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Shaghayegh Esfahani 201011 MASc Thesis
Shaghayegh Esfahani 201011 MASc Thesis
by
Shaghayegh Esfahani
Shaghayegh Esfahani
2010
Abstract
Purification of metallurgical grade silicon (MG- Si) by a combination of solvent refining and
physical separation has been studied. MG-Si was alloyed with iron and solidified under different
cooling rates to grow pure Si dendrites from the alloy. The Si dendrites and FeSi 2, that were
formed after solidification were then separated by a gravity-based method. The separation
method relies on significantly different densities of Si and FeSi2, and uses a heavy liquid with
specific gravity between the two phases to float the former on the surface of a heavy liquid,
while the latter sinks to the bottom. The effect of particle size and cooling rate on the Si yield
and separation efficiency of the Si phase was investigated. The floated Si particles were further
purified by removing the physically adherent Fe-Si phase, using an acid leaching method.
Analysis of the produced silicon indicates that several impurity elements including P and B can
be efficiently removed using this simple and low-cost technique.
ii
In the Name of God
To my parents who have sacrificed so much for their children and for being an
endless source of inspiration and love in my life.
and also,
iii
Acknowledgments
First and foremost I offer my sincerest gratitude to my supervisor, Prof. Mansoor Barati, who has
supported me throughout my thesis with his patience and knowledge. I attribute the achievement
at this academic level to his encouragement and effort and without him this thesis, too, would not
have been completed or written. One simply could not wish for a better or friendlier supervisor.
I am grateful of Dr. Hiroshi Soda for his the time he has offered me during this period and for the
encouragement he has given me each day.
I would like to thank Sal Boccia of MSE Dept. (SEM), Geroge Kretschmann of Geology Dept.
(XRD) and Dan Mathers of Chemistry Dept. (ICP) for their continues assistance and support and
the useful skills they have taught me.
I am indebted to my colleagues Dr. Murray Johnston, Yasha Chaugule and Karim Danaie who
helped me in laboratory work.
I owe my deepest gratitude to my father Prof. Mohammad Reza Esfahani and mother Mrs.
Narjes Ebrahmi whose unwavering support from my childhood to present has made this
undertaking possible. I also wish to thank my husband Mr. Farshid Bahrami for his moral
support. His encouragement brightened the frustrating moments of my work and helped me
move on.
I would like to thank the professors in Iran for the knowledge they have provided me before
starting my Masters degree, with special thanks to Prof. Vahdati and Dr. Moayed.
I would like to thank the University of Toronto Open Fellowship, ARISE Technologies
Corporation and NSERC for their financial support.
iv
Table of Contents
Acknowledgments.......................................................................................................................... iv
v
2.9.5 Slagging .........................................................................................................................15
2.14 Summary...............................................................................................................................33
3.2 Experimental Procedure- Part Two: Quenching above the Eutectic Temperature ...............44
3.3.1 Scanning Electron Microscopy (SEM) and Electron Diffraction X-Ray (EDX): .........46
vi
4.2 Effect of Specific Gravity of Heavy Medium on Separation of Si.......................................51
Bibliography ..................................................................................................................................82
vii
List of Tables
Table 2-Segregation coefficient of some impurities in metallurgical grade silicon at melting point
of silicon [16, 25]. ......................................................................................................................... 12
Table 4-Segregation coefficient of impurities between solid Si and liquid Si-Al and those
between solid Si and liquid Si at silicon`s melting temperature [8]. ............................................ 18
Table 5-The impurity content of initial Si (ppmw) and final Si in solvent refining of Si and Al
[49]. ............................................................................................................................................... 22
Table 6-Maximum solubility of some elements in solid silicon from Ref. [25]........................... 30
viii
List of Figures
Figure 1-Furnace used for reduction of silica with carbon [14]. .................................................... 5
Figure 2-Impurity concentration verses efficiency curves in p-type silicon :(1) semiconductor-,
(2) solar-, and (3) metallurgical-grade silicon [14, 16]. .................................................................. 7
Figure 8-Mechanism of continuous solidification of Si from Si-Al melt under induction heating
[50]. ............................................................................................................................................... 23
Figure 9-Si dendrites agglomerated at the bottom of the sample [50]. ......................................... 23
Figure 10-Ellingham diagrams for stability of (a) borides and (b) phosphides. ........................... 27
Figure 12-Correlation between segregation coefficient and solid solubility of impurities in MG-
Si [25, 57-63] ................................................................................................................................ 29
ix
Figure 14-Solid solubility in silicon [26]. ..................................................................................... 32
Figure 19-Sample cut in half and taken out of the crucible. ......................................................... 40
Figure 21-Backscattered SEM image of (a) as–solidified and (b) crushed alloy dispersed in dark
background epoxy. ........................................................................................................................ 41
Figure 22-Separation of the particles after one minute suspension in the heavy liquid. .............. 42
Figure 26- Alumina crucible used in the second set of experiments. ........................................... 46
Figure 30-Recovery and grade in various S.G. of heavy liquid plotted for sample with cooling
rate= 3C/min and particle size= 600–800 µm. ............................................................................ 52
Figure 31-Recovery verses grade plotted for samples with cooling rate (a) 0.5 C/min, (b) 1.5
C/min and (c) 3 C/min. .............................................................................................................. 54
x
Figure 32-Separation efficiency verses particle size for samples with different cooling rates. ... 56
Figure 35-(a) Micrograph of the solidified alloy and (b) EPMA analysis for P across the line
shown in (a)................................................................................................................................... 61
Figure 36-(a) Micrograph of the solidified alloy and (b) EPMA analysis across the line shown in
(a) .................................................................................................................................................. 62
Figure 37-Effect of particle size on (a) P and (b) B concentration in final Si product. ................ 63
Figure 39-Number of refining stages verses impurity ratio in final Si to initial Si. ..................... 67
Figure 40-Solubility of P in Fe–Si melts at 1450 °C (reproduced from data in Ref. [71]) .......... 69
xi
Figure 50-XRD of 10wt%Ca for Ca3P2 detection......................................................................... 78
xii
List of Abbreviations
G: Grade
R: Recovery
P: phosphorus
B: boron
xiii
1
Chapter 1: Introduction
Silicon is the material of choice for manufacture of solar cells, accounting for over 90 percent of
today's PV materials [1]. Traditionally, Solar Grade Silicon (SoG-Si) was supplied from the off-
specification semiconductor grade silicon which is inherently more pure than the requirements
for PV applications. Higher cost and insufficient supply of electronic grade silicon rejects
together with a growing demand for SoG-Si, driven by need for clean energies, has created a
substantial thrust for developing a dedicated method of SoG-Si production. One stream of
research explores refining of Metallurgical Grade Silicon (MG-Si) to SoG-Si by inexpensive
metallurgical refining routes.
MG-Si is a relatively low purity source of Si (~98% Si). However, its availability in large
quantities and low price favors the use of MG-Si as the primary feedstock for SoG-Si production.
A conventional method called Siemens is already in use by many manufacturers but the
production cost is rather high due to energy consumption. Corrosive chemicals which are used in
this process are another drawback for this technology.
It is believed that a single metallurgical refining process is not sufficient to lower the impurity
level of MG-Si to SoG-Si specifications, due to presence of numerous impurities with different
chemical properties. A successful refining process should likely combine several refining stages,
each responsible for lowering a certain number of impurities to meet the purity requirements.
However, it is worth bearing in mind that metallurgical purification processes such as oxidation,
slagging, and controlled solidification are relatively cheap. Thus a multi-stage process could still
provide an economically attractive option for upgrading MG-Si to SoG-Si.
Solvent refining process is used for the purification of MG-Si by alloying with a solvent metal
and growing purified Si dendrites in the matrix. This process essentially mimics the crystal
growth techniques (such as zone refining – float zone – or Czokralski), but is in a much smaller
scale. Unlike similar float zone techniques in which the impurity elements are rejected to the
solid-liquid Si interface during solidification, in the solvent refining process impurities are
rejected to a second phase which has higher affinity for impurities.
2
In the current research, the solvent refining of MG-Si using iron as the impurity getter combined
with physical separation has been investigated.
Chapter 2 of this thesis provides a review of the previous literature pertinent to this study. In
Chapter 3, the experimental procedures are discussed. Chapters 4 and 5 present the findings
including the effectiveness of the physical separation and the extent of silicon purification using
the technique. A summary of the research is presented in Chapter 6 and the conclusions are
drawn.
3
In the last few decades there have been two main issues regarding energy, making it one of the
critical problems of the new millennium. On one hand, energy demand has increased due to the
population growth, as well as higher consumption. On the other hand, the ability of the earth to
sustain this rate of growth and consumption is fast decreasing. For finding solutions to the
environmental problems that humanity faces today, long term potential actions for sustainable
development is needed. Considering these facts, exploiting renewable energy resources such as
solar energy appears to be one of the most efficient solutions.
The concept of sustainable development is developing the economy while protecting the
environment or avoiding exhaustion of the earth limited resources. World Commission of
Environmental Development (WCED) has defined sustainable development as: “development
that meets the needs of the present without compromising the ability of future generations to
meet their own needs”. There are many factors that contribute to achieving sustainable
development. Today, one of the main factors that must be considered in discussions of
sustainable development is energy, and one of the most important issues is the requirement of
energy that is fully sustainable [2, 3].
Fossil fuel energy may be inexpensive and plentiful in nature but the problem lies within the
emission of greenhouse gas that it causes. Despite the well known consequences of fossil fuel
combustion on the environment such as global warming, ozone depletion and acid rain, it is
expected that by the year 2025 the world’s oil consumption be increased by 62% reaching 123
million barrels per day [4].
4
There are two alternatives to avoid the impact of these phonamena, one is to improve the fossil
fuels quality, so that it would cause less harm on the environment, the other is to subtitute it with
other sources of energy which are clean and renewable. Among these sources, solar energy is one
of the best choices due to its abundance and even ditribution in nature than any other renewable
energy type such as wind, geothermal, hydro, wave, and tidal energies [5].
Harnessing of solar energy dates back to 1960’s when “Solar Cells” provided electricity for
several space vehicles [6]. The energy crisis of 70’s motivated the terrestrial use of solar power.
Since then many investigations have been done on the conversion of solar energy to electricity.
2.3 Silicon
The essential component of a solar panel is a silicon wafer photovoltaic cell. Silicon is mostly
found in the form of silica and silicates in nature and makes up 25.7% of the earth’s crust [7].
The main issue in the PV industry is to convert this highly available material to pure silicon. In
fact, the production of silicon in a metallic form is even more difficult than extracting gold. The
reason for this is the high affinity of silicon to combine with other elements, especially with
oxygen so it is not easy to remove impurities by oxidation refining, which is a common
purification technique in the production of metals such as steel and copper.
Metallurgical grade silicon is a cost effective alternative for the production of solar cells, the
reason for this will be discussed in Section 2.7. The commercial method to convert SiO2 to
metallurgical grade silicon is carbothermal reduction which will be discussed in the next section.
input of
quartz and
carbon
electrode holder
electric contact
carbon electrode
trapping electrode
Liquid silicon is collected at the bottom of the furnace, and is drained and cooled.
The purity level of this silicon (MG-Si) is about 98-99%. The major source of impurities are the
raw materials used (specially the reductant mixture consisting of lignite, petroleum, coke,
charcoal and wood chips) [15]. A typical analysis of commercial MG- Si is given in Table 1.
As mentioned before, the purity in metallurgical grade silicon is around 98%. It has been well
recognized that the high impurity concentrations prevent the use of MG-Si directly for
photovoltaic applications. To reach the requirements of solar grade, the purity level should reach
6–7N. Therefore, it is necessary to remove most of the impurities of MG–Si. Figure 2 shows the
degradation thresholds of solar cells conversion efficiency (the percentage of power converted
from absorbed light to electricity when the cell is connected to electrical circuit) as a function of
the concentration of various elements in silicon.
In solar cell, recombination centers are energy levels in the middle of the band gap that will
enhance carrier (electrons and holes) recombination and reduce the total current. Diffusion length
is defined as the effective path length of the free carriers before recombination. Impurities and
precipitates form recombination centers in the band gap and thus degrade the performance of
solar cell by reducing diffusion length and device short circuit current [18].
Most transition metal impurities exist as interstitial impurity in silicon when they are below the
solid- solubility limit. The chemical state of impurities is related to their rate of diffusion in
silicon. Ni, Cu and Co have high diffusion coefficient (Figure 3) and almost always completely
precipitate out at surfaces or internal defects during cooling after crystal growth. Small fraction
of these impurities may remain as substitutional form, but if they do, they are believed to have
very little effect on photovoltaic silicon materials [19].
Impurities which have moderate diffusivities such as Fe, Cr and Mn tend to co- precipitate at the
same sites of Ni and Cu and form silicides [19].
Ti, Mo and V are examples of very slow diffusing impurities which are uniformly distributed
during crystal growth, unless initially present as undissolved inclusions in the melt. Most of these
impurities tend to be in interstitial form. Their low diffusivity also results in being very resistant
to gettering at temperatures and times which are normally used for processing silicon devices.
As mentioned before, the distribution and chemical state of impurities differ and consequently,
their influence on solar cell efficiency will be different. Thus, the distribution and chemical state
of impurities should be taken into consideration rather than just their average concentration.
Generally, point-like impurities such as Ti, Mo and V have higher influence on decreasing the
cell efficiency since they have greater recombination strength “per atom” than metal impurities
which exist as precipitated silicides such as Ni, Cu, Co, Fe, Mn and Cr [19].
9
First, Si is converted to SiHCl3 in a fluid bed reactor via the reaction shown below:
The gaseous product of this reaction is volatile SiHCl3 (Trichlorosilane or TSC) with boiling
point of 31.8°C which is more pure than Si but still needs to be purified.
The impure TCS gas is distilled to remove impurities, based on their different boiling points,
resulting in much more pure TCS. The pure gas is converted to Si through Eq. 2, in the presence
of hydrogen. The decomposition of TCS takes place on an inverse U–shaped silicon rod that is
heated electrically to 1000-1100 oC.
It is believed that P and B are removed during this process. The Si product is very fine-grained
and of high purity.
There are two main problems associated with this method. Firstly, it involves the production of
chlorosilanes and reactions with hydrochloric acid. In addition to being toxic, these compounds
are corrosive, causing irritations on the skin and mucous membranes [22]. The second is the high
energy consumption since it needs high temperature for long periods of operation.
Despite these problems, the Siemens process is currently the dominant method of producing
ultra-pure Si for electronic industry. A schematic diagram of the process flow is demonstrated in
Figure 4.
11
of phase equilibrium such that most impurities, but not all of them, are left in the liquid phase
and the remaining will be purified solid silicon. The amount of removal of a specific element
depends on its segregation coefficient which is the ratio of the concentration of an element in
silicon at its liquid state to its concentration in silicon at solid state. Since many elements such as
Cu, Fe, Al, Ni etc. have segregation coefficients ranging from 10-6 to 10-1 (Table 2) by repeated
directional solidifications, impurity levels can be reduced to a great extent. However, while most
of the impurities have low segregation coefficients, P and B have segregation coefficients close
to unity (0.35 and 0.8 respectively) so it is not possible to remove them effectively by directional
solidification. Therefore, other purification methods have to be used along this method in order
to remove P and B efficiently. Some approaches to this problem will be discussed later.
The advantage of the directional solidification process is that it is an easy process and does not
use any chemical reactions. However silicon losses occur since the portion of silicon which
solidifies at the last stage should be disposed of because all impurities are concentrated in this
section. Another disadvantage is that elements such as phosphorus and boron cannot be removed
and an additional process has to be applied in order to make PV-grade silicon.
13
As mentioned before, impurities except P and B have very low segregation coefficients in
silicon, indicating that they have low solubility in solid silicon compared to its liquid state. This
will result in the concentration of impurities in grain boundaries during solidification. If the
solidified metal is crushed, cracks are most likely to form through these grain boundaries, as
grain boundaries are usually concentrated from the impurities and are thus more brittle. Silicon
crystals have high corrosion resistance against most acids except the combination of hydrofluoric
acid in the presence of an oxidant. When solidified samples are pulverized to small particle sizes
the impurities in the grain boundaries will dissolve and be removed by acid leaching. The acids
used can be one or a combination of hydrofluoric acid, hydrochloric acid, aqua regia and sulfuric
acid.
The efficiency of leaching depends on three main parameters: particle size, time of leaching, and
leaching temperature. In a study by Dietl [26], these parameters have been studied and high
purity silicon with impurity amounts shown in Table 3 was achieved. In order to achieve this
level of purity very fine grinding up to 20 μm is required which is not favorable in terms of
materials handling.
Fe Ca Mn Ti Al
Although leaching has showed success in removing some impurities, not all elements could be
removed by this method. Impurities that exist in solid solution or impurities that are trapped as
separated phases within the silicon crystals will not be removed. In other words, acid leaching is
14
an effective method to remove the impurities that have already been separated during the
solidification.
The efficiency of the acid leaching can be improved by the addition of calcium. In a study by
Schei [27] in Elkem, silicon containing few percents of calcium was cast, cooled slowly and
crushed into lumps around 5cm. A CaSi2 phase formed at the grain boundaries contained most of
the impurities. Exposing the silicon lumps to hydrochloric acid and ferric chloride, disintegrated
them into silicon crystals of below 2mm. These crystals were further purified by hydrofluoric
acid in combination with an oxidizing agent.
In a work done by Delannoy [30], the three main steps of a plasma refining process have been
described as following: 1) transport of the impurities in the liquid silicon to the free surface of
the melt 2) evaporation or chemical reaction of impurities to transfer to the gas phase 3) blowing
the gas away from the surface by plasma torch. In order for these steps to take place, the silicon
should be maintained in liquid state throughout the process, the shape of the surface should be
controlled and the liquid should be electromagnetically stirred for the rapid transport of
impurities from the bulk to the surface. The plasma torch is composed of a mixture of water and
argon and the velocity of the flow was (10–40 m/s). A schematic diagram of the purification
system is presented in Figure 5.
15
The most effective method to remove B is oxidation refining utilizing plasma. Since B forms
more stable species than SiO2 such as B2O3 at temperatures higher than 1623 K, by oxidation
refining utilizing plasma the concentration can be lowered to 0.1 ppm [31].
2.9.5 Slagging
Slag refining is based on liquid-liquid extraction. It consists of reduction and oxidation reactions
of impurities in the interface of slag-liquid. These reactions are based on relative thermodynamic
stability of the formed oxide compounds. The oxides can either float on top or sink to the bottom
of the liquid. The slag which is used for extraction of impurities should have these main
properties [33]:
16
- The MG-Si which is going to be purified should be low in elements which their oxides are less
stable than the slag constituents
- Fluidity of slag should be high so that the mass transport can readily take place
- There should be a density difference between the slag and the liquid for easier separation.
Inert gas can also be used to promote stirring and to increase the reaction rate of reactive gas
with impurities [22].
Solvent refining is based on a physic phenomenon called gettering. Gettering has different
definitions with regards to silicon technology. The definition which is relevant to solvent refining
is that when silicon is alloyed with an element such as aluminum, metal impurities will have
higher solubility in the alloy melt if the temperature exceeds the eutectic temperature of that
binary system. The binary system should be in such a way that the element to be alloyed with
silicon should have no (or little) solubility in silicon. The binary system of Si and Al have a
unique characteristic and that is no intermetallic compound is formed thus the two phases that are
formed, are only eutectic and purified Si dendrites. The eutectic phase which contains most of
17
the impurities and can be dissolved in acid will be removed easily. For better understanding of
this binary system the Al-Si phase diagram is presented in Figure 6.
Eq. 3
where and are the contents of M in solid and liquid silicon respectively and is the
segregation coefficient. Equilibrium values can in principle be read from the phase diagram
of M-Si, but often special measurements give more accurate results [35]. This value is fairly
constant with temperature, when the concentration of the element in silicon is low.
The smaller this value is for a specific impurity, the more it will be distributed in the liquid phase
compared to the solid phase. Therefore, the amount of removal of a specific element in solvent
refining depends on its segregation coefficient. Since many elements such as Cu, Fe, Al, Ni etc.
have small segregation coefficients, (Table 2) their levels can be reduced substantially by
18
repeated directional solidification. However, as mentioned before, while most of the impurities
have low segregation coefficients, P and B have relatively large segregation coefficients that
render them unresponsive to directional solidification. However, since P has high vapor pressure
in silicon, removal of P can be achieved to a great extent by methods such as vacuum treatment
[36]. B can also be removed by oxidizing plasma treatments with Ar/H2O gas. Both of these
methods, however; are very energy consuming since they need high operating temperatures at
long periods of time and thus are not considered economical. Therefore, other purification
methods have to be used along directional solidification in order to remove P and B efficiently.
When silicon is alloyed with a getter element such as aluminum, metal impurities will have
higher solubilities in the alloy melt compared to solid silicon melt. The segregation coefficient in
this ternary Si-getter-impurity system is defined as the concentration of impurities in solid silicon
to the concentration of impurity in the Si-getter alloy melt. This segregation coefficient has been
proven to be lower than the segregation coefficient of non-alloyed silicon. An example for this is
the work done by Morita et al. [8] with Al being the getter element. In Table 4 these two
segregation coefficients for some impurities have been presented from their work.
Table 4-Segregation coefficient of impurities between solid Si and liquid Si -Al and
those between solid Si and liquid Si at silicon`s melting temperature [8].
Segregation ratio between Si-Al Segregation ratios between solid/liquid
Element melt and solid Si at 1000°C silicon at melting point of silicon
1410°C
P 8.5×10-2 3.5×10-1
B 1.5×10-1 8.0×10-1
Al 4.9×10-4 2.8×10-3
Fe 5.8×10-9 6.4×10-6
Ti 5.7×10-7 2.0×10-6
Cu 4.9×10-6 4.0×10-4
Ag 8.2×10-7 5.0×10-5
Pb 2.9×10-4 2.0×10-3
19
The different methods in solvent refining vary by two main factors: the alloying getter-element
and the method of separating the dendrites. In the following paragraphs a brief review on the
history of solvent refining is presented.
The earliest metallurgical application of solvent refining is desilvering of lead. Zinc is added to
silver-lead melt as the getter. Since silver is more soluble in zinc than in lead, by lowering the
temperature a layer of solid silver-zinc floats on top and skimmed off. The zinc is later distilled
at high temperature leaving pure silver behind.
One of the earliest researches concerning the use of this technique for purification of silicon is
the work by Wakefield et al. in 1976 [37]. They developed a method for refining silicon by
introducing silicon in a tin–lead alloy at about 1000°C. At this temperature the impurities in
silicon were believed to dissolve in the alloy. On cooling, the silicon dendrites were formed from
the alloy, leaving the impurities in the melt. The dendrites were then recovered by floating to the
surface, due to density difference, and were adhered to a crystal of Si that was pulled out from
the melt at 800°C as a single crystal. For performing this, a single crystal seed of silicon was kept
in contact with the surface of the melt and was pulled out as the purified crystal. The impurities
were believed to precipitate out as insoluble slicides that drop to the bottom of the melt.
In another study, Kotvel et al. [38] used aluminum as the getter metal. Silicon dendrites were
precipitated and separated from the melt by filtration. The dendrites were cleaned from the
adherent eutectic phase by 4-37% HCl acid leaching. It has been mentioned that while
mechanical or other means of mixing is optional during alloying silicon with aluminum; it may
be not desirable to stir the alloy during cooling. Stirring would break the silicon dendrites that
will consequently make their recovery difficult. In this process, iron and aluminum contents were
reduced from 0.48 and 1.26 wt% in the starting silicon to respectively 1000–1500 ppm and 20–
50 ppm in the refined product. Since Al has relatively high segregation coefficient in silicon
(2.8×10-3), some amounts might stay in the silicon product.
The solvent refining step can be followed by a slag oxidation refining process to remove the
microscopic inclusions of aluminum eutectic that are retained in the silicon dendrites. This step
20
involves mixing and melting of silicon dendrites in contact with high purity slag. The slag
removes aluminum from the silicon by oxidation forming Al2O3.
Kramer et al. [39] added Ti to form TiB2 with the boron present in MG–Si. It has been
mentioned the Ti amount should not exceed 0.2wt% and preferably 0.1wt%.
Gumaste et al. [40] studied the effect of cooling rate and holding time on the purity of the silicon
dendrites precipitated from Al-35% Si melt. They found that higher cooling rates are less
effective for removing impurities since faster cooling restricts the rejection of the impurities to
the liquid, hence, the solid composition approaches that of the liquid melt. Among three different
cooling rates of 20, 40, 60oC/ hr, 20 °C/hr resulted in the highest purity of the dendrites. Holding
the melt temperature about 100 °C above the eutectic temperature resulted in larger dendrites and
higher recovery of silicon. However, the purity of silicon decreased by increasing the holding
time. They discussed that this could be because of the increase in the concentration of impurity
elements in the residual alloy which is present in the interdendritic spacing during the last stage
of dendrite growth.
Some transition metal impurities are removed effectively through this method. However, with
regards to elements such as Al, Fe, P, Cu, Ti there seems to be no significant change and has
been suggested to remove these impurities further by slag refining, vacuum boiling and blowing
moist argon.
As mentioned earlier, in metallurgical refining of Si for solar cell production, removal of B and P
are most challenging due to their high segregation coefficient. The latest work done on solvent
refining is by Morita and his co-workers [8, 41-49]. They have studied the effect of alloying
silicon with aluminum on the removal of impurities specially P and B. Their work is based on
thermodynamic calculations as well as experiments. Their main goal was to find out if the
segregation coefficient of silicon impurities, specially P and B, in Si-Al melt is lower than the
segregation coefficient in pure silicon. In other word if Si-Al has more solubility for impurities
than pure silicon.
As a result of their studies, the activity coefficient of B and P and the interaction parameter
between Al and B in solid Si in solid silicon is also found. All this has been achieved by
21
Temperature Gradient Zone Melting (TGZM) method which is described briefly in the following
paragraphs.
The basis of this method is an experimental apparatus which is shown in Figure 7. An Al–(0.3-
1.1) wt-% B foil of 100μm thick is placed between two single crystalline silicon plates in a
temperature gradient zone in the furnace and is held in an argon atmosphere for 24 hours. The
instrument is designed to form equilibrium between Si-Al melt and solid Si so the distribution of
P or B between these two phases can be studied in such equilibrium conditions. The distribution
of P or B between these two phases (at 900-1100 °C temperature range) will result in finding the
segregation coefficient of P or B i.e. the ratio between the solubility of P or B in solid Si and Si-
Al melt at their infinite dilution. This ratio is then compared to the segregation coefficient of
solid/liquid silicon at its melting point.
Their results show that segregation coefficients of P and B were reduced from 0.35 and 0.8 to
0.08 and 0.15 respectively at 1000 °C. The reduction for other impurities was shown earlier in
Table 4 . This means that Si-Al melt has the tendency to dissolve such impurities and can be
effective in purification of MG-Si by the means of solvent refining.
22
After the decrease in the segregation coefficient as a result of alloying Si with Al is proven, it is
necessary to find an appropriate method for separating the bulk Si grains from Si-Al melt. Acid
leaching is an effective way for the removal of the inter-grains composed of Si-Al eutectics
between Si grains after the solidification of the alloyed melt. In order to improve the acid
leaching one other method is necessary to be applied prior to leaching to collect the Si grains and
produce a higher density of the grains. Therefore, two methods were investigated by Morita’s
group. One was separation by gravity force and the other electromagnetic force during
solidification which will be explained in the following paragraphs.
In regards to the latter it was found out that separation of the solidified Si grains is not possible
during solidification, since after melting and quenching the Si grains were found to be dispersed
uniformly in the sample. The reason for this, mentioned by the authors, is the high viscosity of
the melt in which particles dispersed. The other reason could be the low density difference
between the eutectic melt and the Si grains which is approximately 0.1 g/cm3. It was thus
concluded that the use of gravity force was not an effective separation method. The other method
was continuous solidification of Si from Si-Al melt under induction heating. In this method, the
separation of Si dendrites was investigated by solidification under fixed alternating magnetic
field (Figure 8). The Si dendrites are agglomerated at the bottom of the sample although the
density of these dendrites is lower than the eutectic phase Figure 9. After performing refining
test, the effective removal of impurities such as Fe, Ti, B, P and Al by this method was
confirmed.
Table 5-The impurity content of initial Si (ppmw) and final Si in solvent refining of
Si and Al [49].
Fe Ti Al B P
Induction
coil
B B
The second set of experiments was to investigate the removal of B from Si with solidification of
Si-Al melt containing B by Ti addition. This was studied by melting Si-Al-B alloy and holding
the sample close to the eutectic temperature of the Si-Al alloy in an induction furnace. The
solidification was performed under electromagnetic force. The part of the sample with high
density of Si dendrites was crushed into particles less than 840 µm. The adherent eutectic phase
to the particles was leached in aqua regia containing H2SO4 . In addition to TiB2, (Al, Si)3Ti may
also form. Since these precipitates are soluble in aqua regia, they can be removed and will not
affect the purity of the obtained solidified silicon. The final results reveal that Ti addition can
reduce the B content of MG-Si to a few ppma with no Ti contamination in the final product.
Effect of Ca Addition
Min and Sano [53] have investigated the formation of Ca3P2. The reaction of Ca and P has been
expressed by the reaction bellow:
25
In their study, it has been reported that Ca3P2 is a stable compound and Ca and P show attractive
interaction in molten silver. The stability of this compound is also shown in the phosphide
ellingham diagram that is plotted with Factsage software [54] shown in Figure 10. Hence; it was
expected that Ca has great affinity for P and can reduce the activity coefficient of P in molten
silicon. In other words it can reduce the segregation coefficient of P in Si. To confirm the affinity
and also study the affinity of Ca for B, Morita [36] has conducted some experiments and by
some thermodynamic analysis, it was found that although the interaction parameter between Ca
and B was slightly negative, that between Ca and P showed a large negative value. This
compound was found to segregate in the grain boundaries of silicon and was removed by acid
leaching. When 5.92 at% of Ca was added to molten silicon, the removal fraction of P was
reported to be 80.4%, while this fraction for B appeared to be 40% when 6.2 at% of Ca was
added.
On the other hand, as mentioned before in Section 2.9.2.2., Ca will also improve the leaching of
impurities such as Fe and Ti.
difference in the density of the formed eutectic phase and silicon. Thus, the higher the density of
the solvent, the easier it can be removed.
Low solubility in Si (the maximum solid solubility has been reported to be 1.1ppmw
[25]).
High affinity for impurity elements, particularly phosphorus and boron that are difficult
to remove by other methods such as directional solidification. Ellingham diagrams for
formation of phosphides and borides of several elements are generated using FactSage
[54] and presented in Figure 10. As seen, Fe has a higher tendency than Si to form
compounds with both P and B.
Higher density of Fe (~7.9 g/cm3) compared to Si (2.3 g/cm3) allows for gravity
separation of the Si dendrites from the matrix alloy.
The very low segregation coefficient of iron in Si (8× 10–6) [19, 25] allows the removal
of dissolved iron through subsequent directional solidification.
The remaining alloy (FeSi2) being ferrosilicon can be recycled and used in metallurgical
operations.
The phase diagram of Fe-Si is presented in Figure 11. As seen, the eutectic temperature is
1207oC. The eutectic structure is either β-FeSi2 or α-FeSi2 depending on the cooling conditions.
27
Low solubility and segregation coefficient of iron are evident in Figure 12. This figure
demonstrates that from these aspects, Fe, Zn, Mn, and Co are superior to Cu and Al, as the getter
elements.
(a)
(b)
Figure 10-Ellingham diagrams for stability of (a) borides and (b) phosphides.
28
100000
As
P
10000 Sn Sb
Solubility / Concentration
B
Ga
1000
Al
(ppmw)
Mg
Bi
100 Ca
Ni
Cu
Au O
10
Zn
Mn
1 Co
Fe
Cr
0.1
-7 -6 -5 -4 -3 -2 -1 0
10 10 10 10 10 10 10 10
Segregation Coefficient
In another reference [35] the maximum solid solubility of iron in silicon has been reported to be
1.1 ppmw which is much lower than the solubility of most elements in Table 6.
Table 6-Maximum solubility of some elements in solid silicon from Ref. [25]
This behaviour means that during solidification of Fe with silicon even if there are some
percipitates formed that cannot be separated later during leaching, as long as they are micron
sized, they will not affect the cell performance.
33
2.14 Summary
In order to convert MG-Si to SoG-Si a combination of methods should be used because various
impurities behave differently under different processes. The main challenge in these methods is
the removal of P and B which because of their properties in silicon, are much more difficult to
remove.
Directional solidification has proven to be a simple and effective way to reduce impurities but
elements such as B and P which have high segregation coefficient cannot be removed to the
levels that are needed for PV industry. Some other elements can only be removed to the desired
amount if this process is applied several times but due to the energy consumption it will not be
cost effective.
Plasma and vacuum refining are methods that can be used to remove P and B to desired levels
but these two processes are applied in very high temperatures and for long periods of time and
hence are not economically favored.
Acid leaching is another process which is used but can remove impurities that have been
separated during the solidification meaning that this method needs to be combined with other
methods to be effective for the removal of different impurities that exist in silicon.
Based on this review, it can be concluded that a combination of solvent refining, acid leaching
and solidification refining is a suitable choice for upgrading metallurgical grade silicon to solar
34
grade silicon. A review of the properties of iron showed that it could be an effective getter
metal. Its usefulness in purification of silicon is the focus of the present work and will be
discussed in the subsequent chapters.
35
In this chapter the experimental approach of the investigation is presented together with the
materials used. This chapter is presented in two main sections since two sets of cooling
conditions were examined.
Powder Mixing
MG-Si+Fe
Alloy Melting
Solidification
Crushing and
Grinding
Physical
Separation
Leaching
Directional
solidification
About 200 g of the powder mix was placed in a mullite crucible (height=10 cm, larger
diameter=5cm) sealed with a mullite lid covering the crucible and attached to it by ceramic paste
(Figure 16).
Al 980 Li 3
B 27 Ni 118
Mn 158 Zn 23
K 39 Be 1
V 86 Cr 5
Cd 38 Mg 57
Ba 12 P 68
As 5 Pb 20
Cu 100 Zn 50
Mn 1000 Cl 20
Ni 5000 S 10
The solidified samples containing Si dendrites and FeSi2 phase were then cut in half (Figure 19).
The dendrite size ranges were analyzed. For this purpose 20 dendrites were analyzed in each
sample (an example of these images is shown in Figure 20). Four widths along each dendrite
were measured; therefore, 80 data points for each sample was collected overall. These
measurements were performed by Image J software and the images were taken by a digital
camera.
39
5 mm
Si
FeSi2
(a) (b)
Figure 21-Backscattered SEM image of (a) as–solidified and (b) crushed alloy
dispersed in dark background epoxy.
42
The above analysis allowed to quantify the degree of separation of each phase, based on the
number of particles floated or (sank), and the composition of the particle (%Si or FeSi2). In
addition to this semi–empirical treatment, the actual (effective) separation of Si was also
investigated. 17 g of each of the four samples were suspended in 10 ml of HM in glass tubes
(Figure 22) then agitated manually and left for 24 hours. The lighter Si particles float on top
while the heavier FeSi2 particles sink to the bottom. The floats were scooped out and the sinks
were separated by filtering the remaining liquid. Some tools that were found suitable for
removing the floats are shown in (Figure 23), one being a plastic tube with a conical tip cut along
its vertical axis with a hole in the bottom. The tube is inserted in the floats and taken out once
filled with particles. This will limit the loss of heavy media.
The heavy liquid was cleaned for recycling by passing through several filters. Both the Si and
FeSi2 particles were rinsed with DI-water for a few times.
Figure 22-Separation of the particles after one minute suspension in the heavy
liquid.
43
The main change was the quenching temperature of the samples from bellow eutectic to
above eutectic temperature.
The iron powder was changed to electrolytic iron with 99.99% purity from Alfa Aeser.
The crucible in which the powder mix was solidified was cylindrical alumina Figure 26
in much smaller size (D=40, H=50 mm) than the previous set of experiments.
45
The melting and solidification were performed in a horizontal tube furnace and under
argon atmosphere. First the sample was heated to 1600°C at the rate of 10°C/min, left at
this temperature for 4 hours then cooled at the rate of 0.5°C/min to 1220°C.
The quenching temperature which was changed from 1007°C to 1220°C (from B to A in
Figure 25) in which the two phases of liquid Fe-Si and solid Si exist.
The composition was changed from 72wt% Si to 83wt% Si which will result in the
formation of about 50vol% of Si after solidification at the new quenching temperature.
The sample was not sieved since the main aim of these experiments was to study the
extent of purification and investigation of the physical separation was not of interest.
3.3 Characterization
3.3.1 Scanning Electron Microscopy (SEM) and Electron
Diffraction X-Ray (EDX):
The Hitachi S570 scanning electron microscope was used for observing the structure and
distribution of the phases in the solidified samples and also for image analysis of the crushed
particles. The samples were mounted in epoxy and carbon coated to cover the non-conductive
surface with a conductive layer. As described earlier, backscattered SEM images provided
adequate contrast between the two phases for quantitative analysis of their area. The scanning
electron microscope was operated at 20kV and with a 15 mm working distance.
EDX was also used to confirm the composition of the two Si and FeSi2 phases.
For this purpose Philips Diffractometer (model PW 3710) with X’PERT graphics software
package was employed. A rectangular aluminum-glass composite sample holder (2cm×1cm×0.2
47
cm) was filled with the powdered sample. The samples were analyzed using a CuKα radiation
(λ= 1.54056Å) with nickel filter. Bragg’s angel (2theta) range of 10-50° and a scan speed of 0.72
degree per minute with a step-size of 0.015° were used. The Philips diffractometer was operated
at 40 kV and 40 mA. The structural pattern was recorded and analyzed with X’PERT HighScore
TM
software.
Where C* is the difference of the concentration of element in solution and in the blank sample.
It should be noted that when the amount of an element is reported as a negative value the
detection limit of the element is used instead of C* in the equation above.
The detection limit of phosphorus was about 100 ppm. The as-solidified samples were mounted
and carbon coated then placed in the probe chamber. The lines of interest were chosen. About
10-20 points per interface were analyzed on each line giving the profile of elements in both
48
phases. The distance between the points varied from 7-70 microns. The main element of interest
was phosphorus. It should be pointed out that EPMA was not capable of measuring boron.
49
Variations of the width of the Si primary dendrites with cooling rate are presented in Figure 28
and Figure 29. As expected, faster cooling yields finer Si crystals. Based on the principles of
segregation, slower cooling during growth of Si crystals allows for more rejection of impurities
with small segregation coefficient to the liquid, thus increases the Si purity. Slow cooling also
results in growing thicker dendrites, that are easier to separate from the alloy as (a) in order to
liberate Si from the matrix, fine crushing is not required, and (b) larger particles sink/float faster,
50
thus gravity separation is accelerated. However, these advantages may be offset by the longer
solidification time and more consumption of energy associated with it. Therefore, it is critical to
identify the optimum separation conditions for each cooling rate.
Eq. 4
Eq. 5
52
In these equations, mi and fi are the total mass of particle and mass fraction of Si in particle i,
respectively, t is the total number of particles studied (sample population) and n is the number of
particles with density greater than that of the heavy medium.
An example of the recovery and grade variations with the specific gravity of the liquid is
displayed in Figure 30. As seen, an increase in the SG of the liquid gives rise to higher recovery,
while grade drops. This is expected, as by an increase in the liquid density, larger fraction of the
feed can float, which in turn increases the recovery. On the other hand, since this increase is
obtained at the cost of floating more heavy particles (that naturally contain more FeSi2), the iron
content of the floats increases, lowering the grade.
Figure 30-Recovery and grade in various S.G. of heavy liquid plotted for sample
with cooling rate= 3C/min and particle size= 600–800 µm.
The results in Figure 30 may also be interpreted as a drop in the recovery by increasing the grade
that implies an inverse relationship between G and R. This is the typical dependence of recovery
and grade, as the two quantities are not independent. Increasing the grade would require that only
highly pure Si particles (i.e. with less adherent FeSi2 phase) float, which inherently decrease the
recovery of Si. Therefore, in a perfect separation process, R and G are decided by how well the
53
Si crystals are liberated from the matrix. Consequently, maximizing both parameters is not
possible and selecting optimum conditions will depend on the particular operation and involves a
trade–off between grade and recovery. On the other hand, it is possible to increase both recovery
and grade simultaneously, by increasing the degree of liberation of Si particles. For example, by
grinding the alloy to fine particles, the amount of the composite Si-FeSi2 particles is reduced,
thus both higher grade and recovery can be achieved.
Figure 31 shows the recovery-grade relationship for the three samples cooled under various rates.
As seen, in each case smaller particles yield higher grade and recovery, although the inverse
relationship between the two parameters still holds. Although beneficial to extent of separation,
the finer particles are generally associated with more difficult handling, higher grinding costs,
and slower separation. Therefore, grinding should be limited to the largest size that also provides
acceptable grade and recovery.
54
(a)
(b)
(c)
Figure 31-Recovery verses grade plotted for samples with cooling rate (a) 0.5
C/min, (b) 1.5 C/min and (c) 3 C/min.
55
Eq. 6
In this equation, R Si denotes recovery of the desired phase (Si) and R FeSi 2 represents the
For a series of tests performed using heavy medium with SG of 2.90, the separation efficiency
was calculated based on the actual recoveries of Si and FeSi2. The results are plotted in Figure 32
against particle size for samples with different cooling rates i.e. different dendrite thickness.
From this figure it can be found that with the decrease of particle size SE will also decrease.
Moreover, SE is higher for lower cooling rates or larger dendrite sizes.
56
Figure 32-Separation efficiency verses particle size for samples with different
cooling rates.
According to the justification made earlier, it is logical that more important than the dendrite
thickness or the particle size, it is the ratio of the two that controls the SE. In Figure 33, SE is
plotted against r= (particle size)/(dendrite thickness). As shown, the results of all experimental
conditions with various cooling rate and dendrite width fit well on a single curve that shows an
increase in SE as r is decreased. The SE however reaches a maximum and plateaued when r
drops below unity. This indicates that the optimum size to which the alloy has to be crushed
before the physical separation is equal to the average thickness of the primary Si dendrites. In
other words, grinding the alloy to a critical size, that is equal to the dendrite thickness, increases
the liberation of Si. Any further size reduction beyond this critical value will not improve the
separation efficiency.
57
It may be concluded from Figure 33 that slower cooling rate for formation of larger dendrites is
favorable as fine grinding is not required and the comminution costs are lowered. Also, the
physical separation process is accelerated for larger particles; resulting is higher throughput.
However, determination of the optimum cooling, grinding, and phase separation conditions for
solvent refining of Si require additional considerations. For high purity requirements such as
SoG–Si, dependence of the purity of the Si crystals on the growth conditions has to be
investigated. This will be discussed in Chapter 5.
58
The ultimate objective of this research was purification of MG–Si. As discussed previously, the
effect of cooling conditions including cooling rate and also the quench temperature were
investigated on the Si purity.
The effectiveness of the solvent refining process is expressed in terms of Purification Ratio (PR)
here that is the ratio of concentration of an impurity in the final Si product to that in the starting
metallurgical grade silicon (MG–Si). Based on this definition, elements with a PR smaller than
unity are effectively removed from Si, the concentration of those with PR=1 remains unchanged,
and elements with PR>1 favour Si over the Fe–Si phase and are segregated to Si. Clearly,
smaller PR values indicate greater removal of the element from MG–Si. In the following
sections, the extent of Si purification is discussed for the various cooling conditions.
Eq. 7
Eq. 8
This surprising response of B and P to the solvent refining process was justified as follows, and
based on the observations of impurity concentration dependence on the particle size of Si.
During the precipitation of the Si dendrites, the impurities including P and B are rejected to the
growth front, creating a large concentration of the impurities at the interface. The transport of the
impurities and their distribution in the liquid is limited because of either slow liquid–phase
diffusion, or solidification of the eutectic liquid from the melt bulk towards the dendrites.
Therefore, on complete solidification, an impurity–enriched layer is formed at the interface
60
between Si and Fe–Si matrix, as experimentally evidenced in Figure 35 and Figure 36. Although
the liquid Fe–Si alloy favours impurities (P and B) over the solid Si, the same behavior may not
hold when this liquid is solidified to the intermetallic phase FeSi2. Therefore, the tendency is
reversed towards rejection of the impurities from the FeSi2 matrix to the Si. This process is
inherently slow as it involves solid state diffusion. Nevertheless, the relatively slow cooling rates
of 0.5–3.0 °C/min and the large difference between the eutectic and quenching temperatures (~
200 °C) allow enough time (~1–7 hours) for back–diffusion of large quantities of the impurities
to the Si. At the same time, solidification of the eutectic phase followed by quenching leaves
significant residual stresses and microcracks at the Si/Fe–Si interface (see Figure 35(a) and
Figure 36(a)). As a consequence, grinding generates a distribution of particles where majority of
the small Si particles are from the edge of the dendrites. The larger particles, on the other hand,
are more produced from the core of dendrites. The combined effects of the back–diffusion
phenomenon and the breakage pattern of Si result in higher concentration of the impurities in the
finer particles. This hypothetical mechanism is supported by some results such as the
concentration variations seen in Figure 37.
61
Si
FeSi2
(a)
(b)
Figure 35-(a) Micrograph of the solidified alloy and (b) EPMA analysis for P across
the line shown in (a)
62
(a)
(b)
Figure 36-(a) Micrograph of the solidified alloy and (b) EPMA analysis across the
line shown in (a)
63
(a)
(b)
Figure 37-Effect of particle size on (a) P and (b) B concentration in final Si
product.
64
Based on the above suggested mechanism for impurity re–distribution, it is expected that
quenching the alloy just after precipitation of the dendrites and while the eutectic phase is still
liquid, would retain the impurities in the matrix. This would prevent the reverse segregation of
the impurities to Si, as no time is essentially given for the diffusion. Accordingly, the
experimental procedure was modified to quench the alloy just above the eutectic temperature.
The results are discussed in the following section.
In Table 10 the composition of MG–Si and the final purified Si together with the removal
percentages are presented for the major impurities. It is clear that for MG–Si, impurity reductions
over 90% are realized for all elements except Cr and P that showed still substantial 80% and 57%
removal percentages, respectively. Interestingly, the final iron content of the purified Si is about
1 ppmw, although large quantities of iron have been used in contact with Si, as the getter
element. This is presumably because of the very small segregation coefficient of iron being
8×10–6[25].
65
Al 980 10 99.0
B 27 2 92.6
Mn 158 3 98.1
K 39 1 97.4
V 86 <0.3 99.7
Cd 38 3 92.1
Ba 12 <0.1 99.2
Li 3 <0.2 93.3
Ni 118 3 97.5
Zn 23 <0.4 98.3
Be 1 <0.1 90.0
Cr 5 1 80.0
Mg 57 <0.1 99.8
P 68 29 57.4
Fe 3108 1 100.0
In order to investigate the suitability of the Si product as feedstock for SoG–Si manufacture, the
tolerable content of impurities before directional solidification together with the amounts
achieved in this investigation were compared (Table 11). As seen, the refined Si exceeds the
requirements of directional solidification feedstock for all impurities except P. One approach to
67
achieve even higher purity levels is to repeat the above process, by using the purified Si product
as the starting feed. Figure 39 shows the impurity ratio in final Si to initial Si against the number
of refining stages. For phosphorous, a second time refining would decrease the concentration
from initial 69 ppmw to 12.5 ppmw, that is below the acceptable level for directional
solidification.
Al B Mn K V Cd Ba Li Ni Zn Be Cr Mg P Fe
Current
10 2 3 1 <0.3 3 <0.1 <0.2 3 <0.4 <0.1 1 <0.1 29 1
Study
Ci ( Si) Eq. 9
k i eff
Ci ( SiM )
where Ci (Si) and Ci ( Si M ) are the concentrations of impurity i in solid Si and liquid Si–M,
respectively. The smaller this value is for a specific impurity, the more the element will be
segregated to the liquid phase compared to solid silicon.
By using the concentration of the impurity in Si dendrites and Si–Fe matrix, as Ci (Si) and Ci ( Si M )
respectively, it is possible to calculate the effective segregation coefficient for the Si–Fe system.
According to the result, ki–eff of phosphorous between Si–Fe melt and solid Si at 1220°C is 0.42
that is about the same value between solid and liquid Si (0.35). This implies that addition of iron
has not been very effective on P removal. As discussed earlier, Figure 10(b) suggests higher
affinity for P of iron than Si, thus one expects that in the presence of iron, the segregation
coefficient of P in Si is lowered. However, the anticipation may not be valid, as previous studies
on Fe-Si-P [71] show that the activity coefficient of P in Fe–Si melts increases by addition of
iron up to about 50 wt% Fe (close to the eutectic composition). The increase causes a drop in the
solubility of P in Fe–Si melt, as seen in Figure 40. In fact, the solubility is minimum, where our
eutectic composition (matrix composition) is. Therefore, the higher affinity of Fe for formation
of phosphates does not necessarily translate into more gettering of P, because of the effect of
activity coefficient of dissolved phosphorous. In other words, although the activity of P is lowerd
69
by solidification of iron, the increase in the activity coefficient causes a decrease in the P content
of Fe-Si.
In the case of boron, the segregation coefficient is reduced to 0.07 that is over one order of
magnitude lower than that in Si (0.8). It may then be assumed that the activity coefficient of
boron in Fe–Si melts is not increased as it does for phosphorous.
Therefore, in order to compare the effectiveness of impurity removal of the current process with
directional solidification, the following was carried out. First, the impurity removal in directional
solidification was calculated for a given fraction of recovered silicon (the remaining being sliced
off as the impurity–laden part of the ingot). For phosphorus, the concentration profile of the
solidified fraction of the sample in Figure 41 was plotted based on the Scheil equation given
below.
Eq. 10
From the obtained profile, the average concentration of the impurity for a certain fraction of the
ingot (fx) can be calculated by integrating the equation and dividing by the fraction recovered (fx).
This fraction is decided to be equal to the yield of silicon in the solvent refining process, in order
to make a reasonable comparison between the two techniques. In other word, it is attempted to
answer the question that “how would the final concentration of P in solvent refining and
directional solidification compare, if the amounts of Si recovered in both processes were equal?”.
71
(a)
(b)
Figure 41-Phosphorus concentration profile of solidified sample based on Scheil
equation a) complete solidification and b) about 50wt% of sample solidified.
72
5.5.1 Zinc
The properties that are believed to make zinc a good gettering element are listed below:
- Zinc has low maximum solid solubility (2.8 ppmw) at about 1320°C [26] in solid silicon
and at the same time a very low segregation coefficient (1×10-5 [16]) (Figure 12).
- The binary system is such that solvent refining can be performed at lower temperatures
Figure 42.
- As shown from the Si-Zn phase diagram, the binary system has a simple eutectic with no
intermetallic compounds, indicating that the leaching of the product will be simple.
- Zinc has much higher density than silicon (7.14 g/cm3compared to 2.33 g/cm3), allowing
for gravity separation of the two produced phases.
- Zinc phosphide and boride are more stable than silicon boride and phosphide (see
ellingham diagram plotted for phosphides and borides in Figure 10).
Experiments:
An alloy with the composition of 75wt% Zn powder with MG-Si was prepared. 200 g of the
mixed powder was placed in alumina crucibles (Figure 26) with a covering lid that was attached
by ceramic paste. The crucible was heated in a vertical tube furnace and under argon atmosphere.
The heating profile of the sample is shown in Figure 44.
After quenching the sample at 300°C, it was found that most of the zinc had evaporated from the
crucible. This was expected from the very low boiling point of zinc being 907°C and the
resulting high vapor pressure inside the crucible.
This experiment was repeated with better sealing of the crucible but the result was the same. In
all cases microcracks were visible on the crucible sealing, where zinc was presumably escaped
from.
Unfortunately the available furnaces did not allow for further investigation of this process.
75
5.5.2 Calcium
As discussed in Section 2.11, calcium can have two purification effects when alloyed with MG-
Si. First, it will improve leaching of impurities from MG-Si by forming CaSi2 at the grain
boundaries and acting as a collector phase for the impurities. It can then be easily dissolved using
aqua regia. The other is that it can form strongly stable phases with P and B, specially with P.
The stability of Ca3P2 can be seen in the ellingham diagrams (Figure 10).
In the study that was done on solvent refining using iron, it was thought that after the iron-
alloying the purified Si product can be further purified by adding calcium since in the proposed
process the removal of phosphorus was found to be less successful compared to boron.
Experiments:
10wt% granular calcium from provided from Sigma- Aldrich (99% purity and 6 mesh) was
added to MG-Si, doped with 0.3wt% P and 0.3wt% B and placed in ceramic crucibles same as
Zn-Si experiments and heated in a horizontal tube furnace. The heating profile of the sample was
as shown in Figure 46. As expected from the phase diagram, the SEM images show the two
phases of Ca and CaSi2 (Figure 47). The EDS results showed the darkest phase was Si, the
lightest was CaSi2 rich in Fe and the light gray phase was CaSi2. The iron in the Fe rich phase is
from the iron in the MG-Si (more than 0.3wt%).
76
Si 48 62
Ca 21 19
Fe 31 19
Ca 42 66
Si 58 34
The XRD pattern results show the formation of Ca3P2 phase that are not able to be detected by
SEM.
The sample was crushed to >106 µm. 1g of the sample was leached for 4 hrs at 75°C in 20 ml of
HNO3: HCL: H2O with ratio of 1:3:6 respectively. 0.25 g of the remaining solid was then
analyzed by ICP-AES. The ICP analysis is shown in Figure 51. In this figure the distribution of
impurities in CaSi2 and Si is presented. The columns show the ratio of impurities in CaSi2 to Si
meaning that when this ratio is higher than 1, CaSi2 phase has higher affinity for impurities than
Si and is successfully removed. Therefore, calcium treatment can be used as an alternative
refining to repeated Fe alloying, after Si was purified with Fe solvent refining.
The results of the dendrite purification indicate that when samples are quenched above the
eutectic temperature i.e. within the solid Si and Fe–Si melt region, the removal of impurities is
significantly improved compared to the case when quenched from fully solid state. This was
attributed to back–diffusion of impurities to Si, during the slow cooling period of the latter
conditions. By alloying Si with Fe, the effective segregation coefficient of B was reduced from
0.8 (between solid Si and Si melt) to 0.07 (between solid Si and Fe–Si melt). Not such decrease
was observed for P, because of an increase in the activity coefficient of P in Si, in the presence of
iron. It was found that the solvent refining of MG–Si with Fe as the getter can reduce the
concentration of the impurities significantly, to levels below the tolerable levels in directional
solidification. The total concentration of the major impurities was reduced from 4700 to 53
81
ppmw by one stage of solvent refining. It is believed that the process may be repeated to achieve
substantially higher purity.
The results show that the proposed method has less effect on the removal of phosphorus
compared to that of boron. Based on literature review and the preliminary experiments
that were done on calcium, this element is believed to have a significant effect on the
removal of phosphorus from MG-Si by forming Ca3P2 and also improving the
leachability after solvent refining. For further studies, iron and calcium can be used
together or subsequently in MG-Si purification.
It is suggested that this process be repeated several times to further purifiy the silicon. A
model that takes into account the yield of silicon can be established to estimate the
overall operating cost of the process.
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As 188.979 2 0.2
Bi 223.061 2 0.2
Cs 455.531 1 0.1
Ge 209.426 2 0.2
89
K 766.490 2 0.02
P 178.221 3 0.3
Pb 220.353 1 0.1
Pt 265.945 1 0.1
Rb 780.023 3 0.3
S 180.669 3 0.3
Sb 206.836 1 0.1
Se 196.026 5 0.5
Sn 189.927 3 0.3
Te 214.281 1 0.1
Th 283.730 5 0.5
Tl 190.801 3 0.3
1) Energy
Heating/Melting:
The energy needed to melt 1kg of alloy is about 5 MJ=1.4 kWh
Considering a thermal efficiency of 50%, the total energy required is: 1.4×2=2.8kWh
(heat loss)
Grinding: According to the Bond’s equation the energy needed to grind 1 ton of
ferrosilicon from is:
Where is the Bond work index for ferrosilicon, P is the diameter in microns
that 80% of the product passes and F is the size in which 80% of the feed passes [69].
From this equation: the energy needed to grind 1 inch ferrosilicon lumps to 200μm
particles is about 0.007 kWh/kg.
1 kg of 83wt%Si will result in about 600g of Si dendrites. If 80% of the dendrites are
recovered in the physical separation the total amount of purified Si will be 480g. Therefore,
the energy required per kg of Si is 6 kWh/kg Si that is significantly below the energy
consumption for the Siemens process (120-160 kWh)
2) Leaching
1 kg of Si product will consume 2 lit of hydrofluoric acid which will cost about $1.2.
92
3) Physical Separation
In industrial scale, the gravity separation can be done at much lower cost than the heavy
medium used in laboratory scale of this study. For example in upgrading coal where low-
ash coal is separated from the heavier high-ash coal, cheap heavy media such as high
density slurries are used [69].
4) Labor Work and other
Total cost:
From the above calculations it is estimated that the cost for producing 1 kg of purified Si
in industrial scale will be about $2 based on $0.5/kg as labor and physical separation.
93
Conference Articles
Other Presentations
S. Esfahani, “A Novel Purification Method for Production of Solar Grade Silicon”, 2010-
ASM Ontario Chapter Poster Presentations, McMaster University, Hamilton, Ontario,
Canada- March 2010.