JPH0151445B2 - - Google Patents
Info
- Publication number
- JPH0151445B2 JPH0151445B2 JP58208432A JP20843283A JPH0151445B2 JP H0151445 B2 JPH0151445 B2 JP H0151445B2 JP 58208432 A JP58208432 A JP 58208432A JP 20843283 A JP20843283 A JP 20843283A JP H0151445 B2 JPH0151445 B2 JP H0151445B2
- Authority
- JP
- Japan
- Prior art keywords
- trichlorosilane
- complexing agent
- impurities
- solution
- trichloride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 239000012535 impurity Substances 0.000 claims description 53
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 claims description 27
- 239000005052 trichlorosilane Substances 0.000 claims description 26
- 239000008139 complexing agent Substances 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 22
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 21
- 238000007254 oxidation reaction Methods 0.000 claims description 17
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 16
- 230000003647 oxidation Effects 0.000 claims description 15
- 229910052698 phosphorus Inorganic materials 0.000 claims description 15
- 239000011574 phosphorus Substances 0.000 claims description 15
- 238000004821 distillation Methods 0.000 claims description 13
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 12
- 239000007800 oxidant agent Substances 0.000 claims description 9
- RLOWWWKZYUNIDI-UHFFFAOYSA-N phosphinic chloride Chemical compound ClP=O RLOWWWKZYUNIDI-UHFFFAOYSA-N 0.000 claims description 8
- 229910019213 POCl3 Inorganic materials 0.000 claims description 5
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 5
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 5
- 229910052787 antimony Inorganic materials 0.000 claims description 4
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052785 arsenic Inorganic materials 0.000 claims description 4
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052797 bismuth Inorganic materials 0.000 claims description 4
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 4
- 229940117975 chromium trioxide Drugs 0.000 claims description 4
- WGLPBDUCMAPZCE-UHFFFAOYSA-N chromium trioxide Inorganic materials O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 4
- GAMDZJFZMJECOS-UHFFFAOYSA-N chromium(6+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Cr+6] GAMDZJFZMJECOS-UHFFFAOYSA-N 0.000 claims description 4
- 238000000354 decomposition reaction Methods 0.000 claims description 4
- PDPJQWYGJJBYLF-UHFFFAOYSA-J hafnium tetrachloride Chemical compound Cl[Hf](Cl)(Cl)Cl PDPJQWYGJJBYLF-UHFFFAOYSA-J 0.000 claims description 3
- RCJVRSBWZCNNQT-UHFFFAOYSA-N dichloridooxygen Chemical compound ClOCl RCJVRSBWZCNNQT-UHFFFAOYSA-N 0.000 claims 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims 2
- 238000010438 heat treatment Methods 0.000 claims 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims 2
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 238000001704 evaporation Methods 0.000 claims 1
- 230000008020 evaporation Effects 0.000 claims 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical class Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 39
- 239000005046 Chlorosilane Substances 0.000 description 38
- 239000000243 solution Substances 0.000 description 22
- 150000001875 compounds Chemical class 0.000 description 18
- 229910052710 silicon Inorganic materials 0.000 description 16
- 239000010703 silicon Substances 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 14
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 13
- 238000000746 purification Methods 0.000 description 9
- 239000002841 Lewis acid Substances 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 8
- 150000007517 lewis acids Chemical class 0.000 description 7
- 230000001590 oxidative effect Effects 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 5
- 238000004587 chromatography analysis Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- -1 silicon halide Chemical class 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- 150000003624 transition metals Chemical class 0.000 description 4
- 238000009835 boiling Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000003574 free electron Substances 0.000 description 3
- 230000000737 periodic effect Effects 0.000 description 3
- 150000003018 phosphorus compounds Chemical class 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 239000000370 acceptor Substances 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 235000011089 carbon dioxide Nutrition 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 238000010668 complexation reaction Methods 0.000 description 2
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 239000005049 silicon tetrachloride Substances 0.000 description 2
- 239000012086 standard solution Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 229910015900 BF3 Inorganic materials 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910003902 SiCl 4 Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- SLLGVCUQYRMELA-UHFFFAOYSA-N chlorosilicon Chemical compound Cl[Si] SLLGVCUQYRMELA-UHFFFAOYSA-N 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 238000007539 photo-oxidation reaction Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910000051 zinc hydride Inorganic materials 0.000 description 1
Landscapes
- Silicon Compounds (AREA)
Description
ãçºæã®è©³çŽ°ãªèª¬æã
çºæã®èæ¯
æ¬çºæã¯ãé»åæ©åšçšã®ã±ã€çŽ ã補é ãããã
ã®çŽç²ãªããªã¯ããã·ã©ã³ã®è£œé ã«ä¿ããããç¹
å®çã«ã¯ã埮éã®é»åäŸäžæ§äžçŽç©ãç¹ã«ãªã³å
ã³ãã®ä»ã®ç¬¬æå
çŽ ã®ååç©ãé€å»ããæ°èŠãª
æ¹æ³ã«ä¿ããBACKGROUND OF THE INVENTION The present invention relates to the production of pure trichlorosilane for the production of silicon for electronic devices, and more particularly to the production of pure trichlorosilane containing trace amounts of electron-donating impurities, particularly phosphorus and other The present invention relates to a novel method for removing compounds of group elements.
åå°äœåã³ãã©ã³ãžã¹ã¿çã®åŠãé«åºŠã«é²æ©ã
ãé»åå·¥åŠçšéã«ãã€ãŠã¯ãè¶
é«çŽåºŠã®ã±ã€çŽ ã
å¿
èŠãšããããåšç¥ã®ããã«ã埮éã®äžçŽç©ã§ã
ã±ã€çŽ å«æé»åå·¥åŠéšåã®æ§èœã倧ããæãããš
ã«ãªãã For highly advanced electronic applications such as semiconductors and transistors, ultra-high purity silicon is required. As is well known, even trace amounts of impurities can significantly impair the performance of silicon-containing electronic components.
äžè¬ã«ãåå°äœçšå
çŽ ã±ã€çŽ ã¯ãããã²ã³åã±
ã€çŽ äŸãã°åå¡©åã±ã€çŽ ïŒSiCl4ïŒãããªã¯ããã·
ã©ã³ïŒHSiCl3ïŒåã¯ãžã¯ããã·ã©ã³ïŒH2SiCl2ïŒ
ããæ°ŽçŽ ãäºéããããªãŠã åã¯éå±æ°ŽçŽ åç©ã§
éå
ããŠè£œé ãããŠãããã±ã€çŽ ã¯ã·ã©ã³
ïŒSiH4ïŒã®ç±å解ã«ãã€ãŠãåŸãããããã·ã©ã³
ã¯ç©ºæ°ãšæ¥è§Šãããšççºçã«ççŒããã®ã§å å·¥å
æ±ãå°é£ã§ããã Generally, elemental silicon for semiconductors is a silicon halide such as silicon tetrachloride (SiCl 4 ), trichlorosilane (HSiCl 3 ) or dichlorosilane (H 2 SiCl 2 ).
is produced by reducing it with hydrogen, zinc, sodium or metal hydride. Silicon can also be obtained by thermal decomposition of silane (SiH 4 ), but silane is difficult to process because it burns explosively when it comes into contact with air.
é«çŽåºŠã±ã€çŽ ããé€å»ããã®ãæãå°é£ãªäžçŽ
ç©ã®ãã¡ã®ïŒçš®ã¯ãªã³ã§ãããä»ã®äžçŽç©äŸãã°
é
ãéåã³ãã³ã¬ã³çã¯éåžžã®ææ³ïŒäŸãã°åž¯å
溶è粟補ãçµæ¶åŒäžãçïŒã§æ¯èŒç容æã«é€å»ã§
ãããããªã³ã¯ã±ã€çŽ ãšãã䌌ãç©æ§ãæããŠã
ããããããããåé¢ããã«ã¯è©Šè¡ãç¹°ãè¿ãã
ããªãã®ã§ãããæŽã«ããªã³ã¯ã¯ããã·ã©ã³çã®
åºçºç©è³ªã«é¡äŒŒã®æ§è³ªãæããååç©ã圢æãã
ããããããåºçºç©è³ªã®ç²Ÿè£œæ¿çž®ããã¯ãåæ§ã«
å°é£ã§ããã One of the most difficult impurities to remove from high purity silicon is phosphorus. Other impurities, such as copper, iron, and manganese, can be removed relatively easily by conventional methods (e.g., zone melt refining, crystal pulling, etc.), but phosphorus has physical properties similar to silicon, so these impurities can be removed relatively easily. The only way to separate them is through repeated trials. Furthermore, since phosphorus forms compounds with similar properties to starting materials such as chlorosilanes, purification and concentration of these starting materials is similarly difficult.
ã±ã€çŽ åã¯ããã²ã³åã±ã€çŽ ååç©ãããªã³ã®
åŠãäžçŽç©ãé€å»ããããã«çŸåšãŸã§ã«ææ¡ãã
ãæ¹æ³ã§ã¯ãå
žåçã«ã¯ãåºäœã®æ°Žåéå±é
žåç©
é¯åå€ãšæ¥è§£ãããŠäžçŽç©ãåžçãããããå
ã¯ãå®å®ãªä»å ååç©ãçæã次ãã§çŽç²ãªã±ã€
çŽ åã¯ããã²ã³åã±ã€çŽ ãæ²æ®¿åã¯èžçãããã
ã®ãããªåŠçã®è©³çŽ°ã«ã€ããŠã¯ãäŸãã°ãç±³åœç¹
蚱第2971607å·ïŒã«ã¹ãŠãšã«ïŒãç3069239å·ïŒãŠ
ã€ã³ã¿ãŒçïŒã第3071444å·ïŒã¹ãŠãšã©ãŒïŒã第
3188168å·ïŒãã©ããã¬ãŒïŒåã³è±åœç¹èš±ç¬¬
929696å·ïŒãžãŒã¡ã³ã¹ãŒã·ãŠãã±ã«ããŽãšã«ã±æ ª
åŒäŒç€ŸïŒãåç
§ãããããåãæ¬åºé¡äººã®ç±³åœç¹
èš±åºé¡ïŒ»åºé¡äººDocket339â1696ïŒ60SIâ609ïŒ
614ïŒïŒœåã³ïŒ»åºé¡äººDocket339â1698ïŒ60SIâ
708ïŒ710ïŒ711ïŒ716ïŒïŒœã«ã¯ãæ¹è¯æ¹æ³ãé瀺ã
ããŠãããç¶ããªããããããã®æ¹æ³ã«ããäžçŽ
ç©åçã倧éåŠçã®å°é£æ§ã®åé¡ãããã Methods proposed to date for removing impurities such as phosphorus from silicon or silicon halide compounds typically involve adsorption of the impurities by conjugation with a solid hydrated metal oxide complexing agent. or, forming a stable addition compound and then precipitating or distilling pure silicon or silicon halide. For details of such processing, see, for example, U.S. Pat.
No. 3188168 (Bradley) and British Patent No.
Please refer to No. 929696 (Siemens-Suchkertwerke Ltd.). Also, the applicant's U.S. patent application [Applicant's Docket 339-1696 (60SI-609/
614)] and [Applicant Docket 339-1698 (60SI-
708/710/711/716)] disclose an improved method. However, these methods also have problems such as impurity regeneration and difficulty in large-scale processing.
äžèšã®ç¹èš±åã³ç¹èš±åºé¡ãåŒçšããŠæ¬æ现æžäž
ã«å
å«ããã The above patents and patent applications are incorporated herein by reference.
çºæã®æŠèŠ
åšæåŸè¡šç¬¬æå
çŽ ãäžäŸ¡ã®ä»ã«äºäŸ¡ã«ããªã
åŸããšããæ§è³ªãå©çšããŠããããã®å
çŽ ãå«ã
ãªã³ååç©ãã®ä»ã®ååç©ãã¯ããã·ã©ã³æº¶æ¶²ã
ãé€å»ãåŸãããšãçºèŠããããè¶
çŽç²ã¯ããã·
ã©ã³æº¶æ¶²äžã«ååšããéåžžäžäŸ¡ã®äžçŽç©ãé
žåã
ãŠäºäŸ¡ç¶æ
ã«ããããšã«ãããéåžžã®èžçã«ãã€
ãŠãåã¯å¥œãŸããã¯ãäžçŽç©ãæŽã«é¯åå€ãšçµå
ã次ãã§èžçããããšã«ãã€ãŠããããã®äžçŽç©
ããã¯ããã·ã©ã³ã容æã«åé¢ãåŸãããšãç¥èŠ
ãããã®ã§ãããäŸãã°ãäžå¡©åãªã³ïŒPCl3ïŒ
ã¯è¶
çŽç²ããªã¯ããã·ã©ã³äžã«å
±éã«æ®åããäž
çŽç©ã§ãããæ¬çºæã§ã¯ãããªã¯ããã·ã©ã³ãåŠ
çããªã³äžçŽç©ããªãã·å¡©åãªã³ïŒPOCl3ã沞ç¹
105.3âïŒã«å€æãããããã®ãªãã·å¡©åãªã³ã¯
PCl3ïŒæ²žç¹75.5âïŒãããããªã¯ããã·ã©ã³ïŒæ²ž
ç¹31.8âïŒããã®èžçã«ããåé¢ã容æã§ããã
æãã¯ããã®POCl3ã¯æ¬çºæã«åŸã€ãŠæŽã«ããçš®
ã®é¯åå€ãšåå¿ãããç±çå®å®æ§ããã倧ãªé¯äœ
ã圢æããŠæ¬¡ã®èžçã容æã«ããããšãã§ãããSummary of the invention It has been discovered that phosphorus compounds and other compounds containing these elements can be removed from a chlorosilane solution by taking advantage of the property that group elements of the periodic table can be pentavalent as well as trivalent. . The normally trivalent impurities present in the ultrapure chlorosilane solution can be oxidized to the pentavalent state, by conventional distillation, or preferably by further combining the impurities with a complexing agent and then distilling. Therefore, it has been found that chlorosilane can be easily separated from these impurities. For example, phosphorus trichloride (PCl 3 )
is a common residual impurity in ultrapure trichlorosilane. In the present invention, trichlorosilane is treated to remove phosphorus impurities from phosphorus oxychloride (POCl 3 , boiling point
105.3â), but this phosphorus oxychloride is
It is easier to separate by distillation from trichlorosilane (boiling point 31.8°C) than from PCl 3 (boiling point 75.5°C).
Alternatively, this POCl 3 can be further reacted with some complexing agent according to the present invention to form a more thermally stable complex to facilitate subsequent distillation.
ãã®ããã«ãæ¬çºæã®ç®çã¯ããžã¯ããã·ã©
ã³ãããªã¯ããã·ã©ã³ãåå¡©åã±ã€çŽ åã¯ããã
ã®æ··åç©ã®åŠãã¯ããã·ã©ã³ã®æ°èŠãªç²Ÿè£œæ¹æ³ã
æäŸããããšã§ããã It is thus an object of the present invention to provide a new method for the purification of chlorosilanes such as dichlorosilane, trichlorosilane, silicon tetrachloride or mixtures thereof.
æ¬çºæã®ä»ã®ç®çã¯ãã¯ããã·ã©ã³æº¶æ¶²ãããª
ã³ååç©ãã®ä»ã®ïœâåäžçŽç©ãé€å»ããæ¹æ³ã
æäŸããããšã§ããã Another object of the present invention is to provide a method for removing phosphorus compounds and other n-type impurities from chlorosilane solutions.
æ¬çºæã®æŽã«ä»ã®ç®çã¯ãäžå¯éçã§äžã€å€§é
粟補系ã«é©çšå¯èœãªç²Ÿè£œæ³ãæäŸããããšã§ã
ãã Yet another object of the present invention is to provide a purification method that is irreversible and applicable to large-scale purification systems.
åãæ¬çºæã®å¥ã®ç®çã¯ãã¯ããã·ã©ã³æº¶æ¶²äž
ã®ãªã³ãã®ä»ã®ïœâåäžçŽç©ã®æ°èŠãªé
žåæ¹æ³ã
æäŸããããšã§ããã Another object of the present invention is to provide a novel method for oxidizing phosphorus and other n-type impurities in chlorosilane solutions.
æŽã«ãæ¬çºæã®ä»ã®ç®çã¯ãäºäŸ¡ã®ãªã³äžçŽç©
ãã¯ããã·ã©ã³ããé€å»ããããã®æ°èŠãªæ段ã
æäŸããããšã§ããã Furthermore, another object of the present invention is to provide a new means for removing pentavalent phosphorous impurities from chlorosilanes.
ãããã®ç®çåã³ãã®ä»ã®ç®çã¯ãæ¬çºæã«ã
ã€ãŠæäŸãããæ¹æ³ãå³ã¡ãåšæåŸè¡šç¬¬æå
çŽ
ã®äžäŸ¡ååç©ãå«ãäžçŽç©ã§æ±æãããã¯ããã·
ã©ã³æº¶æ¶²ã®ç²Ÿè£œæ¹æ³ã«ãã€ãŠéæããããæ¬çºæ
ã®æ¹æ³ã¯æ¬¡ã®å·¥çšãå«ããå³ã¡ã
(A) åèšäžçŽç©ãé
žåããŠåèšå
çŽ ãäºäŸ¡ç¶æ
ã«
ããååç©ãåŸãå·¥çšãåã³ããã®åŸã«è¡ãªã
ãã
(B) 粟補ãããã¯ããã·ã©ã³ãèžçã«ãã€ãŠååº
ååããå·¥çšãã§ããã These and other objects are achieved by the method provided by the present invention, ie, the purification of chlorosilane solutions contaminated with impurities containing trivalent compounds of elements of Group Group of the Periodic Table. The method of the present invention includes the following steps. That is, (A) a step of oxidizing the impurities to obtain a compound in which the element is in a pentavalent state, and a subsequent step (B) of extracting and recovering purified chlorosilane by distillation.
æ¬çºæã®å¥œãŸããæ
æ§ã§ã¯ã第æå
çŽ ãå«ã
äžçŽç©ã®é
žåæ段ã¯ãäžé
žåã¯ãã åã¯äºé
žåã
ã³ã¬ã³ããéžæãããé
žåå€ãšæ¥è§Šãããããšã§
ããã In a preferred embodiment of the invention, the means for oxidizing the group element-containing impurity is by contacting it with an oxidizing agent selected from chromium trioxide or manganese dioxide.
æ¬çºæã®ä»ã®å¥œãŸããæ
æ§ã§ã¯ã第æå
çŽ äž
çŽç©ã®é
žåæ段ã¯ãã¯ããã·ã©ã³æº¶æ¶²ã玫å€ç·
ïŒUVïŒç
§å°äžã§é
žçŽ ãšæ¥è§Šãããããšã§ããã In another preferred embodiment of the invention, the means for oxidizing Group element impurities is contacting the chlorosilane solution with oxygen under ultraviolet (UV) irradiation.
æ¬çºæã§æå³ããä»ã®æ
æ§ã§ã¯ãäžçŽç©ãäºäŸ¡
ç¶æ
ã«é
žåããå·¥çšã®åŸã«ä»å çãªå·¥çšãå«ãã
ãã®å·¥çšã§ã¯ãäžçŽç©ãé·ç§»éå±ååç©åã¯ã«ã€
ã¹é
žãšæ¥è§Šããããããããé·ç§»éå±ååç©åã¯
ã«ã€ã¹é
žã¯é¯åå€ãšããŠäœçšãç±çã«å®å®ãªé¯äœ
ãçæãããããããé¯äœã¯ã¯ããã·ã©ã³ã®èžç
ã®éã«æ®çé€å»ãããã Other embodiments contemplated by the invention include an additional step after the step of oxidizing the impurity to the pentavalent state.
In this step, impurities are brought into contact with transition metal compounds or Lewis acids, which act as complexing agents to form thermally stable complexes, which are then used during the distillation of chlorosilane. Residues are removed.
çºæã®è©³çŽ°ãªèª¬æ
æ¬çºææ¹æ³ã¯ãã¯ããã·ã©ã³æº¶æ¶²äžã«äžçŽç©ãš
ããŠååšãåŸããªã³ã®åŠãäžäŸ¡ã®ç¬¬æå
çŽ ã®å
åç©ãé
žåããŠããã®å
çŽ ãäºäŸ¡ç¶æ
ã«ããåå
ç©ã圢æããå·¥çšãå«ãããã®ããã«åŠçããã¯
ããã·ã©ã³ããåçãåã¯é¯åå€ãšã®åå¿åŸã®çŽ
ã¯ããã·ã©ã³ã®èžççã«ããåŠçããããšã§ãäž
çŽç©ã容æäžã€å¹ççã«é€å»ã§ãããæ¬çºææ¹æ³
ã¯ã埮éã®ãªã³ãã®ä»ã®éåžžã®ïœâåäžçŽç©ãäŸ
ãã°ãçŽ ãã¢ã³ãã¢ã³ããã¹ãã¹çããã¯ããã·
ã©ã³ç¹ã«ããªã¯ããã·ã©ã³ããé€å»ããã®ã«ç¹ã«
æå¹ã§ãããæ¬çºæã«ãããšãäŸãã°ããªã¯ãã
ã·ã©ã³æº¶æ¶²äžã®ãªã³å«éã0.5ppb以äžã«ãŸã§äœæž
ã§ãããDETAILED DESCRIPTION OF THE INVENTION The method of the invention comprises the step of oxidizing a compound of a trivalent Group element, such as phosphorus, which may be present as an impurity in a chlorosilane solution to form a compound in which the element is in the pentavalent state. . Impurities can be easily and efficiently removed by treating the chlorosilane thus treated by fractional distillation or distillation of pure chlorosilane after reaction with a complexing agent. The process of the invention is particularly effective for removing traces of phosphorus and other common n-type impurities such as arsenic, antimony, bismuth, etc. from chlorosilanes, especially trichlorosilanes. According to the present invention, for example, the phosphorus content in a trichlorosilane solution can be reduced to 0.5 ppb or less.
æ¬çºææ¹æ³ã¯ããªã³ãã®ä»ã®ç¬¬æå
çŽ ãã¯ã
ãã·ã©ã³ããé€å»ããã®ã«æçšã§ããããã®ã¯ã
ãã·ã©ã³ã¯æ¬¡ã«é»åçšéçšã®çµæ¶æ§ã±ã€çŽ ã«éå
ãããããªã³åã³ãã®å§åŠ¹å
çŽ ã§ãã第æå
çŽ
äŸãã°ãçŽ ãã¢ã³ãã¢ã³åã¯ãã¹ãã¹ã¯ãéå°ã®
èªç±é»åãäŸäžãããããé»åæ©åšçšã±ã€çŽ ã®è£œ
é ã«æŒããŠç¹ã«éèŠãªãã®ã§ããããããã®å
çŽ
ãã±ã€çŽ ãããªãã¯ã¹äžã«æ·»å ããããšãéå°ã®
é»åã¯ãã±ã€çŽ çµæ¶ã®ïŒäžæ§ã®ïŒé»æ°ç¹æ§ãå€å
ããããåãçµæ¶ã«åå°äœç¹æ§ãäžããããã«ã
ãã«å«ãŸããããŒãã³ã°å€ã«å¹²æžããããããã®
éå°é»åã¯è² é»è·ãšããŠå¯äžããããã«ããªã³ç
ã®äžçŽç©ã¯âïœââåïŒè² ïŒäžçŽç©ãšãããããã
æ¬æ现æžäžã§ã¯ããã®çšèªã¯ã»ãŒçŽç²ãªã¯ããã·
ã©ã³äžã«ãããšæãããäžçŽç©ãå³ã¡ãªã³åå
ç©ã第æå
çŽ ã®ååç©åã³ãã®ä»ã®é»åã«å¯ã
ååç©ããæå³ãããã®ã§ããã The process of the present invention is useful for removing phosphorus and other Group elements from chlorosilanes that are then reduced to crystalline silicon for electronic applications. Phosphorus and its sister group elements such as arsenic, antimony or bismuth are of particular importance in the production of silicon for electronics because they donate an excess of free electrons. When these elements are added into the silicon matrix, the excess electrons change the (neutral) electrical properties of the silicon crystal and also interfere with the doping agents it contains to give the crystal semiconducting properties. do. Since these excess electrons contribute as negative charges, impurities such as phosphorus are called "n"-type (negative) impurities.
As used herein, the term also refers to impurities that may be present in substantially pure chlorosilane, namely phosphorus compounds, compounds of group elements, and other electron-rich compounds.
æ¬çºæã«ããé
žåé€å»ããã第æå
çŽ ã¯ãå
ž
åçã«ã¯ãç¹ã«é«æ°ŽæºïŒäŸãã°æ®çïœâåäžçŽç©
ãç·éã§200ppbããäœãïŒã®çŽåºŠã§ããã¯ãã
ã·ã©ã³äžã«ãäžå¡©åç©åã¯äžäŸ¡ã®å¡©çŽ æ°ŽçŽ åç©ç¶
æ
ã§èŠãåºãããããããã®äžçŽç©ã¯äžè¬åŒ
AHnCloã§è¡šãããããã®åŒäžã§ãã¯ãªã³ãã
çŽ ãã¢ã³ãã¢ã³åã³ãã¹ãã¹ããéžæãããïœå
ã³ïœã¯ïŒãïŒãïŒåã¯ïŒã§ããäžã€ïœïŒïœã¯ïŒå
ã¯ïŒã§ãããä»ã®åœ¢ã®ç¬¬æå
çŽ ååç©ãæ¬çºæ
æ¹æ³ã§é€å»ãåŸãããã¯ããã·ã©ã³äžã«æ®åãã
äžçŽç©ã®æãæ®åçãªåœ¢æ
ã¯äžåŒã§ç€ºããããã®
ã§ããã The Group elements to be oxidized by the present invention are typically trichloride or trivalent chlorine in chlorosilanes of particularly high purity (e.g. less than 200 ppb total residual n-type impurities). Found in hydride state. These impurities have the general formula
AH n Cl o in which A is selected from phosphorus, arsenic, antimony and bismuth, m and n are 0, 1, 2 or 3 and m+n is 3 or 5. Although other forms of Group element compounds may be removed by the process of the present invention, the most common form of impurity remaining in the chlorosilane is that represented by the above formula.
æ¬çºææ¹æ³ã®å¯Ÿè±¡ã§ãã第æå
çŽ ã®å
±éã®æ§
質ã¯ãããããå
šãŠãã®æå€æ®»é»åè»éã«ïŒåã®
é»åãæããŠããããšã§ããããã®ããšã¯ããã
ã¯ã®ååŠèŸå
žïŒHackhâ²s Chemical Dictionaryã
第çããã¯ã°ããŒãã«åïŒäž500ã501é ããåš
æéâThe Periodic Chainâãã«èšèŒãããŠã
ãããããå
çŽ ã®æãæ®åçãªåå䟡ã¯ïŒïŒïŒäž
䟡ïŒã§ããããå€æ®»ã«ïŒåã®é»åãããããïŒïŒ
å³ã¡äºäŸ¡ç¶æ
ãããšãåŸããäžäŸ¡ã®ç¬¬æå
çŽ å
åç©ãé
žåãããšããã®æå€æ®»è»éã«ããèªç±é»
åããå容äœã§ããé
žçŽ ïŒåå䟡âïŒïŒã«äŸäžã
åŸãã A common property of the group elements that are the object of the method of the invention is that they all have five electrons in their outermost electron orbitals. This is explained in Hackh's Chemical Dictionary.
It is described in ``The Periodic Chain,'' pages 500-501 of McGraw-Hill, 1st edition. The most common valence of these elements is +3 (trivalent), but since there are 5 electrons in the outer shell, +5
That is, it can take on a pentavalent state. When a trivalent group element compound is oxidized, it can donate free electrons in its outermost orbit to oxygen (valence -2), which is an acceptor.
æ¬çºæã®ç¬¬ïŒã®å·¥çšå³ã¡é
žåå·¥çšã§ã¯ãäžçŽç©
ã®é
žåãé²è¡ããæ¡ä»¶äžã§ãã¯ããã·ã©ã³æº¶æ¶²ã«
é
žåå€ãæ¥è§Šããããåã¯é
žåè¥ããã¯ç©ºæ°ãå°
å
¥ãããå€ãã®é
žåå€ãåœæ¥è
ã«å
¬ç¥ã§ãããã¯
ããã·ã©ã³æº¶æ¶²ã«çžæº¶æ§ã§äžã€æ®çããäžçŽç©ã
æå¹ã«é
žåãåŸãéãæ¬çºæã§ã®äœ¿çšã«é©ããŠã
ããç¶ããäžé
žåã¯ãã åã³äºé
žåãã³ã¬ã³ãç¹
ã«æ¬çºæã®ç²Ÿè£œã«é©ããŠãããåŸã€ãŠé
žåå€ã䜿
çšããæ¬çºæã®æ
æ§ã§å¥œãŸãã䜿çšãããããšã
ç¥èŠããããçŽç²ãªO2åã¯ä»ã®ã¬ã¹ãšæ··åãã
å³ã¡ç©ºæ°ãšããŠæ°äœç¶ã§é
žçŽ ãç³»ã«å°å
¥ããæ
æ§
ã§ã¯ã奜ãŸããã¯ãé
žåãä¿é²ããããã«çŽ«å€ç·
ïŒUVïŒç
§å°ãããUVç
§å°ã䜵çšãããšãåå¿é
床ã倧ãããªãããã®ããçŽç²ãªé
žçŽ ã¬ã¹ããå®
䟡ãªç©ºæ°ã䜿çšããŠãå
åãªé
žçŽ ãäŸçµŠã§ããã®
ã§ãããUVâé
žåã¯ã¯ããã·ã©ã³ãããäžçŽç©
ã«å¯Ÿããéžææ§ãé«ãããããã®ããæäœã®å¹ç
ãåäžããã In the first step of the present invention, that is, the oxidation step, the chlorosilane solution is brought into contact with an oxidizing agent or oxidation or air is introduced under conditions that allow oxidation of impurities to proceed. Many oxidizing agents are known to those skilled in the art and are suitable for use in the present invention as long as they are compatible with the chlorosilane solution and can effectively oxidize residual impurities. However, it has been found that chromium trioxide and manganese dioxide are particularly suitable for the purification of the present invention and are therefore preferably used in embodiments of the invention that use oxidizing agents. In embodiments where oxygen is introduced into the system in gaseous form, ie as air, mixed with pure O 2 or other gases, ultraviolet (UV) radiation is preferably applied to promote oxidation. When used in conjunction with UV irradiation, the reaction rate increases, and therefore sufficient oxygen can be supplied even with air, which is cheaper than pure oxygen gas. UV-oxidation is more selective for impurities than chlorosilanes, thus increasing the efficiency of the operation.
æ¬çºæã§äœ¿çšããé
žåå€ã®éã¯ãè¬å€ã®ã¿ã€
ããäžçŽç©ã®æ¿åºŠãå©çšããç¹å®ã®é
žååå¿ã®å
åŠçç¹æ§ãã®ä»ã«äŸåããã§ããããäžè¬ã«ãé
å°ã®äœ¿çšã¯ãç©è³ªåæ¯ã®ç¹ãããããŠå¿
ç¶çã«ã¯
ããã·ã©ã³ãäžéšé
žåãããã奜ãŸãããªããäž
æ¹ãäžçŽç©ã¯å®å
šã«é
žåããããšãæãŸãããã
ã®ãããæäžã®æ¡ä»¶äžã§ã®é
žåã®éäžè¶³ã®æé©ãª
ãã©ã³ã¹ãå®éšçã«ç¢ºãããå¿
èŠãããã奜ãŸã
ãè¬æ
å³ã¡äžé
žåã¯ãã åã¯äºé
žåãã³ã¬ã³ã䜿
çšããå Žåãããªã¯ããã·ã©ã³ãµã³ãã«äžã®äžçŽ
ç©ã®å®å
šé
žåã«ã¯ã倫ã
ãçŽïŒã10åã³çŽ10ã14
ã¢ã«åœéã®é
žåå€ãå¿
èŠã§ããããšãç¥èŠãã
ããé
žåå€ã¯å
žåçã«ã¯çŽæ¥ã¯ããã·ã©ã³ã«æ·»å
ãããŠæ··åããããé
žåã®çšåºŠãç¥ããããé©åœ
ãªééã§ãµã³ãã«ãåãåºãåšç¥ã®ã¯ãããã°ã©
ãã€ãŒã§åæããã The amount of oxidizing agent used in the present invention will depend on the type of agent, the concentration of impurities, the chemistry of the particular oxidation reaction utilized, etc. In general, the use of excess is undesirable from a material balance point of view and because of the inevitable partial oxidation of the chlorosilane. On the other hand, it is desirable that impurities be completely oxidized. For this reason, it is necessary to experimentally confirm the optimal balance between excess and deficiency of oxidation under given conditions. For complete oxidation of impurities in a trichlorosilane sample, when using the preferred formulations i.e. chromium trioxide or manganese dioxide, about 7 to 10 and about 10 to 14
It has been found that molar equivalents of oxidizing agent are required. The oxidizing agent is typically added directly to the chlorosilane and mixed. To determine the degree of oxidation, samples are taken at appropriate intervals and analyzed using well-known chromatography.
第æå
çŽ ååç©ãUVç
§å°ãšå
±ã«ç©ºæ°ïŒåã¯
é
žçŽ ïŒãšæ¥è§ŠãããŠé
žåããå Žåãå¿
èŠãªç©ºæ°ã®
éã¯ãäžçŽç©ã®æ¿åºŠãæ¹æã®çšåºŠãUVç
§å°ã®çš
床ããã®ä»ã®ããã€ãã®èŠå ã«äŸåãããç¶ããª
ãããæ ¹æ¬çã«ãUVç
§å°ãããšé
žåã®ããç³»ã«
éã空æ°ã®éã¯æžå°ã§ããããšãç¥èŠããããã
ã®ç¹ã«ã€ããŠã¯åŸã«è©³è¿°ãããUVç
§å°ã¯ç
§å°ã
åå
¥ããåå¿å®¹åšã«çŽæ¥ããŠãããããå¿è«UV
æºã®åŒ·åºŠã¯é
žåãä¿é²ãããããªãã®ã§ãªããã°
ãªããªãã When group element compounds are oxidized by contacting them with air (or oxygen) along with UV irradiation, the amount of air required depends on the concentration of impurities, the degree of agitation, the extent of UV irradiation, and several other factors. . Fundamentally, however, it has been found that UV irradiation can reduce the amount of air passing through the system for oxidation. This point will be explained in detail later. UV irradiation may be applied directly to the reaction vessel receiving the irradiation, but of course
The strength of the source must be such as to promote oxidation.
é
žåå·¥çšãå®äºãããšãäžçŽç©ãéžæçã«é¯å
ããŠå®å®ãªååç©ã圢æããããšãæå©ã§ããã
ãã®å®å®ååç©ã¯çŽã¯ããã·ã©ã³ã®ãã«ã¯èžçã§
æ®çããã§ãããããã®ç®çã«é©åããé¯åå€
ã¯ãã¯ããã·ã©ã³ãšçžæº¶æ§ã§ã¯ããã·ã©ã³äžã«å
åšããé
žåããã第æå
çŽ ãšéžæçã«çµåãé¯
äœã圢æãããã®ãªãä»»æã§ããããçæããç±
çã«å®å®ãªäžçŽç©ïŒé¯åå€ã®é¯äœããã¯ããã·ã©
ã³ãèžçã«ããåé¢ããã®ã¯å®¹æã§ãããããã¯
é¯åå€ã«ã¯ãé·ç§»éå±ããã²ã³åç©åã³ã«ã€ã¹é
ž
ååç©ãå«ãŸãããããã¯ã¯ããã·ã©ã³ãããªã
ã¯ã¹äžã«ååšããé»åã«å¯ã第æå
çŽ ãšåå¿ã
ãã Once the oxidation step is complete, it is advantageous to selectively complex impurities to form stable compounds.
This stable compound will remain in bulk distillation of pure chlorosilane. Any complexing agent suitable for this purpose may be used as long as it is compatible with the chlorosilane and selectively binds to the oxidized group elements present in the chlorosilane to form a complex. It is easy to separate the chlorosilane from the impurity/complexing agent complex by distillation. Complexing agents include transition metal halides and Lewis acid compounds, which react with the electron-rich Group elements present in the chlorosilane matrix.
æ¬çºæã®ç®çã«é©ããããšãç¥èŠãããé·ç§»é
å±ããã²ã³åç©ã®ãã¡å¥œãŸãããã®ã¯ãåå¡©åãž
ã«ã³ããŠã åã³åå¡©åããããŠã ã§ããããªã³ãª
ãã·å¡©åç©ã®åŠãååç©ãããªã¯ããã·ã©ã³äžã§
åå¡©åãžã«ã³ããŠã ãšïŒïŒïŒé¯äœã圢æããã
ãšãåã³ããã®é¯åå€ãã¯ããã·ã©ã³æº¶æ¶²ããå
èšã®ãããªäžçŽç©ã®99.9ïŒ
以äžãé€å»ãåŸãããš
ãç¥èŠãããããã®çš®ã®ä»ã®é·ç§»éå±ããã²ã³å
ç©ãäžå¿
èŠãªå®éšãããããšãªãã¯ããã·ã©ã³ãš
çžæº¶æ§ã§ãããäžã€æ®çããéåžžã®ç¬¬æå
çŽ ã
å¹ççã«é¯åããããšãç¥èŠãããããããæ¬çº
æã®ç®çãå
åã«éæãåŸãã Preferred transition metal halides found to be suitable for the purposes of the present invention are zirconium tetrachloride and hafnium tetrachloride. It has been found that compounds such as phosphorus oxychloride form a 1:1 complex with zirconium tetrachloride in trichlorosilane and that this complexing agent can remove more than 99.9% of such impurities from chlorosilane solutions. It was done. Other transition metal halides of this type have also been found to be compatible with chlorosilanes without unnecessary experimentation and to efficiently complex residual common group elements, and these are also suitable for use in the present invention. The purpose can be fully achieved.
ãã«ã€ã¹é
žãã¯é»å察ãåãåã€ãŠå
±æçµåã
圢æããïŒå³ã¡ãé»å察å容äœãïŒã§ãããæ¬çº
æã®ç®çãéæããããã«äœ¿çšãåŸããããã¯ã
ãŒãªãŒâãã¬ã³ã¹ãããã®é
žã®å®çŸ©å³ã¡ãããã
ã³äŸäžäœãã®æŠå«ãå
å«ãããäŸãã°äžããåã
ãŠçŽ ïŒBF3Qã¯ãæå€æ®»é»åè»éã«ïŒåã®é»åã
ããã€ãŠããªãã®ã§ãå
žåçãªã«ã€ã¹é
žã§ããã
BF3ã¯èªç±é»å察ãå容ããŠïŒé»åè»éãå®æã
ããåŸåãæããŠãããåºç¯å²ã®ã«ã€ã¹é
žãæ¬çº
æã®å¯Ÿè±¡ã§ããç¹å®ã®ç¬¬æå
çŽ ååç©ãšã®çµå
ã«äœ¿çšã§ããããäžå¡©åããŠçŽ ïŒBCl3ïŒã®ãã
ãªã«ã€ã¹é
žã¯é€å»ãå°é£ãªäžçŽç©ã§ããå
çŽ ãã¯
ããã·ã©ã³ç³»ã«ãã¡èŸŒãããšã«ãªããç¹ã«ããŠçŽ
ã¯é»åæ©åšçšã±ã€çŽ ã®è£œé ã«ãããŠç²Ÿè£œãå°é£ã§
ãããšããåé¡ãæèµ·ãããããããŠçŽ ã®äœ¿çšã¯
éåžžé¿ããã¹ãã§ããããã®ãããæ¬çºæã®ç®ç
ã«å¥œé©ãªã«ã€ã¹é
žé¯åå€ã¯ãã¯ããã·ã©ã³ããã®
é€å»ããã容æãªå
çŽ ãå«ããã®ããããæã奜
ãŸããã®ã¯é
žå第äºéïŒFeCl3ïŒãšå¡©åã¢ã«ãã
ãŠã ïŒAlCl3ïŒã§ããã "Lewis acids" are those that accept a pair of electrons to form a covalent bond (ie, "electron pair acceptors") and may be used to accomplish the objectives of the present invention. This encompasses the Lowry-Brensted definition of acid, i.e., the general meaning of "proton donor." For example, boron trifluoride (BF 3 Q) has only 6 electrons in the outermost electron orbital, so it is a typical Lewis acid.
BF 3 has a tendency to accept free electron pairs to complete the eight-electron orbital. Although a wide variety of Lewis acids can be used to bond with the specific Group element compounds of interest in this invention, Lewis acids such as boron trichloride (BCl 3 ) are difficult to remove impurities in the chlorosilane system. I will bring it in. In particular, the use of boron should generally be avoided as it poses problems of being difficult to purify in the production of silicon for electronics. For this reason, Lewis acid complexing agents suitable for the purpose of the present invention preferably contain elements that are easier to remove from chlorosilane. Most preferred are ferric oxide (FeCl 3 ) and aluminum chloride (AlCl 3 ).
æ±æãããã¯ããã·ã©ã³æº¶æ¶²ã«æ·»å ããé¯åå€
ã®éã¯ããã®ååç©ãšæ¢ã«é
žåãããäžçŽç©ãšã
å
åã«åå¿ãããããªéã§ãããåå¿æéåã³äž
çŽç©ã®å®å
šé€å»ãšããæå³ã§ã¯ãæ±æç©è³ªã®æ¿åºŠ
ã«å¯ŸãäŸãã°ïŒã50åéå°ã®ã¢ã«éã§ãããšæè¯
ã®çµæãåŸããããç¶ããªããã溶液äžã«ååšã
ãäžçŽç©ãšæå¹ã«çµåããéã§ããã°ããããšã¯
ç解ããããã The amount of complexing agent added to the contaminated chlorosilane solution is such that sufficient reaction occurs between this compound and the already oxidized impurities. In terms of reaction time and complete removal of impurities, best results are obtained with a molar excess of, for example, 2 to 50 times relative to the concentration of contaminants. However, it will be understood that the amount may be sufficient as long as it effectively binds to impurities present in the solution.
é¯åå€ã溶液ã«æ··åããåŸãé
žåäžçŽç©ãšé¯å
å€ååç©ãšã®åå¿ãä¿é²ãããããæ··åç©ãå ç±
ããŠããããããŸãé«æž©å³ã¡150âãè¶
ãããšåœ¢
æããé¯äœãå€å°å解ããã§ãããããããŸãäœ
æž©ã§ã¯å
šäžçŽç©ãå¹ççã«é€å»ããã«ã¯äžå
åã§
ãããããã®ãããªçç±ã§ãåå¿æž©åºŠã¯ïŒâãçŽ
125âã奜ãŸãããç¶ããåå¿çæç©ãã¯ããã·
ã©ã³ãšåäžçåã§èžçãããåŸã€ãŠç²Ÿè£œéçšã§æ··
å
¥ããªãéãã«æŒããŠãäžèšç¯å²ä»¥äžã®é«æž©ã䜿
çšãåŸããçŽ100â以äžã®æž©åºŠã§æè¯ã®çµæãåŸ
ããããã¯ããã·ã©ã³ã®æ©æèžçãèµ·ããã®ãé²
ãããã«ãåå¿å®¹åšå
ãå å§ããŠããããæäžã®
æ¡ä»¶äžã§æé©ã®åå¿æž©åºŠåã³å§åã決ããã«ã¯ç°¡
åãªå®éšãããã°ããã After the complexing agent is mixed into the solution, the mixture may be heated to promote the reaction between the oxidized impurities and the complexing agent compound. Too high a temperature, i.e. above 150°C, will cause some decomposition of the complex formed, and too low a temperature may not be sufficient to efficiently remove all impurities. For this reason, the reaction temperature ranges from 0°C to approx.
125°C is preferred. However, elevated temperatures above the above range may be used as long as the reaction products are not distilled in the same fraction as the chlorosilane and are therefore not contaminated during the purification process. Best results were obtained at temperatures below about 100°C. Pressurization may be applied within the reaction vessel to prevent premature distillation of the chlorosilane from occurring. Simple experimentation can be used to determine the optimum reaction temperature and pressure under given conditions.
æ¢ã«èšèŒããããã«ãå®è³ªçã«å
šãŠã®äžçŽç©ã
çµåããŠç±çã«å®å®ãªé¯äœã圢æãããŸã§åå¿ã
ç¶è¡ãããå¿è«ãåå¿æéã¯äœ¿çšããç©è³ªãæž©
床ãå§åçã«ãã€ãŠå€åããã§ããããç°¡åãªå®
éšã«ãã€ãŠæäžã®ç²Ÿè£œã«å¿
èŠãªæé©ã®åå¿æéã
決å®ã§ããã§ãããã As previously described, the reaction is continued until substantially all of the impurities have combined to form a thermally stable complex. Of course, reaction times will vary depending on the materials used, temperature, pressure, etc. Simple experimentation will determine the optimal reaction time required for a given purification.
æ¬çºæã®ç²Ÿè£œæ¹æ³ã«æŒããæçµå·¥çšã¯ãçŽç²ãª
ã¯ããã·ã©ã³ãåå¿æº¶æ¶²ããèžçããããšã§ã
ããã¯ããã·ã©ã³ã«å¯ŸããŠäžçŽç©ã®æ®çºæ§ãäœã
ãªã€ãŠããããããã®æçµèžçå·¥çšãå¯èœã«ãª
ãã The final step in the purification method of the present invention is to distill pure chlorosilane from the reaction solution. This final distillation step is possible because of the reduced volatility of the impurities relative to the chlorosilane.
èžçã¯å€§æ°å§ã§è¡ãªã€ãŠãããããåã¯ã液äœ
ã®æž©åºŠãäžçŽç©ãæ¬çºææ¹æ³ã®åã®å·¥çšã§åœ¢æã
ããäžçŽç©é¯äœã®å解枩床ãè¶ããªãç¯å²ã§å å§
äžã§è¡ãªã€ãŠãããã溶液ã®æž©åºŠã¯çŽ200âãã
äœãæããã®ã奜ãŸããã Distillation may be carried out at atmospheric pressure or under pressure, provided that the temperature of the liquid does not exceed the decomposition temperature of the impurities or impurity complexes formed in the previous steps of the process. Preferably, the temperature of the solution is kept below about 200°C.
åœæ¥è
ãæ¬çºæã®å®æœã容æã«ããã®ãå©ãã
ã¹ãã説æã®ããã«ä»¥äžã«å®æœäŸãæ²ããããæ¬
çºæã¯ããã«éå®ããããã®ã§ã¯ãªãã To assist those skilled in the art in practicing the invention, the following examples are provided for illustrative purposes, but the invention is not limited thereto.
å®æœäŸ ïŒ
é
žåå€ã䜿çšããŠã®PCl3ããPOCl3ãžã®å€æ
500ppmã®äžå¡©åãªã³ãå«ãããªã¯ããã·ã©ã³
ã®æšæºæº¶æ¶²ãåå¿å®¹åšã«å
¥ããã溶液ãæ¿ããæ¹
æããªããäºé
žåãã³ã¬ã³ãæ·»å ããåå¿æ··åç©
ã®ãµã³ãã«ãåšæçã«åãåºããäžå¡©åãªã³ãšãª
ãã·å¡©åãªã³ã®å€«ã
ã®æ¿åºŠãã¯ãããã°ã©ãã€ãŒ
ã§æž¬å®ããã10ã14ã¢ã«åœéã®äºé
žåãã³ã¬ã³ã
å®å
šãªé
žåã«å¿
èŠã§ããããªã³ãïŒæé以å
ã«å®
éçã«äºäŸ¡ç¶æ
ã«é
žåãããããšãå€æãããExample 1 Conversion of PCl3 to POCl3 using an oxidizing agent A standard solution of trichlorosilane containing 500 ppm phosphorous trichloride was placed in a reaction vessel. Manganese dioxide was added to the solution with vigorous stirring, and samples of the reaction mixture were taken periodically to determine the respective concentrations of phosphorus trichloride and phosphorus oxychloride by chromatography. It was found that 10-14 molar equivalents of manganese dioxide were required for complete oxidation and that phosphorus was quantitatively oxidized to the pentavalent state within 2 hours.
å®æœäŸ ïŒ
å
é
žåã«ããPCl3ã®POCl3ãžã®å€æ
5000ppmã®äžå¡©åãªã³ãå«ãããªã¯ããã·ã©ã³
ã®æšæºæº¶æ¶²ãããã©ã€ã¢ã€ã¹ã³ã³ãã³ãµãŒåã³ã¬
ã¹å°å
¥å£ãåããéæãªãã©ã¹ã³ã«å
¥ããã也ç¥
空æ°ã50cm3ïŒåã§å°å
¥å£ããå
¥ãæ¹æããŠæ¥éã«
åæ£ãããããã©ã€ã¢ã€ã¹ã³ã³ãã³ãµãŒã¯ãã¬ã¹
æµäžã®ããªã¯ããã·ã©ã³ãå·åŽåçž®ããã®ã«å
å
ã§ãã€ããããªã¯ããã·ã©ã³æº¶æ¶²ã®ãµã³ãã«ãå®
æçã«åãåºããäžå¡©åãªã³ãšãªãã·å¡©åãªã³ã®
çžå¯Ÿæ¿åºŠãã¯ãããã°ã©ãã€ãŒã§æž¬å®ããã16ã¢
ã«éå°ã®é
žçŽ ïŒç©ºæ°äžïŒãç³»ã«éããæç¹ã§ã¯ïŒ
ãïŒïŒ
ã®PCl3ããPOCl3ã«é
žåãããŠããªãããš
ãå€æãããExample 2 Conversion of PCl3 to POCl3 by photooxidation A standard solution of trichlorosilane containing 5000 ppm phosphorus trichloride was placed in a transparent flask equipped with a dry ice condenser and a gas inlet. Dry air was introduced from the inlet at 50 cm 3 /min and stirred to rapidly disperse the mixture. A dry ice condenser was sufficient to cool and condense the trichlorosilane in the gas stream. Samples of the trichlorosilane solution were taken periodically and the relative concentrations of phosphorus trichloride and phosphorus oxychloride were determined by chromatography. 1 when a 16 molar excess of oxygen (in air) is passed through the system.
It was found that only ~5% of PCl3 was oxidized to POCl3 .
空æ°ãå°å
¥ãæ¹æåæ£ããªãããµã³ãã«ãç
§å°
ããŠå®éšãç¶è¡ãããPCl3ã®å®å
šãªé
žåã«ã¯2.4
ã¢ã«éå°ã®é
žçŽ ã§å
åã§ããããšãå€æããã The experiment was continued by introducing air and irradiating the sample while stirring and dispersing it. 2.4 for safe oxidation of PCl 3
A molar excess of oxygen has been found to be sufficient.
å¿
èŠãªé
žçŽ éãæžå°ããããšã¯ãé
žçŽ ã«å¯Ÿãã
PCl3ã®ååŠéè«éã2.5ã§ããããšãæå³ããã®
ã§ã¯ãªããã¢ã«æ¯ã質éäœçšã«ãã€ãŠæ±ºå®ããã
ããšã瀺åãããã®ãšæãããã The reduction in the amount of oxygen required means that
This does not imply that the stoichiometry of PCl 3 is 2.5, but rather suggests that the molar ratio was determined by mass action.
å®æœäŸ ïŒ
é·ç§»éå±ããã²ã³åç©ã®é¯åå€ã䜿çšãã
POCl3ã®é¯äœå
ãªãã·å¡©åãªã³1.5éééšãå«ãããªã¯ããã·
ã©ã³450éééšã®æº¶æ¶²ã«4.6éééšã®åå¡©åãžã«ã³
ããŠã ãæ·»å ããã溶液ãäžæ©æ¹æããåŸãã¯ã
ããã°ã©ãåæã«ãããšPOCl3ãããªã¯ããã·ã©
ã³æº¶æ¶²ããå®éçã«é€å»ãããŠãããExample 3 Using a transition metal halide complexing agent
Complexation of POCl 3 To a solution of 450 parts by weight of trichlorosilane containing 1.5 parts by weight of phosphorous oxychloride, 4.6 parts by weight of zirconium tetrachloride were added. After stirring the solution overnight, chromatographic analysis showed that POCl 3 was quantitatively removed from the trichlorosilane solution.
å®æœäŸ ïŒ
ã«ã€ã¹é
žé¯åå€ã䜿çšããPOCl3ã®é¯å
ãªãã·å¡©åãªã³1.7éééšãå«ãããªã¯ããã·
ã©ã³402éééšã®æº¶æ¶²ã«äžå¡©åã¢ã«ãããŠã 5.0é
ééšãæ·»å ãããæ··åç©ãïŒã®åå¿å®¹åšã«å
¥ã
100âã«å ç±ãããå®æçã«ãµã³ãã«ãåãåºã
POCl3ã®æ¿åºŠã枬å®ãããïŒæéåŸãäžéšã¬ã¹ã«
ã¯POCl3ã¯æ€åºãããªãã€ããExample 4 Complexation of POCl 3 using a Lewis acid complexing agent 5.0 parts by weight of aluminum trichloride were added to a solution of 402 parts by weight of trichlorosilane containing 1.7 parts by weight of phosphorous oxychloride. Put the mixture into reaction container 1.
Heated to 100°C. Take samples regularly
The concentration of POCl3 was measured. After 1 hour, no POCl 3 was detected in the upper gas.
Claims (1)
åã³ãã¹ãã¹ããæã矀ããéžæãããå çŽ ïŒçš®
以äžã®äžå¡©åç©ãè¶ é«çŽåºŠã®ããªã¯ããã·ã©ã³ã
ãé€å»ããæ¹æ³ïŒ (A) åèšäžå¡©åç©ãå®å šã«é žåããŠåèšå çŽ ãäº
䟡ã®ãªãã·å¡©åç©ã«ããã®ã«æå¹ãªæéããã
ãŠãåèšäžå¡©åç©ã®ã¢ã«æ¿åºŠã«å¯ŸããŠéå°éã®
é žåå€ãåèšäžå¡©åç©ã«æ¥è§ŠããïŒãã ããå
èšé žåå€ã¯çŽ«å€ç·ã«æãããŠããO2ãäžé žå
ã¯ãã åã³äºé žåãã³ã¬ã³ããæã矀ããéžæ
ãããïŒïŒ (B) åèšããªã¯ããã·ã©ã³ã«å¯ŸããŠãåèšãªãã·
å¡©åç©ã®ã¢ã«æ¿åºŠã«å¯ŸããŠïŒã50åéå°éã®é¯
åå€ãæ·»å ããŠïŒãã ããåèšé¯åå€ã¯åå¡©å
ãžã«ã³ããŠã ãåå¡©åããããŠã ãå¡©å第äºé
åã³å¡©åã¢ã«ãããŠã ããæã矀ããéžæãã
ãïŒïŒ (C) åèšãªãã·å¡©åç©ãšåèšé¯åå€ãšã®éã«ç±å®
å®æ§ã®ããé¯äœã圢æãããã®ãä¿é²ããã®ã«
ååãªæéããããŠçŽïŒâãçŽ125âã®æž©åºŠã«
åèšããªã¯ããã·ã©ã³ãå ç±ããäžæ¹ãåèšã
ãªã¯ããã·ã©ã³ã®èžçºãé²æ¢ããã®ã«æå¹ãªå§
åæ¡ä»¶ãç¶æããŠïŒãããã (D) åèšã®ç±å®å®æ§ã®ããé¯äœã®å解ãæãæž©
床ã»å§åæ¡ä»¶ãé¿ããªããçŽ100â以äžã®æž©åºŠ
ã«ãããŠèžçã«ãã粟補ããªã¯ããã·ã©ã³ãå
åºãã ïŒ åèšé žåå·¥çšïŒ¡ã«ãããŠãçŽïŒã10ã¢ã«åœé
ã®äžé žåã¯ãã ãŸãã¯çŽ10ã14ã¢ã«åœéã®äºé žå
ãã³ã¬ã³ãåèšäžå¡©åç©ã«æ¥è§Šãããç¹èš±è«æ±ã®
ç¯å²ç¬¬ïŒé èšèŒã®æ¹æ³ã ïŒ åèšé žåå·¥çšïŒ¡ã«ãããŠãO2ã玫å€ç·ã®å
åšäžã§ããªã¯ããã·ã©ã³ã«å°å ¥ããç¹èš±è«æ±ã®ç¯
å²ç¬¬ïŒé èšèŒã®æ¹æ³ã ïŒ äžèšã®å·¥çšãããªãPCl3äžçŽç©ãè¶ é«çŽåºŠ
ã®ããªã¯ããã·ã©ã³æº¶æ¶²ããé€å»ããç¹èš±è«æ±ã®
ç¯å²ç¬¬ïŒé èšèŒã®æ¹æ³ïŒ åèšããªã¯ããã·ã©ã³æº¶æ¶²ã«çŽ«å€ç·ãããŠãªã
ããã®æº¶æ¶²ã«ç©ºæ°ãå°ããŠãåèšPCl3ãå®è³ªäž
æ®ããPOCl3ã«é žåããŠïŒ åèšPOCl3ã®ã¢ã«æ¿åºŠã«å¯ŸããŠïŒã50åéå°é
ã®é¯åå€ãæ·»å ããäžæ¹ïŒãã ãåèšé¯åå€ã¯å
å¡©åãžã«ã³ããŠã ãåå¡©åããããŠã ãå¡©å第äº
éåã³ã¢ã«ãããŠã ããæã矀ããéžæãããïŒã
åèšæº¶æ¶²ãïŒã125âã®æž©åºŠã«å ç±ããŠãåèšé¯
åå€ãšå®è³ªçã«ãã¹ãŠã®åèšPOCl3ãšã®éã«ç±å®
å®æ§ã®ããé¯äœã圢æãïŒãããã åèšã®ç±å®å®æ§ã®ããé¯äœã®å解ãé¿ããªãã
çŽ100â以äžã®æž©åºŠã«ãããŠèžçã«ãã粟補ããª
ã¯ããã·ã©ã³ãååºãã[Claims] 1. A method for removing trichloride of one or more elements selected from the group consisting of phosphorus, arsenic, antimony, and bismuth from ultra-high purity trichlorosilane, comprising the following steps: (A) The above-mentioned An excess amount of oxidizing agent relative to the molar concentration of the trichloride is applied to the trichloride for a period of time effective to completely oxidize the element to the pentavalent oxychloride. (B) the molar concentration of the oxychloride relative to the trichlorosilane; by adding a 2 to 50 times excess of a complexing agent relative to the complexing agent, wherein said complexing agent is selected from the group consisting of zirconium tetrachloride, hafnium tetrachloride, ferric chloride and aluminum chloride; C) heating the trichlorosilane to a temperature of from about 0°C to about 125°C for a period of time sufficient to promote the formation of a thermally stable complex between the oxychloride and the complexing agent. while maintaining pressure conditions effective to prevent evaporation of said trichlorosilane; and (D) to about 100°C while avoiding temperature and pressure conditions that would lead to decomposition of said thermally stable complex. Purified trichlorosilane is removed by distillation at the following temperatures: 2. The method of claim 1, wherein in the oxidation step A, about 7 to 10 molar equivalents of chromium trioxide or about 10 to 14 molar equivalents of manganese dioxide are brought into contact with the trichloride. 3. The method according to claim 1, wherein in the oxidation step A, O 2 is introduced into trichlorosilane in the presence of ultraviolet light. 4. The method according to claim 1 for removing PCl 3 impurities from an ultra-high purity trichlorosilane solution, which comprises the following steps: While exposing the trichlorosilane solution to ultraviolet rays, air is introduced into this solution to remove the PCl 3 impurities from the solution. Oxidize substantially all of 3 to POCl 3 ; while adding a complexing agent in an excess amount of 2 to 50 times with respect to the molar concentration of POCl 3 (however, the complexing agent may be zirconium tetrachloride, hafnium tetrachloride, , ferric chloride and aluminum);
heating the solution to a temperature of 0 to 125°C to form a thermostable complex between the complexing agent and substantially all of the POCl3 ; Purified trichlorosilane is removed by distillation at a temperature below about 100°C while avoiding decomposition.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US43978382A | 1982-11-08 | 1982-11-08 | |
US439783 | 1982-11-08 |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS5997518A JPS5997518A (en) | 1984-06-05 |
JPH0151445B2 true JPH0151445B2 (en) | 1989-11-02 |
Family
ID=23746124
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP20843283A Granted JPS5997518A (en) | 1982-11-08 | 1983-11-08 | Purification of chlorosilanes |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS5997518A (en) |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5325003U (en) * | 1976-08-10 | 1978-03-03 |
-
1983
- 1983-11-08 JP JP20843283A patent/JPS5997518A/en active Granted
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5325003U (en) * | 1976-08-10 | 1978-03-03 |
Also Published As
Publication number | Publication date |
---|---|
JPS5997518A (en) | 1984-06-05 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US4374110A (en) | Purification of silicon source materials | |
EP2634142B1 (en) | Method for purifying chlorosilanes | |
US3540861A (en) | Purification of silicon compounds | |
JP4714198B2 (en) | Purification method of chlorosilanes | |
Audrieth | Inorganic Syntheses, Volume 3 | |
US20100278706A1 (en) | Method for reducing the content in elements, such as boron, in halosilanes and installation for carrying out said method | |
JP2008520535A (en) | Method and plant for purifying trichlorosilane and silicon tetrachloride | |
US4755370A (en) | Purification of silicon halides | |
US20110052474A1 (en) | Installation and method for reducing the content in elements, such as boron, of halosilanes | |
KR100501049B1 (en) | PURIFICATION OF GROUP IVb METAL HALIDES | |
JP5317707B2 (en) | Recycling method of high-boiling compounds in chlorosilane integrated plant | |
US4481178A (en) | Purification of chlorosilanes | |
KR100721090B1 (en) | Separation Process of Boron Compounds in Chlorosilanes and Composition for Evaporating Chlorosilanes | |
EP0620189A1 (en) | Process for separating arsenic acid from an aqueous mixture comprising sulfuric and arsenic acids | |
JPH0151445B2 (en) | ||
US3216785A (en) | Process for the purification of halogenated volatile compounds of germanium and silicon | |
US2812235A (en) | Method of purifying volatile compounds of germanium and silicon | |
JPS59137312A (en) | Purification of chlorosilane | |
US2821460A (en) | Method of purifying silicon tetrachloride and germanium tetrachloride | |
JPH0238521B2 (en) | FUTSUKASUISOSAN NOSEISEIHO | |
JPH0152326B2 (en) | ||
EP0105328A1 (en) | Purification of silicon halides | |
TWI811520B (en) | Process for producing purified chlorosilanes | |
JPH0640710A (en) | Production of high-purity phosphorus | |
JPS63195107A (en) | Production of silane |