Purification of Rice Hulls as a Source of Solar Grade

Silicon for Solar Cells

James A. Amick

J. Electrochem. Soc. 1982, Volume 129, Issue 4, Pages 864-866.

doi: 10.1149/1.2123989

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864 J. Electrochem. Soc.: S O L I D - S T A T E S C I E N C E AND T E C H N O L O G Y April 1982

Fig. 11. SEM photographs of a four chip module with one chip removed, (a, left; b, right).

REFERENCES 6. B. S. Berry and I. Ames, ibid., 13, 286 (1969).

1. P. A. Totta a n d R. P. Sopher, IBM J. Res. Dev., 13, 7. W. Anacker, IEEE Spectrum (May 1979).
8. I. Ames, IBM J. Res. Dev., 24, 188 (1980).
226 (1969). 9. J. H. G r e i n e r et al., ibid., 24, 195 (1980).
2. L. F. Miller, ibid., 13, 239 (1969). 10. W. Anacker, ibid., 24, 107 (1980).
3. L. S. Goldman, ibid., 13, 251 (1969). 11. A. V. Brown, ibid., 24, 167 (1980).
4. K. C. Norris a n d A. M. Landsberg, ibid., 13, 266 12. J. Yeh, U n p u b l i s h e d results.
(1969). 13. H. C. Jones and D. H. Herrel, IBM J. Res. Dev., 24,
5. S. Oktay, ibid., 13, 272 (1969). 172 (1980).

Purification of Rice Hulls as a Source of Solar Grade Silicon for Solar

Cells
James A. A m i c k *
Exxon Research and Engineering Company, Linden, New Jersey 07036

ABSTRACT
Rice hulls, a by-product of rice refining, naturally contain both silica and carbon compounds. The metallic impur-
ity content of these hulls can be greatly decreased by appropriate leaching techniques, making the purified material
suitable as a source of upgraded metallurgical silicon. The impurity level in the hulls after leaching, and after appro-
priate coking, is described, as well as techniques for adjusting the carbon to silica ratio in the coked materials.

In the m a n u f a c t u r e of p r e s e n t - d a y solar cells, semi- Metallurgical silicon is inexpensive compared with

conductor grade polycrystalline silicon prepared by the
Siemens process is employed. While the cost of this
material is acceptable for the preparation of integrated
circuits and transistors, it poses a major b a r r i e r to the
reduction of solar cell costs. Accordingly, intensive
efforts to reduce the cost of polycrystalline silicon for
use i n solar cells are in progress u n d e r both govern-
m e n t and private funding.
* Electrochemical Society A c t i v e Member.
Key words: rice hulls, purification, solar grade silicon, f e e d s t o c k
for silicon.
Siemens process polysilicon, but the i m p u r i t y content
of commercially available metallurgical silicon is high.
Metallurgical silicon is consequently unacceptable for
the preparation of high lifetime silicon needed for high
efficiency solar cells. Programs to upgrade m e t a l l u r g i -
cal silicon to "solar grade" have been u n d e r t a k e n (1,
2), but none of these has reached the stage of c o m m e r -
cial production. Nevertheless, the concept of preparing
solar grade silicon by a m e t a l l u r g i c a l process from u p -
graded starting materials r e m a i n s attractive.
Vol. 129, No. 4 PURIFICATION OF RICE HULLS 865

M e t a l l u r g i c a l silicon is produced in huge q u a n t i t i e s - - with smaller amounts of aluminum, copper, sodium,

se v er al h u n d r e d thousand m e t r i c tons per y e a r - - b y a
c a r b o t h e r m i c process ~in w h i c h silicon dioxide (as
quartzite) is red uc e d in an arc f u r n a c e in the presence
of carbon. For u p g r a d e d m e t a l l u r g i c a l silicon, high
p u r i t y quartz and carbon are needed. These source
materials are limited in a v a i l a b i l i t y and are substanti-
ally h i g h e r in cost than the source m a t e r i a l s n ow used
in the m a n u f a c t u r e of m e t a l l u r g i c a l grade silicon. Rice
hulls offer an alternative, low cost, s o l a r - p r o d u c e d
source m a t e r i a l containing both silicon dioxide and
carbon. By simple leaching treatments, the m e t a l ion
content of these hulls can be g r e a t l y decreased, m a k i n g
t h e m p o t en t i al l y suitable as a source m a t e r i a l for solar
grade polysilicon.
Availability and Composition of Rice Hulls
Rice hulls are the n a t u r a l sheath, or protective cover,
w h i ch forms o v e r the rice grains during t h e ir growth.
R e m o v e d during the refining of rice, these hulls are of
little c o m m e r c i a l v a lu e (3). Because of their silicon
dioxide content, they are not useful as feed for humans
or cattle, and t h e y are not r e a d i ly biodegradable;
n e i t h e r do t h e y h a v e m u c h fuel value.
The 1978/1979 w o r l d rice crop was estimated at 373
mi l l i o n m e t r i c tons (4), the U.S. h a r v e s t being about
7 m i l l i o n m e t r i c tons (4). Rice hulls r e p r e s e n t about
one-fifth of the w e i g h t of rice harvested, or about 75
m i l l i o n tons w o r l d w i d e in 1978/1979. The silica content
of the r a w hulls is about 15% by weight, or about 11
m i l l i o n m e t r i c tons. P o t e n t i a l l y r e c o v e r a b l e silicon is
about half this value, or a p p r o x i m a t e l y 5 million m e t -
ric tons, 1 n e a r l y 1O00 times the c u r r e n t consumption of
silicon b y the semiconductor i n d u s t r y worldwide. The
residual 80% of the r a w hulls is m a d e up of organic
compounds that can be p y r o l y z e d to carbon. The r e-
sult of this pyrolysis is a g r a n u l a r m a t e r i a l consisting
of about 55% b y w e i g h t SiO2 and 45% by w e i g h t car-
bon. This corresponds to an atomic ratio C : S i of about
4:1.
Pyrolyzed, or "coked" rice hulls have been used to
p r e p a r e silicon carbide whiskers for s t r e n g t h e n i n g
such m a t e r i a l s as plastics and a l u m i n u m (5). Rice
hulls h a v e also been explored as a potential source of
silicon chloride for later reduction to silicon (6) and
for f o r m i n g silicon dioxide to be s u b s e q u e n t l y reduced
to silicon (7). However, no c o m m e r c i a l process has yet
been d ev el o p ed for these types of conversion.
Purification of Rice Hulls (8)
N a t u r a l rice hulls contain substantial levels of m e t a l -
lic impurities. As seen in Table I, the principal i m p u r i -
ties are calcium, magnesium, manganese, and iron,
1Potential silicon f r o m U.S. harvested rice is about 100,000
metric ions.
titanium, and boron. Phosphorus is not seen in the
emission spectrographic analysis. Th e total i m p u r i t y
content, obtained by adding t o g e t h e r the values r e -
ported for the i n d i v i d u a l impurities, is about 10,000
ppm, or about 1%. This i m p u r i t y content is c o m p a r -
able to that for c o m m e r c i a l l y available q u ar t zi t e used
for p r e p a r i n g m e t a l l u r g i c a l silicon.
The i m p u r i t y levels are reduced substantially by
leaching the r a w rice hulls w i t h boiling aqueous h y -
drochloric acid, followed by thorough rinsing w i t h
distilled or with "polished" w a t e r as used in the semi-
conductor industry. 2 As seen f r o m Table I, this t r e a t -
m e n t substantially lowers the levels of manganese,
iron, copper, sodium, calcium, and magnesium. Levels
of boron, aluminum, and t i t a n i u m are not ap p r e c i a bl y
affected by this treatment, but can be r ed u ced in a
subsequent step.
In the e x p e r i m e n t s r e p o r t e d here, the dried rice hulls
w e r e pyrolyzed, e.g., in a 2 in. ID quartz tube fur na c e
o p er at i n g at 900~176 the hulls being contained in a
quartz boat. D u r i n g the pyrolysis, an argon flow of
about 7 l i t e r s / r a i n was employed. To this was added
1% anhydrous HC1 to assist in the r e m o v a l of metallic
impurities. During pyrolysis, the organic compounds
present in the rice hulls are decomposed to carbon. As
seen from the final column of TaMe I, this t r e a t m e n t
reduces the total metallic i m p u r i t y content from about
350 ppm after the extraction step to less than 100 p p m
after pyrolysis.
If this m a t e r i a l were co n v er t ed into silicon w i t h no
increase in the i m p u r i t y levels, and the silicon was
s u b s e q u e n t l y recrystallized, the i m p u r i t y levels w oul d
be f u r t h e r reduced, except for the boron. It is antici-
pated that acceptable solar cells could be p r e p a r e d
from such recrystallized material.
Adjustment of the Carbon to Silicon Ratio
For p r e p a r i n g e l e m e n t a l silicon by a c a r b o t h e r m i c
process, the mol ratio of carbon to silica should be
about 2: 1, according to the equation
2C + SiO2 --> Si -[- 2CO
With pyrolyzed rice hulls, the carbon content is n e a r l y
4:1. The carbon content of the rice hulls can be ad-
justed to any desired value, however, by t r e a t m e n t
w i t h a suitable o x i d an t such as carbon dioxide. This
m a t e r i a l reacts e n d o t h e r m i c a l l y with the carbon, p r e -
v en t i n g hot spots that m i g h t be obtained w i t h oxidants
such as air or oxygen. H e a t - t r e a t m e n t of the p y rol yz e d
rice hulls can c o n v e n i e n t l y be carried out in a fluid bed
r eact o r at a t e m p e r a t u r e of about 900~ As seen in Fig.
1, the r e m o v a l of carbon is linear w i t h time for a gi ve n
2For example, "Super Q" ( d e i o n i z e d , m i c r o f i l t e r e d w a t e r )
equipment f r o m Millipore Corporation, B e d f o r d , Massachusetts.

Table I. Emissionspectrographicanalysesof cleaned rice hulls

!:3 aqueous 1: 1 a q u e o u s
Impurities Rice hulls Water washed HC1 c l e a n e d tIC1 c l e a n e d HC1 c o k e d

Dopants B I0 40 i0 10 5
A1 200 900 100 60 I0
P N.D. Present N.D. N.D. N.D.
L ~ e t i m e killers Cr N.D. N.D. N.D. N.D. N.D.
Mn 1500 160,0 30 30 10
Fe 900 700 50 40 10
CU 10 20 N.D. N.D. N.D.
Ni N.D. N.D. N.D. N.D. N.D.
Ti 20 200 60 60 N.D.
Zn N N.D. N.D. N.D. N.D.
Mo . . . . .
Mobileions Na 400 600 I0 I0 I0
K N 2000 30 I0 I0
Mg 3000 2200 60 60 20
Ca 4000 6300 70 50 N.D.
Miscellaneous Pb -- I0 N.D. N.D. N.D.
Pd . . . . .
Total 10,040 14,620 420 830 75
( O t h e r than Si)
Residue 13.39% 13.58% 18.82% 56.74=%
(Ash)
866 J. Electrochem. Soc.: S O L I D - S T A T E S C I E N C E A N D T E C H N O L O G Y April I982
4O I I I I

32.8
t 30
Z

Z
O
~9
Z
o
L~
20

~ e 1 6 . o

\
l0 I I I I
60 90 120 160 190
TIME OF CO2 FLOW (MINUTES)" ~
Fig. 1. Carbon content of pyrolyzed rice hulls vs. combustion
time in C02. Star marks C:Si = 2:1 atomic composition.

carbon~ dioxide flow rate. By selecting the a p p r o p r i a t e

time, a n y desired carbon to silicon ratio m a y be ob-
tained.
A l t e r n a t i v e l y , high p u r i t y quartzite m a y be a d d e d to
a d j u s t the a v e r a g e carbon to silicon ratio. The value of
carbon in the rice hulls is t h e r e b y increased. If suitable
quartzite is not available, a portion of the rice hulls
m a y be c o m p l e t e l y f r e e d of carbon b y combustion in
air. The resulting silica can t h e n be a d d e d to the p y r o -
lyzed hulls to p r o v i d e a n y desired carbon to silicon
ratio.
Characteristics of Pyrolyzed Rice Hulls
P y r o l y z e d rice hulls are free-flowing granules with
v i r t u a l l y no dusting tendency. F o r raw, u n g r o u n d
hulls, the i n d i v i d u a l granules are about 5 m m long and
about 1 m m across. Viewed at 50• in an optical
microscope, t h e y have an a p p e a r a n c e of m i n i a t u r e
corn cobs, as seen in Fig. 2. The r a w hulls can be
ground in a mill to give particles about 1 • 1 mm. The
analyses in Table I were o b t a i n e d for ground hulls;
similar results are obtained for the u n g r o u n d starting
material.
Conclusions
Rice hulls, a n a t u r a l b y - p r o d u c t of rice refining, have
little commercial value, l a r g e l y because of t h e i r high
silica content. A l t h o u g h the metallic i m p u r i t y concen-
t r a t i o n in r a w hulls is high, it can be r e d u c e d to less
than about 100 p p m b y e x t r a c t i o n in hot aqueous HC1,
followed b y pyrolysis in an a m b i e n t containing a n h y -
drous HC1. As desired, the carbon to silicon ratio in
p y r o l y z e d hulls can be adjusted, either b y p a r t i a l com-
bustion of the carbon or b y addition of a suitable silica
source. The m a t e r i a l offers promise for a low cost
source of silicon suitable for p r e p a r a t i o n of solar cells.
Acknowledgment
F o r t h e i r p a r t i c i p a t i o n in and contributions to the
rice hull program, I would like to express a p p r e c i a t i o n
and thanks to John Milewski, F r a n k Wright, Archie
Young, P. Natanson, and Dick Long.
Fig. 2. Photomicrographs of caked (pyrolyzed) rice hulls; back-
ground: 10 X 10 to the cm graph paper.
M a n u s c r i p t r e c e i v e d Aug. 14, 1981. This was P a p e r
264 p r e s e n t e d at the Hollywood, Florida, Meeting of the
Society, Oct. 5-10, 1980.
A n y discussion of this p a p e r will a p p e a r in a Dis-
cussion Section to be pubAshed in the D e c e m b e r 1982
JOURNAL. AI1 discussions for the D e c e m b e r 1982 Dis-
cussion Section should be s u b m i t t e d b y Aug. 1, 1982.
Publication costs o~ this article were assisted by
Exxo,n Research and Engineering Company.
REFERENCES
1. V. D. Dosaj, L. P. Hunt, a n d A. Schei, J. Metal, 8
( J u n e 1978); See also reports on J P L Contract
No. 954559.
2. P. K o t v a l and H. B. Strock, U.S. Pat. 4,124,410 (1978).
3. J. H. Hough and H. T. Barr, "Possible Use for Waste
Rice Hulls in Building Materials and Other P r o d -
ucts," B u l l e t i n No. 507, A g r i c u l t u r a l E x p e r i m e n t
Station, P.O. D r a w e r E, Louisiana S t a t e University
and A g r i c u l t u r a l a n d Mechanical College, Baton
Rouge, L A 70803.
4. "Rice Situation," Economics, Statistics, and Coopera-
tives Service, U.S. D e p a r t m e n t of Agriculture,
Bulletin RS-33; M a r c h 1979, U.S. D e p a r t m e n t of
Agriculture, Washington, D.C. 20250, c5. pages 4, 6.
5. J. Cook and B. Bechtold, in "Metal M a t r i x Com-
posites in High Modulus A l u m i n u m Alloys," D.
Webster, Editor, P l e n u m Press, N e w York, In
press.
6. P. K. Basu, AIChE J., 19~ 3 (1973).
7. R. Singh and B. K. Dhindaw, A b s t r a c t 0331 p r e -
sented at the I n t e r n a t i o n a l Solar E n e r g y Congress
( I S E S ) , N.ew Delhi, India, Jan. 16-21, 1978.
8. J. A. Amick, J. V. Milewski, and F. J. Wright, U.S.
Pat. 4,214,920 (1980).