arriving at a nominal capacity of 200 tons/year. The
PHOTOSIL process includes metallurgical and plasma Total 1108.49 5.165 99.53
purification techniques, giving rise to a complete vertical Final purity 99.88 99.9995 –
integration from the metallurgical silicon production to the (%)
fabrication of exploitable multi-crystalline silicon ingots
for the PV industry, of either p- or n-type [34].

2.3.5. UNICAMP
Developing a study using electron beam melting
principle. The main advantages of an electron beam
melting furnace are: (1) high vacuum processing, which
allows the elimination of elements whose vapor pressures
are higher than that of silicon and (2) the use of a
refrigerated copper crucible, which does not contaminate
the silicon. As the conventional chemical process (trichlor-
osilane) is not used, large amounts of chemical wastes
are not produced and there is no aggression to the
environment.
The principle of this technique is the generation of a
beam of free electrons that are accelerated towards a target
conductor such as a metal. An interaction occurs at the Fig. 4. Electrochemical cell [35].
point of action of the beam with the atoms of the material,
converting the electron beam’s kinetic energy into other
forms of excitation energy. A 99.9995% purity silicon is
obtained (Table 4) [15]. salt processes occur at temperatures below 1000 1C; (4) very
pure silicon can be deposited from dissolved silicon [35].
2.4. Other routes This academic project is involving NTNU (Norwegian
University of Science and Technology) and the SINTEF
2.4.1. NTNU and SINTEF (Foundation for Scientific and Industrial Research).
The Department of Electrochemical Technology of Characteristics of the process (Fig. 4):
Norwegian University of Science and Technology proposes
the use of the electrochemical process based on the  Anode material: Pt, graphite
dissolution of quartz in fluoride. The silicon is deposited  Anode product: Oxygen
on an electrode, after which it is ground and washed in an  Cathode material: Si-alloy, another conducting metal or
acid solution. The material is then cast into ingots (there is refractory (nitride, carbide)
a possibility that the plasma technology may be associated  Cathode product: Si(s), Ca
in this stage). The process is considered promising for
several reasons, i.e., (1) most of the contaminants of 3. Conclusions
metallurgical silicon derive from the raw materials (quartz,
carbon and processing equipment); (2) carbon can be The photovoltaic (PV) industry has a growth of 30%, a
eliminated in the electrochemical process; (3) aluminum situation that many other industries can only dream about.
 ARTICLE IN PRESS
424 A.F.B. Braga et al. / Solar Energy Materials & Solar Cells 92 (2008) 418–424
Today, the majority of solar cells are made of silicon, and
experts believe that it will take at least a decade before any
other PV technology based on other materials will become
competitive. The dramatic growth in the PV industry has,
however, caused a lack of solar-grade silicon (SoG-Si), i.e.,
silicon with the required chemical purity for PV applica-
tions, resulting in increased prices for such material.
Presently, the shortage of low-cost SoG-Si is the main
factor preventing environmentally friendly solar energy
from becoming a giant in the energy market in a generation
or two. A direct metallurgical route for production of SoG-
Si can be five times more energy efficient than the
conventional Siemens process that uses more than
200 kWh/kg. Several companies (Wacker, REC Silicon,
etc.) are making a big effort to economize the chemical
route further with the aim to produce SoG-Si instead of
semiconductor grade. Tokuyama is testing a strongly
modified filament reactor for their ‘‘vapour-to-liquid
deposition (VLD)’’ process. Several companies and re-
search institutes are working towards employing metallur-
gical processes in order to produce SoG-Si. Elkem Solar
has shown that their SoG-Si may be used to produce cells
of an efficiency of 15–16%.
Acknowledgments
The authors acknowledge FAPESP, Brazil, for funding
this research. We are also indebted to technician Emı́lcio
Cardoso for his assistance.
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