Silicon (2012) 4:121–125
DOI 10.1007/s12633-011-9105-8
ORIGINAL PAPER
Low-Temperature Purification of Silicon by Dissolution
and Solution Growth in Sodium Solvent
Haruhiko Morito & Taiki Karahashi &
Masahito Uchikoshi & Minoru Isshiki & Hisanori Yamane
Received: 9 August 2011 / Accepted: 29 November 2011 / Published online: 1 March 2012
# Springer Science+Business Media B.V. 2011
Abstract Efficient low-cost processes for solar-grade Si
production are needed to overcome the deficiency in the
supply of Si. We have demonstrated a new method for the
purification of Si crystal. Low-purity Si powder was dissolved
in a Na melt (solvent), and Si grains were crystallized by Na
evaporation from the Na-Si solution at 1173 K. Glow
discharge mass spectrometry analysis revealed that the
concentrations of impurity elements, except Na and B,
were decreased in the crystallized Si grain. In particular,
the concentration of Fe which was mainly included in the Si
powder decreased from 3200 ppm by mass to 1.5 ppm by
mass in a refined Si grain. Iron disilicide was crystallized from
the solution before the crystallization of Si. It was suggested
that impurities were reduced not only by crystallization from
the Na-Si melt but also by the dissolution of Si into the melt.
Na contaminating the refined Si grain was eliminated down to
0.055 mass ppm by heating at 1723 K under vacuum.
Keywords Silicon . Sodium . Purification . Solution growth
1 Introduction
The recent demand for Si for use in solar batteries has greatly
expanded and surpassed the supply of Si from the semicon-
ductor industries. Semiconductor-grade Si (purity: 11 N) has
been produced by trichlorosilane (SiHCl3) distillation followed
H. Morito (*) : T. Karahashi : M. Uchikoshi : M. Isshiki :
H. Yamane
Institute of Multidisciplinary Research for Advanced Materials,
Tohoku University,
2-1-1 Katahira, Aoba-ku,
Sendai 980-8577, Japan
e-mail: morito@tagen.tohoku.ac.jp
by hydrogen reduction of SiHCl3 at high temperature [1], i.e.
the Siemens method. In addition to this method, some
other chemical methods have been investigated; the zinc re-
duction method, the fluidized bed reactor method and the tube
furnace method [1]. These are relatively high-cost processes
because large amounts of electrical energy are consumed and
the production yield is not enough. Alternative and efficient
low-cost processes for the solar-grade Si (6–7 N) production
are needed to overcome the deficiency in the Si supply.
The solidification method has been studied for the puri-
fication of Si [1, 2]. This is a representative metallurgical
refining method based on the difference between impurity-
element solubilities in the solid phase and the melt phase of
Si. In a Cu-Si alloying method [3], Si was alloyed with Cu
to trap impurities and the purified Si was recovered by
grinding and gravity separation [3]. A low-temperature pu-
rification method using an aluminum melt (melting point of
Al, 933 K) has been studied [4]. In this work, the impurities
of Si were efficiently removed because the solubilities of
impurities in the Si crystals decrease with decreasing temper-
ature [5]. However, after crystallization of Si from a Si-Al
solution, Al should be dissolved in an acid solution in order to
separate the Si, and about 500–600 ppm by mass of Al is
included in the Si crystals [4].
Recently, Morito et al. proposed a Na-Si binary phase
diagram showing that Si dissolves into a Na melt by about
55 at% at 1173 K [6]. Poly- and single-crystalline Si were
prepared by vaporizing Na from Na-Si solutions at 1073–
1173 K [6, 7]. The Na solvent can be removed completely
by evaporation due to the high vapor pressure of Na at a
high temperature. In the present study, the concentrations
of impurity elements were reduced by dissolving low
purity Si into the Na melt and by crystallizing Si from
the solution.
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2 Experimental
Lumps of Si 10–30 mm in size (Hiranoseizaemonsyouten,
99% purity) and pieces of Na (Nippon Soda, 99.95% purity)
were used as starting sources. The impurity concentrations of
the Si lumps as listed by the supplier are Fe : 0.176%, Al :
0.071%, and Ca : 0.011%. However, the actual concentrations
of the impurities in the lumps varied. In order to obtain
uniform impurity concentrations, the Si lumps were crushed
into a powder with a particle size <75 μm in an iron mortar
with a pestle. The Si powder obtained was used for the
refining experiment.
In an Ar gas-filled glove box (O2 and H2O<1 ppm by
mass), the Si powder (0.5 g) and Na pieces (0.6 g) were
weighed at a Si composition of 40 mol%, and charged in a
boron nitride (BN) crucible (Showa Denko; 99.95%; 16 mm
inner diameter; 13 mm depth). As shown in Fig. 1, the crucible
containing Si and Na and another crucible containing 2.0 g of
Si powder were set at upper and lower positions in a stainless
steel container (SUS 316, 35 mm inner diameter; 40 mm
depth), respectively. The container was sealed by welding a
stainless steel cap, and set in an electric furnace with two
heating zones. The temperatures of the top and bottom parts
of the container and the difference between the temperatures
were defined as Ttop, Tbottom, and ΔT0Ttop–Tbottom, respec-
tively. The Ttop and Tbottom were set at 1173 K (ΔT00) for 1 h,
and then Tbottom was decreased to 1123 K (ΔT050) in 30 min.
The temperatures of Ttop 01173 K and Tbottom 01123 K were
then maintained for 64 h. After heating, the container was
cooled to room temperature in the furnace, and then cut open
in the glove box. The sample obtained in the upper crucible
was washed with ethanol and distilled water in air.
X-ray diffraction (XRD) patterns of the samples were
measured on an X-ray diffractometer (Rigaku RINT2200)
with CuKα radiation. Elemental analysis was carried out
Fig. 1 Schematic illustration of the experimental setup
Silicon (2012) 4:121–125
with an energy-dispersive X-ray (EDX) analyzer (EDAX,
New XL-30) attached to a scanning electron microscope
(SEM, Philips, ESEM XL-30).
The impurities in the raw Si powder and refined Si
grains were analyzed by glow discharge mass spectrometry
(GD-MS, VG Elemental Co., VG-9000). The amounts of
the impurities are shown in ppm by mass (hereafter ppm).
The samples for the GD-MS analysis were fixed on a high
purity indium disk (JX Nippon Mining & Metals Corporation,
7 N). Analysis of the refined Si grains was carried out at the
surface of the as-prepared grain (surface) and at the surface
obtained by grinding about 2 mm off the surface of the grain
(inside).
3 Results and Discussion
Figure 2 shows a photograph of the sample obtained by
heating at Ttop 01173 K and Tbottom 01123 for 64 h in the
upper crucible (a) with a schematic of the cross-sectional
view of the sample in the crucible (b). No Na was observed
in the upper crucible. In this experiment, we set a long
heating time of 64 h to make sure of the removal of Na
from the product, but such a long heating time is probably
not needed. A few grains of Si, about 5 mm in size, were
crystallized in the crucible. These dense, massive Si grains
had metallic luster and crystal facets. Some parts of the
upper surface were covered with dark brown precipitates.
Growth steps of Si were observed by SEM on the metallic
parts exhibiting luster (Fig. 2(c)). On the undersurface of the
grains facing the bottom of the crucible, aggregates of
precipitates and rectangular crystals, with a size of a
few micrometers, were observed (Fig. 2(d)). In addition
to the characteristic X-ray peak of Si, the peaks of Na, Al, Fe,
Ca, Ti, and Cr were shown in the EDX spectrum from the
precipitates (Fig. 3). The chemical composition of the rectan-
gular crystals was determined to be FeSi2 by EDX analysis.
Si, Na, Al, Fe, Ca, Ti, and Cr were also detected from
dark brown deposits or precipitates observed on the bottom
of the crucible by EDX analysis (Fig. 2(a)). Figure 4 shows
the X-ray diffraction pattern of the deposits. In addition to
the reflections from Si and BN scraped off the bottom of the
crucible, the reflections of FeSi2 and CrSi2 were identified.
Small peaks could be explained by SiC.
The results of the GD-MS analysis for the raw Si
powder and for the surface and inside of a refined Si
grain are shown in Table 1. The concentration of Fe
(3200 ppm), which was highest among those of the im-
purities in the raw Si powder, decreased to 170 ppm at the
top surface of the refined Si grain and to 1.5 ppm inside
the grain. In the refined Si grain, the concentrations of most
impurity elements were decreased from those in the raw Si
powder as follows; Al: 510→6.0 ppm, Ca: 96→1.7 ppm,
Silicon (2012) 4:121–125
Fig. 2 a Photograph of the
sample prepared in the upper BN
crucible, b schematic of the
sample cross section, scanning
electron micrographs taken of c
the top surface and d the lower
surface of the Si grain
Ti: 170 → 0.016 ppm, Cr: 520 → 1.6 ppm, Mn: 260 →
0.49 ppm, and Ni: 61→0.18 ppm.
Removal of P by solidification of Si from the Si melt is
unattainable due to the high segregation coefficient of P
(0.35) between the solid phase and melt phase of silicon
[5]. Yoshikawa and Morita demonstrated that P was effi-
ciently removed to 0.72 ppm from Si by solidification of Si
from a Si-Al solution at around 1323 K [4]. In the present
study, P was also decreased from 73 ppm in the raw Si
powder to 3.4 ppm in the refined Si grain.
According to Newman and Wakefield, the solubility of C
in solid silicon is 3×1018 atoms/cm3 (about 30 ppm) at
1675 K [8]. The C solubility should be much lower at
Fig. 3 EDX spectrum of the precipitates observed on the lower surface
of the Si grain shown in Fig. 2 (d)
123
1173 K, and most carbon contained in the refined Si grain
(70 ppm) presumably exists as inclusions.
The Si purification process proposed in the present study
is schematically presented in Fig. 5. According to the Na-Si
binary phase diagram [6], the composition of the liquidus
line at 1173 K is estimated to be at a molar ratio Na:Si04:6.
Thus, all of the Si powder in the upper crucible was
dissolved in the Na melt and formed a solution with a
composition of 40 mol% Si. As described above, the pre-
cipitates of impurities were observed between the Si grains
and on the bottom of the crucible. This suggests that some
amounts of impurities could not be dissolved into the Na
melt during the dissolution of Si (selective dissolution). The
Fig. 4 XRD pattern of the deposit scraped off the bottom of the BN
crucible
124 Silicon (2012) 4:121–125

Table 1 Results of GDMS analysis for the Si powder and the Si grain must be greater than the density of the Na-Si melt (the
Element Impurity concentration (mass ppm) density of solid NaSi is 1.74 Mg/m3).
According to the liquidus line of the Na-Si binary phase
Raw Si powder Refined Si grain diagram [6], the crystallization of Si began in addition to the
precipitation of impurities when the Na composition in the
Surface Inside
melt decreased to 40 mol% or lower by Na evaporation. The
Li 0.22 0.036 0.012 polycrystalline Si crusts observed around the Si grains were
B 9.1 490 120 formed at the last stage. The evaporation rate of Na at this
C 330 8700 70 stage was presumably faster than that before this stage due
O 2300 9800 150 to the small volume of the melt and the increase of the
Na 2.6 480 85 specific surface area.
Mg 12 12 0.13 Since the melting point of the ternary compound NaAlSi
Al 510 2400 6.0
is at around 1150 K, the Na-Al-Si melt coexists with the Na-
P 73 34 3.4
Si melt at 1173 K. Si and Al can also be crystallized by
Ca 96 82 1.7
evaporation of Na from the Na-Al-Si melt. The concentra-
tion of Al at the refined Si grain surface was higher than that
Sc 0.35 1.1 0.001
in the raw Si powder, suggesting that the Na-Al-Si melt
Ti 170 2.3 0.016
remains until the Na evaporates completely.
V 7.9 0.24 0.005
The concentration of B which affects electric properties of
Cr 520 31 1.6
Si was 120 ppm in the refined Si grain, higher than that in the
Mn 260 44 0.49
raw Si powder (9.1 ppm). This was presumably introduced
Fe 3200 170 1.5
into the melt from the BN crucible during heating of the
Co 1.7 0.11 0.002
sample. It would be possible to avoid B contamination by
Ni 61 7.6 0.18
using a crucible made of other materials, e.g. SiC.
The concentration of Na was increased from 2.6 ppm in
crystallization of transition metal silicides, such as FeSi2 and the raw Si powder to 85 ppm in the refined Si grain. In the
CrSi2, from the melt started before the crystallization of Si production of solar cells, Si is melted to form ingots or
because these crystalline phases were also observed between plates. It was expected that Na could be removed from Si
the bottom of the crucible and the undersurface of the by melting under vacuum because of the high vapor pres-
refined Si grain (Fig. 2(d)). The densities of FeSi2 and CrSi2 sure of Na at high temperature. The Si grains obtained by
are 4.85 Mg/m3 and 4.98 Mg/m3, respectively, [9, 10] which crystallization in the present study were placed in a BN
crucible, heated at 1723 K for 8 h, and then cooled to room
temperature in a vacuum furnace. The Na concentration
decreased from 85 ppm to 0.055 ppm, which was smaller than
that in the raw Si powder (1.5 ppm). Furthermore, after
heating, the concentration of volatile elements, Mg, P, and
Ca, were decreased down to 0.023, 0.40, and 0.12 ppm,
respectively. Yuge has reported that P, having a high vapor
pressure, can be removed by electron-beam melting in a
vacuum atmosphere [2]. The results of the present study
indicate that melting and heating at 1723 K under vacuum is
effective for the removal of Na and other volatile elements
from highly Na-contaminated Si grains.
After heating the container to 1173 K, the Na metal was
not contained in the upper crucible. The vaporized Na
reacted with the Si powder in the lower crucible heated at
1123 K (ΔT050) and was recycled in NaSi formed by
cooling. NaSi can be used as the source of the next purifi-
cation process by crystallization of Si from the Na-Si melt.
The impurity level in the refined Si grain obtained in
Fig. 5 Schematic illustration of the process for the dissolution of low-
the present study was insufficient for solar-grade Si. The
purity Si powder, recrystallization of a Si grain, and segregation of impurities could be decreased by repeating the crystalli-
impurities zation process. Although Na is a reactive metal and must
Silicon (2012) 4:121–125
be handled with care, we assumed that the safe handling
of Na has already been established because Na has been
used in various industry fields. For example, a large
amount of Na has been used as a reducer in the tantalum
refining industry and as electrodes of Na molten-salt batteries.
The Na solution process may be a candidate for a low-cost,
mass production method for solar-grade Si.
4 Summary
We have reported the new purification method of Si using
Na solvent. Silicon grains, a few millimeters in size, were
crystallized at 1173 K by evaporation of Na from a Na-
40 mol%Si solution in which low-purity Si powder was
dissolved. The concentrations of most impurity elements,
in particular, the following transition metals: Ti, V, Cr, Mn,
Fe, Co, and Ni, were decreased in the refined Si grains. The
Na contained in the Si grains can be removed by heating at
1723 K in a vacuum atmosphere.
Acknowledgements This work was supported in part by a Grant-in-
Aid for Young Scientists (Start-up) (No.20860016) from the Ministry
of Education, Culture, Sports, Science and Technology and a Grant-in-
Aid for Research Seeds Quest Program (Lower Carbon Society) from
the Japan Science and Technology Agency.
125
References
1. Braga AFB, Moreira SP, Zampieri PR, Bacchin JMG, Mei PR
(2008) New processes for the production of solar-grade poly-
crystalline silicon: a review. Sol Energy Mater Sol Cells
92:418–424
2. Yuge N, Abe M, Hanazawa K, Baba H, Nakamura N, Kato Y,
Sakaguchi Y, Hiwasa S, Aratani F (2001) Purification of
metallurgical-grade silicon up to solar grade. Prog Photovolt: Res
Appl 9:203–209
3. Mitrašinović AM, Utigard TA (2009) Refining silicon for solar cell
application by copper alloying. Silicon 1:239–248
4. Yoshikawa T, Morita K (2009) Refining of silicon during its
solidification from a Si-Al melt. J Cryst Growth 311:776–779
5. Trumbore FA (1960) Solid solubilities of impurity elements in
germanium and silicon. Bell System Technical Journal
39:205–233
6. Morito H, Yamada T, Ikeda T, Yamane H (2009) Na-Si binary
phase diagram and solution growth of silicon crystals. J Alloys &
Comp 480:723–726
7. Morito H, Yamane H (2010) Double helical silicon microtubes.
Angew Chem, Int Ed 49:3638–3641
8. Newman RC, Wakefield J (1961) The diffusivity of carbon in
silicon. J Phys Chem Solids 19:230–234
9. Aronsson B (1960) A note on the compositions and crystal structures
of MnB2, Mn3Si, Mn5Si3 and FeSi2. Acta Chem Scand 14:1414–
1418
10. Tanaka K, Nawata K, Inui H, Yamaguchi M, Koiwa M (2001)
Refinement of crystallographic parameters in refractory metal
disilicides. Mater Res Soc Symp Proc 646:N4.3.1–N4.3.5