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USO05706674A
United States Patent [191 [11] Patent Number: 5,706,674
Hsiung et a1. [45] Date of Patent: Jan. 13, 1998

[54] ARGON RECOVERY FROM SILICON FOREIGN PATENT DOCUMENTS

CRYSTAL FURNACE 489387 3/1992 Japan.
624962 4/1994 Japan ........................... .. c0113 23/00
[75] Inventors: Thomas Hsiao-Ling Hsiung. Emmaus; 733581 2/1995 Japan ............................. .. c303 5/00
Zbigniew Tadeusz Fidkowski.
Macungie; Rakesh Agrawal. Emmaus. OTHER PUBLICATIONS
all of Pa.
Semiconductor Crystal Growth for the 90s and Beyond by
[73] Assignee: Air Products and Chemicals, Inc.. Peter Disessa. appearing in Semiconductor Fabtech. pp.
Allentown. Pa. 133-135.
The Recovery and Recycling of High Purity Argon in the
[21] Appl. No.: 785,515 Semiconductor Industry" by J. V. OBrien and J. V. Schurter.
presented at the AIChE 1988 Spring National Meeting. Mar.
[22] Filed: Jan. 17, 1997 6-10. 1988.
Related US. Application Data Primary Examiner-Ronald C. Capossela
Attome); Agent, or Firm-Geotfrey L. Chase
[60] Continuation-impart of provisional application No. 60/012,
439, Feb. 28, 1996. [57] ABSTRACT
[51] Int. Cl.6 ....................................................... .. F25J 1100 The present invention is directed to two embodiments of a
62/632; 62/636; 62/924 process for recycling an impure argon e?luent from a silicon
Field of Search ............................. .. 62/636. 924. 632 crystal growing furnace using cryogenics. The ?rst embodi
ment uses cryogenic distillation techniques, and the second
[56] References Cited embodiment uses cryogenic adsorption. both of which use
U.S. PATENT DOCUMENTS catalytic treatments and adsorption in conjunction with their
cryogenic process steps to provide a pure argon recycle
3,181,306 5/1965 Greist et a1. ............................ .. 62/924 stream for a silicon crystal growth furnace.
3,805,536 62/924
5,106,399 .... .. 62/22
5,220,797 6/1993 Knishnamurthy et a1. .............. .. 62/924 15 Claims, 2 Drawing Sheets
US. Patent Jan. 13, 1998 Sheet 1 of 2 5,706,674
 5,706,674
1 2
ARGON RECOVERY FROM SILICON A typical silicon crystal furnace and the operation of
CRYSTAL FURNACE growing silicon crystals is identi?ed in the article. Semi
conductor Crystal Growth for the 90s and Beyond by Peter
CROSS-REFERENCE TO RELATED Disessa, appearing in Semiconductor Fabtech. pp. 133-135.
APPLICATIONS Japanese Public Patent Disclosure Number 4-89387 dis
closes a process for inert gas recovery for single crystal
This is a continuation-in-part of provisional patent appli pullers comprising the recovery of argon from a single
cation Ser. No. 60/012,439 ?led Feb. 28. 1996. crystal silicon furnace by a vacuum pump with the removal
BACKGROUND OF THE INVENTION
of particulates. The compressed impure argon is passed
through a zeolite-packed pressure swing adsorption bed to
The present invention is directed to the ?eld of recovering remove nitrogen, carbon monoxide and carbon dioxide
argon from the inerting atmosphere used in conjunction with before being passed to a palladium catalyst bed. a deoxo unit
growth of silicon crystals used in the semiconductor indus and an adsorption tower to remove hydrogen. oxygen,
try. More speci?cally, the present invention is directed to carbon monoxide, water and carbon dioxide. The puri?ed
recovery, cleanup, puri?cation and recycle of argon for argon is then returned to the furnace for further duty in
15 inerting the silicon crystal growth process.
inerting the environment from a silicon furnace where a
silicon crystal is pulled for crystal growth and formation. Japanese Public Patent Disclosure Number 7-33581 dis
The semiconductor industry consumes large volumes of closes an argon purification and recycle process for silicon
crystal furnaces in which impurities such as carbon
silicon crystals as the semiconductor substrate for use in
monoxide. oxygen and hydrogen are converted in a catalyst
producing various electronic media, including integrated bed to result in carbon dioxide and water, which are removed
circuits and memory devices. The end use requires very in an adsorptive section of a puri?cation device. The impure
uniform silicon crystals with minimal impurities and aber argon is recovered from the silicon furnace with a dry
rations in the crystal lattice. vacuum pump and particulate silicon dioxide is captured in
The Czochralski process is the method of choice for high a bubble column apparatus.
volume, reliable production of large diameter silicon 25 Japanese Public Patent Disclosure Number 6-24962 dis
monocrystal ingots. This process consists of freezing mate closes a method of recovering highly pure argon from the
rial from a molten pool onto the end of a single crystal seed exhaust gases of a silicon crystal manufacturing furnace.
of the same material. The material that becomes frozen The process involves removing the impure argon from a
replicates the single crystal structure of the seed. The result silicon crystal furnace and retaining it in a storage vessel.
is a small seed eventually becomes a large crystal. The 30 The impure argon is passed through a venturi to remove
process is fundamentally quite simple and is thermodynamic particulates and then is compressed before having oil from
in nature. A solid-liquid interface is formed by maintaining compression contamination removed and passing the impure
a temperature gradient that must be precisely controlled argon through a deoxo catalyst tube to remove oxygen by the
along with the seed pull rate. In order to maintain the heat addition of hydrogen over the catalyst. The oxygen-depleted
?ux along the solid-liquid interface, the molten silicon 35 impure argon is then passed through catalyst beds of cupric
contained in the quartz crucible must be raised within the oxide to remove hydrogen and carbon monoxide and convert
furnace hot zone as liquid is displaced from the equilibrium them to carbon dioxide and water. The cupric oxide catalyst
point and the crystal is formed. The raising process helps to beds are provided in tandem for switching mode of on-line
maintain precise control over the temperature distribution in and regeneration. The moist and carbon dioxide containing
three dimensions, and therefore both seed lift and crucible impure argon is then passed through switching beds of an
lift precise control mechanisms are required. The seed and appropriate zeolite to remove water and carbon dioxide.
crucible are continuously rotated during the process to Nitrogen is then removed from the argon in an additional set
improve temperature uniformity, as well as to maintain of tandem switching adsorptive beds of a zeolite. The
uniform dopants distribution in both the axial and radial nitrogen adsorption is conducted on the zeolite beds at 50
directions. In order to achieve production-worthy silicon 45 C. The zeolite may be a mordenite adsorbent. The argon is
crystals, the process requires the complex interaction and then ready for recycle for utilization. .
control of various process parameters. U.S. Pat. No. 5.106399 discloses an argon puri?cation
These silicon ingots are grown in a process atmosphere system. The impure argon is passed through a bed of
typically comprising high purity argon in order to avoid molecular sieve adsorbent to adsorb water and carbon diox
deposition or incorporation of impurities into the evolving ide. The dehydrated impure argon is then passed through a
silicon crystal lattice. These impurities may exist in the catalytic material to chemasorb oxygen. hydrogen and car
silicon bath, the degradation of the quart crucible or in bon monoxide. Finally, the argon is passed through an
atmospheres that are present in the absence of the argon adsorbent bed at cryogenic temperatures to adsorb nitrogen
purge gas. and hydrocarbons before recovering a puri?ed argon stream
Because the utilization of argon is large and the avail SS for reutilization. Argon recovery and recycle has also been
ability of argon on the commercial market is modest. various described in an article. "The Recovery and Recycling of
attempts to reutilize the argon have been identi?ed in the High Purity Argon in the Semiconductor Industry by l. V.
prior art. and each of these attempts has tried to overcome OBrien and J. V. Schurter, presented at the AIChE 1988
the problem of taking the contaminated, impure argon Spring National Meeting, Mar. 6l0. 1988. The article
e?luent from the silicon crystal furnace and treating it to describes the recycling of contaminated argon from a silicon
remove particulates, dopants and other contaminating impu crystal growth furnace using compression. catalytic reaction
rities in the form of gases for recycle of acceptably pure of carbon monoxide and methane with oxygen. catalytic
argon for reutilization in the silicon crystal furnace. A key reaction of excess oxygen with hydrogen in a dcoxo process,
criteria is the recovery and puri?cation of such argon in a the removal of carbon dioxide and water on molecular sieve
technically feasible, yet economically viable, process so as 65 beds, and the cryogenic distillation of the argon to remove
to be competitive with the commercial costs of fresh argon hydrogen and nitrogen prior to recycling the argon for
from the industrial gas market. reutilization in the silicon crystal-growing furnace.
 5,706,674
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The prior art has attempted to resolve the high consump DE'I'AHBD DESCRIPTION OF THE
tion rate of argon in the growth of silicon crystals for the INVENTION
semiconductor industry. However, the prior art processes for
argon recovery and puri?cation to reutilize argon in silicon The present invention for the recovery of impure argon
crystal furnaces has sulfered from undue complication and from a silicon crystal growth furnace for puri?cation and
ine?iciency resulting in costly processing and expensive recycle will now be described in greater detail with regard
apparatus. Ftn'thermore. the prior art has no methods to to the two embodiments. one. cryogenic distillation and the
remove volatile dopants that could be present in the impure other, cryogenic adsorption. with reference to the drawings.
argon. The present invention as described below overcomes With reference to FIG. 1. the embodiment of the present
these problems in the prior art argon recycling ?eld to invention directed to argon recovery, puri?cation and
provide an e?icient and inexpensive mode of argon recovery recycle using cryogenic distillation will now be described.
and puri?cation for utilization in silicon crystal growth An impure argon e?luent gas 20 is removed from a
furnaces.
furnace 18 where silicon crystals are grown using. for
BRIEF SUMMARY OF THE INVENTION instance. the Czochralski process. The stream 20 has impu
The present invention utilizes cryogenic distillation or rities of nitrogen. oxygen, water, hydrogen, carbon dioxide,
cryogenic adsorption in two separate process embodiments carbon monoxide. hydrocarbons and various dopants and
for the recovery, puri?cation and recycle of argon to a silicon particulates. The impure argon is compressed to a pressure
crystal growth furnace. The ?rst embodiment utilizing cryo of 140 psia in a compressor 23 as stream 25 before being
genic distillation recovers impure argon and compresses it aftercooled in heat exchanger 27 to 90 F. and passed as
before sending it to a scrubber to remove contaminating stream 30 through a liquid scrubber 33 which uses various
dopants by absorption using solvents or liquid agents. The caustic solutions, solvents or liquid scrubbing agents. such
argon is then passed through a deoxo unit with the addition as aqueous sodium or potassium hydroxide, to remove
of hydrogen, if needed. to convert oxygen content in the dopants, such as oxides and hydrides of arsenic, phosphorus.
impure argon on an appropriate deoxo catalyst bed. The antimony. gallium and boron. and particulates, such as
deoxygenated argon is then passed through switching tem 25 silicon dioxide. from the impure argon. The impure argon 35
perature swing adsorption beds to remove carbon dioxide is then heated in a heat exchanger 37 to approximately 350
and water before being sent to a double-column distillation F. in stream 40 before being introduced into a deoxo catalyst
column to recover pure argon by recti?cation. In the high unit 43 where hydrogen reacts with oxygen contained in the
pressure or lower distillation zone. argon is separated from impure argon over a catalyst bed to eliminate oxygen in the
nitrogen. hydrogen or carbon monoxide. In the low pressure impure argon as it is removed in line 45. The deoxo catalyst
or upper distillation zone. pure argon is recovered from may be any commercially available deoxo catalyst such as
residual hydrocarbons. The liquid argon makeup. in addition various forms of palladium. platinum/palladium mixtures.
to the recycled argon. is admitted as a midpoint stream in the The deoxygenated. impure argon in line 45 heat exchanges
low pressure. upper distillation column for recti?cation and against rewarming cold pure argon in a heat exchanger 47 to
puri?cation. The pure argon is then heat exchanged against 35 return to a temperature in stream 50 of 90 F. The stream can
the incoming impure argon and sent to further use as a pure be further cooled in a chiller heat exchanger before being
argon stream in the silicon crystal furnace. passed through switching zeolite adsorptive beds 55a and
In a second embodiment. impure argon is removed from 55b operated on a temperature swing adsorption process to
the silicon crystal growth furnace and is compressed and remove carbon dioxide and water from the impure argon.
cooled before being subjected to a wet scrubber using The zeolite can be any zeolite which is selective to adsorb
various caustic agents, liquid scrubbers or solvents to water and carbon dioxide. such as l3X-zeolite. 4A-zeolite,
remove contaminating dopants contained in the impure SA-zeolite and mixtures thereof. Stream 60 has no oxygen,
argon. Any solid particles present are also removed in the water or carbon dioxide. This stream is then mixed with
wet scrubber. The argon is then subjected to a deoxo process argon 70 from a downstream cryogenic distillation column.
to remove oxygen with the addition of hydrogen, if needed. 45 and the combined stream in line 100 is heat exchanged in
over a catalyst bed containing typical deoxo catalyst before heat exchanger 80 against various process streams coming
the impure deoxygenated argon is then passed through from the cryogenic distillation column before being intro
switching cupric oxide catalyst beds to convert carbon duced as stream 120 as the reboil stream for the high
monoxide and hydrogen to water and carbon dioxide. The pressure or lower column 128 of a dual column distillation
impure argon containing water and carbon dioxide is then 50 column 125. After reboil duty, the impure argon in line 130
passed through switching zeolitic beds to remove the water is split into a feed 140 to the high pressure or base column
and carbon dioxide by adsorption. Finally. the dry argon is 128 and a re?ux in stream 150 for condensing vapor in the
then passed through calcium X-zeolite switching beds at low pressure or upper distillation column 129 of the dual
cryogenic temperature conditions, along with any makeup distillation column 125. In the base or high pressure distil
argon. to remove nitrogen and methane before being heat SS lation column 128, nitrogen. hydrogen and/or carbon mon
exchanged against incoming impure argon and recycled for oxide is separated from a partially puri?ed argon, wherein
utilization in the silicon crystal growing furnace. the argon containing some hydrocarbons. such as 200 ppm
of methane. is removed as a stream in line 200 to be mixed
BRIEF DESCRIPTION OF THE SEVERAL with makeup liquid argon 205. while carbon monoxide is
VIEWS OF THE DRAWINGS removed in line 210 for rewarming against incoming,
FIG. 1 is a schematic illustration of the ?rst embodiment impure argon in a heat exchanger 80 before being removed
of the present invention using cryogenic distillation to in line 215. The makeup liquid argon and the partially
recover, purify and recycle argon to a silicon crystal growth puri?ed argon in stream 200 are introduced into the low
furnace. pressure or upper distillation column 129 of the dual distil
FIG. 2 is a schematic illustration of a process to recover. 65 lation column 125 where they are recti?ed for further
purify and recycle argon using cryogenic adsorption for a puri?cation by being reboiled against the overhead of the
silicon crystal growing furnace. high pressure column and re?uxed by the cold, impure argon
 5,706,674
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in stream line 150. The liquid in the sump of the low slip stream 279 of the puri?ed argon and by warming to
pressure distillation column 129 generates re?ux for the high ambient temperature. The puri?ed argon from the calcium
pres sure column 128 by indirect heat exchange. The puri?ed X-zeolite beds 267a and 267b which is now depleted of
argon in line 230 is removed, rewarmed against incoming nitrogen and methane contained therein is removed in line
impure argon in heat exchanger 80 and 47 and recycled in 270 at a temperature of 220 F. and a pressure of 97 psia
line 240 and stream 15. Makeup argon 10 can be added to and is rewarrned against impure argon in line 260 and.
argon 15. The argon in line 230 is at a temperature of further. warmed in line 275 against impure argon in line 250
approximately 261 F. Its pressure is 97 psia. A waste to a temperature of 70 F. and a pressm'e of 95 psia before
stream of hydrocarbons are removed as the liquid from the being recycled 276 with argon makeup 210 for reintroduc
base of the low pressure upper distillation column 129 in line 10 tion into the silicon crystal growing furnace in line 215.
220. Alternatively. the makeup argon in line 280 at 250 F. and
The present invention can also use cryogenic technology 98 psia may be passed through the nitrogen and methane
to purify an argon e?iuent stream from a silicon crystal removal calcium X-zeolite beds 267a and 267b with the
growing furnace using adsorptive techniques rather than the recycling impure argon before being sent to the crystal
cryogenic recti?cation and distillation of the ?rst embodi growing furnace 218.
ment. The second embodiment will be described with ref Having described the two embodiments of cryogenic
erence to FIG. 2. An impure argon e?luent stream in line 220 argon ptn'i?cation for silicon crystal growth in furnaces. it is
is removed from a silicon crystal growing furnace 218 readily apparent that the present invention uses cryogenic
wherein the impure argon stream contains nitrogen, oxygen, conditions to uniquely purify argon. either by distillation or
water. hydrogen. carbon dioxide. carbon monoxide. hydro 20 adsorption. in a simpli?ed manner and in a unique series of
carbons and potentially dopants, such as oxides and hydrides process steps which allow for the most appropriate removal
of arsenic. phosphorus. antimony. gallium and boron, and of contaminants from the argon in order to minimize volu
various particulates, such as silicon dioxide. The stream is metric ?ows of gas through catalytic, adsorptive and distil
compressed to a pressure of approximately 110 psia through lation process stations. while providing for ready regenera
a compressor 223 and is removed in line 225 for aftercooling tion of those process stations requiring such regeneration
through a heat exchanger 227 to result in a stream in line 230 with a minimal of capital investment in equipment. while
at 90 F. and 108 psia. This stream is introduced into a wet providing for low cost operation and high purity argon
scrubber 233 using caustic agents. solvents or liquid recycle.
absorbents, such as aqueous sodium or potassium We claim:
hydroxide, to remove contained dopants and particulates as 1. A process for the recovery and puri?cation of impure
recited above for the ?rst embodiment. The scrubbed, argon containing residual dopants from a silicon crystal
impure argon is collected in the surge tank 234 and passed growth furnace using the steps of:
as stream 235 to be heated in a heat exchanger 237 from a (1) contacting the impure argon with a deoxygenation
temperature of 90 F. in stream 35 to 350 F. in line 240 catalyst and hydrogen to remove any contained oxy
before being passed to a deoxo unit 243 to remove contained 35 gen;
oxygen over a catalyst in the presence of hydrogen. The (2) contacting the impure argon with a zeolitic adsor
deoxo catalyst may be any commercially available deoxo bent selective to the adsorption of water and carbon
catalyst such as various forms of palladium, platinum! dioxide from the impure argon to remove any water
palladium mixtures, various forms of nickel and mixtures and carbon dioxide from the impure argon;
thereof. The deoxygenated impure argon in line 245 is then (3) further purifying the impure argon in a cryogenic
introduced into one of a tandem pair of switching cupric temperature separation to remove remaining impu
oxide catalyst beds 246a and 246b which convert carbon rities from the impm'e argon and produce an argon
monoxide and hydrogen to water and carbon dioxide in the product stream having a purity of at least 99.5% by
impure argon stream. The olf-line cupric oxide bed can be volume;
regenerated using a mixture of oxygen and nitrogen in line 45 the improvement comprising removing dopants from the
251. and ?nally purged with a slipstream of the product impure argon prior to step (1) by contact of the impure
argon in line 277. The water and carbon dioxide containing argon with a liquid absorbent to strip the dopants from
impure argon in line 250 is then cooled against puri?ed the impure argon.
argon from downstream in a heat exchanger 247 and is at a 2. The process of claim 1 wherein the cryogenic tempera
temperature of 80 F. in line 255 before being introduced 50 ture separation is a cryogenic dual column distillation sepa
into one of a tandem pair of switching zeolite adsorbent beds ration with a high pressure distillation column separation of
256a and 2561: that remove water and carbon dioxide from nitrogen and carbon monoxide from the impure argon and a
the impure argon. The zeolite can be any zeolite which is low pressure distillation column separation of hydrocarbons
selective to adsorb water and carbon dioxide, such as from the impure argon.
l3X-zeo1ite, 4A-zeolite, SA-zeolite and mixtures thereof. 55 3. The process of claim 2 wherein the cryogenic tempera
The o?-line bed can be regenerated using a nitrogen purge ture is no greater than 260 F.
gas 252 and ?nally purged by a slipstream of product argon 4. The process of claim 1 wherein the impure argon after
in line 278. The dried and carbon dioxide depleted impure contact with the deoxygenation catalyst is contacted with a
argon in line 60 still contains nitrogen and methane at a cupric oxide catalyst to convert carbon monoxide and hydro
temperature of 80 F. and pressure of 99 psia. The stream in gen to water and carbon dioxide.
line 60 is further cooled by heat exchange in heat exchanger 5. The process of claim 4 wherein the cupric oxide
262 against the puri?ed argon stream 270 to cool the impure catalyst is contained in two parallel switching adsorbent
argon to a temperature of 220 F. before being passed with beds with one bed contacting the impure argon while the
makeup argon 280 in stream 265 through one of a tandem other bed is being regenerated with an oxygen containing
pair of switching calcium X-zeolite beds 267a and 26'7b to 65 inert gas and portion of the argon product stream.
remove nitrogen and methane by cryogenic adsorption. The 6. The process of claim 4 wherein the cryogenic tempera
off-line calcium X-zeolite bed may be regenerated using a ture separation is a cryogenic selective adsorption of nitro
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gen and hydrocarbons from the impure argon on a calcium 13. A process for the recovery and puri?cation of impure
X-zeolite adsorbent. argon containing residual dopants from a silicon crystal
7. The process of claim 6 wherein the cryogenic tempera growth furnace using the steps of:
ture is no greater than 220 F. (l) contacting the impure argon with a deoxygenation
8. The process of claim 1 wherein the argon product 5 catalyst and hydrogen to remove any contained oxy
stream is recycled to the silicon crystal growth furnace. gen;
9. The process of claim 1 wherein the liquid absorbent is (2) contacting the impure argon with a cupric oxide
selected from the group consisting of sodium hydroxide. catalyst to convert carbon monoxide and hydrogen to
potassium hydroxide and mixtures thereof.
10. The process of claim 1 wherein the cryogenic tem 10 water and carbon dioxide;
perature is no greater than 200 F.
(3) contacting the impure argon with a zcolitic adsor
11. A process for the recovery and puri?cation of impure bent selective to the adsorption of water and carbon
argon containing residual dopants from a silicon crystal dioxide from the impure argon to remove any water
gowth furnace using the steps of: and carbon dioxide from the impure argon;
(1) contacting the impure argon with a deoxygenation (4) contacting the impure argon at a cryogenic tem
catalyst and hydrogen to remove any contained oxy perature with calcium X-zcolite adsorbent to remove
gen; nitrogen and hydrocarbons from the impure argon
(2) contacting the impure argon with a zeolitic adsor and produce an argon product stream having a purity
bent selective to the adsorption of water and carbon of at least 99.5% by volume; and
dioxide from the impure argon to remove any water (5) recycling the argon product stream to the silicon
and carbon dioxide from the impure argon; crystal growth furnace;
(3) introducing the impure argon into a cryogenic the improvement comprising removing the dopants from
distillation column to separate nitrogen from the the impure argon prior to step (1) by contact of the
impure argon to produce an argon product stream impure argon with aqueous sodium hydroxide to strip
having a purity of at least 99.5% by volume; and 25
the dopants from the impure argon.
(4) recycling the argon product stream to the silicon
14. The process of claim 13 wherein the calcium X-zeolite
crystal growth furnace; adsorbent is contained in two parallel switching adsorbent
the improvement comprising removing the dopants from beds with one bed contacting the impure argon while the
the impure argon prior to step (1) and performing step other bed is being regenerated with a portion of the argon
(3) in a cryogenic dual column distillation separation
with a high pressure distillation column separation of product stream.
nitrogen. hydrogen and carbon monoxide from the 15. The process of claim 13 wherein the zeolite adsorbent
impure argon and a low pressure distillation column is contained in two parallel switching adsorbent beds with
separation of hydrocarbons from the impure argon. one bed contacting the impure argon while the other bed is
12. The process of claim 11 wherein the zeolite adsorbent 35 being regenerated initially with nitrogen gas and then by a
is contained in two parallel switching adsorbent beds with portion of the argon product stream.
one bed contacting the impure argon while the other bed is
being regenerated by elevated temperature. * * * * *