Produccion Silicon Grade Solar

DE-EE0007550
Continuous Silicon Consolidation and Reduction

SRI International
Final Technical Report: DOE-SRI0007550-1
Project Title: Continuous Silicon Consolidation and Reduction

Project Period: 10/1/2016 – 9/30/2018
Project Budget: $1,000,000 (including $100,000 cost share)
Submission Date: 12/19/18
Recipient: SRI International
Address: 333 Ravenswood Ave
Menlo Park, CA 94025
Award Number: DE-EE0007550
Project Team: Solar Power & Light LLC
Mosaic Fertilizer, LLC
Mr. Tony Galles
Contacts: Anoop Nagar, Sr. Materials Engineer
Phone: 650-859-3942
Email: anoop.nagar@sri.com
Acknowledgment: This material is based upon work supported by the

Department of Energy, Office of Energy Efficiency and
Renewable Energy (EERE), under Award Number DE-
EE0007550.
Disclaimer: This report was prepared as an account of work sponsored by

an agency of the United States Government. Neither the
United States Government nor any agency thereof, nor any of
their employees, makes any warranty, express or implied, or
assumes any legal liability or responsibility for the accuracy,
completeness, or usefulness of any information, apparatus,
product, or process disclosed, or represents that its use would
not infringe privately owned rights. Reference herein to any
specific commercial product, process, or service by trade
name, trademark, manufacturer, or otherwise does not
necessarily constitute or imply its endorsement,
recommendation, or favoring by the United States
Government or any agency thereof. The views and opinions
of authors expressed herein do not necessarily state or reflect
those of the United States Government or any agency thereof.
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Executive Summary
The goal of the Department of Energy’s (DOE’s) Sunshot program is to increase the
adaptability of photovoltaic (PV) solar power generation by reducing the cost of power
generation. The cost of polysilicon is one of several factors affecting the costs of a solar
power module. The National Renewable Energy Laboratory (NREL) assumes module
manufacturing costs (all-in vertically integrated module production) of $0.63/Wdc (2015
NREL data). If the NREL polysilicon costs are replaced by the SRI International (SRI)
polysilicon costs, the module manufacturing costs are reduced to $0.58/Wdc (2015 basis)
i.e., reduction of $0.05/Wdc. The NREL cost model (System Advisor Module, SAM) is
based on $20/kg of blended polysilicon silicon cost. The Continuous Silicon Consolidation
and Reduction (CoSiRC) process is estimated to produce polysilicon at $8.06/kg.
In addition, SRI’s CoSiRC process introduces a commercially viable path to recycle and
reclaim kerf loss silicon fines that would otherwise go to a landfill, thereby reducing a
precious resource from going to waste.
The results of this project demonstrate that SRI’s silicon production process that uses a
reduction reaction can be successfully integrated with a kerf loss reclaiming process. The
combined process was first demonstrated at lab scale and then fit to a bench-scale
process. Leveraging the industrial expertise of the commercial partners, it is feasible to
adapt industrial-scale equipment for SRI’s CoSiRC process.
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Table of Contents
I. Background 4
II. Introduction 5
III. Project Results and Discussion 8
IV. Conclusions 48
V. Budget and Schedule 48
VI. Path Forward 50
VII. Publications Resulting from this Work 51
VIII. References 52
IX. Si Process Drawings 54
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I. Background
By the end of 2018, the installed annual global photovoltaic (PV) electrical-power-
producing capacity is expected to be over 100 GW with a total cumulative capacity of
near 400 GW; in addition, PV projected growth is estimated to approach 1 TW of capacity
installed by 2023 [1-2]. To feed this growth, the nominal global production capacity for
solar-grade Si has increased to c.a. 400,000 MTY [3]. In parallel to this development, a
continuous effort is being made to significantly lower the energetic cost for production of
solar-grade Si and to increase the rate and extent of PV deployment. At present, most Si
is produced using the modified Siemens gas-solid process, which has limitations in both
the rate and extent of deposition. Consequently, it requires an energetic investment of
well over 100 kWh per kilogram of polycrystalline Si produced. This requirement results
in over 40 TWh of annual energy costs, and it will take almost one decade for the solar
panels fabricated from Si to pay back that energetic investment.
Growing single crystals and casting polysilicon blocks requires additional energy
expenditures of 36 kWh/kg-Si and 9 kWh/kg-Si, respectively. However, when these
energy-rich Si crystals or blocks are sliced into thin wafers, about one-third of them end
up as a very fine Si powder known as kerf waste Si fines. To minimize the energy
consumption and shorten the payback period of the final solar cell, several approaches
are being pursued by the PV industry. These include the development of other more
effective reactors to produce Si such as fluidized bed reactors (FBRs) as well as new
metallurgical processes with much higher throughputs and lower energetic and financial
costs. Unfortunately, FBRs have operational problems that have limited their proliferation,
and refinement of metallurgical Si has limitations that make it difficult to obtain Si with B
and P levels below 1 ppm levels without multiple, expensive purification steps.
A different type of process that may have some synergism with the reuse of Si fines is the
direct production of solar-grade Si by reduction of a silicon halide, such as SiF4, with a
reactive metal such as Na or Mg [4-7]. These processes are very exothermic with
adiabatic temperatures near 2000 K, and the energy cost is less than 50 kWh/kg-Si—
most of which is due to the production of the reducing metal. The processes initially
produce Si fines in a molten fluoride but, because of the high temperature, the Si particles
grow and can eventually melt-coalesce into Si pool that is immiscible with the molten
fluoride. This process has been demonstrated up to the pilot-plant level (100 MTY) by
several industrial groups and by itself can produce Si feedstock with B and P impurities
levels below the 0.1 ppm level and subsequent solar cells with over 18% efficiency [8].
We reported in our previous publications [4-8] that when an Si/NaF or Si/MgF2 mixture
was heated to above 1685 K (1412◦C) (the melting point of Si), Si droplets could, in
minutes, coalesce and form a unique pool, which solidified into a clean Si ingot upon
cooling. The molten salt provides a good heat transfer media; wets and protects the silicon
from interaction with the crucible; and it dissolves the surface SiO2 from the silicon
particles, avoiding formation of SiO. In addition, because liquid fluorides have low surface
tension and viscosity, the tiny Si droplets can therefore spontaneously and easily
coalesce into a single pool.
Traditionally, slicing silicon ingots into Si wafers was accomplished by wire sawing that
uses SiC slurry as the abrasive cutting medium. The Si kerf loss goes into a slurry waste,
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which contains silicon, silica (or oxidized silicon), silicon carbide, metal fragments, and
glycol-based slurry media. Over the years, several recovery processes have been
developed aiming at reclaiming the high-purity silicon from this waste kerf slurry. They
included alloying process [9], hydrobromination [10,11], supercritical water [12],
electrophoresis and gravitational settling [13,14], phase-transfer separation [15], and
centrifugation [16-18]. However, none of these processes have been scaled-up or
commercialized for recovering the high-purity silicon from the kerf loss slurry.
Recent advancement of photovoltaic industry shifted away from SiC slurry cutting to a
diamond wire sawing (DWS) process, which exhibits higher productivity, reduced kerf
loss, thinner wafers, and reduced environmental impact through the use of water-based
cutting fluid. The waste silicon usually comprises very fine powders that are
contaminated. Exposure to the cutting environment usually results in contamination by a)
metallic species eroded/corroded from the wires, b) diamond particles, and c) surfactant,
anticorrosion, and/or dispersant species. In addition, the fines are covered by surface
oxide and hydroxide species, but with no SiC species. Most of these materials are
currently discarded.
Fortunately, these contaminants often are on the surface and easily removed by washing
or chemical etching. Even if the external surface contamination is removed, direct heating
of these Si fines in an inert atmosphere to melt silicon has several limitations: (1) The rate
of heat transfer into a porous bed is limited and difficult; (2) When radiation becomes
important (temperature > 1473K (1200◦C)), the core Si starts reacting with the surface
SiO2 to generate SiO vapors. This reaction results in losses of significant amounts of the
original Si as yellowish SiO vapors, particularly for the fines powders (<1 micron) with
high surface-to-volume ratio; (3) Condensation or disproportionation of SiO vapor on the
cooler regions of the furnace requires extra cleaning in between runs, decreasing overall
production rates; and (4) The residual silicate or SiC forms a slag surrounding liquid
silicon droplets and limits Si coalescence, thus creating, upon cooling, a plurality of
attached Si pellets rather than a unique ingot. This complicates the separation and
recovery of Si and makes it relatively labor intensive.
In short, a tremendous amount of energy-intensive high-purity silicon is wasted as silicon
fines during the wafer-cutting process. In addition, other industrial processes, such as
silicon crushing and use of a fluidized bed reactor (FBR), also generate high-purity silicon
fines as a byproduct. In this Department of Energy (DOE)-funded project, we aim to pre-
process various types of silicon fines and co-feed these Si fines into SiF4 -Na reaction to
produce solar-grade silicon feedstock. This approach is designed to take advantage of
the heat and molten NaF generated in this reaction to simultaneously wet, clean, protect,
and incorporate the Si fines into the Si/NaF product.
II. Introduction
Program Goal and Objectives

The SRI International-led team developed an innovative technology (Continuous Silicon
Reduction and Consolidation (CoSiRC)) process that combines low-cost production of
polysilicon from SiF4-Na reaction with recycling of Si fines (either from kerf loss, wafer
grinding, or fluidized bed processes). SRI had already demonstrated the two individual
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processes that are the building blocks of this technology before. The goal in this program
is to decrease the perceived technical risk for future stakeholders to invest in the
technology for rapid scale-up to production in the timeframe needed to meet Sun Shot’s
levelized cost of energy (LCOE) targets.
The project has the following objectives:
• To demonstrate that the CoSiRC process can produce solar-grade silicon (Si).
• To demonstrate that effective removal of impurities from different types of fines
is carried out to a level that ensures that the final product meets solar-grade
specifications.
• To study the effect of oxygen on the viscosity of the flux agent and establish the
window of operation that allows the process to be carried out.
• To engineer key components in the system and, in particular, incorporate the
addition of Si fines to the reactors used for polysilicon production by the SiF4-
Na process.
The outcomes of the project are (1) a bench-scale prototype for the CoSiRC process, (2)
a window of operating conditions, (3) specifications for the Si fines that can be recycled,
(4) a techno-economic analysis of the process, (5) a design of the core elements in a
pilot-scale manufacturing system (reactor, furnace, and process control), and (6) a
commercialization plan to transfer the technology to an industrial partner.
Technical Scope Summary

The project consists of two 1-year budget periods (BPs). During BP1, the experimental
work focused on lab-scale integration of all steps and defining the level of impurities
needed to be reached in the starting Si fines and the maximum ratio between fines and
new Si that can be used for fines with several particle sizes and oxygen content. All
process development work will be done in laboratory batch systems. The go/no-go
decision at the end of BP1 will be associated with a successful demonstration of the
CoSiRC process with the product quality described in the milestones section. In parallel,
we will develop a preliminary techno-economic analysis based on available data from the
individual reduction and consolidation processes to date. We will also start
commercialization efforts.
During BP2, the experimental efforts were dedicated to the construction and operation of
a bench-scale prototype of a reactor to run the CoSiRC process. We also updated the
techno-economic analysis for the CoSiRC process that includes the process flow
diagram, mass and energy balances, sizing and description of equipment, and estimated
capital and operating costs. From this input, we estimated a levelized cost of primary
product and develop a cost sensitivity analysis. We also completed a preliminary design
for the key elements of the process that includes reactor, furnace, and process control
(other auxiliary units may be included in the future design with different levels of detail).
We completed the following two tasks related to commercialization: supply chain analysis
for Si fines (key players, relationships, and price points) and industry engagement (which
helped us envision the challenges of a commercialization strategy based on technology
transfer from SRI to an industrial company).
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I. Major Task/Milestone Schedule

SOPO Milestone Completion Date
Task Start
Task # Task Title and Milestone Description Performer Original Revised Percent Progress Notes
Date Actual
M.S. # Planned Planned Complete
T1.1 Laboratory process development of integrating reduction and consolidation processes
T1.1.1 Determine pretreatment steps needed to purify Si fines
Demonstrate silicon consolidation with
M1.1.1 SRI 10/1/2016 12/31/2016 12/31/2016 100%
lab scale reactor
T1.1.2 Batch parametric study
10g batch, >10% fines, <1ppma B and
M1.1.2 SRI 10/1/2016 3/31/2017 12/31/2016 100%
P, <10ppma TM
T1.1.3 Rheology of flux agent
Specs on Oxygen content for recycled Oxide content up to 20%
M1.1.3 SRI 4/1/2017 9/30/2017 9/30/2017 100%
Si feedstock is usable
T1.2 Techno-economic analysis
M1.2 Prelinimary TEA SRI/SP&L 10/1/2016 6/30/2017 9/30/2017 100%
T1.3 Manufacturing systems development
Preliminary conceptual commercial
M1.3 SRI/SP&L 2/1/2017 9/30/2017 9/30/2107 100%
design for equipment completed
T1.4 Commercialization
M1.4 Supply chain analysis is completed SRI/SP&L 1/1/2017 3/31/2017 3/31/2017 100%
T1.5 Project Management
M1.5 Subcontracts executed SRI 10/1/2016 3/31/2017 12/31/2016 100%
Purity specfications met
100g Si with >25% Kerf loss Si, with
M BP1 SRI 10/1/2016 9/30/2017 9/30/2017 100% with consolidated kerf
purity and cost targets
silicon
T2.1 Laboratory process development of integrating reduction and consolidation processes (continued)
T2.1.1 Determine pretreatment steps needed to purify Si fines (continued)
Simulated CoSiRC
100g Si with>25% Kerf loss Si, SEMI
M2.1.1 SRI 10/1/2017 12/31/2017 12/31/2017 100% reaction 1kg product,
purity standard
50% Kerf
T2.1.2 Lab-scale testing of key engineering units of bench-scale prototype
Design of key engineering units of bench 3/31/2018
M2.1.2 SRI 10/1/2017 3/31/2018 100%
scale prototype complete
Construction of test of bench-scale
T2.1.3 SRI 2/1/2018 3/31/2018 100%
prototype
TEA published, path to $0.04/Wdc
M2.2 SRI/SP&L 10/1/2017 9/30/2018 9/30/2018 100% Submitted
reduction in poly-Si price
T2.3 Manufacturing system development
Conceptual commercial equipment
M2.3 SRI/SP&L 10/1/2017 9/30/2018 9/30/2018 100%
design
Pilot scale demonstartion
M2.4 Technology Transfer negitiations initiated SRI/SP&L 10/1/2017 6/30/2018 9/30/2018
required
T2.5 Project management SRI 10/1/2017 9/30/2018 100%
Bench-scale, 1kg Si >50% fines, MOU
M BP2 SRI 10/1/2017 9/30/2018 9/30/2018 100%
for scale-up to pilot-scale
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III. Project Results and Discussion
1. Demonstrating CoSiRC process with FBR Si Fines

In this project, the CoSiRC process exploited the synergies of the exothermic direct
sodium reduction of SiF4 with the consolidation of Si fines by combining them into one
process. The process flow
diagram, shown schematically in
Figure 1, illustrates that various
waste Si fines can be fed into SiF4-
Na reactor system. To test the
feasibility of the process, we
started our demonstration by using
the purest silicon fines, the fines
from industrial FBR reactors.
We know from basic
thermochemical estimates and
experimental evidence that the
reaction (SiF4(g) + 4Na(l) =
4NaF(c) + Si(c)) is very exothermic
(-140 kcal/mol of SiF4 reacted).
The adiabatic temperature of the Figure 1. Process schematic that shows combining the SiF4-Na
reaction and incorporation of Si fines waste in one process.
SiF4-4Na system can reach
2299 K (2026oC) according to calculation using HSC Chemistry 8, from Outotec, which is
well above the melting point of Si 1685K (1412oC). Practically, some heat is lost to the
reactor walls (which are kept at or above 873 K (600oC)), and only the center of the
reaction zone can reach values close to the estimated adiabatic temperature.
Nevertheless, the temperature is high enough to allow the molten NaF to wet,
encapsulate and protect all Si fines. After this process, a melt-separation step is needed
to separate the high-purity Si (as an ingot) from the NaF byproduct.
This process of producing solar-grade silicon has the following advantages: 1) SiF4 and
Na or Mg are low-cost and pure precursors; 2) the reaction is fast and complete, and
products are condensed and easy-to-handle; 3) it is a high-throughput Si production
method utilizing exothermic reaction heat; 4) the waste Si fines are directly incorporated;
and 5) the reaction byproduct (NaF) wets, etches the surface SiO2 surface film of the Si
particles, and protects Si fines from reaction with or contamination by the reactor walls.
In the following pages, we will present our experimental results obtained from co-feeding
FBR Si fines into the SiF4-Na reaction and melt separating Si from NaF. We will discuss
some of the observed aspects of the reaction mechanism and product morphologies and
describe melt separation of Si ingots as well as the final Si purity.
1.1 Materials and Methods
1.1.1. FBR silicon fines

Several kilograms of Si FBR fines were directly procured from an industrial partner. As
expected, the dopant and metallic impurity content of the fines were relatively low
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according to glow discharge mass

spectrometry (GDMS). LECO® analysis
indicated these waste Si fines contained
~ 1000 ppmw of oxygen likely due to
surface silicon oxide. Since the oxygen
content is relatively low and can be
dissolved in molten NaF, we used the Si
fines as received without etching them with
hydrofluoric acid. An scanning electron
microscope (SEM) photo of the Si fine,
shown in Figure 2, illustrates the Si grain
size was less than 100 nm, and porous
agglomerates consisting of up to micron- Figure 2. An SEM picture of the silicon fine from the
sized particles were formed. FBR process showing the nanometer size of particle
agglomerates.
1.1.2. Co-feeding Si fines to the SiF4–Na reaction

The FBR Si fines were mixed with high-purity NaF powder (from J.T. Baker) in a
4:1 weight ratio, and then the powder mixture was pelletized manually into 13-mm
diameter cylindrical pellets using a die and a press, or 6-mm tablets using a manual
pelletizer. These pellets were then stored in air in a plastic bag before they were loaded
into a hopper attached to the reactor.
The SiF4-Ns reactor has been described in our previous publications [4-7]. A schematic
of the reactor system is illustrated in Figure 3. Briefly, it consists of a gas-tight cylindrical
chamber (150-cm high,
30-cm inner diameter) made
of Inconel lined with a nickel
liner and then a layer of
Grafoil®. The reactor bottom
and wall were initially heated
to an ignition temperature
(> 873K (600°C)) before Na
was fed as a liquid through
the center top. Pre-made
pellets of Si/NaF fines were
fed into the reactor through a
lateral conic hopper attached
to the reactor’s top. The SiF4
gas pressure inside the
reactor was kept around
1 atm. An MKS pressure Figure 3. SiF4-Na reactor with SiF4 gas, Si Fines, and liquid Na
transducer was used to feeding units.
monitor the SiF4 pressure
inside the reactor and control a proportional valve, which was open to feed more SiF4 as
the inside pressure dropped with consumption by Na; the valve was closed as the reactor
pressure reached 1 atm. A mass flow meter and a totalizer (from Aalborg) were used to
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determine instantaneous flow rate and total volume of SiF4 gas, respectively. Sodium, at
temperatures around 393K (120°C), was injected into the reactor as liquid in pulses. A
sodium supply tank sits on an electronic floor balance, which was used to determine
weight loss from the tank after each pulse of Na was added into the reactor. As the first
Na pulse reacted vigorously with surrounding SiF4 gas, extra heat and some dust
indicative of partial homogeneous reaction were generated. When the reaction turbulence
subsided and the SiF4 pressure returned to 1 atm, the next Na pulse was fed into the
reactor. The same procedure was repeated a few times as the temperature of the reactor
bottom increased to above a target temperature; then, a group of Si/NaF pellets was
added on top of the now-hot reaction products, followed by another sodium pulse. As the
SiF4-Na reaction subsided, another group of Si fines/NaF pellets was fed into the reactor
from the top and followed by an additional Na pulse. These were repeated until all the
pellets were added into the reactor. After this reaction/production step was completed,
the residual SiF4 gas was removed from the reactor, and it was refilled with argon and
allowed to cool down to room temperature. A cylindrical mass of several kilograms of
reaction products and incorporated Si fines confined by the Grafoil® liner was then
collected and weighed.
Run #1: The FBR Si fines (150 g) were pre-loaded into the bottom of the Inconel reactor,
which was heated to over 773 K (500◦C). Then, we carried out the SiF4-Na reaction in the
Inconel reactor by feeding the Na on top of the Si fines in the SiF4 atmosphere.
Run #2: The SiF4-Na reaction was carried out by co-feeding the Si fines/NaF pellets. The
Si-NaF pellets were made by mixing Si fines (80 wt%) and NaF powder (20 wt%), followed
by pressing individual pellets using a ½” die and a uniaxial press at a load of 10 tons. The
SiF4-Na reduction was first carried out until the reactor bottom temperature reached
> 973 K (700◦C); then, the pellets in the hopper were added into the reactor in between
Na pulses. The external reactor walls were maintained at 973 K (700◦C) by controlling
the rate of Na addition. A total 1150 g of Na and 110 g of Si/NaF pellets (85 g of FBR Si)
were added. Therefore, 350 g Si was produced from the SiF4-Na reaction, and 85 g of Si
fines were externally added, corresponding to a 25% Si production increase from the
recycled Si fines.
Run #3: In the third experiment, 6-mm tablets, each containing 80 wt% Si fines and
20 wt% NaF, were made using a manual pelletizer, and the SiF4-Na reaction was carried
out by co-feeding the tablets as in Run 2 but with more added Si/NaF tablets. A total of
~ 1500 g of Na was added in 15 pulses in ~ 45 minutes; thus, 457 g of Si were expected
to be produced from the SiF4-Na reaction. In addition, 560 g Si/NaF pellets, corresponding
to 448 g of Si fines, were externally added so that 50 wt% of Si in the final expected
product was from the recycled FBR Si fines.
1.1.3 Separation of Si from NaF

To separate the Si product from the NaF byproduct, we heat the mixture to temperatures
about 1693 K (1420°C) so that molten Si droplets coalesced completely into a single pool
and the two resulting molten phases, Si and NaF, are immiscible. The melt-separation
step has been described in detail in previous work with the Si-NaF system [4,7,19]. Briefly,
the reaction product, consisting of (a) Si fines added; (b) Si produced by the SiF4-Na
reaction; and (c) byproduct NaF, was loaded into a graphite crucible and heated to 1693 K
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(1420°C) in a high-temperature furnace under flowing argon gas. We used a gas-tight

graphite resistance-heating furnace. The temperature was held right above the melting
point of Si (1685 K (1412°C)) for about 20 minutes, and the furnace was then cooled down
and the product was collected. The Si ingot can be separated from the surrounding NaF
by mechanical fracturing.
1.2. Results
1.2.1. Co-feeding Si fines to the SiF4–Na reaction

Run #1: The FBR Si fines were preloaded into the metal reactor. During the reaction
process, we observed a rise in the external temperature of the reactor walls from 773 K
(500◦C) to about 873 K (600◦C). After the run, the pre-loaded Si fines were found still
loosely packed at the bottom of the reactor and had not fused with the SiF4-Na reaction
product. In addition, some unreacted Na was found at the bottom of the reactor. We
believe the pre-loaded Si fines at the bottom trapped some Na at the beginning of the
process when the temperature of the system was still low. It was only at a later stage of
the process, when the heat generated by the SiF4-Na reaction raised the reactor
temperature, that the Na was completely consumed by the reaction. In addition, the
reaction heat was only localized at the reaction zone, and thus molten NaF did not reach
the Si fines at the bottom of the reactor. We concluded that pre-loading the Si fines at the
bottom of the reactor was not an efficient way to incorporate Si fines into the SiF4-Na
reaction product.
Run #2: In the second run, the
following modifications were
employed: (1) the initial heating
temperatures of the reactor
bottom and wall were
increased to 823 K (550◦C),
and (2) Si fines were co-fed as Pellet
pellets into the reactor after the
reactor wall reached 973 K
(700◦C) due to the reaction
heat. Post-reaction analysis of
the products showed the
pellets were tightly embedded
into the reaction product mass.
In some cases, distinct
cylindrical shapes of the pellets Figure 4. Cross-section of the reaction product in which a
were still discernible inside the pellet was discernible in the left lower corner.
reaction products, as indicated
by the arrows in Figure 4. These pellets became strong and hard to crush, and they were
more compact than the original pellets; this indicates that the NaF (within and outside the
pellets) became molten, wetted and infiltrated the pellets of Si fines, and partially sintered
some of the Si fines at the high-temperature peaks achieved in the reaction zone. The
white-colored regions in Figure 4 are pure NaF.
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Run #3: The Si-NaF tablets were prepared using a manual pelletizer as shown in
Figure 5A. Each 6-mm diameter table contained ~ 0.14 g of powder (80 wt% Si and
20 wt% NaF). These tablets were co-fed into the metal reactor in pulses after the reactor
wall temperature exceeded 973 K (700◦C) due to the heat from SiF4-Na reaction. A total
of ~ 3.6 kg of product was recovered from this run. Upon crushing the product, we found
tablets localized in some regions as shown in Figure 5b. Although the tablets were not
homogenously distributed though the product, they were hard and grayer in color than
the original tablets, indicating some Si sintering and NaF melting in these tablets during
the process. About 50% of Si produced from this run was from the recycled FBR Si fines,
corresponding to a 100% Si production increase as compared with SiF4-Na alone.
a b
Figure 5. (a) Pellets of 80% Si - 20% NaF and a manual pelletizer; (b) a section of the reaction
product showing the pellets incorporated with the SiF4-Na reaction product.
1.2.2. Melt separation of Si from NaF

Representative samples of the
reaction product (from Runs #2 b
and #3) containing the
incorporated pellets of Si fines
were heated to over 1693K
(1420◦C) in a graphite crucible.
After cooling, we obtained a Si
ingot at the bottom and a top
cylinder of pure white NaF in
each run. All silicon had
coalesced into one Si ingot, Figure 6. (a) Si ingot as it broke off from the top section of NaF
which could easily be detached wrapped by the dark black Grafoil; (b) Si ingot easily detached
from the top portion of the white from the graphite bottom liner showing a thin layer of NaF in
NaF as well as from the between the Si and graphite.
graphite liner at the bottom by striking it with a plastic hammer. Figures 6a and 6b show
the separated Si ingot and NaF after melt separation.
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The Si ingots were then washed with deionized (DI) water to remove a residual thin crust
of adherent NaF. The Si ingots were cut along a vertical plane into two halves. The half
ingots were etched lightly with an HF-HNO3 mixture to remove surface impurities and sent
out to an independent analytical lab for impurity analysis. A Si slab cut from a half ingot
is shown in Figure 7. After a light acid etch, centimeters-long grains are clearly visible in
Figure 7.
1.2.3. Purity of melt-separated silicon

After demonstrating the feasibility of
recovering and melt-consolidating the waste
FBR silicon fines, the second critical question
for this work was to determine the purity of the
final silicon product because the final goal was
to produce solar-grade silicon. Of critical
importance is the final levels of dopant
elements B and P. Table 1 shows the impurity
content in the initial waste Si fines and two Si
ingots produced from melt separation of
product of Run #2, as determined by GDMS.
The two melt separation experiments were Figure 7. Si slab cut from the ingot after light
conducted differently—after melting, one Si etching with acid, showing large-grain structure.
ingot was quenched (Sample 1), and another
one was slowly cooled from 1693K (1420◦C) to 1643K (1370◦C) in 1 hour (Sample 2).
The Si ingots obtained in both cases had very low B and P levels; both elements were
found at sub-ppm levels. The original concentrations of B and P in the FBR Si fines were
0.057 ppmw and 0.17 ppmw, respectively. The B and P levels in the final Si ingots were
around 0.03-0.04 ppmw, significantly lower than the original levels in the waste Si fines.
As listed in Table 1, all other metal impurities, except Ti, Fe, and Na, were very low (near
0.1 ppmw or below). The slight increase of Ti level in these Si ingots was attributed to
contamination from the graphite furnace, which we had been used for melting Ti metal in
previous experiments.
This hypothesis is confirmed by the results in other experiments where we used a
different, RF induction furnace to melt silicon, and a Ti level of < 0.01 ppmw was achieved.
The Fe levels in the Si ingots were around 1-2 ppmw—slightly lower than in the Si fines
(~ 5 ppmw). Finally, the level of Na in the quenched Si ingot (Sample #1) was 60 ppmw
but only 6 ppmw in Sample #2, which was produced by slowly cooling the molten Si. This
lower Na level is closer to the reported solid solubility of Na in Si [20]. We believe the high
levels of Na observed in Sample #1 were mainly come from NaF traces that were
entrapped during rapid Si solidification in some voids in the last fraction of Si to solidify.
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Table 1. The impurity contents in the initial FBR Si fines and Si ingots produced from the new process, as
determined by GDMS.
Impurity Levels (ppmw)

Impurity Silicon Fine Silicon Ingot Silicon Ingot
Element (FBR) (Sample #1) (Sample #2)
B 0.057 0.034 0.04
P 0.17 0.035 0.028
Al 0.27 0.11 0.15
Na 5.9 60 6.9
Mg 1.1 0.023 < 0.01
K 0.33 0.093 0.031
Ca < 0.1 < 0.1 < 0.1
Ti 0.029 1.4 0.60
V < 0.01 0.021 < 0.01
Cr 1.9 0.074 0.061
Mn 0.047 0.027 0.019
Fe 4.7 1.6 1.0
Co < 0.01 < 0.01 < 0.01
Ni 0.34 0.18 0.20
Cu < 0.1 < 0.1 < 0.1
Zn < 0.1 < 0.1 < 0.1
Zr < 0.01 < 0.01 < 0.01
Nb < 0.01 < 0.01 < 0.01
Mo < 0.01 < 0.01 < 0.01
Note: Silicon ingot Sample #1 was obtained by heating the reaction product at 1693K (1420◦C) followed
by fast cooling to ambient temperature, while Sample #2 was obtained the reaction product at 1693 K
(1420◦C) followed by slow cooling to 1643K (1370◦C) and dwell for 30 minutes before fast cooling to
ambient temperature.
The fact that the B and P levels and most of the transition metals in these Si ingots were
well below the 0.1-ppm level suggests they are suitable as Si feedstock for making solar
cells. A few metal impurities (such Fe) were around 1ppmw in the ingot. This will not be
an issue because the metallic impurities generally have very favorable segregation
coefficients, and significant purification can be achieved by unidirectional solidification.
In summary, we demonstrated that Si fines could be recovered, and a high-purity Si ingot
can be produced at bench scale via this new process. It involves (1) co-feeding pellets of
FBR Si fines into SiF4-Na reaction thus increasing overall Si production, and (2) melt
separation from NaF to produce Si ingots. We think that even purer Si feedstocks can be
produced via this process if melting of the Si-NaF mixture is followed with unidirectional
solidification using reusable crucibles and a simple casting furnace.
1.3. Discussion
During the peak of SiF4-Na reaction, the temperature in the reaction zone can climb briefly
(in seconds) to near the adiabatic temperature (which is above the Si melting point,
1685 K (1412oC)), and thus resulting in the liquid NaF wetting and infiltrating the added
silicon pellets and even some degree of local Si melt coalescence/consolidation. In our
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earlier study on SiF4-Na reaction processes [4,7], silicon ranged in size from 100 microns
to mm- or even cm-long elongated segregated zones in the Si-NaF mixture when the
external temperature of the metal reactor reached 1073 K (800°C). In these experiments,
we found evidence of the hardening of the pellets indicating liquid NaF infiltration and
even metallic grayish areas indicative of partial Si melt coalesce. Complete Si
coalescence and bulk separation of Si from molten NaF still requires maintaining the
entire system above 1693 K (1420◦C) for several minutes.
To achieve complete melt separation of Si from NaF, the temperatures need to be raised
above 1693 K (1420◦C), at which point Si mini-droplets are formed first in the liquid NaF
and their coalescence is driven by minimization of the surface energy. We have estimated
that Si has a surface energy of ~ 550±50 ergs/cm2 in molten NaF, while NaF’s surface
energy is 185 ergs/cm2 at 1273 K (1000 oC) and decreases with temperature i.e., to
<180 ergs/cm2 at 1378 K (1105oC) [21-23]. Coalescence is also aided by the very low
viscosity of molten NaF ranging from 1.84 cp at 1290 K (1017oC) to < 1.15 cp at 1470 K
[23]. Upon melting, Si density increases to over 2.5 g/cm3 while NaF density decreases
with temperature from 2.34 g/cm3 to < 2 g/cm3 at around 1693K (1420°C) [21-23].
Consequently, Si droplets fall to the bottom of the crucible sweeping and coalescing with
other droplets until they form a unique pool at the bottom. The molten NaF keeps the
surface of the silicon clean by etching and dissolving any oxide film and forming a soluble
fluoroxysilicate that dissolves into the NaF phase. All of these factors help the movement
and coalescence of small molten silicon droplets into one large, unique Si pool that sinks
to the bottom where it is wetted and encapsulated by the lower surface energy molten
saltthis behavior also keeps Si from reacting with the graphite walls to produce SiC.
In the present studies, we investigated the SiF4-Na reaction process and melt separation
of Si-NaF mixture using two separate reactors and examined each step individually.
However, in industrial practice, the two steps could be accomplished in one single reactor,
particularly if a custom-designed reactor can be built for the scale-up effort. For example,
both reaction and melt separation could be performed sequentially in a large, relatively
low-cost graphite container, and some degree of unidirectional solidification during
cooling could also be applied. Note that in this mode, the impurities tend to go into the
liquid Si as is well known in unidirectional solidification; however, in this case, because
the molten Si is, in turn, in contact with molten fluoride, that acts as a thermodynamic
sink, and a further removal of impurities will take place. There is considerable potential to
obtain even higher-purity silicon in very large batches (tons), and this type of partial
unidirectional solidification and simultaneous slagging is already being used by the
metallurgical industry to purify Si at the ton level. In that case, refining metallurgical-grade
Si in molten slags (typically silicates) generates silicon pure enough to be blended with
other purer silicon sources for an overall solar-grade silicon [24].
With respect to the energetic cost of production of Si, this approach of the recovery and
melt consolidation of Si fines in Si4-Na process will result in the lowest-cost option to
produce solar-grade silicon. The original SiF4-Na reaction is very exothermic, and the
main energy input is in the form of Na metal. Assuming an energetic cost of ~10 kWh per
kg of Na [25], this represents an energetic input of ~ 35 kWh per kg of Si produced in the
original reaction. We estimate that all the other energetic requirements, including
generation of SiF4, melt separation, another melting purification of Si, and running
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ancillary equipment will require ~ 15 extra kWh/kg of Si. Thus, the total energy
consumption will be ~ 50 kWh/kg of Si one half of the energy needed in the Siemens
process for just the SiF4-Na process alone. In addition, the reactor is very hot and at least
part of the heat of reaction (equivalent to about 5 kWh/kg of Si) could be recovered or
reused to generate SiF4 as we have demonstrated in the past [26].
When waste Si fines from the FBR are added to the SiF4-Na process, the combined
process can be envisioned as a path to recover the energy originally invested in producing
those Si fines, or to augment the throughput of the SiF4-Na reactor. In the latter scenario
and given that Si production was doubled, the estimated total energetic consumption
would be below 30 kWh/kg of Si, equivalent to ~ 1/3 of the energy input required for
Siemens process. Without taking credit for using what would otherwise be a waste
product, the cost is less than half the cost of the Siemens process. Furthermore, we
believe an even higher loading of Si fines can incorporated into this process, which would
decrease the energetic and financial costs even further.
1.4. Conclusion
FBR silicon fines are a high-purity silicon waste, and without pre-cleaning step, this type
of Si fine can be added into the CoSiRC process to produce solar-grade Si ingots as we
demonstrated in this program. Next, we will report our efforts of adding Si fines from
crushing and wafer slicing operations into the CoSiRC process.
2.0 Pre-purification of Various Silicon Fines

Besides FBR Si fines, there are several types of silicon fine wastes generated from
different stages of the solar cell manufacture. For example, “crushed silicon fines” are
generated during the crushing of Si rods from the Siemens process; “kerf loss silicon
fines” are generated during cutting and slicing Si crystals into thin wafers. These types of
Si fines are generally contaminated with some impurities and need to be pre-purified
before being recycled into solar-grade silicon. In this program, we characterized various
types of Si fine wastes, studied several low-cost purification processes to pre-clean these
Si fines, and evaluated the feasibility of incorporating them into CoSiRC process. In this
section of the report, we will summarize our studies on pre-purification of crushed Si fines
and kerf loss silicon fines, respectively.
2.1 Characterization of Crushed Silicon Fines

Two samples of Si fines were procured in kg quantities from industrial crushing
operations. They had different particle size and distributions; one sample consisted of
relatively coarse Si particles (mm size), and the second sample consisted of finer particles
(submillimeter to micron size).
Sample 1 consists of crushed polycrystalline semiconductor-grade Si particles ranging in
size from several mm to ~ 0.5 mm. The physical appearance of this fine, shown in
Figure 8, exhibits typical silver-gray color of polysilicon. According to the supplier, the
original impurity level in the bulk Si ingot was very low with an original dopant content (B
and P) below 1 ppba and total transition metal impurities (TMIs) (Fe, Cr, Ni, Na, Zn and
Cu) below 30 ppba. However, the actual powder was more contaminated, possibly on the
surface, and contained Fe, Cr, Cu, Na, Ni, and Zn in 10 to 100 ppm levels.
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Bulk Impurity Specification

• Boron: ≤ 0.2 ppba
• Donor: ≤ 0.9 ppba
• Carbon: ≤ 1.0 ppma
• Total bulk metals: ≤ 30.0 ppba
(Fe, Cu, Ni & Cr)
Surface Impurity Specification
• Total surface metals: ≤ 150 ppma
(Fe, Cu, Ni, Cr, Na, Zn)
Size Specification
• meet following: 0.001 – 8.0 mm
Figure 8. General appearance of coarse mm-sized Si fines (sample 1) and the bulk specifications.
The TMI level in this Si powder is consistent with the Si particles in contact with stainless
steel (SS) equipment during the crushing procedures. We assumed, and subsequent
experiments seemed to confirm, the TMIs were concentrated on the surface of the Si and
possibly existed as small SS particles because of rubbing, erosion, and other mechanical
mechanisms during crushing, transport, and/or storage of the Si. During the Si crushing
procedure, newly fractured surfaces are very reactive, and their surfaces oxidize almost
instantaneously to a thickness ranging from one to several nm. At the same time, the
sharp edges of the Si particles erode the SS walls when they come in contact so that Fe,
Cr, and other TMIs may smear on the Si surfaces. Upon exposure to normal air, oxidation
of those surfaces is also expected to occur, so the metal impurity species may be present
as oxides or even silicates.
These types of silicon fines were sent out for impurity analysis using inductively coupled
plasma mass spectrometry (ICP-MS) by an independent analytical lab, and results
confirmed the fine was relatively pure. The dopant levels (B and P) were below
< 0.1 ppmw, and each metal impurity level was < 1 ppm, except Al and Fe were ~ 5 ppmw
and 11 ppmw, respectively.
The second sample of Si fines (Sample 2) from an industrial crushing operation had a
dark gray appearance (shown in Figure 9) typical of the fine Si powders with surface
Bulk Impurity Specification
• Boron: ≤ 5.0 ppba
• Donor: ≤ 15.0 ppba
• Carbon: ≤ 5.0 ppma

Size Specification
• At least 90% of product, by weight, will
meet following: 0 – 0.5 mm
Figure 9. Finer Si fines from crushing Si ingots (sample 2): general appearance and the bulk
specifications.
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oxidation. Some of bigger particles are visible to the naked eye. Observed under an
optical microscope with magnifications up to 45, the sample consisted of a mixture of fine
powders and broken Si pieces ranging in size from a submicron to 500 µm. The fractured
surfaces had sharp edges and appeared similar to crushed polycrystalline silicon.
According to the supplier, these Si fines originated from Si ingots with a bulk content of
B < 5.0 ppba and P < 15 ppba—well below the levels required for good solar-grade Si
feedstocks. The overall approximate concentration of TMIs in the bulk was not provided
by the supplier. A qualitative analysis by X-ray fluorescence (XRF) of the Si fines revealed
the material was heavily contaminated, probably on the surface, with metal impurities
(e.g., 4500 ppmw of Fe). The other TMIs were present at levels around a few hundred
ppmw, which is near the detection limit of our XRF instrument.
The original oxygen content in this Si fines was also analyzed via LECO analysis by an
independent analytical lab. The Si powder contained ~ 930 ppmw of oxygen, which may
be attributed mostly to surface silicon oxide on the Si fines and is typical in a sample with
such a small particle size and concomitant large surface area.
2.2 Purification of Crushed Silicon Fines

The Si particles of sample 1 were coarse, relatively clean, had low oxide content, and no
pre-purification was attempted. For more contaminated Si fines with higher oxide content
(sample 2), we first studied the effect of pre-purification using various aqueous acids,
followed by melt consolidation of pre-cleaned Si fines with NaF. We studied the etching
effects of removing impurities qualitatively using an in-house XRF. The XRF results of
several experiments of acid etching of sample 2 are summarized in Table 2 along with
the original impurity contents. Due to the presence of TMIs on the surface of the particles,
where they are exposed directly to the X-rays, XRF data may give higher-than-actual
levels of each element. Therefore, these values should be considered qualitative;
nevertheless, evaluating them allowed us to follow the trends of etching.
Table 2. TMI levels in sample 2 following acid washing.
Original Approx. HCl HCl-HNO3 HF-HCl HF-HCl-HNO3

Limit
Detection washed washed washed washed
(ppm)
Fe 4520 50 237 172 136 51
Cr 293 90 271 267 181 90
Ni 180 50 148 181 95 58
Cu 90 20 74 78 50 29
Zn 55 10 41 47 28 17
Co 84 ND ND ND ND ND
Oxygen 930 51
Etching with HCl: Sample-2 powders were etched in a hot HCl aqueous solution (1 N,
328K (55◦C)) aided by sonication for 60 minutes. Then the slurry was centrifuged, and
the resulting powder was rinsed with DI water three times before drying. This etching
removed most of the Fe. The levels of the other TMIs also dropped slightly; however,
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since they approached the background level, the values are only a general indication of
etching efficacy.
Etching with HCl and HNO3: We used this more aggressive acid combination to oxidize,
etch, and dissolve any metal particles present in the powder or surface of the fines. A
sample of 50 g of crushed Si fines was leached with a solution consisting of 350 g H2O;
20 g of conc. HCl (11.6 M); and 20 g of conc. HNO3 (15.6 M). The molarities of HCl and
HNO3 in this acid mixture were 0.51 M and 0.58 M, respectively. The Si samples were
added to this acid mixture and stirred at 20◦C for 1 hour. The slurry was filtered, the
resulting powder was rinsed with DI water, and then dried. The resulting power was
analyzed using in-house XRF and exhibited lower levels of Fe and other TMIs than those
from HCl washing alone, so we assumed the oxidation of impurities enhanced TMI
removal. The plausible reason for the limited removal of Cr and Ni is that these elements
may be embedded in or covered by an insoluble layer such as a SiO2 or silicate film
formed during crushing in an air-filled environment.
Etching with HF and HCl: Based on the previous experiments, we explored the combined
effects of HF and HCl to remove protective silica or silicate layers and form H2SiF6 or
soluble fluorocomplexes of transition metals. A mixture of 0.11 M HCl/0.08 M HF was
added to Si fines, followed by filtering, rinsing, and drying. The resulting powder was
analyzed using in-house XRF. The results show all six TMI levels were significantly
reduced (see column 5 in Table 2). Although the HF was diluted in this experiment, adding
HF acid resulted in more effective removal of the TMIs than just using HCl. For
comparison, the silicon fines were sent to an independent analytical lab for a more
sensitive impurity analysis using ICP-MS.
Etching with HF, HCl, and HNO3: To over-etch and remove as many potential impurities
as possible from the surface of sample, we tested the combined etching power of three
acids. Samples of 50 g of the Si fines were first etched in baths containing 400 g DI H2O,
10 g conc. HF, and 10 g conc. HCl. The molarities of HF and HCl in this solution were
0.48 M and 0.23 M, respectively. The slurry was stirred for 60 minutes at room
temperature. A metallic gray Si-rich foam formed on the surface of aqueous solution. The
slurry and foam were centrifuged, and the solids settled at the bottom. After decanting, a
second aqueous solution containing 0.26 M HCl and 0.22 M HNO3 was added and stirred
for 60 minutes. After centrifuging and decanting, the Si fines were filtered and rinsed with
DI water three times before drying them. The resulting powder was analyzed using in-
house XRF.
The resulting impurity levels as detected by XRF are listed in the last column of Table 2.
These data likely represent the real background/detection limits of our XRF instrument
for this type of fine powders. The actual impurity levels should be lower than these XRF
data.
The ICP-MS data from the HCl-HF etched powder is shown in Table 3. It confirms the
etched Si fines samples were significantly purer than the original Si fines. We concluded
the level of impurities in the etched sample was low enough to proceed to the melt
consolidation and that the crushed silicon fines—though heavily contaminated with
surface TMIs (sample 2)—can be purified by simple acid etching.
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Table 3. Impurity content of Si fines in sample 2 after acid leaching as determined by ICP-MS.
Impurity B, P Al Ti Cr Fe Co Ni Cu Zn
Level, < 0.1 3.2 2 1.3 15 0.4 0.8 3.2 0.7
ppmw
2.3 Characterization of Kerf Loss Silicon Fines

Two different samples of kerf loss waste were procured directly from industrial operations
that slice silicon crystals into wafers using diamond wire saws. One sample (sample 3)
was received as powders and cakes; the second (sample 4) was received as a dispersed
aqueous slurry that contained silicon fines. In addition, we also obtained another type of
kerf loss silicon fines (sample 5), which were generated from the industrial operation that
slice silicon crystals into wafers using SiC slurry with metal wire saw. However, this type
of kerf fine was heavily contaminated with SiC particles and metallic impurities, and we
were unable to reclaim this type kerf loss silicon into silicon ingots in the CoSiRC process.
Consequently, we will focus our discussion on reclaiming kerf loss fines (sample 3 and
sample 4) from diamond wire sawing in this report.
2.3.1. Physical appearance

The solid waste material (sample 3) came directly
from diamond wire-cutting operations at the
source company. It was dewatered and partially
dried at the supplier and received at SRI as
powders and cakes. The physical appearance of
materials as received is illustrated in Figure 10.
This sample contains some moisture and exhibits
inhomogeneities as evidenced by the presence
of an efflorescence white layer (likely silica) on
some of the cakes. The individual particle size
ranges from <1 micron to nm sizes as observed
in SEM images. The as-received cake was dried
under vacuum at 423 K (150⁰C) for 4 hours,
resulting in a 20-25% weight loss mainly Figure 10. Appearance of kerf waste Si
fines/cake from diamond wire-cutting
attributable to moisture and possibly some operations as received from the supplier.
organic volatiles. The dried powder was sent out
for oxygen and carbon analysis to determine the
silica and carbon contents in the sample. A LECO analysis indicated the Si fines
contained 6-7 wt% of oxygen and ~ 0.4 wt% of carbon. Assuming all of the oxygen was
in the form of silica, the Si fines would contain 12-14 wt% of silicon oxide. Considering
the inhomogeneity of the materials, precise silica content in these kerf fines is difficult to
determine based upon data from the LECO analysis using a sample size of only 100 mg.
We estimated this dried kerf material contained silica and/or silicate in a range of 12-
20 wt%.
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2.3.2. XRD pattern of the Si fines

The X-ray diffraction (XRD) pattern of the powder as received is shown in Figure 11 and
exhibits strong peaks of crystalline Si. No diffraction peaks associated with any crystalline
diamond phases were detected. There are two tiny peaks illustrated as * in pattern A,
which may be attributable to phases associated with graphite. The XRD of the white
powder scraped from the surface of the cakes (pattern B) exhibits a broad peak in addition
to the silicon peaks. This broad shoulder at low diffraction angles is probably due to the
amorphous surface silica.
Si (111)
Si (220) Kerf Si fines as received
Si (311)
* Si (400) Si (331)
* White powder on Kerf Si cakes
10 20 30 40 50 60 70 80
Two theta
Figure 11. (A) XRD of the kerf Si fines as received; (B) XRD of white powder scraped from the surface of
the cake exhibits a broad peak background in addition to the silicon peaks.
2.3.3. Thermogravimetric analysis of the Si fines

Although XRD of the kerf Si fines did not detect any crystalline diamond phases, small
amounts of diamond or graphite particles might be present as result of erosion and
fracture during saw slicing. In addition, residual organic compounds, such as dispersants,
surfactants, and anticorrosion agents, etc., which may be added in the cooling water
during the cutting process, are expected to be present. Those carbon species and organic
molecules, if not removed, can pyrolyze and generate C species during the Si melting
procedure and subsequently form SiC, which affects the tendency of Si to coalesce into
a pool. Therefore, it is generally believed that removing carbon species before melting
silicon at high temperature is important [27].
A batch of kerf fine cakes were first dried in a vacuum furnace at 423K (150◦C) to remove
residual moisture. To estimate carbon contents in this Si fines, we performed a thermo-
gravimetric analysis (TGA) of this kerf Si fine under an air flow, and the result is shown
as the solid curve in Figure 12. As the curve illustrated, the dried kerf fine displayed a
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weight loss of 0.1 wt%

as the temperatures TGA in Air
reached 373 K 103.0
(100◦C); this can be dash line: Kerf Si fines after being heated at 500◦C in air
102.5
attributed to the loss of solid line: kerf Si fines after being dried at 100◦C in vacuum
adsorbed moisture on 102.0
the surface of the fines.
The weight loss 101.5
Weight (%)
continued and became
101.0
pronounced above
523 K (250◦C) and 100.5
reached the plateau of
100.0
0.5 wt% at a
temperature of 773 K 99.5
(500◦C). The weight
loss between 523 K- 99.0
0 100 200 300 400 500 600 700 800 900 1000
773 K (250-500◦C)
Temperature (◦C)
may be attributed to
first pyrolysis and then Figure 12. A TGA of the Sample 1 Si Kerf fine after being dried at 373K
combustion of the (100◦C) in vacuum (solid line) and heated in air at 773K (500◦C) (dashed
organic species and C line).
species presented in the Si fines (during which CO2 gas was presumably evolved).
Heating above 773 K (500◦C), the weight of sample increased. The weight increase at
high temperature is an indication that further oxidation of Si occurs even though the kerf
waste already contains a significant fraction (up to 20 wt%) of SiO2. Therefore, the TGA
results indicated this kerf Si fine contained ~ 0.4 wt% of carbon species, which we
assumed could be removed by heating in air in a temperature range of 723K-773 K (450-
500◦C).
To test this hypnosis, we then heated a bigger batch (~ 600 g) of this kerf Si fine on a
quartz tray inside a box furnace at 743 K (470◦C) for 3 hours. As the temperature climbed
above 673 K (400◦C), we noticed a smell of organics burning, and the final weight loss of
this bigger batch of fines was again 0.5 wt%, consistent with our TGA results. The
resulting powder was again analyzed using TGA, and the result is shown in Figure 12 as
a dashed-line curve. Clearly, after an initial weight loss of ~ 0.1 wt% below 373 K (100◦C)
(attributed to loss of adsorbed moisture), this sample kept a constant weight until the
temperature reached 773 K (500◦C), above which silicon oxidation occurred. In fact, this
TGA curve (dash line) confirmed that carbon species in the original fines were effectively
removed upon the heating treatment in air at 743 K (470◦C).
2.3.4. Kerf loss slurry

The second kerf waste sample (sample 4) was obtained from drums containing aqueous
slurries of well-dispersed kerf Si fines from an industrial manufacturer of Si wafers. The
slurries were taken directly from the industrial process tanks, and they consisted of kerf
Si fine (2-3 wt%) dispersed in the industrial cutting fluid. According to the vendor, the
cutting fluid is a light yellowish aqueous solution with surfactants and inhibitors, which
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contains 5-10 wt% of cyclic carboxylic acid and alkanolamines. This waste slurry had a
dark gray color (blackish) and a sweet odor.
We first tried to use filtration to recover the Si fines, but the Si particles were so small and
well-dispersed that they partially passed through fine filter papers (#5 filter paper from
Whatman). We then tried to recover the fines by centrifuging the slurry in Nalgene bottles
at 1500 rpm for 60 minutes. After the centrifugation, a black solid cake settled at the
bottom of the bottle and we poured out a dark-brown supernatant liquid. However, the
liquid still contained ~ 0.5 wt% of solids as determined by weight measurements after
drying. This accounted for ~ 1/4 of solid remaining as dispersed in this supernatant. Since
it is well known that the isoelectric point of Si in the aqueous solution can be adjusted by
changing the pH of the solution, we then tried adding a small amount of strong acid into
the slurry/dispersion, and the Si fines started to agglomerate. The acids included HF, HCl
or HNO3, at loading of ~0.1wt% with respect to the total slurry weight. After centrifugation,
the kerf fines settled into a cake at the bottom, and the top supernatant liquid was clear
indicating that all the fines were collected at the bottom. The Si cake was then dried in
vacuum at 423K (150°C) to eliminate any physi-absorbed and chemi-absorbed water,
and the resulting powder agglomerates were used as the source of kerf Si fine (sample 4).
Using an SEM photo of the silicon fines on a filter paper, we estimated most of the larger
particles ranged in sizes from 150 nm to 250 nm. We estimate that most (90%) of these
industrially available waste kerf loss Si fines will have a surface area of over 10 m2/g.
Another important feature is the presence of an oxide film on the surface of the Si
particles, which can be 1 to 2 nm in thickness. The oxygen and carbon contents of this
kerf fine were ~ 6 wt% of O and ~2 wt% of C according to LECO analysis. We estimated
12 wt% of the weight of this kerf Si fine was surface oxides, similar to the level of sample 3.
We expect the surface oxides and hydroxides may be a sink for adsorbed impurity
species, including metallic ions and organic species present in the cutting fluid. The XRD
pattern of this kerf Si fine is identical to that of Sample 3 (shown in Figure 11), and no
other peaks associated with diamond and other crystalline phases were detected by XRD.
Thermal analysis of the dried powder using TGA under an air flow shows that, at
temperatures ranging from 523 K (250°C) to 723 K (450°C), there is a loss of weight of
~ 2 wt%. We attribute the weight loss to pyrolysis and oxidation of remaining organic
species in the silicon surface. This is consistent with the LECO analysis results indicating
carbon content of ~2 wt% in this kerf, which is significantly higher than that of Sample 3.
This data suggests carbon species in this kerf Si fine can be removed by heating it in air
between 673K-773K (400-500◦C) without significantly oxidizing the silicon.
A small amount of this recovered kerf loss Si fine (sample 4) was sent for impurity analysis
using GDMS, and results indicated the Si was heavily doped with N-type dopants,
including 1500 ppmw of As and 70 ppmw of P. Besides the dopants, this Si waste was
also contaminated with a few ppm of transition metals such as Ni, Ti, Fe, Cr, and Cu.
Presumably the contaminants are from the metals in the cutting tools. We speculate that
this waste stream was generated while cutting high-conductivity silicon wafers, such as
those used in some power applications, which contained highly doped arsenic.
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2.4 Purification of Kerf Loss Silicon Fines

In general, kerf Si fines containing dispersion or slurry with accompanying solvents and
surfactants should be filtered, and the resulting powder cake generally contains metallic
contaminations from the wire, silicon oxide, small diamond pieces, and organic residues
from surfactants. In order to recover these Si fines as solar-grade silicon ingots, we
believe that they generally need to be pre-purified to remove metallic and carbon
impurities before incorporating them into CoSiRC process.
For sample 3, our industrial kerf supplier had filtered and partially dried kerf waste fines
into cakes at its facility. To determine the impurity levels in sample 3, we dried this kerf Si
fine and sent it to an analytical lab for GDMS analysis. The results of GDMS analysis
indicated it contained low levels of dopants: 1-2 ppmw of B and P, thousands of ppmw of
Al and K species, as well as hundreds of ppmw of some TMI such as Fe, as listed in
Table 4. However, the GDMS results did not tell us where these impurities were located,
whether in the bulk of Si or simply as additives residing mostly on the surface. Below, we
will summarize two essential steps of purifying kerf loss Si fines.
2.4.1. Acid washing of the kerf fines

We therefore washed the kerf fines with deionized (DI) water as well as with different
dilute acidic solutions, such as HCl, HNO3, and HF/HCl, and sent them out for GDMS
analysis again. Most of high-level impurities in the original Si kerf fines were significantly
reduced via simple washing even with DI water, indicating these impurities are located on
the surface of the Si fines. The dopant levels (B & P) decreased from 1-2 ppmw to
< 0.05 ppmw with acid washing.
Another purpose of acid etching, especially with HF acid, is to remove surface oxide. It is
well known that silicon oxide can be dissolved in aqueous HF acid. The LECO analysis
of the dried kerf fine as-received indicated its oxygen level was 6-7 wt%, which
corresponds to 12-14 wt% of silica. After etching the Si fines with an HF solution, we
examined the oxygen contents of the recovered kerf fines again, and this showed the
oxygen level was similar to that of the original fines, indicating the presence of the same
amount of silicon oxide.
2.4.2. Selective oxidation of the kerf fines

It was a bit surprising we did not detect any expected crystalline diamond fragments via
XRD in these two industrial kerf Si fines samples. We concluded that either the fragment
level is very low, they became a thin layer of graphite smeared on Si particles surface, or
they were washed away during the decanting and/or filtering prior to drying. According to
our kerf suppliers, organics were added into the Si slurries as surfactant dispersants and
corrosion inhibitors, etc. Therefore, the kerf Si fines cakes recovered from the waste-
cutting slurries contain carbon species, either as graphite or organic species.
Previous efforts by Vazquez-Pufleau et al. [27] demonstrated that carbon elimination from
kerf was feasible using a furnace aerosol reactor. Fortunately, we found these carbon
species in kerf fines started to oxidize at 523 K (250◦C) and were completely burned at
723 K (450◦C) when heated in air. This TGA result is consistent with the presence of
species of K, Na, and Fe in the Si kerf fines (see Table 4), which are well known as
catalysts for oxidation of carbon species [28, 29]. The oxidation not only removes organic
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molecules that may be adhered or trapped in the silica oxide and hydroxide surrounding
the Si, but also most of the C species produced by pyrolysis and small fragments of
diamond from cutting process.
3. Melt Consolidation of Various Silicon Fines with NaF

Although this program is about incorporating various type of silicon fines into the CoSiRC
process, which involves co-feeding Si fines into SiF4-Na reaction system to produce solar-
grade silicon, we also used melt consolidation of Si fines with NaF powder as a screening
tool to evaluate whether various silicon fines (with and without pre-purification) can be
recovered into solar-grade silicon ingot. This melt consolidation involves of heating the
mixture of the Si fines with NaF to a temperature slightly above the melting point of silicon
(1412◦C). After cooling, the Si ingot, if coalesced, can be easily retrieved and analyzed.
This is a much simpler and quicker way to test whether various types of silicon fines can
be consolidated into Si ingots.
Using crushed Si fines (sample 1 and sample 2), we found they could be easily
consolidated into silicon ingots by heating the fines with NaF powder. However, sample 2
needed pre-washing to remove metallic impurities to produce high-purity silicon ingots.
To avoid repetitive reporting, we will only focus on our studies of kerf silicon fines
(sample 3 and sample 4) in this section since these two samples were dirtier and more
difficult to process.
3.1 Melt Consolidation of Kerf Si Fines (Sample 3), Without Pre-washing

Dried, as-received Si fines (sample 3, 30 g) were mixed with NaF (90 g), loaded into a
graphite crucible, and heated in Ar to around 1693 K (1420 (±10) ◦C). When short melt
consolidation times (15 minutes) were attempted above the Si melting temperature, there
was incomplete Si coalescence as evidenced by a plurality of small silicon balls/beads
surrounding one big Si ingot. We suspected the carbon species, though only ~ 0.4 wt%,
prevented full Si coalescence. (See more discussion in later sections). We had to
increase the period from 15 to 45 minutes at high temperature to achieve near-complete
Si coalescence. After complete melt consolidation, the Si formed one cylindrical domed
ingot of ~ 2.5 cm in diameter and 1.2 cm in height at the bottom of the graphite crucible;
Top
Bottom
B
Figure 13. Consolidated Si ingot: (A) surrounded with some NaF and (B) after the ingot was removed
from the surrounding NaF and cut in two.
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it was surrounded/encapsulated underneath and laterally by a layer of NaF (100 microns

to mm), and the bulk of the NaF was sitting on top. The Si ingot with part of the NaF still
attached on top is shown in Figure 13A following a simple separation induced by
mechanical fracture of the product. The NaF phase encapsulating the Si ingot displays a
slightly grayish color rather than the white/transparent hue typical of the NaF crystals
when pure. Since we know this kerf Si fine contains as much as 12-14 wt% SiO2 and
0.4 wt% of carbon species and metal impurities in hundreds of ppmw, we believe the color
of NaF phase was from impurities such as metals, SiC, and fluorosilicate species. This
experiment demonstrated it was possible to melt-consolidate Si fines that contain a high
level of SiO2. The recovered Si ingot weighed 23 g, equivalent to a raw Si recovery yield
of ~ 77 wt% (23 g/30 g). Because the original fines contained an estimated 4.5 g of SiO2,
the net Si yield was 90%.
We cut this Si ingot in two vertically, and one half was sent to an outside commercial
analytical lab, where two prismatic samples (pin/electrodes) measuring approximately
5 mm × 5 mm×20 mm were cut out at two different heights from the half ingot for GDMS
analysis. The sample locations are marked by rectangles in Figure 13B and were chosen
to determine if there is any gradient in the concentration of impurities along the height of
the ingot. The shape of the Si ingot shown in Figure 13B also demonstrates the effect of
NaF; it provided a rounded
protective envelope to the Table 4. The GDMS analysis of impurity levels in Si kerf loss fine
and consolidated Si ingot from different analytical labs.
solidifying silicon so that it
did not stick to the graphite From dried Kerf cake (no acid washing)
crucible. The large grains kerf fines 1st half Si
with straight grain received, 1st half Si ingot- 2nd half Si 2nd half Si
boundaries revealed after a dired ingot-top bottom ingot ingot
light etch (visible in GDMS - GDMS - GDMS -1st GDMS - ICPMS -
Figure 13B) also illustrate 1st lab 1st lab lab 2nd lab 3rd lab
that encapsulation of Si by B 0.99 0.05 0.09 0.12 0.03
liquid NaF does provide a Al 2485 0.03 0.03 <.05 3.70
homogeneous interface P 1.80 0.30 0.32 0.57 0.74
(without heterogeneous As 0.32 <0.03 <0.03 <.05 N/A
nucleation points) during S 1.70 <0.03 0.04 <.05 N/A
the Si solidification so that Na 790 17 11 12 921162
only a few large grains with Mg 25 <0.01 <0.01 <.05 0.04
straight boundaries were Ca 250 <0.1 <0.1 <.1 0.30
grown. The impurity levels K 2250 0.64 0.25 <.1 1.65
for each pin (labeled as Ti 14 0.03 0.04 <.01 1.98
ingot-top and ingot-bottom, V <0.05 <0.01 <0.01 <.01 <.01
respectively) as well as Mn 45 0.17 0.08 <.05 2.98
those of original kerf Si fines Cr 1.50 0.01 0.02 <.05 0.45
are given in Table 4. As Fe 210 0.99 0.77 0.34 12.63
compared to the kerf Si
Co 0.41 <0.01 <0.01 <.01 <.01
fines, essentially all the
Ni 17 0.06 0.15 0.65 3.83
impurity levels in the ingot
Cu 4 <0.1 0.22 2.70 3.87
were lowered by at least
Y 1.2 <0.01 <0.01 <.01 N/A
one order of magnitude,
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and the P level was decreased ~ 6 times by this procedure. The dopant TMIs in the
resulting silicon ingot were low enough so it qualified as solar-grade silicon. The fact that
both samples (ingot-top and ingot-bottom) contain similarly low impurity levels indicates
the impurity distribution in the bulk of this Si ingot was homogenous.
To confirm these results, the other half of the Si ingot was sent to a second industrial lab
for independent analysis using two different and complementary analytical techniques,
GDMS and ICP-MS. The results are listed in the last two columns of Table 4. The GDMS
results from the second lab were essentially identical to the first analysis and clearly
confirmed the results. The ICP-MS analysis for dopants B and P also confirmed their low
levels as well as those of most TMIs. However, the unusually high Na content, which was
accompanied by high levels of Al, Fe, and other TMIs at ppm levels from ICP-MS analysis,
can be attributed to the presence of small inclusions of NaF and impurity accumulations
inside the tiny voids near the top of the Si ingot (visible in Figure 13B).
This experiment indicates most of the impurities in the original kerf fines are likely to be
present on the surface, and they all end up in the NaF phase upon dissolution and melt
consolidation. The solidification in these experiments was too fast (15 min) to generate
any appreciable extra purification via directional solidification.
In summary, the molten NaF phase was able to (1) dissolve surface silica, (2) absorb
most of the impurities, (3) improve heat transfer, (4) prevent molten Si from reacting with
graphite, and (5) facilitate coalescence of molten Si into a pool.
Table 5. The GDMS analysis
3.2. Melt-Consolidation Kerf Si Fines (Sample 3), results of kerf fines after acid
With Pre-washing washing and obtaining the Si ingot
from the fines.
Because the original waste kerf Si fines contained K
Kerf fines,
and Al in thousands ppm, as well as Ca and Fe
acid washed Si-ingot
impurities at levels of 200 ppm, and dopants (B and P)
B < 0.03 < 0.03
at levels of 1-2 ppmw as listed in Table 4, we tried pre-
Al 7.60 0.04
washing the Si fines to explore if (1) the metal
impurities and surface silica could be easily removed P < 0.05 0.14
upon washing, and (2) if removing these metal As < 0.1 < 0.1
impurities as well as the surface oxide before melt S 3.3 0.56
consolidation can result in an Si ingot with higher Na 2.9 14.0
purity. The GDMS analysis of the fine after HF acid Mg 1.70 0.23
washing is shown in the second column in Table 5, Ca < 0.1 < 0.1
and it clearly illustrates that a simple washing with HF K 0.70 0.21
acid was able to reduce metal impurity levels from Ti 1.80 0.54
thousands ppm down to a few ppm, and dopant levels V < 0.05 < 0.01
to < 0.03 ppmw and <0.05 ppmw, for B and P, Mn < 0.05 < 0.01
respectively. This result confirmed that most of these Cr 1.80 0.07
impurities were on the surface and not in the bulk of Fe 2.70 1.40
the kerf Si fines. Later experiments showed that Co < 0.1 < 0.1
washing the original fines with DI water could Ni < 0.1 0.09
essentially remove most of metal impurities as well. Cu < 0.1 0.22
Y N/A < 0.01
Zr < 0.05 < 0.05
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To find out whether a higher purity of the Si ingot can be obtained by starting with cleaner
Si fines, we repeated the melt-consolidation experiment by mixing the pre-washed kerf Si
fines with NaF. We followed the same procedure and conditions described earlier to
produce a Si ingot. The relevant impurity levels in the resulting Si ingot obtained by GDMS
analysis are summarized in the third column of Table 5 along with those of the pre-etched
fines for comparison. This Si ingot had a significantly lower content of several metal
impurities (Al, Mg, Cr, Ti, Fe) with respect to the pre-washed fines, and it should be
acceptable as solar-grade silicon feedstock. The Na level in the Si ingot is at the level
expected for solid solubility of Na in Si. Based on our past experience, we expect the
minor increase in the P level in the ingot (compared to that in the fines) is most probably
due to cross contamination from the Grafoil® liner materials. This low level of
contamination can be minimized further in scale-up operations because the Grafoil®-to-
product ratio will be much smaller and also by using purified Grafoil® liners. Compared to
the impurity levels of the Si ingot obtained from unwashed Si fines (Table 4), only a small
improvement in Si purity was achieved by using cleaner pre-washed Si fines.
3.3. Large-scale Melt Consolidation Kerf Si Fines (Sample 3)
3.3.1. Pre-washing
Kerf loss Si cakes (Figure 10) of 600 g as received from our supplier were first ground
and sieved through 0.8-mm metal sieves, and the resulting powder was placed onto a
filter paper inside a 1 L plastic funnel. Then 600 mL of DI water was poured into the funnel,
and the mixture was stirred before the filtrate was allowed to slowly drain to a bottom
receiving basket. This procedure was repeated three times before the cake was left to air
dry; this was followed by drying in a vacuum furnace. Dried powder of 490 g was
recovered, indicating the original cake contained ~ 20% of moisture. This type of pre-
washing was performed with three batches, and a total ~1 .5 kg of pre-washed kerf fine
was obtained.
3.3.2. Selective oxidation

The resulting kerf fines were then heated in a furnace at 470◦C for 2 hours under an air
flow. A smell of burning organics was noticed during the heating. The final weight lost in
this heating was ~ 0.5 wt%, indicating the residual carbon species was removed.
3.3.3. Larger-scale melt separation

This pre-treated kerf silicon fine of 500 g was mixed with 1500 g of NaF (> 99% from
J.T. Baker) in a plastic bottle. Then the mixture was loaded into a graphite crucible inside
a Grafoil® liner as shown in Figure 14A. The crucible was first heated to 1200◦C (above
the melting point of NaF) in a RF furnace under argon flow and then cooled down; the
resulting loaded powder mixture condensed and shrank as shown in Figure 14B. Then,
an additional powder mixture of 200 g of kerf fines and 600 g of NaF was added into the
crucible, which was reheated to 1420◦C under argon flow for 2 hours. The silicon melted
and coalesced into a pool and sank to the bottom of the graphite crucible. Upon cooling,
the crucible was taken out of the furnace (as shown in Figure 14C), and product was
retrieved and is shown in Figure 15. A total of 535 g of silicon ingot was recovered from
700 g of silicon fines, corresponding to a yield of ~ 76%. This recovered yield is
reasonable considering that the starting dried kerf fines contained ~ 20 wt % of silica.
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B C
Figure 14. Top views of (A) mixture of kerf Si fines and NaF powder inside a graphite crucible, the
gray color is from kerf fines; (B) results of heating the mixture to 1373 K (1100◦C) and cooling it
down—the mixture shrank into a sand-castle structure; (C) results of heating the mixture to 1693 K
(1420◦C) and cooling it down—this shows the off-white NaF phase coating the Si ingot.
A B
Figure 15. (A) Product retrieved from melting the crucible and showing (top) the off-white NaF
layer and (bottom) a layer of metallic shiny silicon. (B) Recovered silicon ingot and pieces of
weighing 535 g after the NaF was broken and washed off.
3.3.4. Remelting
About 1 kg of the silicon chunks and ingot recovered from melt consolidation (from two
different batches) was loaded into the quartz crucible shown in Figure 16A. The quartz
crucible was then loaded into a graphite crucible, which was heated to 1420◦C under
vacuum to remove residual Na in the silicon. The resulting silicon ingot of ~ 1kg, shown
in Figure 16B, displayed large dendrites and a grain formation, indicating a high purity of
the silicon. A small slab of this Si ingot and was cut and sent out for GDMS analysis. The
analytical result, shown in Figure 17, confirms its high purity.
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A B
Figure 16. (A) Silicon ingot and chunks from melt consolidation was loaded into a quartz; (B)
1 kg silicon ingot produced after 2nd melting in vacuum, from which large grains are visible.
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Figure 17. GDMS results of 1 kg silicon ingot from remelting silicon, confirming its high
purity.
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3.4. Melt Consolidation of Another Kerf Si Fine (Sample 4)

Run #1. A mixture of 9 g of dried kerf Si fines, recovered from the kerf slurry (sample 4),
and 36 g of NaF power was loaded into a graphite crucible. We followed the same
procedure described before, and the crucible was heated in Ar to 1693 K (1420◦C) for
15 minutes before cooling down. These kerf Si fines melted and coalesced into small
droplets that were immobilized as small spheres dispersed in the gray NaF matrix. The
cross-section and top view (after partial detachment of the top NaF layer) of the material
after melt consolidation are shown in Figures 18A and 18B, respectively. The solid Si
spheres ranged in size from 100 microns to 1 mm, clearly indicating the Si fines had only
partially consolidated and formed hundreds of these Si balls. After retrieving and washing
off the NaF adhering to the Si surface, we examined the Si spheres and their surface
morphologies under an optical microscope. The images confirmed the Si fines had melt-
coalesced into droplets much larger than the original particle size of the fines as
evidenced by the spherical shape shown in Figure 16C. The rough surface may be due
to the presence of species such as SiC that precipitated at the interface because these
fines contained ~2 wt% of carbon species. The Si balls did not continue to grow bigger
and had rough features on the surface, which indicates the presence of a surface species
that changed the surface tension of the Si or the salt surrounding it. The asymmetric bump
formations on the Si spheres represent the last fraction of Si to solidify; this is the result
of some degree of directional solidification. The tips of each Si ball correspond to the last
part to solidify.
A B C
Figure 18. (A) cross section of the consolidated materials showing the off-white NaF phase on top of
and underneath the Si balls; (B) the Si balls retrieved after NaF phase was dissolved; (C) higher
optical magnification of the surface of the Si balls. The largest ball was ~1 mm in diameter.
After washing out the NaF and physically removing the large Si balls from the melting
residue, an insoluble gray powder was collected on a filter paper. The XRD pattern of this
powder revealed it contained Si, SiC, and carbon. The diffraction peaks associated with
SiC and carbon were not observed in the XRD pattern of the original kerf fines. The
presence of carbon and SiC in this residue after melt consolidation again confirmed that
the starting Si fine reacted with carbon species to form SiC, which may prevent liquid
silicon from coalescing into a single
Run #2. A mixture of 10 g of the same Si fines and 60 g of NaF was loaded in a melt-
consolidation crucible. We followed the same heating profile as the first run except stayed
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above melting point of Si (1693 K 1420°C) for 40 minutes. The appearances of the
resulting products after melt consolidation were similar to those in the first run but with
larger Si spheres. After mechanically extracting the Si balls and washing the residual NaF
from their surfaces, the Si spheres, shown in Figure 19, were larger than those obtained
in Run #1—the largest balls had diameters of over 2 mm.
Nevertheless, the longer treatment time above the melting point of Si and the higher ratio
of NaF-to-Si in Run #2 still did not result in complete coalescence of Si. Again, SiC was
detected by XRD of the residue, which indicated that a C species was producing SiC and
inhibiting complete Si coalescence.
Consequently, we attempted to eliminate the
carbon species in the Si fines before melt
consolidation as described in the next run.
Run #3. To eliminate the possibility that the
residual organic surfactants used for sawing
and detected in our TGA analysis of these
kerf fines would end up forming SiC on the
surface of Si during the melting, we used the
information obtained from TGA analysis in air
to develop a simple procedure to remove the
C species as CO2 and H2O without significant
Si oxidation. We heated the kerf Si fines in air
to 773 K (500 °C) for 4 hours. The
temperature was designed to be high enough
Figure 19. The Si spheres produced from melt
to burn organics but too low for appreciable consolidation were the result of partial
silicon oxidation. Using this heat treatment, coalescence.
we observed the kerf fines lost ~ 2 wt% of
their weight.
We then mixed 10 g of the heat-treated kerf
Si fines with 60 g of NaF, loaded them in a
graphite crucible, and heated them to 1693 K
(1420°C) for 40 minutes as in previous runs.
After cooling and removing the products, we
observed that the Si fines had completely
coalesced and consolidated into one Si ingot
encrusted with NaF with as shown in
Figure 20. The Si ingots were easily
mechanically detached from the NaF matrix.
The residual NaF adhered to the Si ingots Figure 20. Complete coalescence of a silicon
surfaces was readily dissolved with water. ingot encapsulated inside the NaF phase; the
The surface of the Si ingots seemed clean, phase and ingot were easily separated.
bright, and reflective. The rounded shapes
indicated the pool of Si solidified uniformly and upward with the characteristic Si
protuberance on top (there were segregated impurities in it). A silicon ingot of 7.1 g was
obtained upon consolidation, indicating a Si recovery yield of 71%.
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The ingot was cut vertically, and one half was sent for elemental impurity analysis. Some
impurity levels in the Si ingot as well as in the kerf fines, obtained by GDMS analysis, are
shown in Table 6. The last row contains purification factors, which are the ratios between
the fine and ingot for each element. This result suggests one could not significantly reduce
the As or P dopant levels of heavily doped silicon by melting it in NaF. Nevertheless, it
did give us reliable segregation and purification factors for As and P.
Table 6. Some impurity levels in kerf Si fines (sample 4) and the resulting Si ingot.
Impurity B P Al As Ti Cr Fe Ni Cu
(ppmw)
Kerf Si fines 0.03 70 7.8 1500 9.4 5.1 3.7 18 3.2
Si ingot <0.03 21 0.08 315 0.6 0.2 2.3 6.8 <0.1
Purification >1 3 100 5 >10 25 >1 >2 >30
factor
3.5. Discussion
The experimental results described here clearly demonstrate that it is possible to recover
waste kerf loss Si fines with an oxygen content was 10-15 wt% by melt consolidation in
molten NaF. The recommended process steps include (1) a pre-cleaning step involving
air oxidation and aqueous acid or DI water washing, and (2) heating the mixture of kerf
Si fines with NaF to a temperature slightly above the melting point of silicon (1685 K
(1412◦C)). After cooling, one Si ingot with high purity can be easily retrieved. In this
section, we will discuss the roles of molten NaF and carbon impurity as well as the Si
purification mechanism during the melt consolidation process.
3.5.1. Roles of NaF

The surface energy of molten NaF is <180 ergs/cm2 at 1373 K (1100◦C) [30], while that
of solid silicon is around 900 ergs/cm2 at 1373 K (1100◦C) in Ar, and that of liquid silicon
is 840 ergs/cm2 at 1685K (1412◦C) [31]. When heating a mixture of Si-NaF to 1373 K
(1100◦C) (NaF melts at 1265K (992◦C)), the minimization of energy of the system drives
molten NaF to wet and coat every Si particle. Indeed, when we heated a mixture of Si
fines and NaF (shown in Figure 17A) to 1373 K (1100◦C), we observed experimentally
that the NaF locally encapsulates each Si particle, forming a body that resembles a “sand
castle”, in which Si fine particles were glued to each other by the surface tension of the
NaF (shown in Figure 17B). During this heating process, the surface silica on kerf fines
in contact with molten NaF, would react according to:
3SiO2 (c) + 6 NaF (l) = Na2SiF6 (in NaF) + 2Na2SiO3 (in NaF) (1)
Both products and some more complex fluoro-oxysilicates would be formed, be soluble
in molten NaF and, upon cooling, solidify as glass phases. Progressively heating the
mixture to above the melting point of silicon (1685 K, 1412◦C) culminates with all materials
in the system being molten and separate because molten NaF and Si are immiscible.
Therefore, molten Si droplets sink and run into each other, growing and eventually
coalescing into a single pool driven by minimization of the system energy. When the
droplets with sizes ranging from nm to submicron levels coalesce into a common
centimeter-sized pool, the excess surface Gibbs energy of the system, on the order of
kJ/g-Si, is released to achieve a much lower surface area and surface energy. As silicon
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melts, its density increases to 2.6 g/cc and thus exceeds that of NaF of < 2 g/cc. The
molten silicon pool sinks to the bottom, and the molten NaF phase stays above and
encapsulates the Si pool as illustrated in Figures 13, 15, and 18. This prevents silicon
from reacting with graphite crucible.
Pure molten NaF has a very low viscosity, for example < 1.15 cp at 1473 K (1200◦C) [30],
and such a low viscosity would also facilitate the ease of Si droplet mobility and
coalescence. When the silicon fine is relatively clean, the resulting NaF phase will be
clear white after cooling. Working with these kerf Si fines, the surface silica (> 10 wt%)
reacting with NaF results in the formation of a glass polymeric species, fluoro-oxysilicates,
which can increase the viscosity of the molten salt and reduce the mobility of Si droplets
in it—affecting coalescence of Si. Therefore, one can use a higher loading of NaF (NaF/Si
ratio) to circumvent the effect of glass polymeric species, and we found that a NaF/Si ratio
of 3 was adequate in this case, while much lower ratios (1) can be used with fines
containing less silica.
In summary, the favorable characteristics of molten NaF, including low surface energy,
low viscosity, ability to dissolve SiO2, minimum reactivity with Si, and good heat transfer
media, make it a perfect medium for melt-consolidation of kerf Si fines. In fact, we found
that many alkaline and alkaline earth fluorides could be used in a similar fashion to
consolidate Si fines. Nevertheless, considering all the factors, NaF is the best choice. In
addition, NaF is the cheapest metal fluoride, is commercially available in bulk quantity,
and can be purified and reused simply by dissolution and recrystallization in water.
3.5.2. Effects of the carbon species in the kerf fines

It was a bit surprising that we did not detect any expected crystalline diamond fragments
via XRD in these two industrial kerf Si fines samples. We concluded that either the
fragment level is very low, they became a thin layer of graphite smeared on Si particles
surface, or they were washed away during the decanting and/or filtering prior to drying.
According to our kerf suppliers, organics were added into the Si slurries as surfactant
dispersants and corrosion inhibitors, etc. Therefore, the kerf Si fines cakes recovered
from the waste-cutting slurries are expected to contain carbon species, either as graphite
or organic species.
When these carbon species were not removed before melt consolidation, silicon
coalescence was difficult, as evidenced by formation of many small silicon balls instead
of one big ingot. We believe the presence of SiC on the surface of molten Si prevented
silicon droplets from coalescing. This idea is supported by the identification of a SiC phase
in the XRD pattern of the residual matter in between the silicon balls. We suspect the
carbon species, most likely from pyrolysis of the organic molecules not wetted by molten
NaF, can react with the rain of molten Si droplets to form SiC at high temperature. Only
a small amount of carbon can be dissolved in molten Si (carbon solubility in molten Si is
65 ppm at 1685K [1412◦C]) [32]. As the tiny Si droplets coalesced to grow into larger
droplets, the surface-to-volume ratio decreased, resulting in less relative surface.
Consequently, it is conceivable that molten Si droplets are covered by continuous films
of SiC that prevented them from further coalescence. This explains why more C content
and less time at temperature results in the smaller droplets. Experimentally, we observed
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more pronounced inhibition of Si coalescence when the Si fines contained carbon species
> 0.2 wt%.
Previous efforts by Vazquez-Pufleau et al. [27] demonstrated that carbon elimination from
kerf was feasible using a furnace aerosol reactor. Fortunately, we found these carbon
species in kerf fines started to oxidize at 523 K (250◦C) and were completely burned at
723 K (450◦C) when heated in air. This result is consistent with the presence of species
of K, Na, and Fe in the Si kerf fines (see Table 4), which are well known as catalysts for
oxidation of carbon species [33, 34]. The oxidation can remove not only organic
molecules that may be adhered or trapped in the silica oxide and hydroxide surrounding
the Si, but also most of the C species produced by pyrolysis and small fragments of
diamond from cutting process.
In summary, the presence of C species in the original kerf fine leads to formation of SiC
at high temperature. Our experiments demonstrated that if these C species were not
eliminated before melt consolidation, Si droplets coalescence was hindered, and small Si
balls were obtained. When the carbon species were completely removed in advance, melt
consolidation resulted in Si coalescing into a single pool. The removal of the carbon
species can be easily accomplished by heating the Si kerf in air < 773 K (500◦C) for a few
hours.
3.5.3. Silica on the kerf fines

The kerf Si fines typically contain very high levels of surface silica as evidenced by the
thin white film on the dried cake of the kerf waste. Our LECO analysis confirmed that the
kerf Si fines contained at least 12-14 wt% of surface silica. In comparison, Si fines that
exhibited similar particle size from the FBR process only contained ~ 0.1 wt% of oxygen.
The high level of oxygen in the kerf Si fines is believed to be due to oxidation, which is
experienced locally by each Si particle during the cutting process in an aqueous media.
When heating this type of fine with NaF during melt consolidation, we expect the molten
NaF will dissolve surface silica to form stable silicate (according to equation 1) or
complicated fluorosilicate species, which could result in slightly more viscous molten NaF.
A more viscous molten NaF medium could potentially slow down Si coalescence, which
can be easily alleviated by starting with more NaF. The benefit of this reaction is that it
removes the silica before it can react with core silicon to form SiO vapor.
In theory, surface SiO2 can be removed by a reaction with HF in H2O to produce soluble
fluorosilicic acid according to:
SiO2 (c) + 6 HF (aq) = H2SiF6 (aq) + 2H2O (2)
In addition, once this acid is liberated, it also contributes to the solubility of transition metal
ions as soluble fluosilicates with very high solubilities. Therefore, before melt
consolidation, we also attempted washing the original kerf fine in an aqueous solution of
HF to remove SiO2 and other impurities including transition metal and their oxides or
hydroxides that might be embedded in the surface silica. As illustrated in Table 5, metal
impurities in the fine were indeed significantly reduced upon washing with an aqueous
HF solution. However, the oxygen level of the resulting HF-etched Si fines remained
unchanged. It is likely the newly exposed Si surface (after HF etching) was re-oxidized by
H2O and/or air as the fines were dried. In addition, the Si ingot, which was produced from
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an HF-etched Si fine, exhibited a similarly good purity as the ingot obtained from non-HF
etched Si kerf fines (GDMS data in Tables 4 and 5). Consequently, we think that removing
silica via HF washing prior to melt consolidation may not be necessary but washing the
kerf fine with DI water or dilute acid may be beneficial to produce cleaner Si fines. Melt
consolidation using cleaner Si fines is advantageous to produce high purity silicon ingot.
3.5.4. Impurity migration during the melt consolidation

The other important mechanism in the melt-consolidation process is the identification of
impurity sources and purification paths provided by our process. The main group metal
impurities, such as Ca, K, Na, and Al in the fine are likely originated from the cooling water
used in the cutting process. Therefore, they are likely on the surface of the fines and can
be washed away easily. Indeed, we found that a simple wash of the fine with DI water
could remove most of these impurities. The TMIs such as those of Fe, Cr, and Ni that are
present in kerf loss Si fines presumably originates from the Ni-coated steel wires during
mechanically aggressive cutting. The materials in the saw wires may be smeared on or
attached to the Si particles or simply eroded away. As the slurry of kerf Si fines contains
some oxygen and typically is kept in air for long periods, oxygen activity is significant and
contributes to the oxidation of these metallic species to form their oxidized species. As
the data in Tables 4 and 5 shows, most metallic impurities were significantly removed by
acid washing the kerf loss Si fines. Even without pre-washing, the molten NaF was also
able to remove many impurities, presumably into the NaF phase, as shown in the melt-
consolidation experiments with untreated kerf Si fines. In this section, we will focus on the
purification effect of molten NaF during melt consolidation.
To produce solar-grade silicon feedstock, one needs to use relatively pure NaF for melt
consolidation of kerf Si fines. Dopant (B and P) levels in NaF are particularly important in
preventing contamination of the Si during the melting
process. We used a commercially available NaF that Table 7. Levels of some crucial ®
contains 0.14 ppmw of B, 0.5 ppmw of P, and TMIs at impurities in NaF salt and Grafoil
low ppm levels (as shown in Table 7). This worked well Impurity NaF salt Grafoil®
with our process, but a higher-purity NaF could improve (ppmw) GDMS liner
it further. In addition, we favor use of high-purity B 0.14 0.02
Grafoil®, which contains 0.02 ppmw of B and 0.19 ppm P 0.5 0.19
of P, as a liner material inside a high-purity graphite Fe 3.2 0.15
crucible. The liner materials help with easy retrieval of Cr 0.8 <0.1
the product from graphite crucible. The original kerf Si Co 0.5 <0.05
fines generated by slicing bulk Si crystals contained Ni 0.8 0.01
relatively low levels of dopant elements (< 0.1 ppm), Na Major 0.08
and we reclaimed these fines into Si ingots with less
than 1 ppm of the dopants, i.e., (B 0.03 to 0.1 ppmw and; P 0.15 to 0.7 ppmw) upon melt
consolidation. The slight increase of P in the Si ingot likely came from cross contamination
by the Grafoil®. This will not occur in large-scale melt separations since the Grafoil®-to-
product ratio will be a fraction of that in our lab experiments.
The other kerf fine (sample 4) contained high levels of Group V, N-type dopants, and we
found the As level decreased from 1500 ppm to 315 ppm, and the P level dropped from
70 ppmw to 21 ppmw, shown in Table 6. The mechanism for this purification is not clear.
Thermo-chemical models applied to the elements in Si and simple fluorides in the melt
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indicate that As and P fluorides should dope into Si, as observed in samples with lower
starting level of such dopants. Even if fluorocomplexes such as sodium
hexafluoroarsenate (NaAsF6) or hexafluorophosphate (NaPF6) are considered, at the Si
melting temperature they should mostly decompose to form gaseous PF5 or AsF5. Since
the solubility of As in Si at 1373K (1100◦C) is above 1020 atom/cm3[35], much higher than
300 ppm, we assume the decreasing As level in the Si ingot was a consequence of
unplanned unidirectional solidification.
The results in Table 6 indicate several relevant TMIs such as Ti, Cr, and Mn were purified
by one order of magnitude with respect to the levels in the original Si fines upon melt
consolidation in NaF. The Ni levels only dropped by one third, and Fe levels remained
essentially the same after melt consolidation. Again, possible explanations for the relative
noble metals such as Ni and Cu are not clear, since thermochemically they should end
up in the Si if they presented as metallic forms in the fine. If they were in oxide forms in
the fines, they most probably found added thermochemical stability in the molten salt by
forming complex oxyfluorides. The elevated Na content in the resulting Si ingots (see
Tables 1 & 2) were typically in tens to hundreds of ppmw levels, which probably came
from dissolved Na and entrapped NaF during Si solidification. We demonstrated that the
residual Na can be removed upon a second melting of the Si ingot in vacuum, during
which the residual Na and/or NaF evaporated and thus were removed. Upon this second
melting of the Si followed with a unidirectional solidification, we can produce very high-
purity Si ingot that meets the specifications of solar-grade silicon feedstock.
In summary, significant purifications were achieved for all the elements upon melt
consolidation of the kerf Si fine in molten NaF, suggesting that most of the impurities in
the Si fines end up in the NaF phase. This is important industrially because the resulting
impure NaF can be easily dissolved in water and recrystallized to obtain pure NaF; thus,
the impurities can be removed from the loop, and the recrystallized NaF salt may be
recycled for further melt consolidation.
3.6. Conclusions
We demonstrated that kerf loss Si fines can be recovered in high yield as solar-grade Si
ingots by melt consolidation in molten NaF. The kerf Si fines came from the industrial
process in which diamond wire saws (not SiC slurry) were used to slice Si crystal into
wafers. The general procedure of our methods to converting waste kerf Si fine into high-
purity Si ingot includes: (1) Selective oxidation, which involves heating the fines to ~ 773 K
(500◦C) in air for a few hours to remove organic and carbon residue from the cutting
process; (2) Acid leaching, which consists of washing the Si fines in dilute acid aqueous
solution to remove metal impurities; (3) Melt consolidation, which involves heating the
pre-cleaned Si fines in molten NaF to ~ 1693 K (1420◦C); and (4) Re-melting and
unidirectional solidification. The resulting Si ingot can meet solar-grade Si feedstock
requirements if the original Si fines contain low dopant levels.
4.0 Demonstrating CoSiRC Process with Kerf Loss Si Fines

Upon demonstrating that kerf loss silicon fines from diamond wire slicing process can be
recycled into high-purity silicon ingots using sodium fluoride, we subsequently attempted
the CoSiRC process using the kerf loss Si fines from this program.
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First, the kerf loss Si fines were washed with HF aqueous solution, and then filtered and
dried in a vacuum furnace. The dried fines were then mixed with high-purity NaF powder
(from J.T. Baker) in a 4:1 weight ratio and pelletized into 6-mm tablets (similar to those
shown in Figure 5A) using a manual pelletizer. A total 760 g of this type of pellets was
pressed. The pellets were then stored in a plastic bag before they were loaded into a
hopper attached to the reactor. We followed a similar procedure to that described in
Section 1.1.2 early in this report, a total of ~ 2000 g of Na was added in 18 pulses in
~ 70 minutes; thus, 608 g of Si were expected to be produced from the SiF4-Na reaction.
760 g Si/NaF pellets, corresponding to 608 g of Si kerf fines (though containing >10%
silica), were externally added. The initial heating temperatures of the reactor bottom and
wall were set to 550◦C and 650◦C, respectively. Si fines pellets were co-fed into the
reactor after the reactor wall reached 750◦C due to the reaction heat.
A total 4.55 kg of product and 230 g of loose pellets and powder were collected from the
reactor. Post-reaction analysis of the products showed the pellets were loosely embedded
into the reaction product mass. Distinct shapes of the pellets were still discernible inside
the reaction products, as shown in Figure 21. It also appeared some unreacted Na left
inside the product. We concluded that this CoSiRC run didn’t reach a temperature high
enough to melt NaF product locally, and thus NaF and silicon product appear as fine
brownish powders mixture along with added Si pellets. A higher operating temperature
and better heat management during the CoSiRC process should result in better product.
No melt separation of NaF and Si was attempted using this product.
Figure 21. (a) The cylindrical product retrieved from the reactor after CoSiRC process. (b)
breaking the cylindrical product showed loosely packed Si pellets.
5. Techno-economic Analysis of CoSiRC Process

The goal of DOE’s Solar Energy Technologies Office and SunShot Initiative is to increase
the adaptability of solar energy for power generation by lowering the cost of electricity
generation. Under the CoSiRC program, SRI has proposed to significantly reduce the
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cost of solar-grade silicon by combing the two processes of solar grade silicon production
and silicon fines consolidation and purification. The cost of polysilicon is one of several
factors affecting the costs of a solar power module. The NREL assumes module
manufacturing costs (all-in vertically integrated module production) of $0.63/Wdc (2015
NREL data). If the NREL polysilicon costs are replaced by the SRI polysilicon costs, the
module manufacturing costs are reduced to $0.58/Wdc (2015 basis) i.e., a reduction of
$0.05/Wdc. The NREL cost model SAM is based on $20/kg of blended polysilicon silicon
cost. The CoSiRC process is estimated to produce polysilicon at $8.06/kg.
SRI’s solar-grade silicon process already has one of the lowest energy requirements
among various production processes 1. The estimated energy cost of producing solar-
grade silicon is less than 50 kWh/kg. This process involves reduction of silicon
tetrafluoride gas using sodium metal, which is highly exothermic with -140 kcal/mol of
SiF4. Utilizing the heat generated during the reduction reaction to consolidate silicon fines
further improves the cost economics of the overall process without sacrificing the product
purity; it also improves the product yield, significantly reduces the cost of silicon
production, and thus enables increased deployment of solar energy generation. In
addition, the combined process addresses the silicon fines waste disposal problem.
Silicon fines are generated during wafer cutting, grinding, lapping and other processing
operations in solar cell fabrication processing. These silicon fines are mixed with metal
impurities, cutting media and fluids, oxide layers, etc. and are collected at fabrication
plants and disposed of as waste product. SRI’s combined process not only reduces the
waste-handling and disposal costs, it also helps recover a valuable resource which
improves the economics of the solar cell fabrication operation.
This study reproduces the cost of equipment, raw material and energy inputs to SRI’s
solar-grade silicon production process and adds the costs related to recovering silicon
fines from kerf losses.
5.1 Solar-grade Silicon by the SRI Process

SRI has developed a process for the production of feedstock silicon from which solar-cell
grade material may be generated. “Feedstock silicon” is defined here as material
containing no more than 1 ppm of the critical impurities boron and phosphorus and
metallic contaminations. The principal raw material for this process is sodium fluosilicate,
which is a relatively inexpensive byproduct of wet process phosphoric acid plants and
sodium metal.
The sodium fluosilicate is dried to remove absorbed water, and then decomposed to
silicon tetrafluoride and sodium fluoride by heating at 650°C. Heat
Na2SiF6(s) → SiF4(g)+ 2NaF(s)
650°
1
A. Sanjurjo, K. M. Sancier, R. M. Emerson and S. C. Leach: Proceedings of the Flat-Plate Solar
Array Project Workshop on Low-Cost Polysilicon for Terrestrial Photovoltaic Solar-Cell Applications.
Feb. 1986. pp 325.
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The sodium fluoride can be recycled within the silicon fines purification step and sold for
industrial applications such as process for water fluoridation, hygiene applications or use
as flux in metal industry.
The silicon tetrafluoride is next reduced with sodium metal with adiabatic temperatures of
the reduction reaction in the range 1200 to 1450°C producing molten silicon and sodium
fluoride.
1200-1450°C
SiF4(g) +4Na(l) → Si(l) + 4NaF(l)
Cooling the reaction products partly solidifies the higher melting point silicon (m.p. 1420°C
versus 990°C for the NaF) such that the NaF can be separated by decantation of the
tapping ladle (“melt separation”). Alternatively, if the above reaction is carried out at lower
temperatures, the solid products are intermixed and may be separated by re-melting the
reaction product at 1450⁰C. Molten NaF can be separated, solidified in trays and crushed
and stored or disposed of. The above reactions have all been successfully demonstrated
at a 100-MTY plant.
The silicon waste recovery process has been demonstrated at lab scale individually, and
combined with the reduction process as an integrated approach thus doubling the silicon
production rate. Silicon fines were obtained from a leading solar cell fabrication facility
and pre-processed before adding the same to the silicon reduction step as described
earlier. The co-feeding of silicon fines uses the heat of reaction between silicon tetra
fluoride and sodium metal to melt-consolidate silicon fines and purify the same using the
sodium fluoride, a byproduct of the reduction reaction.
The routes shown in the process flow diagrams (PFDs) 24157-PF-10-001, 24157-PF-20-
001, 24157-PF-40-001, and 24157-PF-50-001 serve as an illustration of ways to obtain
solar-grade silicon from the reduction of silicon tetrafluoride with sodium by the SRI
process and co-feeding pre-purified silicon fines to the reduction reaction. While all major
steps involved in the process are discussed below and are illustrated in the PFDs, some
of the minor steps are omitted for clarity.
The basis of this study is 2,000 metric tons of silicon production per year, where 1000 MT
silicon product is obtained from SiF4-Na reduction process per year and 1000 MT silicon
is recovered from kerf loss fines.
The sodium fluosilicate solids are received and stored on site. Depending on the source
of sodium fluosilicate, it may have to be powdered, pre-treated, and dried. The clean
powder is stored in a day hopper. The fluosilicate solid is decomposed in an externally
fired rotary retort. This retort is heated on its inlet end of the shell and maybe cooled by
water sprays on the discharge end. Rotary valves, before and after the retort, together
with beds of solids in the feed silo and the discharge cooler-conveyor, are intended to
prevent the escape of silicon tetrafluoride gas. Any gas escaping through these barriers
is vented to a caustic scrubber for precipitation as calcium fluoride and silica. The sodium
fluoride solids discharged from the decomposition retort are stored for recycling and
disposal.
Silicon tetrafluoride (SiF4) gas is filtered through a bag filter and then, via a blower, is fed
to the silicon reduction reactor. Molten sodium at 98°C is fed through spray nozzles in the
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reduction reactor roof. SiF4 gas, entering through an annulus around the sodium spray,
reacts instantaneously to give molten sodium fluoride and solid silicon particles.
Kerf loss Si fines, as received from a solar cell fabrication facility, are crushed and washed
with water to remove soluble impurities. Depending on the type and level of impurities in
the silicon waste, the fines are treated with multiple acid washes before final washing and
drying. The fines may be pelletized for ease of handling and feeding in to the reduction
reactor.
When the reaction chamber is about 75% full of product mixture, it is cooled, and
disconnected from coolant and feed lines. After cooling, the reaction product is transferred
to a melt furnace, like an RF furnace to re-melt and separate sodium fluoride from silicon.
Molten sodium fluoride and silicon can be discharged successively from the bottom of the
melt furnace and are allowed to solidify in the cooling trays. The silicon recovered is
cleaned, crushed, and packaged for storage and transport.
5.2 Process Equipment

The major equipment used in the above processing plant is shown in the attached process
flow diagrams and summarized in Table 8.
Table 8. Bare equipment cost for a 2000 MT solar-grade silicon production plant with integrated silicon
waste recovery from kerf losses
MAJOR EQUIPMENT TYPE LUMPED COST

Tanks and hoppers $290,000
Reactors and melt furnaces $2,184,000
Separators $58,000
Compressors and blowers $580,000
Heat exchangers $70,000
Fired heater and scrubber $220,000
Silicon fines pre-purification $1,160,000
Miscellaneous $280,000
Contingency $610,000
Total bare equipment cost $5,450,000
The bare equipment costs in Table 8 were developed based on cost curves for major
equipment from literature and adjusted for size and material of construction based on
process requirements. The silicon waste processing equipment is sized based on lab-
scale experiments that were carried out for pre-purification processing, and co-feeding
into a reduction reactor, as well as the type of the silicon fines received from a major solar
cell fabricator and processor. In addition to the bare equipment, a silicon production
facility will need interconnects, utilities, and facilities. The estimated capital cost for a
Greenfield 2000 MTY integrated silicon production facility for the process described thus
far is $28,000,000 including costs for installing equipment, piping, electrical, structural,
instrumentation etc., engineering, facility costs, and various contingencies. These
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associated costs are calculated, based on literature 2, as fractions of the bare equipment
cost, and are listed below.
Table 9. Other capital expenses calculated as a fraction of bare equipment cost.
OTHER CAPITAL EXPENSES FRACTION OF BARE EQUIPMENT COST

Installation 0.39
Instrumentation/controls 0.26
Piping 0.31
Electrical 0.1
Buildings 0.29
Yard improvements 0.12
Service Facilities 0.55
Engineering/supervision 0.32
Construction 0.34
Legal 0.04
Contractor fee 0.19
Contingency 0.37
Working capital 0.75
5.3 Raw Materials

Various raw material costs including obtaining silicon fines wastes have been estimated from
various industrial sources and from information available from open sources and detailed in
Table 10. Sodium fluoride is produced during the silicon production process and can be sold as
a byproduct.
Table 10. Raw material cost estimate for a 2000 MTY solar-grade silicon production plant with integrated
silicon waste recovery from kerf losses
MATERIAL FLOW RATE (kg/h) UNIT COST ESTIMATE

Sodium fluorosilicate 1015 $0.50/kg
Sodium metal 450.8 $3.00/kg
Hydrofluoric acid 10.02 $1.20/kg
Quick lime 2.5 $0.23/kg
Silicon fines 147.4 $1.00/kg
Sodium fluoride (net production) 1235 -$0.50/kg*
Raw material costs $1,400/hr**
*Estimated rate at which excess sodium fluoride can be disposed of
**Based on 2000 MTY integrated plant
2
M. Peters, K. Timmerhaus, R. West. “Plant Design and Economics for Chemical Engineers, Fifth Edition.”
January 2002.
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5.4 Utilities
The 2000 MTY integrated plant for producing silicon from combined reduction reaction
and silicon fines recovery will be operated for an estimated 8000 hours per year with
utilities summarized in the Table 11 below.
Table 11. Utilities cost estimate for a 2000 MTY solar-grade silicon production plant with integrated silicon
waste recovery from kerf losses
Utility SiF4 Gas Reduction Finishing Fines Unit Cost Estimated

Generation Step Section Processing Cost
Electricity 52.5 68 1923 100.2 $0.07/kWh $150.06/hr
(kW)
Fuel (kcal/h) 847,200 $1.26/GJ $4.47/hr
Cooling water 0.163 0.81 0.076 $0.08/m3 $5.04/hr
(m3/min)
Demineralized 0.34 0.01 0.8 $0.53/m3 $0.61/hr
water
(m3/min)
Refrigeration 25,000 $60.00/GJ $1.26/hr
(kcal/hr) (20% usage)
Waste water 2681 2.68 810 $0.53/MT $1.85/hr
treatment
(MT/hr)
Total utility $163.29/hr
costs
The above utilities can also be considered in terms of kWh. Table 12 below summarizes
the electricity, fuel, and refrigeration usage in kWh/kg Si for the main process and the
fines processing.
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Table 12 Utility usage estimate in kWh/kg Si for a 2000 MTY solar-grade silicon production plant with
integrated silicon waste recovery from kerf losses.
UTILITY TOTAL UNIT

Not including fines processing:
Electricity (kW) 2043.5 kW
Fuel (kW) 984.6 kW
Refrigeration (kW at -40 C) 29.1 kW
3057.2 total kW for electricity, fuel, and refrigeration
24.5 kWh per kg Si for main process (1000 MT/y)
Energetic cost of Na: 4.0 kg Na per kg Si

10.0 kWh per kg Na
40.0 kWh per kg Si for main process (1000 MT/y)
Total for main process 64.5 kWh per kg Si for main process (1000 MT/y)
Fines processing:
Electricity (kW) 100.2 total kW for fines processing
Total for fines processing 0.8 kWh per kg Si for fines processing (1000
MT/y)
Combined process: 32.6 kWh per kg Si for combined process (2000

MT/y)
5.5 Determining Levelized Cost of Energy (LCOE)

Based on the above plant design description, the total energy input for producing silicon
in the integrated plant is estimated at 33 kWh/kg of silicon. The production rate of silicon
in this analysis is 2000 MTY, including the integrated silicon waste recovery from kerf
losses.
Materials, utilities, and equipment costs each contribute to the cost of the silicon product.
Equipment costs can be converted to a per-kg Si basis by using the Equivalent
Annualized Cost (EAC) method, with an annual interest rate r of 5% and time period t of
10 years.
1
𝑁𝑁𝑁𝑁𝑁𝑁 1−
(1 + 𝑟𝑟)𝑡𝑡
𝐸𝐸𝐸𝐸𝐸𝐸 = 𝑤𝑤ℎ𝑒𝑒𝑒𝑒𝑒𝑒 𝐴𝐴𝑡𝑡,𝑟𝑟 =
𝐴𝐴𝑡𝑡,𝑟𝑟 𝑟𝑟
Using the above formula for equipment costs, the material and utility costs from Tables 10
and 11, and a silicon production rate of 2000 MT/year, the total cost of silicon produced
with the SRI process is reported in Table 13.
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Table 13. Total cost of silicon production in a 2000 MTY solar-grade silicon production plant with
integrated silicon waste recovery from kerf losses.
COST COMPONENT $/KG SI PRODUCED

Capital Costs $1.78
Material Costs $5.63
Utility Costs $0.66
Total $8.06
To convert the production cost of $8.06/kg Si to $/Wdc, it is assumed, based on NREL

documentation, 3 that the approximate net silicon utilization, including kerf and wafer yield
losses, is 4.5 g/Wdc at η = 18%. Using this assumption, the cost of polysilicon produced
with the SRI process is $0.036/Wdc.
The cost of SRI polysilicon compares favorably with the NREL data outlined below for
silicon wafer production in 2015:
• 180-um silicon wafers with surface area 243 cm2 per wafer
• Approximate net silicon utilization including kerf and wafer yield losses 4.5 g/Wdc
at η = 18%
• $20/kg blended polysilicon price
• $0.50/wafer
• Results in $0.09/Wdc for polysilicon
The cost of polysilicon is one of several factors affecting the costs of a solar power
module. The NREL assumes module manufacturing costs (all-in vertically integrated
module production) of $0.63/Wdc (2015 NREL data). If the NREL polysilicon costs are
replaced by the SRI polysilicon costs, the module manufacturing costs are reduced to
$0.58/Wdc (2015).
The SAM4 tool developed by the NREL estimates the cost of energy and predicts the
performance of grid-connected power projects. It allows for numerous system design
inputs to be specified by the user. The Detailed Photovoltaic model type considers the
type of solar module and inverter, the location of the installation, the module lifetime,
losses and battery storage, system costs, and financial parameters including incentives
and depreciation. The NREL references used for comparison in this document used the
SAM to calculate the LCOE of various solar power configurations. Selected baseline
assumptions for system costs are shown in Jones-Albertus et al. 5
3
M. Woodhouse, R. Fu, T. Remo, K. Horowitz, D. Feldman, D. Chung, B. Gallagher, and R. Margolis.
“Economic Factors of Production Affecting Crystalline Silicon Photovoltaics Manufacturing Costs,” In Preparation.
4
https://sam.nrel.gov/
5
R. Jones-Albertus, D. Feldman, R. Fu, K. Horowitz, M. Woodhouse. “Technology advances needed for
photovoltaics to achieve widespread grid price parity.” Prog. Photovolt: Res. Appl. 2016
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Using the same assumptions and SAM inputs as the NREL case studies but replacing
the module cost with the lower module costs using silicon produced by the SRI process,
the LCOE of solar projects using SRI silicon is reported in Table 14.
Table 14. The LCOE of solar projects using SRI silicon.
Silicon Study Type 2015 2015 2015

Commercial Residential Utility
Baseline Baseline Baseline
NREL assumed Real 2015 LCOE (cents/kWh) in 10.6 14.5 8.0
Daggett, CA (best-case location
SRI Real 2015 LCOE (cents/kWh) in 10.14 14.01 7.66
Daggett, CA (best-case location)
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IV. Conclusions
SRI’s CoSiRC process achieved the following:
• Increased silicon yield by 2 times using FBR fines

• Obtained 34% Si from kerf loss (DWS) in an 880 g batch of produced Si
• Recovered silicon from FBR, crushed Si, and DWS, and met solar-grade purity
The SRI team achieved the following:
• Completed first supply chain analysis and contact with industrial partner
• Prepared preliminary CoSiRC Process Flow Diagrams
• Successfully processed up to 20% SiO2 on Si fines
• Prepared a techno-economic analysis showing a cost of silicon <$10/kg
V. Budget and Schedule

Table 15. Budget Summary
Federal Share Recipient Share Total Project Cost

$900,000 $100,000 $1,000,000
Federal Share Spent Recipient Share Spent Total Spent Deviations from Spend Plan
Because of the promise shown
by CoSiRC technology, SP&L,
SRI’s partner in this project,
over contributed cost-share on
$900,000 $139,738 $1,039,738 commercialization efforts.
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I. Major Task/Milestone Schedule

SOPO Milestone Completion Date
Task Start
Task # Task Title and Milestone Description Performer Original Revised Percent Progress Notes
Date Actual
M.S. # Planned Planned Complete
T1.1 Laboratory process development of integrating reduction and consolidation processes
T1.1.1 Determine pretreatment steps needed to purify Si fines
Demonstrate silicon consolidation with
M1.1.1 SRI 10/1/2016 12/31/2016 12/31/2016 100%
lab scale reactor
T1.1.2 Batch parametric study
10g batch, >10% fines, <1ppma B and
M1.1.2 SRI 10/1/2016 3/31/2017 12/31/2016 100%
P, <10ppma TM
T1.1.3 Rheology of flux agent
Specs on Oxygen content for recycled Oxide content up to 20%
M1.1.3 SRI 4/1/2017 9/30/2017 9/30/2017 100%
Si feedstock is usable
M1.2 Prelinimary TEA SRI/SP&L 10/1/2016 6/30/2017 9/30/2017 100%
T1.3 Manufacturing systems development
Preliminary conceptual commercial
M1.3 SRI/SP&L 2/1/2017 9/30/2017 9/30/2107 100%
design for equipment completed
M1.4 Supply chain analysis is completed SRI/SP&L 1/1/2017 3/31/2017 3/31/2017 100%
T1.5 Project Management
M1.5 Subcontracts executed SRI 10/1/2016 3/31/2017 12/31/2016 100%
Purity specfications met
100g Si with >25% Kerf loss Si, with
M BP1 SRI 10/1/2016 9/30/2017 9/30/2017 100% with consolidated kerf
purity and cost targets
silicon
T2.1 Laboratory process development of integrating reduction and consolidation processes (continued)
T2.1.1 Determine pretreatment steps needed to purify Si fines (continued)
Simulated CoSiRC
100g Si with>25% Kerf loss Si, SEMI
M2.1.1 SRI 10/1/2017 12/31/2017 12/31/2017 100% reaction 1kg product,
purity standard
50% Kerf
T2.1.2 Lab-scale testing of key engineering units of bench-scale prototype
Design of key engineering units of bench 3/31/2018
M2.1.2 SRI 10/1/2017 3/31/2018 100%
scale prototype complete
Construction of test of bench-scale
T2.1.3 SRI 2/1/2018 3/31/2018 100%
prototype
TEA published, path to $0.04/Wdc
M2.2 SRI/SP&L 10/1/2017 9/30/2018 9/30/2018 100% Submitted
reduction in poly-Si price
T2.3 Manufacturing system development
Conceptual commercial equipment
M2.3 SRI/SP&L 10/1/2017 9/30/2018 9/30/2018 100%
design
Pilot scale demonstartion
M2.4 Technology Transfer negitiations initiated SRI/SP&L 10/1/2017 6/30/2018 9/30/2018
required
T2.5 Project management SRI 10/1/2017 9/30/2018 100%
Bench-scale, 1kg Si >50% fines, MOU
M BP2 SRI 10/1/2017 9/30/2018 9/30/2018 100%
for scale-up to pilot-scale
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VI. Path Forward

The CoSiRC technology has the potential to reduce the cost of solar-grade silicon by
combining solar-grade silicon production and silicon fines recovery, consolidation, and
purification. The DOE’s Solar Energy Technologies Office and SunShot Initiative have a
mandate to increase the adaptability of solar energy for power generation by lowering the
cost of electricity generation.
The cost of polysilicon is one of several factors affecting the expense of a solar power
module. Based on 2015 NREL data, if we assume module manufacturing costs (all-in
vertically integrated module production) of $0.63/Wdc and a reduction of $0.05/Wdc by
using the CoSiRC process, there is an 8% cost reduction. However, if we use the current
market data, and a module can be purchased in the range of $0.37/Wdc to $0.52/Wdc (or
an approximate average cost of $0.445/Wdc), the cost reduction would ~ 11% if the NREL
polysilicon costs are replaced by the SRI CoSiRC polysilicon costs.
Furthermore, the NREL cost model SAM is based on a $20/kg of blended polysilicon
silicon cost. The CoSiRC process is estimated to produce polysilicon at $8.06/kg, a 60%
cost reduction. And even if we consider more current market pricing of about 15-16/kg,
the CoSiRC process offers the potential to reduce Si material costs by 50%.
Therefore, the CoSiRC process offers the potential to significantly reduce the amount of
waste Si kerf that currently goes to landfills while at the same time lowering the cost of
manufacturing solar-grade silicon by 50-60%. While the current R&D project has shown
feasibility on the lab scale as well as at a limited industrial scale, we believe there are
three major steps to the path forward:
• Complete technology scale-up

• Improve purity levels
• Conduct a pilot-plant demonstration
These steps are based on the collective input from the industrial partners and participants
during the past two years. The project participants who were involved in providing
industrial samples, sample analysis, market study, and economic analysis for the CoSiRC
project have concluded that the technology has merits; however, it needs to be further
developed at a pilot-plant level to show the industrial merits and economic feasibility.
Therefore, further investment is required to complete the technology scale-up and
achieve greater levels of purity in the consolidated ingots—both of these steps should
preferably be done in a pilot-plant setting to simulate industrial-scale equipment and
volumes. Once these steps are achieved, we believe that private investors would step
forward to commercialize the CoSiRC technology.
Market Trend and Industrial Input

The market trend is toward greater module performance and output. Therefore, higher
purity levels and thinner wafers are the industry requirements going forward. This is a
great opportunity for CoSiRC technology because there will be growing volumes of waste
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silicon and kerf fines. The challenge will be to recover these efficiently and process them
cost effectively back to higher-purity ingots.
Going forward, CoSiRC must continue to lower costs, from ~$8/kg to $5-6/kg, while
improving purity levels and achieving both at higher volume levels (going from kilograms
to tons). Based on the limited scale-up work conducted under this project, we believe this
is possible through further work with industrial-scale processing equipment and
appropriately designed large- sized Si processing furnaces.
Further investment by the DOE and/or early/seed investors and industrial partners is
required to achieve the objectives outlined above. The partnership with industry is critical
now that the technology has been developed. A “market-pull” is required from industrial
team members for scale-up and deployment of technology.
Yet another challenge that the team discovered when reaching out to solar companies
and manufacturers is that they are NOT doing the wafer processing or the slicing and
dicing of the silicon ingots in the US. The industry input was that majority if not all of the
wafer-processing work has been outsourced to partners or affiliate operations and
companies in Asia; many US Si processing operations have been shut down or eliminated
during the past several years.
Therefore the commercialization challenges for CoSiRC technology include deployment
in Asia, which is not desirable for US manufacturing standpoint. The next best option
would be to deploy in new plants in the US that plan to build a fully integrated facility,
including the processing of Si ingots into wafers. In this way, the waste generated from
such wafering operations can be recovered, recycled, refined, and put back into the ingot
melting operations or used to produce ingots of solar-grade Si. At present, such ingots
may be on the low side of the purity scale; however, these wafers may be acceptable for
export or for certain customers in the US that require lower module performance levels.
The CoSiRC technology is ready for scale-up and further industrial development. This will
advance the technology, whether as an “Si-recycling furnace” or a “pilot plant to produce
solar-grade Si ingots from waste fines”. Once high-risk funding is obtained and the
process is demonstrated at scale, there will be customers and commercialization partners
to bring the technology to the market.
VII. Publications Resulting from this Work

METHOD FOR CONTINUOUS PRODUCTION AND CONSOLIDATION OF SI FINES
FOR SOLAR GRADE SILICON PRODUCTION, filed September 1, 2017, and assigned
Serial Number 62/553,160.
EFFICIENT SOLAR GRADE SILICON PRODUCTION SYSTEM, filed August 31, 2018
and assigned Serial Number 16/119,918.
X. Xie, M. Hornbostel, A. Nagar, and A. Sanjurjo: “Production of Solar-Grade Silicon:
Recovery of Si Fines from FBR in the SiF4-Na Reaction” 2018, manuscript submitted to
Metallurgical and Materials Transactions B.
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VIII. References
1. “Global Market Outlook for Solar Power 2017-2021” from Solar Power Europe,
Nov 2017.
2. GTM Research Spotlight: “Global Solar PV Installations to Surpass 104 GW in
2018” https://www.greentechmedia.com/articles/read/global-solar-pv-
installations-to-surpass-104-gw-in-2018#gs.TL5a1ig.
3. Association of China PV Industry Chinese PV Industry Road Map, 2016
http://mp.weixin.qq.com/s/Kw3EfsiJoz9_vRN_KjHFzg
4. A. Sanjurjo, K. M. Sancier, R. M. Emerson, and S. C. Leach: Proceedings of the
Flat-Plate Solar Array Project Workshop on Low-Cost Polysilicon for Terrestrial
Photovoltaic Solar-Cell Applications. Feb. 1986, pp. 325.
5. X. Xie, J. Bao, and A. Sanjurjo: Metallurgical and Materials Trans, E; 2016, Vol
3E, (4), pp. 299-307.
6. X. Xie, J. Bao, and A. Sanjurjo: Photovoltaic Specialists Conference (PVSC),
2016 IEEE 43rd, pp. 737-42
7. X. Xie, K. Lau, and A. Sanjurjo: Photovoltaic Specialists Conference (PVSC),
2016 IEEE 43rd, pp. 698-703.
8. X. Xie, K. Gu, D. Xu, D. Shen, B. Zhang, and Y. Xie: in Proceedings of the 12th
China Photovoltaic Conference and International Photovoltaic Exhibition, Beijing,
China September 5-7, 2012
9. Wang HY, Tan Y, Li JY, Li YQ, Dong W. “Removal of silicon carbide from kerf
loss slurry by Al–Si alloying process” Sep. Purif. Technol 2012; Vol 89, pp. 91–3.
10. Tomono K, Okamura Y, Furuya H, Satoh M, Miyamoto S, Komatsu R, et al.
“Selective hydrobromination of metallurgical-grade silicon in a flow reactor
system” J. Mater. Sci. 2012, Vol 47, pp. 3227–32.
11. Tomono K, Furuya H, Miyamoto S, Okamura Y, Sumimoto M, Sakata Y, et al.
“Investigations on hydrobromination of silicon in the presence of silicon carbide
abrasives as a purification route of kerf loss waste” Sep. Purif. Technol. 2013,
Vol 103, pp.109–13.
12. Yoko A, Oshima Y. “Recovery of silicon from silicon sludge using supercritical
water” J Supercritical Fluids 2013, Vol 75, pp. 1–5.
13. Tsai TH. “Silicon sawing waste treatment by electrophoresis and gravitational
settling” J Hazard Mater 2011, Vol 189, pp. 526–30.
14. Wu YF, Chen YM. “Separation of silicon and silicon carbide using an electrical
field” Sep. Purif. Technol. 2009, Vol 68, pp. 70–4.
15. Lin YC, Tai CY. “Recovery of silicon powder from kerfs loss slurry using phase-
transfer separation method” Sep. Purif. Technol. 2010, Vol. 74, pp.170–7.
16. Lin YC, Wang TY, Lan CW, Tai CY. “Recovery of silicon powder from kerf loss
slurry by centrifugation” Powder Technol 2010, Vol. 200, pp. 216–23.
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17. Wang TY, Lin YC, Tai CY, Fei CC, Tseng MY, Lan CW. “Recovery of silicon from
kerf loss slurry waste for photovoltaic applications” Prog. Photovolt. Res. Appl.
2009, Vol 17, pp. 155–63.
18. Wang TY, Lin YC, Tai CY, Sivakumar R, Rai DK, Lan CW. “A novel approach for
recycling of kerf loss silicon from cutting slurry waste for solar cell applications” J.
Crystal Growth 2008, Vol 310, pp. 3403–6.
19. A. Sanjurjo, K. Lau, X. Xie, L. Moro, J. Mariano, G. Krishnan, M. Hornbostel, and
A. Nagar: US Pat 8,475,540 B2 July 2, 2013.
20. J.O. McCaldin, M.J. Little, A.E. Widmer, J. Phys. Chem. Solids 1965, Vol. 26, pp.
1119-23.
21. Z. Zhou, S. Mukherjee, and W.-K. Rhim: J. Cryst. Growth 2003, vol. 257, pp. 350.
22. M. J. Assael, I. J. Armyra, J. Brillo, S. V. Stankus, J. Wu, and W. A. Wakeham.
Phys. Chem. Ref. Data, 2012, vol. 41, 03310.
23. G.J Janz, C.B. Allen, N.P. Bansal, R.M. Murphy, and R.P.T. Tomkins: Physical
Properties Data Compilations Relevant to Energy Storage. II Molten Salts: Data
on Single and Multi-Component Salt Systems. US Department of Commerce,
National Bureau of Standards, April, 1979.
24. M. Li, Y. Dai, W. Ma, B. Yang, and Q. Chu: 2017 IOP Conf. Ser.: Earth Environ.
Sci. 94, 012016.
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26. A. Sanjurjo: US Pat 4590043A. May 20, 1986.
27. M. Vazquez-Pufleau, T. S. Chadha, G. Yablonsky, H. F. Erk, and P. Biswas: Ind.
Eng. Chem. Res., 2015, 54 (22), pp. 5914-20.
28. H. An, and P. J. McGinn: Appl. Catal. B, 2006, 62, pp. 46-56.
29. Z. Zhang, Y. Zhang, Z. Wang, and X. Gao: J. Catal. 2010, 271, pp. 12-21.
30. G.J. Janz, C.B. Allen, N.P. Bansal, R.M. Murphy, and R.P.T. Tomkins: Physical
Properties Data Compilations Relevant to Energy Storage. II Molten Salts: Data
on Single and Multi-Component Salt Systems. US Department of Commerce,
National Bureau of Standards, April. 1979.
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77-83.
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35. V.E. Borisenko and S.G. Yudin: Phys. Status Solidi, A 1987, 101(1), pp. 123-7.
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IX. Si Process Drawings
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Produccion Silicon Grade Solar

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DE-EE0007550

Continuous Silicon Consolidation and Reduction

Final Technical Report: DOE-SRI0007550-1

Project Title: Continuous Silicon Consolidation and Reduction

Acknowledgment: This material is based upon work supported by the

Disclaimer: This report was prepared as an account of work sponsored by

III. Project Results and Discussion 8

V. Budget and Schedule 48

VI. Path Forward 50

VII. Publications Resulting from this Work 51

IX. Si Process Drawings 54

Program Goal and Objectives

Technical Scope Summary

I. Major Task/Milestone Schedule

III. Project Results and Discussion

1. Demonstrating CoSiRC process with FBR Si Fines

1.1 Materials and Methods

1.1.1. FBR silicon fines

according to glow discharge mass

1.1.2. Co-feeding Si fines to the SiF4–Na reaction

1.1.3 Separation of Si from NaF

(1420°C) in a high-temperature furnace under flowing argon gas. We used a gas-tight

1.2.1. Co-feeding Si fines to the SiF4–Na reaction

1.2.2. Melt separation of Si from NaF

1.2.3. Purity of melt-separated silicon

Impurity Levels (ppmw)

2.0 Pre-purification of Various Silicon Fines

2.1 Characterization of Crushed Silicon Fines

Bulk Impurity Specification

• Donor: ≤ 15.0 ppba

• Carbon: ≤ 5.0 ppma

2.2 Purification of Crushed Silicon Fines

Original Approx. HCl HCl-HNO3 HF-HCl HF-HCl-HNO3

2.3 Characterization of Kerf Loss Silicon Fines

2.3.1. Physical appearance

2.3.2. XRD pattern of the Si fines

Si (220) Kerf Si fines as received

* White powder on Kerf Si cakes

2.3.3. Thermogravimetric analysis of the Si fines

weight loss of 0.1 wt%

2.3.4. Kerf loss slurry

2.4 Purification of Kerf Loss Silicon Fines

2.4.1. Acid washing of the kerf fines

2.4.2. Selective oxidation of the kerf fines

3. Melt Consolidation of Various Silicon Fines with NaF

3.1 Melt Consolidation of Kerf Si Fines (Sample 3), Without Pre-washing

it was surrounded/encapsulated underneath and laterally by a layer of NaF (100 microns

3.3. Large-scale Melt Consolidation Kerf Si Fines (Sample 3)

3.3.2. Selective oxidation

3.3.3. Larger-scale melt separation

3.4. Melt Consolidation of Another Kerf Si Fine (Sample 4)

3.5.1. Roles of NaF

3.5.2. Effects of the carbon species in the kerf fines

3.5.3. Silica on the kerf fines

3.5.4. Impurity migration during the melt consolidation

4.0 Demonstrating CoSiRC Process with Kerf Loss Si Fines

5. Techno-economic Analysis of CoSiRC Process

5.1 Solar-grade Silicon by the SRI Process

5.2 Process Equipment

MAJOR EQUIPMENT TYPE LUMPED COST

OTHER CAPITAL EXPENSES FRACTION OF BARE EQUIPMENT COST

5.3 Raw Materials