US20060125129A1 - Vaporizer and apparatus for vaporizing and supplying - Google Patents
Vaporizer and apparatus for vaporizing and supplying Download PDFInfo
- Publication number
- US20060125129A1 US20060125129A1 US11/345,525 US34552506A US2006125129A1 US 20060125129 A1 US20060125129 A1 US 20060125129A1 US 34552506 A US34552506 A US 34552506A US 2006125129 A1 US2006125129 A1 US 2006125129A1
- Authority
- US
- United States
- Prior art keywords
- cvd material
- vaporizer
- vaporizing
- cvd
- supplying
- 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.)
- Abandoned
Links
- 230000008016 vaporization Effects 0.000 title claims abstract description 156
- 239000006200 vaporizer Substances 0.000 title claims abstract description 98
- 239000000463 material Substances 0.000 claims abstract description 288
- 239000007788 liquid Substances 0.000 claims abstract description 86
- 239000007787 solid Substances 0.000 claims abstract description 53
- 238000009834 vaporization Methods 0.000 claims abstract description 48
- 239000012159 carrier gas Substances 0.000 claims abstract description 41
- 239000007789 gas Substances 0.000 claims abstract description 19
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- 239000004065 semiconductor Substances 0.000 claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 claims abstract description 11
- 230000001939 inductive effect Effects 0.000 claims description 34
- 238000002156 mixing Methods 0.000 claims description 15
- 239000003960 organic solvent Substances 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 6
- 238000005304 joining Methods 0.000 claims description 4
- 230000002093 peripheral effect Effects 0.000 claims description 2
- 239000011343 solid material Substances 0.000 abstract description 11
- 230000000087 stabilizing effect Effects 0.000 abstract description 3
- 239000000411 inducer Substances 0.000 abstract 2
- 238000005229 chemical vapour deposition Methods 0.000 description 220
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 72
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 36
- 238000012360 testing method Methods 0.000 description 33
- 239000002904 solvent Substances 0.000 description 25
- 239000010936 titanium Substances 0.000 description 16
- 229910001220 stainless steel Inorganic materials 0.000 description 15
- 239000010935 stainless steel Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 8
- 238000007872 degassing Methods 0.000 description 8
- 239000011344 liquid material Substances 0.000 description 8
- 238000001816 cooling Methods 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 239000000498 cooling water Substances 0.000 description 6
- 229920003002 synthetic resin Polymers 0.000 description 6
- 239000000057 synthetic resin Substances 0.000 description 6
- 239000007983 Tris buffer Substances 0.000 description 5
- 239000010408 film Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- SYBYTAAJFKOIEJ-UHFFFAOYSA-N 3-Methylbutan-2-one Chemical compound CC(C)C(C)=O SYBYTAAJFKOIEJ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 229910052454 barium strontium titanate Inorganic materials 0.000 description 2
- JDIBGQFKXXXXPN-UHFFFAOYSA-N bismuth(3+) Chemical compound [Bi+3] JDIBGQFKXXXXPN-UHFFFAOYSA-N 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 230000002542 deteriorative effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 description 2
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 description 2
- PZHIWRCQKBBTOW-UHFFFAOYSA-N 1-ethoxybutane Chemical compound CCCCOCC PZHIWRCQKBBTOW-UHFFFAOYSA-N 0.000 description 1
- NVJUHMXYKCUMQA-UHFFFAOYSA-N 1-ethoxypropane Chemical compound CCCOCC NVJUHMXYKCUMQA-UHFFFAOYSA-N 0.000 description 1
- CXBDYQVECUFKRK-UHFFFAOYSA-N 1-methoxybutane Chemical compound CCCCOC CXBDYQVECUFKRK-UHFFFAOYSA-N 0.000 description 1
- KTOQRRDVVIDEAA-UHFFFAOYSA-N 2-methylpropane Chemical compound [CH2]C(C)C KTOQRRDVVIDEAA-UHFFFAOYSA-N 0.000 description 1
- OXJUCLBTTSNHOF-UHFFFAOYSA-N 5-ethylcyclopenta-1,3-diene;ruthenium(2+) Chemical compound [Ru+2].CC[C-]1C=CC=C1.CC[C-]1C=CC=C1 OXJUCLBTTSNHOF-UHFFFAOYSA-N 0.000 description 1
- 208000019901 Anxiety disease Diseases 0.000 description 1
- 229910015446 B(OCH3)3 Inorganic materials 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- ZXDZWIUQGOILGY-UHFFFAOYSA-N C[Pt](C1(C=CC=C1)CC)(C)C Chemical compound C[Pt](C1(C=CC=C1)CC)(C)C ZXDZWIUQGOILGY-UHFFFAOYSA-N 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- 229910000617 Mangalloy Inorganic materials 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 229910017333 Mo(CO)6 Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910019651 Nb(OC2H5)5 Inorganic materials 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910007161 Si(CH3)3 Inorganic materials 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical compound C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 description 1
- WMCDPJBMKMIPCP-UHFFFAOYSA-N [Sr].CC(C)O[Ta](OC(C)C)(OC(C)C)(OC(C)C)(OC(C)C)OC(C)C.CC(C)O[Ta](OC(C)C)(OC(C)C)(OC(C)C)(OC(C)C)OC(C)C Chemical compound [Sr].CC(C)O[Ta](OC(C)C)(OC(C)C)(OC(C)C)(OC(C)C)OC(C)C.CC(C)O[Ta](OC(C)C)(OC(C)C)(OC(C)C)(OC(C)C)OC(C)C WMCDPJBMKMIPCP-UHFFFAOYSA-N 0.000 description 1
- VNSWULZVUKFJHK-UHFFFAOYSA-N [Sr].[Bi] Chemical compound [Sr].[Bi] VNSWULZVUKFJHK-UHFFFAOYSA-N 0.000 description 1
- OFJKHPLWPKGHQP-UHFFFAOYSA-N [Sr].[Ta+6].[Ta+6].CC[O-].CC[O-].CC[O-].CC[O-].CC[O-].CC[O-].CC[O-].CC[O-].CC[O-].CC[O-].CC[O-].CC[O-] Chemical compound [Sr].[Ta+6].[Ta+6].CC[O-].CC[O-].CC[O-].CC[O-].CC[O-].CC[O-].CC[O-].CC[O-].CC[O-].CC[O-].CC[O-].CC[O-] OFJKHPLWPKGHQP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000036506 anxiety Effects 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- UXDJAZOVQLXLJJ-UHFFFAOYSA-N cycloocta-1,5-diene;ethylcyclopentane;iridium Chemical compound [Ir].CC[C]1[CH][CH][CH][CH]1.C1CC=CCCC=C1 UXDJAZOVQLXLJJ-UHFFFAOYSA-N 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- TUTOKIOKAWTABR-UHFFFAOYSA-N dimethylalumane Chemical compound C[AlH]C TUTOKIOKAWTABR-UHFFFAOYSA-N 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- GCSJLQSCSDMKTP-UHFFFAOYSA-N ethenyl(trimethyl)silane Chemical compound C[Si](C)(C)C=C GCSJLQSCSDMKTP-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- -1 for example Substances 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- HFGPZNIAWCZYJU-UHFFFAOYSA-N lead zirconate titanate Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ti+4].[Zr+4].[Pb+2] HFGPZNIAWCZYJU-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- ZTILUDNICMILKJ-UHFFFAOYSA-N niobium(v) ethoxide Chemical compound CCO[Nb](OCC)(OCC)(OCC)OCC ZTILUDNICMILKJ-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical compound C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- RLJWTAURUFQFJP-UHFFFAOYSA-N propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CC(C)O.CC(C)O.CC(C)O RLJWTAURUFQFJP-UHFFFAOYSA-N 0.000 description 1
- VRMGPHYEHNLCQW-UHFFFAOYSA-N propan-2-ylcyclopentane;tungsten Chemical compound [W].CC(C)[C]1[CH][CH][CH][CH]1.CC(C)[C]1[CH][CH][CH][CH]1 VRMGPHYEHNLCQW-UHFFFAOYSA-N 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- HSXKFDGTKKAEHL-UHFFFAOYSA-N tantalum(v) ethoxide Chemical compound [Ta+5].CC[O-].CC[O-].CC[O-].CC[O-].CC[O-] HSXKFDGTKKAEHL-UHFFFAOYSA-N 0.000 description 1
- GXMNGLIMQIPFEB-UHFFFAOYSA-N tetraethoxygermane Chemical compound CCO[Ge](OCC)(OCC)OCC GXMNGLIMQIPFEB-UHFFFAOYSA-N 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- BUZKVHDUZDJKHI-UHFFFAOYSA-N triethyl arsorite Chemical compound CCO[As](OCC)OCC BUZKVHDUZDJKHI-UHFFFAOYSA-N 0.000 description 1
- JGOJQVLHSPGMOC-UHFFFAOYSA-N triethyl stiborite Chemical compound [Sb+3].CC[O-].CC[O-].CC[O-] JGOJQVLHSPGMOC-UHFFFAOYSA-N 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- HYWCXWRMUZYRPH-UHFFFAOYSA-N trimethyl(prop-2-enyl)silane Chemical compound C[Si](C)(C)CC=C HYWCXWRMUZYRPH-UHFFFAOYSA-N 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- ZHXAZZQXWJJBHA-UHFFFAOYSA-N triphenylbismuthane Chemical compound C1=CC=CC=C1[Bi](C=1C=CC=CC=1)C1=CC=CC=C1 ZHXAZZQXWJJBHA-UHFFFAOYSA-N 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/448—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials
- C23C16/4485—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials by evaporation without using carrier gas in contact with the source material
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S261/00—Gas and liquid contact apparatus
- Y10S261/65—Vaporizers
Definitions
- the present invention relates to a vaporizer and an apparatus for vaporizing and supplying that are employed for supplying a gaseous CVD material for a chemical vapor deposition (CVD) apparatus used in the manufacture of a semiconductor and the like. More particularly, it pertains to a vaporizer and an apparatus for vaporizing and supplying that are employed for supplying a liquid CVD material or a solution of a liquid CVD material of a solid CVD material in a solvent each at desirable concentration and flow rate in high efficiency for the apparatus used in the manufacture of a semiconductor.
- CVD chemical vapor deposition
- a lead titanate zirconate (PZT) film, a barium strontium titanate (BST) film, a tantalic acid strontium bismuth (SBT) film, a titanic acid zirconate lantern lead (PLZT) film, etc. each having a high dielectric constant and also a high step coverage has been used as an oxide-based dielectric film for a semiconductor memory.
- Pb(DPM) 2 solid material
- Zr ⁇ OC(CH 3 ) 3 ⁇ 4 liquid material
- Zr(DPM) 4 solid material
- Ti ⁇ OCH(CH 3 ) 2 ⁇ 4 liquid material
- Ti(OCH (CH 3 ) 2 ) 2 (DPM) 2 solid material) as Ti sources
- Ba(DPM) 2 solid material
- Sr(DPM) 2 solid material
- a liquid material when being used as a CVD material, is usually introduced into a vaporizer along with a carrier gas via a flow rate controller, and the mixed gas is made into a gaseous form in the vaporizer and thereafter is fed to a CVD apparatus.
- the liquid material has usually a low vapor pressure, a high viscosity and a vaporizing temperature close to a decomposing temperature.
- a solid material although being capable of assuring highly pure material by being kept at an elevated temperature to sublime itself, makes it extremely difficult to assure sufficient supply amount in an industrial scale.
- a solvent such as tetrahydrofuran to make it into a liquid material so as to vaporize.
- a solid material has a vaporizing temperature greatly different from that of a solvent, a solvent alone is more apt to vaporize by heating, thereby making it more difficult to vaporize a liquid material.
- U.S. Pat. No. 6,473,563 B proposes a vaporizer wherein at least a portion of a CVD material feed portion in contact with a CVD material is constituted of a corrosion resistant synthetic resin; and an apparatus for vaporizing and supplying which comprises a cooler and the vaporizer wherein the inside of the CVD material feed portion of the vaporizer and the surface on the side of the vaporization chamber of the CVD material feed portion are constituted of a corrosion resistant synthetic resin; the feed portion in contact with the outside of the vaporizer is constituted of a metal; and the CVD material feed portion which is constituted of a metal and which undergoes heat transfer from the heating means upon heating the vaporization chamber can be cooled with a cooler.
- the foregoing vaporizer enabled, even in the case of using a solid CVD material dissolved in an organic solvent as a CVD material, only the material to be vaporized with an efficiency of 99.9% or higher because any abrupt heating was prevented without generating any deposit of the material accompanied with adhesion thereof.
- the foregoing apparatus for vaporizing and supplying is equipped with a mechanism for cooling the CVD material feed portion at the time of heating the vaporization chamber, and the apparatus was least liable to the adhesion of deposits.
- an object of the present invention is to provide, even in the case of vaporizing and supplying with a decrease in a feed amount of a carrier gas to be supplied accompanying the CVD material employing a solid CVD material, a vaporizer and an apparatus for vaporizing and supplying which comprises the aforesaid vaporizer, which is capable of efficiently vaporizing a CVD material with a desirable concentration and flow rate without causing deposit or adhesion of the solid material in the CVD material feed port.
- the present invention provides a vaporizer comprising a vaporization chamber for a CVD material, a CVD material feed portion supplying the CVD material for the vaporization chamber, a vaporized gas exhaust port and a heating means for heating the vaporization chamber, characterized in that the CVD material feed portion has passageways for the CVD material and for a carrier gas respectively and the passageway for the CVD material has a pressure loss-inducing means for the CVD material.
- the present invention provides an apparatus for vaporizing and supplying that feeds a CVD material to a vaporizer via a liquid flow controller, and after vaporizing the CVD material that supplies the vaporized gas for a semiconductor production apparatus, characterized in having a pressure loss-inducing means for the CVD material between the liquid flow controller and the vaporizer.
- FIG. 1 is a vertical cross-sectional view showing one embodiment of a vaporizer according to the present invention
- FIG. 2 is a vertical cross-sectional view showing another embodiment of a vaporizer according to the present invention.
- FIG. 3 ( 1 ) to ( 6 ) each is a vertical cross-sectional view showing embodiments of a CVD material feed portion according to the present invention
- FIG. 4 ( a ) to ( d ) each is a horizontal cross-sectional view of a-a′ face, b-b′ face, c-c′ face, and d-d′ face of ( 1 ) to ( 4 ) respectively in FIG. 3 ;
- FIG. 5 ( 1 ) to ( 3 ) each is a horizontal cross-sectional view of A-A′ face (a surface of exhausting a CVD material and a carrier gas to a vaporizing chamber) in FIG. 3 ;
- FIG. 6 is a schematic flow diagram illustrating one embodiment of the constitution of an apparatus for vaporizing and supplying according to the present invention
- FIGS. 7 ( 1 ) and ( 2 ) each is a vertical cross-sectional view illustrating an embodiment of a throttle portion and an orifice respectively in the present invention.
- FIG. 8 is a vertical cross-sectional view illustrating an embodiment of a filter in the present invention.
- the present invention is applied to a vaporizer which vaporizes a liquid CVD material or a liquid CVD material made up of a solution of a solid CVD material in a solvent, and which supplies a CVD apparatus or the like with a vaporized gas.
- the vaporizer exhibits its effect particularly in view of the capability of reducing and stabilizing both the pressure fluctuation in the vaporizer and the flow rate fluctuation in the liquid flow controller and the capability of preventing the deposit and adhesion of a solid CVD material inside the vaporizer.
- the vaporizer according to the present invention is a vaporizer in which the CVD material feed portion has passageways for the CVD material and for a carrier gas respectively and the passageway for the CVD material has a pressure loss-inducing means for the CVD material.
- the apparatus for vaporizing and supplying according to the present invention is an apparatus for vaporizing and supplying having a pressure loss-inducing means for the CVD material between the liquid flow controller and the vaporizer.
- the CVD material to which are applicable the vaporizer and the apparatus for vaporizing and supplying is not specifically limited, provided that the CVD material can be kept in liquid state whether it is in liquid state at ordinary temperature or a solution of a solid dissolved in a solvent.
- the CVD material is properly and optionally selected for a use according to the purpose of the use.
- Examples thereof include an alkoxide in liquid state at ordinary temperature such as tetra isopropoxy titanium (Ti(OCH(CH 3 ) 2 ) 4 ), tetra-n-propoxytitanium (Ti(OCH 3 H 7 ) 4 ), tetra-tert-butoxyzirconium (Zr(OC(C 3 ) 3 ) 4 ), tetra-n-butoxyzirconium (Zr(OC 4 H 9 ) 4 ), tetramethoxyvanadium (V(OCH 3 ) 4 ), trimethoxyvanadyloxide (VO(OCH 3 ) 3 ), pentaethoxyniobium (Nb(OC 2 H 5 ) 5 ), pentaethoxytantalum (Ta(OC 2 H 5 ) 5 ), trimethoxyboron (B(OCH 3 ) 3 ), triisopropoxyaluminum (Al(OCH(CH 3 ) 2 ) 3
- Examples of the CVD material in liquid state at ordinary temperature other than the foregoing examples include trimethylaluminum (Al(CH 3 ) 3 ), dimethylaluminumhydride (Al(CH 3 ) 2 )H), triisobutylaluminum (Al(iso-C 4 H 9 ) 3 ), hexafluoroacetylacetonecopper vinyltrimethylsilane ((CF 3 CO) 2 CHCu.CH 2 CHSi(CH 3 ) 3 ), hexafluoroacetylacetonecopper allyltrimethylsilane ((CF 3 CO) 2 CHCu.CH 2 CHCH 2 Si(CH 3 ) 3 ), bis(isopropylcyclopentadienyl)tungsten dihydride ((iso-C 3 H 7 C 5 H 5 ) 2 WH 2 ), tetradimethylaminozirconium (Zr(N(CH 3 ) 2 ) 4 ), pentadimethylaminotantalum
- examples of the CVD material in solid state at ordinary temperature include hexacarbonylmolybdenum (Mo(CO) 6 ), dimethylpenthoxygold (Au(CH 3 ) 2 (OC 5 H 7 )), bismuth (III) tertiallybuthoxyd (Bi(OtBu) 3 ), bismuth (III) tertiallypenthoxyd (Bi(OtAm) 3 ), triphenylbismuth (BiPh 3 ), bis(ethylcyclopentadienyl)ruthenium(Ru(EtCp) 2 ), (ethylcyclopentadienyl) (trimethyl) platinum (Pt(EtCp)Me 3 ), 1,5-cyclooctadiene (ethylcyclopentadienyl) iridium (Ir(EtCp)(cod)), bis(hexaethoxytantalum) strontium (St[Ta(OEt) 6 ),
- heptanedionite titanium (Ti(OtBu) 2 (DPM) 2 ), (di-isopropoxy) bis(2,2,6,6,-tetramethyl-3,5,-heptanedionite) titanium (Ti(OiPr) 2 (DPM) 2 ), (isopropoxy) tris(2,2,6,6,-tetramethyl-3,5,-heptanedionite) zirconium (Zr(OiPr)(DPM) 3 ), (di-isopropoxy) tris(2,2,6,6,-tetramethyl-3,5,-heptanedionite) tantalum (Ta(OiPr) 2 (DPM) 3 ).
- the above-exemplified materials need to be dissolved in an organic solvent in a concentration of usually 0.1 to 1.0 mol/liter, approximately.
- the above-mentioned organic solvent to be used as a solvent for a solid CVD material is that having a boiling point usually ranging from 40 ⁇ to 140 ⁇ .
- the solvent include such ethers as propyl ether, methylbutyl ether, ethylpropyl ether, ethylbutyl ether, trimethylene oxide, tetrahydrofuran and tetrahydropyran; alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol and butyl alcohol; ketones such as acetone, ethylmethylketone, iso-propylmethylketone and iso-butylmethylketone; amines such as propylamine, butylamine, diethylamine, dipropylamine and triethylamine; esters such as ethyl acetate, propyl acetate and butyl acetate; and hydrocarbons such as hexane, heptane and octan
- FIGS. 1 and 2 are vertical cross-sectional views showing embodiments of vaporizers according to the present invention
- FIG. 3 ( 1 ) to ( 6 ) each is a vertical cross-sectional view showing embodiments of a CVD material feed portion according to the present invention
- FIG. 4 ( a ) to ( d ) each is a horizontal cross-sectional view of a-a′ face, b-b′ face, c-c′ face, and d-d′ face of ( 1 ) to ( 4 ) respectively in FIG. 3
- FIG. 5 ( 1 ) to ( 3 ) each is a horizontal cross-sectional view of A-A′ face (a surface of exhausting a CVD material and a carrier gas to a vaporizing chamber) in FIG.
- FIG. 6 is a schematic flow diagram illustrating one embodiment of the constitution of an apparatus for vaporizing and supplying according to the present invention
- FIG. 7 ( 1 ) and ( 2 ) each is a vertical cross-sectional view illustrating an embodiment of a throttle portion and an orifice respectively in the present invention
- FIG. 8 is a vertical cross-sectional view illustrating an embodiment of a filter in the present invention
- the vaporizer according to the present invention comprises a vaporization chamber 1 for a CVD material, a CVD material feed portion 2 supplying the CVD material for the vaporization chamber, a vaporized gas exhaust port 3 and a heating means 4 (heater or the like) for heating the vaporization chamber.
- a cooling means 5 for the CVD material feed portion An example of such a cooling means include a pipe that provides cooling water along the side surface of the CVD material feed portion, etc.
- the vaporizer of the present invention is designed so that a CVD material feed pipe 6 and a carrier gas feed pipe 7 are connected from outside of the vaporizer to the CVD material feed portion of the vaporizer.
- the CVD material feed portion comprises a CVD material passageway 9 and a carrier gas passageway 10 that are connected to the foregoing feed pipes as shown in FIG. 3 .
- These two passageways have the structure that forms a mixing passageway 11 by joining in a manner such as shown in FIG. 3 , thereby exhausting the CVD material and the carrier gas to the vaporizing chamber.
- a pressure loss-inducing means for the CVD material is attached to CVD material passageway 9 .
- the vaporizer of the present invention it is preferable for the vaporizer of the present invention to have another carrier gas passageway 12 that exhaust the carrier gas to the vaporizing chamber from the outer peripheral of an outlet of the mixing passageway 11 as illustrated in FIG. 3 , ( 2 ) and ( 4 ). Furthermore, it is desirable for the exhaust outlet of the carrier gas passageway 12 to be settled in a manner that the direction of the exhaust is slanted toward the exhaust outlet of the mixing passageway 11 to the vaporizing chamber.
- a vaporizing efficiency of the vaporizer becomes extremely superior because both the pressure fluctuation in the vaporization chamber and the flow rate fluctuation in the liquid mass flow controller at the timing of vaporizing and supplying decrease less and less, and at the same time, the deposit or adhesion of the solid CVD material in the vaporization chamber is also further reduced.
- the pressure loss-inducing means provided in CVD material passageway 9 in the vaporizer of the present invention include a capillary with a inner diameter smaller than the inner diameter of mixing passageway 11 for the CVD material and the carrier gas as shown in FIG. 3 , ( 1 ) and ( 2 ), a throttle portion 13 or an orifice 14 , etc., as shown in FIG. 3 , ( 3 ) to ( 6 ). It is preferable for any of the foregoing pressure loss-inducing means in the vaporizer of the present invention to cause a pressure loss in the CVD material of at least 90% of the total pressure in the CVD material feed portion.
- the inner diameter of the capillary is not particularly specified on the assumption that it is smaller than the inner diameter of the mixing passageway, it is usually equal to or less than 50% of the inner diameter of the mixing passageway, and is smaller than 0.2 mm.
- the length of the capillary it should be made longer in proportion that the inner diameter of the capillary becomes large, and it is usually at least 2 cm, or equal to the total length of the whole CVD material passageway, if necessary.
- the capillary might be employed as CVD material feed pipe 6 illustrated in FIG. 1 .
- the aperture of the throttle portion or the orifice is not particularly specified, it is usually equal to or less than 30% of the inner diameter of the mixing passageway, and is smaller than 0.1 mm.
- the positions are desirably selected at where any blockage would not occur except at an exhaust port of the vaporizing chamber. Two or more of them can be employed and they can be employed in combination.
- synthetic resin such as fluororesin or polyimide based resin, or a cavity is preferably applied as the inner surface of the CVD material feed portion in the vaporizer of the present invention.
- metals such as carbon steel, manganese steel, chromium steel, molybdenum steel, stainless steel and nickel steel are preferable.
- the synthetic resin 15 is deployed as illustrated in FIG. 3 , ( 1 ), ( 2 ), ( 3 ), ( 5 ) and ( 6 ).
- the cavity 16 is formed as shown in FIG.
- the apparatus for vaporizing and supplying according to the present invention feeds a CVD material to a vaporizer via a liquid flow controller, and after vaporizing the CVD material, supplies the vaporized gas for a semiconductor production apparatus, and is comprising degassing unit 22 , liquid flow controller 23 such as mass flow controller, vaporizer 26 and carrier gas feed line 28 , etc., as illustrated in FIG. 6 .
- degassing unit 22 liquid flow controller 23 such as mass flow controller, vaporizer 26 and carrier gas feed line 28 , etc.
- FIG. 6 use is made as illustrated therein, of a liquid CVD material vessel 21 containing a liquid CVD material 20 , a liquid flow controller 23 , a vaporizer 26 , a semiconductor manufacturing apparatus 29 , and preferably a degassing unit 22 .
- the apparatus for vaporizing and supplying according to the present invention is an apparatus for vaporizing and supplying having a pressure loss-inducing means for the CVD material between the liquid flow controller and the vapor
- the pressure loss-inducing means for the CVD material provided between the liquid flow controller and the vaporizer in the apparatus for vaporizing and supplying according to the present invention include a capillary with a inner diameter smaller than the inner diameter of a CVD material passageway in the vaporizer at least among pipe 24 between the liquid flow controller and the vaporizer, a throttle portion 30 or an orifice 31 , among the pipe 24 as shown in FIG. 7 , or a filter 32 among the pipe 24 as shown in FIG. 8 , etc.
- any of the foregoing pressure loss-inducing means in the apparatus for vaporizing and supplying of the present invention to cause a pressure loss in the CVD material of at least 90% of the total pressure between a CVD material vessel and the vaporizer.
- the pressure loss-inducing means for the CVD material can be provided both in the CVD material passageway of the foregoing vaporizer and between the liquid flow controller and the vaporizer. Even in these cases, it is preferable for both of the foregoing pressure loss-inducing means to cause a pressure loss in the CVD material of at least 90% of the pressure between the CVD material vessel and the CVD material feed portion of the vaporizer.
- the inner diameter of the capillary is not particularly specified on the assumption that it is smaller than the inner diameter of the CVD material passageway in the CVD material feed portion of the vaporizer, it is usually equal to or less than 50% of the inner diameter of the CVD material passageway, and is smaller than 0.2 mm.
- the length of the capillary it should be made longer in proportion that the inner diameter of the capillary becomes large, and it is usually at least 2 cm.
- the capillary might be employed as the whole pipes between the liquid flow controller and the vaporizer, depending on the necessity.
- the aperture of the throttle portion or the orifice is not particularly specified, it is usually equal to or less than 30% of the inner diameter of the pipe between the liquid flow controller and the vaporizer, and is smaller than 0.1 mm.
- the filter is employed as the pressure loss-inducing means for the CVD material
- the material for the filter is not particularly specified as far as it has an anticorrosion property
- porous filters made of sintered metals, ceramics, fluororesins, etc. are usually employed as the filter.
- the filter it is preferable for the filter to be able to remove particles having diameters corresponding to 0.01 ⁇ m with the rejection rate of 99.99% or more, and it is more preferable for the filter to be able to remove particles having diameters corresponding to 0.001 ⁇ m with the rejection rate of 99.99% or more.
- Typical examples of the filters on the market that can be employed as the foregoing filters include the porous filters (SLF-E, SLF-L, SLF-M and SLF-X all available from Japan Pionics Co., Ltd.) made of stainless steel and the porous filters (XLF-D, XLF-E, XLF-L and XLF-M all available from Japan Pionics Co., Ltd.) made of Teflon membrane. Additionally, two or more of the foregoing capillary, throttle portion, orifice or filter can be employed and they can be used in combination.
- CVD material feed portion having the passageways as illustrated in FIG. 3 ( 1 ) in which the inside thereof was constituted of a fluororesin (PFA), and the portion in contact with the outside of the vaporizer was constituted of stainless steel (SUS316).
- the PFA made portion was a column having an outside diameter of 16 mm and a height of 34.2 mm.
- the stainless steel outside the column had a thickness of 2.0 mm.
- the CVD material feed portion had such constitution that the CVD material passageway and the carrier gas passageway were stainless steel pipes, and the mixing passageway for the CVD material and the carrier gas connected to the vaporization chamber was constituted of a fluororesin (PFA).
- the CVD material passageway was a capillary having an inside diameter of 0.1 mm, the inside diameters of the carrier gas passageway and the mixing passageway for the CVD material and the carrier gas were 1.8 mm and 0.25 mm respectively. Further, a junction joining the CVD material and the carrier gas was settled to be 5 mm upward from the basement of the CVD material feed portion. Additionally, a cooling pipe that provides cooling water along the side surface of the CVD material feed portion was equipped as a cooling means for the CVD material feed portion. There was also prepared, in addition to the foregoing CVD material feed portion, as illustrated in FIG.
- a vaporizer which was made of SUS316 and incorporated with a vaporized gas exhaust port, a heating means for the vaporization chamber and a protrusion housing a heater.
- the vaporization chamber was in the form of a column having an inside diameter of 65 mm and a height of 92.5 mm and a protrusion height at the bottom of 27.5 mm.
- the vaporized gas exhaust port was placed at a height of 15 mm from the bottom of the vaporizer.
- a vaporizing and supplying system as illustrated in FIG. 6 was fabricated by connecting a degassing unit, a liquid mass flow controller, a carrier gas feed line and the like. Additionally, a stainless steel pipe having an inside diameter of 1.8 mm and a length of 10 cm was employed as the pipe between the liquid flow controller and the vaporizer.
- a test for vaporizing and supplying was made in the following manner by the use of the foregoing apparatus.
- the vaporization chamber was set on 1.3 kPa (10 torr) and at the temperature of 250 ⁇ , the CVD material feed portion of the vaporizer was charged with a liquid CVD material having a concentration of 0.3 mol/liter in which Zr(DPM) 4 as a solid CVD material was dissolved in tetrahydrofuran (THF) as a solvent with a flow rate of 0.2 g/min and argon gas with a flow rate of 200 milliliter/min, and then the liquid CVD material was vaporized in the chamber.
- THF tetrahydrofuran
- argon gas argon gas with a flow rate of 200 milliliter/min
- Example 2 was conducted by the use of the same apparatus for vaporizing and supplying as employed in Example 1 and a liquid CVD material having a concentration of 0.3 mol/liter in which Pb(DPM) 2 as a solid CVD material dissolved in tetrahydrofuran (THF) as a solvent was vaporized and supplied in the following manner.
- the vaporization chamber was set on 1.3 kPa (10 torr) and at the temperature of 210 ⁇ , and by feeding the CVD material with a flow rate of 0.36 g/min and argon gas with a flow rate of 300 milliliter/min, the liquid CVD material was vaporized in the chamber.
- cooling water was supplied to maintain the temperature of the stainless steel of the a CVD material feed portion at 30 ⁇ 2 ⁇ .
- Example 3 was conducted by the use of the same apparatus for vaporizing and supplying as employed in Example 1 and a liquid CVD material having a concentration of 0.3 mol/liter in which Ti(OiPr) 2 (DPM) 2 as a solid CVD material was dissolved in tetrahydrofuran (THF) as a solvent was vaporized and supplied in the following manner.
- the vaporization chamber was set on 1.3 kPa (10 torr) and at the temperature of 230 ⁇ , and by feeding the CVD material with a flow rate of 0.2 g/min and argon gas with a flow rate of 100 milliliter/min, the liquid CVD material was vaporized in the chamber.
- cooling water was supplied to maintain the temperature of the stainless steel of the a CVD material feed portion at 30 ⁇ 2 ⁇ .
- Example 2 There was prepared a CVD material feed portion for a vaporizer having the passageways as illustrated in FIG. 3 ( 3 ) similarly as in Example 1 except that a pipe with an inside diameter of 0.25 mm having a throttle portion with an aperture of 0.05 mm was employed as CVD material passageway instead of the capillary.
- Example 4 was conducted by the use of the foregoing apparatus for vaporizing and supplying and a liquid CVD material having a concentration of 0.3 mol/liter in which Zr(DPM) 4 as a solid CVD material was dissolved in tetrahydrofuran (THF) as a solvent was vaporized and supplied in the same manner as Example 1.
- CVD material feed portion having the passageways as illustrated in FIG. 3 ( 2 ) in which the inside thereof was constituted of a fluororesin (PFA), and the portion in contact with the outside of the vaporizer was constituted of stainless steel (SUS316).
- the fluororesin (PFA) made portion was a column having an outside diameter of 16 mm and a height of 34.2 mm.
- the stainless steel outside the column had a thickness of 2.0 mm.
- the CVD material feed portion had such constitution that the CVD material passageway and the neighboring carrier gas passageway were stainless steel double-structured pipes, and the mixing passageway for the CVD material and the other carrier gas passageway connected to the vaporization chamber were constituted of a fluororesin (PFA).
- the inner tube of the double-structured pipe was a capillary having an inside diameter of 0.1 mm and an outside diameter of 1.59 mm, the inside diameter and the outside diameter of the outer tube thereof were 1.8 mm and 3.18 mm respectively.
- the inside diameters of the mixing passageway and the outer carrier gas passageway were 0.25 mm and 1.8 mm respectively.
- a horizontal cross-sectional face of A-A′ (a surface of exhausting a CVD material and a carrier gas to a vaporizing chamber in FIG. 3 ( 2 )) was formed as illustrated in FIG. 5 ( 2 ). Further, a junction joining the CVD material and the carrier gas was settled to be 5 mm upward from the basement of the CVD material feed portion.
- Example 5 was conducted by the use of the foregoing apparatus for vaporizing and supplying and a liquid CVD material having a concentration of 0.3 mol/liter in which Zr(DPM) 4 as a solid CVD material was dissolved in tetrahydrofuran (THF) as a solvent was vaporized and supplied in the same manner as Example 1.
- a CVD material feed portion as shown in FIG. 3 ( 4 ) was prepared similarly as Example 5 except that having a cavity in itself and that a double-structured pipe including a tube having an inside diameter of 0.25 mm with an orifice having an aperture of 0.05 mm was employed as a CVD material passageway instead of the double-structured pipe including the capillary.
- the inside diameter of the outer tube of the double-structured pipe was 1.8 mm.
- Example 6 The same vaporizer as in Example 1 except the use of the foregoing CVD material feed portion was prepared, and an apparatus for vaporizing and supplying was fabricated by connecting a degassing unit, a liquid mass flow controller, a carrier gas feed line and the like as employed in Example 1.
- Example 6 was conducted by the use of the foregoing apparatus for vaporizing and supplying and a liquid CVD-material having a concentration of 0.3 mol/liter in which Zr(DPM) 4 as a solid CVD material was dissolved in tetrahydrofuran (THF) as a solvent was vaporized and supplied in the same manner as Example 1.
- a vaporizer was prepared similarly as Example 1 except that the foregoing CVD material feed portion was employed.
- An apparatus for vaporizing and supplying as illustrated in FIG. 6 was fabricated by connecting a degassing unit, a liquid mass flow controller, a carrier gas feed line and the like as employed in Example 1 with the exception that a capillary made of stainless steel having an inside diameter of 0.1 mm and having a length of 10 cm was employed as a pipe between the liquid flow controller and the vaporizer.
- Example 7 was conducted by the use of the foregoing apparatus for vaporizing and supplying and a liquid CVD material having a concentration of 0.3 mol/liter in which Zr(DPM) 4 as a solid CVD material was dissolved in tetrahydrofuran (THF) as a solvent was vaporized and supplied in the same manner as Example 1.
- Example 8 was conducted by the use of the same apparatus for vaporizing and supplying as employed in Example 7 and a liquid CVD material having a concentration of 0.3 mol/liter in which Pb(DPM) 2 as a solid CVD material was dissolved in tetrahydrofuran (THF) as a solvent was vaporized and supplied in the same manner as Example 2.
- Example 9 was conducted by the use of the same apparatus for vaporizing and supplying as employed in Example 7 and a liquid CVD material having a concentration of 0.3 mol/liter in which Ti(OiPr) 2 (DPM) 2 as a solid CVD material was dissolved in tetrahydrofuran (THF) as a solvent was vaporized and supplied in the same manner as Example 3.
- DPM Ti(OiPr) 2
- THF tetrahydrofuran
- Example 10 was conducted by the use of the foregoing apparatus for vaporizing and supplying and a liquid CVD material having a concentration of 0.3 mol/liter in which Zr(DPM) 4 as a solid CVD material was dissolved in tetrahydrofuran (THF) as a solvent was vaporized and supplied in the same manner as Example 1.
- Example 11 was conducted by the use of the foregoing apparatus for vaporizing and supplying and a liquid CVD material having a concentration of 0.3 mol/liter in which Zr(DPM) 4 as a solid CVD material was dissolved in tetrahydrofuran (THF) as a solvent was vaporized and supplied in the same manner as Example 1.
- Example 7 There was prepared an apparatus for vaporizing and supplying similarly as in Example 7 except that a pipe with an inside diameter of 1.8 mm and with a length of 10 cm having further a porous filter made of stainless steel (SLF-M, uniform particle removing rate of a particle having diameter of 0.01 ⁇ m: 99.9999999%, available from Japan Pionics Co., Ltd.) was employed as CVD material passageway instead of the capillary employed as the pipe between the liquid flow controller and the vaporizer.
- SPF-M uniform particle removing rate of a particle having diameter of 0.01 ⁇ m: 99.9999999%, available from Japan Pionics Co., Ltd.
- Example 12 was conducted by the use of the foregoing apparatus for vaporizing and supplying and a liquid CVD material having a concentration of 0.3 mol/liter in which Zr(DPM) 4 as a solid CVD material was dissolved in tetrahydrofuran (THF) as a solvent was vaporized and supplied in the same manner as Example 1.
- Example 2 There was prepared a CVD material feed portion for a vaporizer having the passageways similarly as in Example 1 except that a pipe with an inside diameter of 0.25 mm was employed as CVD material passageway instead of the capillary.
- Comparative Example 1 was conducted by the use of the foregoing apparatus for vaporizing and supplying and a liquid CVD material having a concentration of 0.3 mol/liter in which Zr(DPM) 4 as a solid CVD material was dissolved in tetrahydrofuran (THF) as a solvent was vaporized and supplied in the same manner as Example 1.
- Comparative Example 2 was conducted by the use of the same apparatus for vaporizing and supplying as employed in Comparative Example 1 and a liquid CVD material having a concentration of 0.3 mol/liter in which Pb(DPM) 2 as a solid CVD material was dissolved in tetrahydrofuran (THF) as a solvent was vaporized and supplied in the same manner as Example 2.
- Comparative Example 3 was conducted by the use of the same apparatus for vaporizing and supplying as employed in Comparative Example 1 and a liquid CVD material having a concentration of 0.3 mol/liter in which Ti(OiPr) 2 (DPM) 2 as a solid CVD material was dissolved in tetrahydrofuran (THF) as a solvent was vaporized and supplied in the same manner as Example 3.
- a liquid CVD material having a concentration of 0.3 mol/liter in which Ti(OiPr) 2 (DPM) 2 as a solid CVD material was dissolved in tetrahydrofuran (THF) as a solvent was vaporized and supplied in the same manner as Example 3.
- a vaporizer and an apparatus for vaporizing and supplying which is capable of reducing and stabilizing both the pressure fluctuation in the vaporizer and the flow rate fluctuation in the liquid flow controller and efficiently vaporizing a CVD material at a desirable concentration and flow rate without causing deposit or adhesion of the solid material in the vaporization chamber are provided.
- a vaporizer and an apparatus for vaporizing and supplying which is capable of reducing and stabilizing both the pressure fluctuation in the vaporizer and the flow rate fluctuation in the liquid flow controller and efficiently vaporizing a CVD material at a desirable concentration and flow rate without causing deposit or adhesion of the solid material in the vaporization chamber are provided.
Abstract
The present invention provides a vaporizer having a vaporization chamber for a CVD material, a CVD material feed portion supplying the CVD material for the vaporization chamber, a vaporized gas exhaust port and a heater for heating the vaporization chamber, wherein the CVD material feed portion has passageways for the CVD material and for a carrier gas respectively and the passageway for the CVD material has a pressure loss inducer for the CVD material. At the same time, the present invention provides an apparatus for vaporizing and supplying that feeds a CVD material to a vaporizer via a liquid flow controller, and after vaporizing the CVD material that supplies the vaporized gas for a semiconductor production apparatus having a pressure loss-inducer for the CVD material between the liquid flow controller and the vaporizer. According to the present invention, even in the case of vaporizing and supplying with a decrease in a feed amount of a carrier gas to be supplied accompanying the CVD material employing a solid CVD material, reducing and stabilizing both the pressure fluctuation in the vaporizer and the flow rate fluctuation in the liquid flow controller and efficiently vaporizing a CVD material at a desirable concentration and flow rate without causing deposit or adhesion of the solid material in the vaporization chamber can be achieved.
Description
- This application is a divisional of U.S. patent application Ser. No. 10/413,204, filed Apr. 15, 2003, now allowed, which is hereby incorporated by reference in its entirety.
- The present invention relates to a vaporizer and an apparatus for vaporizing and supplying that are employed for supplying a gaseous CVD material for a chemical vapor deposition (CVD) apparatus used in the manufacture of a semiconductor and the like. More particularly, it pertains to a vaporizer and an apparatus for vaporizing and supplying that are employed for supplying a liquid CVD material or a solution of a liquid CVD material of a solid CVD material in a solvent each at desirable concentration and flow rate in high efficiency for the apparatus used in the manufacture of a semiconductor.
- Recently in the field of semi-conductors, a lead titanate zirconate (PZT) film, a barium strontium titanate (BST) film, a tantalic acid strontium bismuth (SBT) film, a titanic acid zirconate lantern lead (PLZT) film, etc., each having a high dielectric constant and also a high step coverage has been used as an oxide-based dielectric film for a semiconductor memory. In regard to the CVD material for the foregoing thin films, for example, Pb(DPM)2 (solid material) as a Pb source; Zr{OC(CH3)3}4 (liquid material) and Zr(DPM)4 (solid material) as Zr sources; Ti{OCH(CH3)2}4 (liquid material) and Ti(OCH (CH3)2)2 (DPM)2 (solid material) as Ti sources; Ba(DPM)2 (solid material) as a Ba source; and Sr(DPM)2 (solid material) as a Sr source are employed.
- A liquid material, when being used as a CVD material, is usually introduced into a vaporizer along with a carrier gas via a flow rate controller, and the mixed gas is made into a gaseous form in the vaporizer and thereafter is fed to a CVD apparatus. However, it is difficult to vaporize a liquid material at a desirable concentration and flow rate in high efficiency without deteriorating the quality thereof, since the liquid material has usually a low vapor pressure, a high viscosity and a vaporizing temperature close to a decomposing temperature.
- A solid material, although being capable of assuring highly pure material by being kept at an elevated temperature to sublime itself, makes it extremely difficult to assure sufficient supply amount in an industrial scale. Thus, in general it is dissolved in a solvent such as tetrahydrofuran to make it into a liquid material so as to vaporize. However, since a solid material has a vaporizing temperature greatly different from that of a solvent, a solvent alone is more apt to vaporize by heating, thereby making it more difficult to vaporize a liquid material.
- Such being the case, highly advanced technique is required for manufacturing an insulated thin film by using a material in liquid or solid form. Conversely, an insulated thin film having high quality and high purity is expectable by the use of a liquid material or solid material. Accordingly, a variety of vaporizers and apparatuses for vaporizing and supplying have been developed for the purpose of efficiently vaporizing the aforesaid material without deteriorating the quality thereof.
- For example, U.S. Pat. No. 6,473,563 B proposes a vaporizer wherein at least a portion of a CVD material feed portion in contact with a CVD material is constituted of a corrosion resistant synthetic resin; and an apparatus for vaporizing and supplying which comprises a cooler and the vaporizer wherein the inside of the CVD material feed portion of the vaporizer and the surface on the side of the vaporization chamber of the CVD material feed portion are constituted of a corrosion resistant synthetic resin; the feed portion in contact with the outside of the vaporizer is constituted of a metal; and the CVD material feed portion which is constituted of a metal and which undergoes heat transfer from the heating means upon heating the vaporization chamber can be cooled with a cooler. It is a vaporizer in which at least a portion of the CVD material feed portion in contact with the CVD material is constituted of a corrosion resistant synthetic resin which has not only heat resistance but also heat insulating property and characteristics of less liability to adhesion of the CVD material.
- The use of the foregoing vaporizer enabled, even in the case of using a solid CVD material dissolved in an organic solvent as a CVD material, only the material to be vaporized with an efficiency of 99.9% or higher because any abrupt heating was prevented without generating any deposit of the material accompanied with adhesion thereof. In addition, the foregoing apparatus for vaporizing and supplying is equipped with a mechanism for cooling the CVD material feed portion at the time of heating the vaporization chamber, and the apparatus was least liable to the adhesion of deposits.
- However, although the foregoing vaporizer and apparatus for vaporizing and supplying have effects of preventing the generation of any deposit of the solid CVD material accompanied with adhesion inside the CVD material supplier, a decrease in a feed amount of a carrier gas to be supplied accompanying the CVD material brings about such disadvantage that a solvent alone is vaporized, in the same manner as the conventional vaporizers, thus causing an anxiety of a solid CVD material to be more prone to be deposited in the vaporizer. On the contrary, it is desirable to improve use efficiency by supplying the CVD material having high concentration in chemical vapor deposition.
- In such circumstances, an object of the present invention is to provide, even in the case of vaporizing and supplying with a decrease in a feed amount of a carrier gas to be supplied accompanying the CVD material employing a solid CVD material, a vaporizer and an apparatus for vaporizing and supplying which comprises the aforesaid vaporizer, which is capable of efficiently vaporizing a CVD material with a desirable concentration and flow rate without causing deposit or adhesion of the solid material in the CVD material feed port. Other objects of the present invention will become obvious from the text of this specification hereinafter disclosed.
- Under such circumstances, the present inventors accumulated intensive extensive research and development in order to solve the above-described problems involved in the prior arts. As a result, the following has been found. Specifically, by providing a pressure loss-inducing portion in a CVD material feed portion or between a liquid flow controller and a vaporizer, it is made possible to reduce and stabilize both the pressure fluctuation in the vaporizer and the flow rate fluctuation in the liquid flow controller and to prevent deposit of the solid CVD material less liable to adhere even if such deposit is generated. Thus, the present invention has been accomplished by the foregoing findings and information.
- That is to say, the present invention provides a vaporizer comprising a vaporization chamber for a CVD material, a CVD material feed portion supplying the CVD material for the vaporization chamber, a vaporized gas exhaust port and a heating means for heating the vaporization chamber, characterized in that the CVD material feed portion has passageways for the CVD material and for a carrier gas respectively and the passageway for the CVD material has a pressure loss-inducing means for the CVD material.
- At the same time, the present invention provides an apparatus for vaporizing and supplying that feeds a CVD material to a vaporizer via a liquid flow controller, and after vaporizing the CVD material that supplies the vaporized gas for a semiconductor production apparatus, characterized in having a pressure loss-inducing means for the CVD material between the liquid flow controller and the vaporizer.
-
FIG. 1 is a vertical cross-sectional view showing one embodiment of a vaporizer according to the present invention; -
FIG. 2 is a vertical cross-sectional view showing another embodiment of a vaporizer according to the present invention; -
FIG. 3 (1) to (6) each is a vertical cross-sectional view showing embodiments of a CVD material feed portion according to the present invention; -
FIG. 4 (a) to (d) each is a horizontal cross-sectional view of a-a′ face, b-b′ face, c-c′ face, and d-d′ face of (1) to (4) respectively inFIG. 3 ; -
FIG. 5 (1) to (3) each is a horizontal cross-sectional view of A-A′ face (a surface of exhausting a CVD material and a carrier gas to a vaporizing chamber) inFIG. 3 ; -
FIG. 6 is a schematic flow diagram illustrating one embodiment of the constitution of an apparatus for vaporizing and supplying according to the present invention; - FIGS. 7 (1) and (2) each is a vertical cross-sectional view illustrating an embodiment of a throttle portion and an orifice respectively in the present invention; and
-
FIG. 8 is a vertical cross-sectional view illustrating an embodiment of a filter in the present invention. - The present invention is applied to a vaporizer which vaporizes a liquid CVD material or a liquid CVD material made up of a solution of a solid CVD material in a solvent, and which supplies a CVD apparatus or the like with a vaporized gas. In the case of a decrease in a feed amount of a carrier gas to be supplied accompanying the CVD material employing a solid CVD material, the vaporizer exhibits its effect particularly in view of the capability of reducing and stabilizing both the pressure fluctuation in the vaporizer and the flow rate fluctuation in the liquid flow controller and the capability of preventing the deposit and adhesion of a solid CVD material inside the vaporizer.
- The vaporizer according to the present invention is a vaporizer in which the CVD material feed portion has passageways for the CVD material and for a carrier gas respectively and the passageway for the CVD material has a pressure loss-inducing means for the CVD material. Further, the apparatus for vaporizing and supplying according to the present invention is an apparatus for vaporizing and supplying having a pressure loss-inducing means for the CVD material between the liquid flow controller and the vaporizer.
- The CVD material to which are applicable the vaporizer and the apparatus for vaporizing and supplying is not specifically limited, provided that the CVD material can be kept in liquid state whether it is in liquid state at ordinary temperature or a solution of a solid dissolved in a solvent. The CVD material is properly and optionally selected for a use according to the purpose of the use.
- Examples thereof include an alkoxide in liquid state at ordinary temperature such as tetra isopropoxy titanium (Ti(OCH(CH3)2)4), tetra-n-propoxytitanium (Ti(OCH3H7)4), tetra-tert-butoxyzirconium (Zr(OC(C3)3)4), tetra-n-butoxyzirconium (Zr(OC4H9)4), tetramethoxyvanadium (V(OCH3)4), trimethoxyvanadyloxide (VO(OCH3)3), pentaethoxyniobium (Nb(OC2H5)5), pentaethoxytantalum (Ta(OC2H5)5), trimethoxyboron (B(OCH3)3), triisopropoxyaluminum (Al(OCH(CH3)2)3), tetraethoxysilicon (Si(OC2H5)4), tetraethoxygermanium (Ge(OC2H5)4), tetraethoxytin (Sn(OCH3)4), trimethoxyphosphorus (P(OCH3)3), trimethoxyphosphineoxide (PO(OCH3)3), triethoxyarsenic (As(OC2H5)3) and triethoxyantimony (Sb(OC2H5)3).
- Examples of the CVD material in liquid state at ordinary temperature other than the foregoing examples include trimethylaluminum (Al(CH3)3), dimethylaluminumhydride (Al(CH3)2)H), triisobutylaluminum (Al(iso-C4H9)3), hexafluoroacetylacetonecopper vinyltrimethylsilane ((CF3CO)2CHCu.CH2CHSi(CH3)3), hexafluoroacetylacetonecopper allyltrimethylsilane ((CF3CO)2CHCu.CH2CHCH2Si(CH3)3), bis(isopropylcyclopentadienyl)tungsten dihydride ((iso-C3H7C5H5)2WH2), tetradimethylaminozirconium (Zr(N(CH3)2)4), pentadimethylaminotantalum (Ta(N(CH3)2)5), pentadiethylaminotantalum (Ta(N(C2H5)2)5), tetradimethylaminotitanium (Ti(N(CH3)2)4) and tetradiethylaminotitanium (Ti(N(C2H5)2)4).
- Further, examples of the CVD material in solid state at ordinary temperature include hexacarbonylmolybdenum (Mo(CO)6), dimethylpenthoxygold (Au(CH3)2(OC5H7)), bismuth (III) tertiallybuthoxyd (Bi(OtBu)3), bismuth (III) tertiallypenthoxyd (Bi(OtAm)3), triphenylbismuth (BiPh3), bis(ethylcyclopentadienyl)ruthenium(Ru(EtCp)2), (ethylcyclopentadienyl) (trimethyl) platinum (Pt(EtCp)Me3), 1,5-cyclooctadiene (ethylcyclopentadienyl) iridium (Ir(EtCp)(cod)), bis(hexaethoxytantalum) strontium (St[Ta(OEt)6]2), bis(hexaisopropoxytantalum) strontium (St[Ta(OiPr)6]2),), tris(2,2,6,6,-tetramethyl-3,5 heptanedionite) lanthanum (La(DPM)3), tris(2,2,6,6,-tetramethyl-3,5 heptanedionite) yttrium (Y(DPM)3), tris(2,2,6,6,-tetramethyl-3,5 heptanedionite) ruthenium (Ru(DPM)3), bis(2,2,6,6,-tetramethyl-3,5 heptanedionite) barium (Ba(DPM)2), bis(2,2,6,6,-tetramethyl-3,5 heptanedionite) strontium (Sr(DPM)2), tetra(2,2,6,6,-tetramethyl-3,5 heptanedionite) titanium (Ti(DPM)4), tetra(2,2,6,6,-tetramethyl-3,5 heptanedionite) zirconium (Zr(DPM)4), tetra(2,6,-dimethyl-3,5 heptanedionite) zirconium (Zr(DMHD)4), bis(2,2,6,6,-tetramethyl-3,5 heptanedionite) lead (Pb(DPM)2), (ditertiallybuthoxy) bis(2,2,6,6,-tetramethyl-3.5. heptanedionite) titanium (Ti(OtBu)2(DPM)2), (di-isopropoxy) bis(2,2,6,6,-tetramethyl-3,5,-heptanedionite) titanium (Ti(OiPr)2(DPM)2), (isopropoxy) tris(2,2,6,6,-tetramethyl-3,5,-heptanedionite) zirconium (Zr(OiPr)(DPM)3), (di-isopropoxy) tris(2,2,6,6,-tetramethyl-3,5,-heptanedionite) tantalum (Ta(OiPr)2(DPM)3). The above-exemplified materials need to be dissolved in an organic solvent in a concentration of usually 0.1 to 1.0 mol/liter, approximately.
- The above-mentioned organic solvent to be used as a solvent for a solid CVD material is that having a boiling point usually ranging from 40□ to 140□. Examples of the solvent include such ethers as propyl ether, methylbutyl ether, ethylpropyl ether, ethylbutyl ether, trimethylene oxide, tetrahydrofuran and tetrahydropyran; alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol and butyl alcohol; ketones such as acetone, ethylmethylketone, iso-propylmethylketone and iso-butylmethylketone; amines such as propylamine, butylamine, diethylamine, dipropylamine and triethylamine; esters such as ethyl acetate, propyl acetate and butyl acetate; and hydrocarbons such as hexane, heptane and octane.
- In the following, detailed description will be given of the vaporizer and the apparatus for vaporizing and supplying according to the present invention with reference to FIGS. 1 to 8, which however shall never limit the present invention thereto.
-
FIGS. 1 and 2 are vertical cross-sectional views showing embodiments of vaporizers according to the present invention;FIG. 3 (1) to (6) each is a vertical cross-sectional view showing embodiments of a CVD material feed portion according to the present invention;FIG. 4 (a) to (d) each is a horizontal cross-sectional view of a-a′ face, b-b′ face, c-c′ face, and d-d′ face of (1) to (4) respectively inFIG. 3 ;FIG. 5 (1) to (3) each is a horizontal cross-sectional view of A-A′ face (a surface of exhausting a CVD material and a carrier gas to a vaporizing chamber) inFIG. 3 ;FIG. 6 is a schematic flow diagram illustrating one embodiment of the constitution of an apparatus for vaporizing and supplying according to the present invention;FIG. 7 (1) and (2) each is a vertical cross-sectional view illustrating an embodiment of a throttle portion and an orifice respectively in the present invention; andFIG. 8 is a vertical cross-sectional view illustrating an embodiment of a filter in the present invention As shown inFIGS. 1 and 2 , the vaporizer according to the present invention comprises avaporization chamber 1 for a CVD material, a CVDmaterial feed portion 2 supplying the CVD material for the vaporization chamber, a vaporizedgas exhaust port 3 and a heating means 4 (heater or the like) for heating the vaporization chamber. Further, it is desirable for the vaporizer of the present invention to be equipped with a cooling means 5 for the CVD material feed portion. An example of such a cooling means include a pipe that provides cooling water along the side surface of the CVD material feed portion, etc. - As shown in
FIGS. 1 and 2 , the vaporizer of the present invention is designed so that a CVDmaterial feed pipe 6 and a carriergas feed pipe 7 are connected from outside of the vaporizer to the CVD material feed portion of the vaporizer. The CVD material feed portion comprises aCVD material passageway 9 and acarrier gas passageway 10 that are connected to the foregoing feed pipes as shown inFIG. 3 . These two passageways have the structure that forms amixing passageway 11 by joining in a manner such as shown inFIG. 3 , thereby exhausting the CVD material and the carrier gas to the vaporizing chamber. In the vaporizer of the present invention, a pressure loss-inducing means for the CVD material is attached toCVD material passageway 9. - Further, it is preferable for the vaporizer of the present invention to have another
carrier gas passageway 12 that exhaust the carrier gas to the vaporizing chamber from the outer peripheral of an outlet of the mixingpassageway 11 as illustrated inFIG. 3 , (2) and (4). Furthermore, it is desirable for the exhaust outlet of thecarrier gas passageway 12 to be settled in a manner that the direction of the exhaust is slanted toward the exhaust outlet of the mixingpassageway 11 to the vaporizing chamber. By the application of the foregoing structure of the CVD material feed portion, a vaporizing efficiency of the vaporizer becomes extremely superior because both the pressure fluctuation in the vaporization chamber and the flow rate fluctuation in the liquid mass flow controller at the timing of vaporizing and supplying decrease less and less, and at the same time, the deposit or adhesion of the solid CVD material in the vaporization chamber is also further reduced. - Specific examples of the pressure loss-inducing means provided in
CVD material passageway 9 in the vaporizer of the present invention include a capillary with a inner diameter smaller than the inner diameter of mixingpassageway 11 for the CVD material and the carrier gas as shown inFIG. 3 , (1) and (2), athrottle portion 13 or anorifice 14, etc., as shown inFIG. 3 , (3) to (6). It is preferable for any of the foregoing pressure loss-inducing means in the vaporizer of the present invention to cause a pressure loss in the CVD material of at least 90% of the total pressure in the CVD material feed portion. - In the case where the capillary is employed as the pressure loss-inducing means for the CVD material, although the inner diameter of the capillary is not particularly specified on the assumption that it is smaller than the inner diameter of the mixing passageway, it is usually equal to or less than 50% of the inner diameter of the mixing passageway, and is smaller than 0.2 mm. Regarding the length of the capillary, it should be made longer in proportion that the inner diameter of the capillary becomes large, and it is usually at least 2 cm, or equal to the total length of the whole CVD material passageway, if necessary. The capillary might be employed as CVD
material feed pipe 6 illustrated inFIG. 1 . - Further, in the case where the throttle portion or the orifice is employed as the pressure loss-inducing means for the CVD material, although the aperture of the throttle portion or the orifice is not particularly specified, it is usually equal to or less than 30% of the inner diameter of the mixing passageway, and is smaller than 0.1 mm. Additionally, there are no specialized positions where the foregoing capillary, throttle portion or orifice should be attached in the CVD material passageways. However, the positions are desirably selected at where any blockage would not occur except at an exhaust port of the vaporizing chamber. Two or more of them can be employed and they can be employed in combination.
- Furthermore, synthetic resin such as fluororesin or polyimide based resin, or a cavity is preferably applied as the inner surface of the CVD material feed portion in the vaporizer of the present invention. With regards to a material of construction for contacting with the outside of the vaporizer, metals such as carbon steel, manganese steel, chromium steel, molybdenum steel, stainless steel and nickel steel are preferable. In the case where the inside of the CVD material feed portion is constituted of a synthetic resin, the
synthetic resin 15 is deployed as illustrated inFIG. 3 , (1), (2), (3), (5) and (6). Further, in the case where the inside of the CVD material feed portion is constituted of a cavity, thecavity 16 is formed as shown inFIG. 3 , (4). By the application of the foregoing structure of the CVD material feed portion, even in the case of employing a solid CVD material dissolved in an organic solvent as the CVD material, any vaporization of only the solvent in a passageway induced by an abrupt elevation of the temperature caused by such a heating device as a heater can be prevented. - The apparatus for vaporizing and supplying according to the present invention feeds a CVD material to a vaporizer via a liquid flow controller, and after vaporizing the CVD material, supplies the vaporized gas for a semiconductor production apparatus, and is comprising degassing
unit 22,liquid flow controller 23 such as mass flow controller,vaporizer 26 and carriergas feed line 28, etc., as illustrated inFIG. 6 . InFIG. 6 , use is made as illustrated therein, of a liquidCVD material vessel 21 containing aliquid CVD material 20, aliquid flow controller 23, avaporizer 26, asemiconductor manufacturing apparatus 29, and preferably adegassing unit 22. Further, the apparatus for vaporizing and supplying according to the present invention is an apparatus for vaporizing and supplying having a pressure loss-inducing means for the CVD material between the liquid flow controller and the vaporizer. - Specific examples of the pressure loss-inducing means for the CVD material provided between the liquid flow controller and the vaporizer in the apparatus for vaporizing and supplying according to the present invention include a capillary with a inner diameter smaller than the inner diameter of a CVD material passageway in the vaporizer at least among
pipe 24 between the liquid flow controller and the vaporizer, athrottle portion 30 or anorifice 31, among thepipe 24 as shown inFIG. 7 , or afilter 32 among thepipe 24 as shown inFIG. 8 , etc. It is preferable for any of the foregoing pressure loss-inducing means in the apparatus for vaporizing and supplying of the present invention to cause a pressure loss in the CVD material of at least 90% of the total pressure between a CVD material vessel and the vaporizer. Further, the pressure loss-inducing means for the CVD material can be provided both in the CVD material passageway of the foregoing vaporizer and between the liquid flow controller and the vaporizer. Even in these cases, it is preferable for both of the foregoing pressure loss-inducing means to cause a pressure loss in the CVD material of at least 90% of the pressure between the CVD material vessel and the CVD material feed portion of the vaporizer. - In the case where the capillary is employed as the pressure loss-inducing means for the CVD material, although the inner diameter of the capillary is not particularly specified on the assumption that it is smaller than the inner diameter of the CVD material passageway in the CVD material feed portion of the vaporizer, it is usually equal to or less than 50% of the inner diameter of the CVD material passageway, and is smaller than 0.2 mm. Regarding the length of the capillary, it should be made longer in proportion that the inner diameter of the capillary becomes large, and it is usually at least 2 cm. The capillary might be employed as the whole pipes between the liquid flow controller and the vaporizer, depending on the necessity.
- Further, in the case where the throttle portion or the orifice is employed as the pressure loss-inducing means for the CVD material, although the aperture of the throttle portion or the orifice is not particularly specified, it is usually equal to or less than 30% of the inner diameter of the pipe between the liquid flow controller and the vaporizer, and is smaller than 0.1 mm.
- In the case where the filter is employed as the pressure loss-inducing means for the CVD material, although the material for the filter is not particularly specified as far as it has an anticorrosion property, porous filters made of sintered metals, ceramics, fluororesins, etc. are usually employed as the filter. Furthermore, it is preferable for the filter to be able to remove particles having diameters corresponding to 0.01 μm with the rejection rate of 99.99% or more, and it is more preferable for the filter to be able to remove particles having diameters corresponding to 0.001 μm with the rejection rate of 99.99% or more.
- Typical examples of the filters on the market that can be employed as the foregoing filters include the porous filters (SLF-E, SLF-L, SLF-M and SLF-X all available from Japan Pionics Co., Ltd.) made of stainless steel and the porous filters (XLF-D, XLF-E, XLF-L and XLF-M all available from Japan Pionics Co., Ltd.) made of Teflon membrane. Additionally, two or more of the foregoing capillary, throttle portion, orifice or filter can be employed and they can be used in combination.
- This invention will be described in further detail with reference to Examples, which does not limit the scope of this invention.
- There was prepared a CVD material feed portion having the passageways as illustrated in
FIG. 3 (1) in which the inside thereof was constituted of a fluororesin (PFA), and the portion in contact with the outside of the vaporizer was constituted of stainless steel (SUS316). The PFA made portion was a column having an outside diameter of 16 mm and a height of 34.2 mm. The stainless steel outside the column had a thickness of 2.0 mm. The CVD material feed portion had such constitution that the CVD material passageway and the carrier gas passageway were stainless steel pipes, and the mixing passageway for the CVD material and the carrier gas connected to the vaporization chamber was constituted of a fluororesin (PFA). The CVD material passageway was a capillary having an inside diameter of 0.1 mm, the inside diameters of the carrier gas passageway and the mixing passageway for the CVD material and the carrier gas were 1.8 mm and 0.25 mm respectively. Further, a junction joining the CVD material and the carrier gas was settled to be 5 mm upward from the basement of the CVD material feed portion. Additionally, a cooling pipe that provides cooling water along the side surface of the CVD material feed portion was equipped as a cooling means for the CVD material feed portion. There was also prepared, in addition to the foregoing CVD material feed portion, as illustrated inFIG. 1 , a vaporizer which was made of SUS316 and incorporated with a vaporized gas exhaust port, a heating means for the vaporization chamber and a protrusion housing a heater. The vaporization chamber was in the form of a column having an inside diameter of 65 mm and a height of 92.5 mm and a protrusion height at the bottom of 27.5 mm. The vaporized gas exhaust port was placed at a height of 15 mm from the bottom of the vaporizer. Subsequently, a vaporizing and supplying system as illustrated inFIG. 6 was fabricated by connecting a degassing unit, a liquid mass flow controller, a carrier gas feed line and the like. Additionally, a stainless steel pipe having an inside diameter of 1.8 mm and a length of 10 cm was employed as the pipe between the liquid flow controller and the vaporizer. - A test for vaporizing and supplying was made in the following manner by the use of the foregoing apparatus. The vaporization chamber was set on 1.3 kPa (10 torr) and at the temperature of 250 □, the CVD material feed portion of the vaporizer was charged with a liquid CVD material having a concentration of 0.3 mol/liter in which Zr(DPM)4 as a solid CVD material was dissolved in tetrahydrofuran (THF) as a solvent with a flow rate of 0.2 g/min and argon gas with a flow rate of 200 milliliter/min, and then the liquid CVD material was vaporized in the chamber. During the foregoing process, cooling water was supplied to maintain the temperature of the stainless steel of the a CVD material feed portion at 30±2 □.
- After continuous test for vaporizing and supplying for ten hours, investigation was made on the state of adhesion of the solid CVD material in the passageway of the CVD material feed portion and in the vaporization chamber. As a result, no deposition or adhesion of the solid CVD material was recognized by the human observation. Accordingly, tetrahydrofuran (THF) was fed from the CVD material passageway and after washing away and recovering the solid CVD material adhered in the passageway of the CVD material feed portion and in the vaporization chamber, the amount of the adhesion of the solid CVD material obtained by the evaporation of tetrahydrofuran (THF) was weighed. The results are shown in Table 1. Further, the result of the measurement of both the pressure fluctuation in the vaporization chamber and the flow rate fluctuation in the liquid mass flow controller during the vaporizing and supplying test are shown in Table 1. Additionally, the averaged mean values of the greatest coefficient of fluctuation measured every five minutes were employed as the each value of the pressure fluctuation and the flow rate fluctuation.
- Example 2 was conducted by the use of the same apparatus for vaporizing and supplying as employed in Example 1 and a liquid CVD material having a concentration of 0.3 mol/liter in which Pb(DPM)2 as a solid CVD material dissolved in tetrahydrofuran (THF) as a solvent was vaporized and supplied in the following manner. The vaporization chamber was set on 1.3 kPa (10 torr) and at the temperature of 210 □, and by feeding the CVD material with a flow rate of 0.36 g/min and argon gas with a flow rate of 300 milliliter/min, the liquid CVD material was vaporized in the chamber. During the foregoing process, cooling water was supplied to maintain the temperature of the stainless steel of the a CVD material feed portion at 30±2 □.
- After continuous test for vaporizing and supplying for ten hours, the amount of the adhesion of the solid CVD material, both the pressure fluctuation in the vaporization chamber and the flow rate fluctuation in the liquid mass flow controller during the vaporizing and supplying test were obtained in the same manner as Example 1. The results are shown in Table 1.
- Example 3 was conducted by the use of the same apparatus for vaporizing and supplying as employed in Example 1 and a liquid CVD material having a concentration of 0.3 mol/liter in which Ti(OiPr)2(DPM)2 as a solid CVD material was dissolved in tetrahydrofuran (THF) as a solvent was vaporized and supplied in the following manner. The vaporization chamber was set on 1.3 kPa (10 torr) and at the temperature of 230 □, and by feeding the CVD material with a flow rate of 0.2 g/min and argon gas with a flow rate of 100 milliliter/min, the liquid CVD material was vaporized in the chamber. During the foregoing process, cooling water was supplied to maintain the temperature of the stainless steel of the a CVD material feed portion at 30±2 □.
- After continuous test for vaporizing and supplying for ten hours, the amount of the adhesion of the solid CVD material, both the pressure fluctuation in the vaporization chamber and the flow rate fluctuation in the liquid mass flow controller during the vaporizing and supplying test were obtained in the same manner as Example 1. The results are shown in Table 1.
- There was prepared a CVD material feed portion for a vaporizer having the passageways as illustrated in
FIG. 3 (3) similarly as in Example 1 except that a pipe with an inside diameter of 0.25 mm having a throttle portion with an aperture of 0.05 mm was employed as CVD material passageway instead of the capillary. The same vaporizer as in Example 1 except the use of the foregoing CVD material feed portion was prepared, and an apparatus for vaporizing and supplying was fabricated by connecting a degassing unit, a liquid mass flow controller, a carrier gas feed line and the like as employed in Example 1. Example 4 was conducted by the use of the foregoing apparatus for vaporizing and supplying and a liquid CVD material having a concentration of 0.3 mol/liter in which Zr(DPM)4 as a solid CVD material was dissolved in tetrahydrofuran (THF) as a solvent was vaporized and supplied in the same manner as Example 1. - After continuous test for vaporizing and supplying for ten hours, the amount of the adhesion of the solid CVD material, both the pressure fluctuation in the vaporization chamber and the flow rate fluctuation in the liquid mass flow controller during the vaporizing and supplying test were obtained in the same manner as Example 1. The results are shown in Table 1.
- There was prepared a CVD material feed portion having the passageways as illustrated in
FIG. 3 (2) in which the inside thereof was constituted of a fluororesin (PFA), and the portion in contact with the outside of the vaporizer was constituted of stainless steel (SUS316). The fluororesin (PFA) made portion was a column having an outside diameter of 16 mm and a height of 34.2 mm. The stainless steel outside the column had a thickness of 2.0 mm. The CVD material feed portion had such constitution that the CVD material passageway and the neighboring carrier gas passageway were stainless steel double-structured pipes, and the mixing passageway for the CVD material and the other carrier gas passageway connected to the vaporization chamber were constituted of a fluororesin (PFA). The inner tube of the double-structured pipe was a capillary having an inside diameter of 0.1 mm and an outside diameter of 1.59 mm, the inside diameter and the outside diameter of the outer tube thereof were 1.8 mm and 3.18 mm respectively. The inside diameters of the mixing passageway and the outer carrier gas passageway were 0.25 mm and 1.8 mm respectively. A horizontal cross-sectional face of A-A′ (a surface of exhausting a CVD material and a carrier gas to a vaporizing chamber inFIG. 3 (2)) was formed as illustrated inFIG. 5 (2). Further, a junction joining the CVD material and the carrier gas was settled to be 5 mm upward from the basement of the CVD material feed portion. Additionally, a cooling pipe that provides cooling water along the side surface of the CVD material feed portion was equipped as a cooling means for the CVD material feed portion. The same vaporizer as in Example 1 except the use of the foregoing CVD material feed portion was prepared, and an apparatus for vaporizing and supplying was fabricated by connecting a degassing unit, a liquid mass flow controller, a carrier gas feed line and the like as employed in Example 1. Example 5 was conducted by the use of the foregoing apparatus for vaporizing and supplying and a liquid CVD material having a concentration of 0.3 mol/liter in which Zr(DPM)4 as a solid CVD material was dissolved in tetrahydrofuran (THF) as a solvent was vaporized and supplied in the same manner as Example 1. - After continuous test for vaporizing and supplying for ten hours, the amount of the adhesion of the solid CVD material, both the pressure fluctuation in the vaporization chamber and the flow rate fluctuation in the liquid mass flow controller during the vaporizing and supplying test were obtained in the same manner as Example 1. The results are shown in Table 1.
- In the preparation of the CVD material feed portion for the vaporizer described in Example 5, a CVD material feed portion as shown in
FIG. 3 (4) was prepared similarly as Example 5 except that having a cavity in itself and that a double-structured pipe including a tube having an inside diameter of 0.25 mm with an orifice having an aperture of 0.05 mm was employed as a CVD material passageway instead of the double-structured pipe including the capillary. The inside diameter of the outer tube of the double-structured pipe was 1.8 mm. The same vaporizer as in Example 1 except the use of the foregoing CVD material feed portion was prepared, and an apparatus for vaporizing and supplying was fabricated by connecting a degassing unit, a liquid mass flow controller, a carrier gas feed line and the like as employed in Example 1. Example 6 was conducted by the use of the foregoing apparatus for vaporizing and supplying and a liquid CVD-material having a concentration of 0.3 mol/liter in which Zr(DPM)4 as a solid CVD material was dissolved in tetrahydrofuran (THF) as a solvent was vaporized and supplied in the same manner as Example 1. - After continuous test for vaporizing and supplying for ten hours, the amount of the adhesion of the solid CVD material, both the pressure fluctuation in the vaporization chamber and the flow rate fluctuation in the liquid mass flow controller during the vaporizing and supplying test were obtained in the same manner as Example 1. The results are shown in Table 1.
- On the other hand, another tests for vaporizing and supplying under the same condition confirmed that the pressure loss-inducing means for the CVD material caused a pressure loss in the CVD material of at least 90% of the total pressure in the CVD material feed portion in Examples 1 to 6.
- There was prepared a CVD material feed portion for a vaporizer having the passageways similarly as in Example 1 except that a pipe with an inside diameter of 0.25 mm was employed as CVD material passageway instead of the capillary.
- A vaporizer was prepared similarly as Example 1 except that the foregoing CVD material feed portion was employed. An apparatus for vaporizing and supplying as illustrated in
FIG. 6 was fabricated by connecting a degassing unit, a liquid mass flow controller, a carrier gas feed line and the like as employed in Example 1 with the exception that a capillary made of stainless steel having an inside diameter of 0.1 mm and having a length of 10 cm was employed as a pipe between the liquid flow controller and the vaporizer. Example 7 was conducted by the use of the foregoing apparatus for vaporizing and supplying and a liquid CVD material having a concentration of 0.3 mol/liter in which Zr(DPM)4 as a solid CVD material was dissolved in tetrahydrofuran (THF) as a solvent was vaporized and supplied in the same manner as Example 1. - After continuous test for vaporizing and supplying for ten hours, the amount of the adhesion of the solid CVD material, both the pressure fluctuation in the vaporization chamber and the flow rate fluctuation in the liquid mass flow controller during the vaporizing and supplying test were obtained in the same manner as Example 1. The results are shown in Table 1.
- Example 8 was conducted by the use of the same apparatus for vaporizing and supplying as employed in Example 7 and a liquid CVD material having a concentration of 0.3 mol/liter in which Pb(DPM)2 as a solid CVD material was dissolved in tetrahydrofuran (THF) as a solvent was vaporized and supplied in the same manner as Example 2.
- After continuous test for vaporizing and supplying for ten hours, the amount of the adhesion of the solid CVD material, both the pressure fluctuation in the vaporization chamber and the flow rate fluctuation in the liquid mass flow controller during the vaporizing and supplying test were obtained in the same manner as Example 1. The results are shown in Table 1.
- Example 9 was conducted by the use of the same apparatus for vaporizing and supplying as employed in Example 7 and a liquid CVD material having a concentration of 0.3 mol/liter in which Ti(OiPr)2(DPM)2 as a solid CVD material was dissolved in tetrahydrofuran (THF) as a solvent was vaporized and supplied in the same manner as Example 3.
- After continuous test for vaporizing and supplying for ten hours, the amount of the adhesion of the solid CVD material, both the pressure fluctuation in the vaporization chamber and the flow rate fluctuation in the liquid mass flow controller during the vaporizing and supplying test were obtained in the same manner as Example 1. The results are shown in Table 1.
- There was prepared an apparatus for vaporizing and supplying similarly as in Example 7 except that a pipe with an inside diameter of 1.8 mm and with a length of 10 cm having a throttle portion with an aperture of 0.05 mm was employed as CVD material passageway instead of the capillary employed as the pipe between the liquid flow controller and the vaporizer. Example 10 was conducted by the use of the foregoing apparatus for vaporizing and supplying and a liquid CVD material having a concentration of 0.3 mol/liter in which Zr(DPM)4 as a solid CVD material was dissolved in tetrahydrofuran (THF) as a solvent was vaporized and supplied in the same manner as Example 1.
- After continuous test for vaporizing and supplying for ten hours, the amount of the adhesion of the solid CVD material, both the pressure fluctuation in the vaporization chamber and the flow rate fluctuation in the liquid mass flow controller during the vaporizing and supplying test were obtained in the same manner as Example 1. The results are shown in Table 1.
- There was prepared an apparatus for vaporizing and supplying similarly as in Example 7 except that a pipe with an inside diameter of 1.8 mm and with a length of 10 cm having an orifice with an aperture of 0.05 mm was employed as CVD material passageway instead of the capillary employed as the pipe between the liquid flow controller and the vaporizer. Example 11 was conducted by the use of the foregoing apparatus for vaporizing and supplying and a liquid CVD material having a concentration of 0.3 mol/liter in which Zr(DPM)4 as a solid CVD material was dissolved in tetrahydrofuran (THF) as a solvent was vaporized and supplied in the same manner as Example 1.
- After continuous test for vaporizing and supplying for ten hours, the amount of the adhesion of the solid CVD material, both the pressure fluctuation in the vaporization chamber and the flow rate fluctuation in the liquid mass flow controller during the vaporizing and supplying test were obtained in the same manner as Example 1. The results are shown in Table 1.
- There was prepared an apparatus for vaporizing and supplying similarly as in Example 7 except that a pipe with an inside diameter of 1.8 mm and with a length of 10 cm having further a porous filter made of stainless steel (SLF-M, uniform particle removing rate of a particle having diameter of 0.01 μm: 99.9999999%, available from Japan Pionics Co., Ltd.) was employed as CVD material passageway instead of the capillary employed as the pipe between the liquid flow controller and the vaporizer. Example 12 was conducted by the use of the foregoing apparatus for vaporizing and supplying and a liquid CVD material having a concentration of 0.3 mol/liter in which Zr(DPM)4 as a solid CVD material was dissolved in tetrahydrofuran (THF) as a solvent was vaporized and supplied in the same manner as Example 1.
- After continuous test for vaporizing and supplying for ten hours, the amount of the adhesion of the solid CVD material, both the pressure fluctuation in the vaporization chamber and the flow rate fluctuation in the liquid mass flow controller during the vaporizing and supplying test were obtained in the same manner as Example 1. The results are shown in Table 1.
- On the other hand, another tests for vaporizing and supplying under the same condition confirmed that the pressure loss-inducing means for the CVD material caused a pressure loss in the CVD material of at least 90% of the total pressure in the CVD material feed portion in Examples 7 to 12.
- There was prepared a CVD material feed portion for a vaporizer having the passageways similarly as in Example 1 except that a pipe with an inside diameter of 0.25 mm was employed as CVD material passageway instead of the capillary. The same vaporizer as in Example 1 except the use of the foregoing CVD material feed portion was prepared, and an apparatus for vaporizing and supplying was fabricated by connecting a degassing unit, a liquid mass flow controller, a carrier gas feed line and the like as employed in Example 1. Comparative Example 1 was conducted by the use of the foregoing apparatus for vaporizing and supplying and a liquid CVD material having a concentration of 0.3 mol/liter in which Zr(DPM)4 as a solid CVD material was dissolved in tetrahydrofuran (THF) as a solvent was vaporized and supplied in the same manner as Example 1.
- After continuous test for vaporizing and supplying for ten hours, the amount of the adhesion of the solid CVD material, both the pressure fluctuation in the vaporization chamber and the flow rate fluctuation in the liquid mass flow controller during the vaporizing and supplying test were obtained in the same manner as Example 1. The results are shown in Table 1.
- Comparative Example 2 was conducted by the use of the same apparatus for vaporizing and supplying as employed in Comparative Example 1 and a liquid CVD material having a concentration of 0.3 mol/liter in which Pb(DPM)2 as a solid CVD material was dissolved in tetrahydrofuran (THF) as a solvent was vaporized and supplied in the same manner as Example 2.
- After continuous test for vaporizing and supplying for ten hours, the amount of the adhesion of the solid CVD material, both the pressure fluctuation in the vaporization chamber and the flow rate fluctuation in the liquid mass flow controller during the vaporizing and supplying test were obtained in the same manner as Example 1. The results are shown in Table 1.
- Comparative Example 3 was conducted by the use of the same apparatus for vaporizing and supplying as employed in Comparative Example 1 and a liquid CVD material having a concentration of 0.3 mol/liter in which Ti(OiPr)2(DPM)2 as a solid CVD material was dissolved in tetrahydrofuran (THF) as a solvent was vaporized and supplied in the same manner as Example 3.
- After continuous test for vaporizing and supplying for ten hours, the amount of the adhesion of the solid CVD material, both the pressure fluctuation in the vaporization chamber and the flow rate fluctuation in the liquid mass flow controller during the vaporizing and supplying test were obtained in the same manner as Example 1. The results are shown in Table 1.
- According to the present invention, even in the case of vaporizing and supplying with a decrease in a feed amount of a carrier gas to be supplied accompanying the CVD material employing a solid CVD material, a vaporizer and an apparatus for vaporizing and supplying, which is capable of reducing and stabilizing both the pressure fluctuation in the vaporizer and the flow rate fluctuation in the liquid flow controller and efficiently vaporizing a CVD material at a desirable concentration and flow rate without causing deposit or adhesion of the solid material in the vaporization chamber are provided. As a result, it became possible to improve use efficiency by supplying the CVD material with high concentration in chemical vapor deposition, etc.
- While there has been described what is at present considered to be the preferred embodiment of the invention, it will be understood that various modifications may be made therein, and it is intended to cover in the appended claims all such modifications as fall within the true spirit and scope of the invention.
Claims (17)
1. A vaporizer which comprises a vaporization chamber for a CVD material, a CVD material feed portion supplying said CVD material for said vaporization chamber, a vaporized gas exhaust port and a heating means for heating said vaporization chamber,
wherein said CVD material feed portion comprises passageways for said CVD material and for a carrier gas respectively and said passageway for said CVD material comprises a pressure loss-inducing means for said CVD material;
wherein said CVD material feed portion comprises passageways for said CVD material and for a carrier gas and a mixing passageway for joining said foregoing passageways and for connecting to said vaporization chamber; and
wherein said pressure loss-inducing means for said CVD material is a capillary with an inner diameter smaller than a inner diameter of said mixing passageway for said CVD material and said carrier gas.
2. The vaporizer according to claim 1 , wherein said CVD material feed portion further comprises a passageway exhausting said carrier gas from an outer peripheral of an outlet of said mixing passageway to said vaporizing chamber.
3. The vaporizer according to claim 1 , wherein said pressure loss-inducing means for said CVD material causes a pressure loss in said CVD material of at least 90% of the total pressure in said CVD material feed portion.
4. The vaporizer according to claim 1 , wherein said capillary has an inner diameter of 0.2 mm or smaller.
5. The vaporizer according to claim 1 , wherein said capillary has a length of 2 cm or longer.
6. The vaporizer according to claim 1 , wherein said CVD material is a liquid CVD material made up of a solid CVD material dissolved in an organic solvent.
7. An apparatus for vaporizing and supplying that feeds a CVD material to a vaporizer via a liquid flow controller, and after vaporizing said CVD material that supplies a vaporized gas for a semiconductor production apparatus, comprising a pressure loss-inducing means for said CVD material between said liquid flow controller and said vaporizer,
wherein said pressure loss-inducing means for said CVD material is a capillary.
8. The apparatus according to claim 7 , wherein said pressure loss-inducing means for said CVD material causes a pressure loss in said CVD material of at least 90% of the pressure between a CVD material vessel and said vaporizer.
9. The apparatus according to claim 7 , wherein said capillary has an inner diameter of 0.2 mm or smaller.
10. The apparatus according to claim 7 , wherein said capillary has a length of 2 cm or longer.
11. The apparatus according to claim 7 , wherein said CVD material is a liquid CVD material made up of a solid CVD material dissolved in an organic solvent.
12. An apparatus for vaporizing and supplying that feeds a CVD material to a vaporizer via a liquid flow controller, and after vaporizing said CVD material that supplies a vaporized gas for a semiconductor production apparatus, comprising a pressure loss-inducing means for said CVD material between said liquid flow controller and said vaporizer,
wherein said pressure loss-inducing means for said CVD material is a filter.
13. The apparatus according to claim 12 , wherein said filter removes particles having diameters corresponding to 0.01 μm with a rejection rate of 99.99% or more.
14. The apparatus according to claim 12 , wherein said CVD material is a liquid CVD material made up of a solid CVD material dissolved in an organic solvent.
15. A vaporizer which comprises a vaporization chamber for a CVD material, a CVD material feed portion supplying said CVD material for said vaporization chamber, and a vaporized gas exhaust port and a heating means for heating said vaporization chamber,
wherein said CVD material feed portion comprises passageways for said CVD material and for a carrier gas respectively and said passageway for said CVD material comprises a pressure loss-inducing means for said CVD material;
wherein said pressure loss-inducing means for said CVD material is a capillary with an inner diameter smaller than an inner diameter of said mixing passageway for said CVD material and said carrier gas;
wherein said capillary has an inner diameter of 0.2 mm or smaller; and
wherein said capillary has a length of 2 cm or longer.
16. An apparatus for vaporizing and supplying that feeds a CVD material to a vaporizer via a liquid flow controller, and after vaporizing said CVD material that supplies vaporized gas for a semiconductor production apparatus, comprising a pressure loss-inducing means for said CVD material between said liquid flow controller and said vaporizer,
wherein said pressure loss-inducing means for said CVD material is a capillary;
wherein said capillary has an inner diameter of 0.2 mm or smaller; and
wherein said capillary has a length of 2 cm or longer.
17. An apparatus for vaporizing and supplying that feeds a CVD material to a vaporizer via a liquid flow controller, and after vaporizing said CVD material that supplies vaporized gas for a semiconductor production apparatus, comprising a pressure loss-inducing means for said CVD material between said liquid flow controller and said vaporizer,
wherein said pressure loss-inducing means for said CVD material is a filter; and
wherein said filter removes particles having diameters corresponding to 0.01 μm with a rejection rate of 99.99% or more.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US11/345,525 US20060125129A1 (en) | 2002-05-13 | 2006-02-02 | Vaporizer and apparatus for vaporizing and supplying |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2002-136892 | 2002-05-13 | ||
JP2002136892A JP3822135B2 (en) | 2002-05-13 | 2002-05-13 | Vaporization supply device |
US10/413,204 US7036801B2 (en) | 2002-05-13 | 2003-04-15 | Vaporizer and apparatus for vaporizing and supplying |
US11/345,525 US20060125129A1 (en) | 2002-05-13 | 2006-02-02 | Vaporizer and apparatus for vaporizing and supplying |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10/413,204 Division US7036801B2 (en) | 2002-05-13 | 2003-04-15 | Vaporizer and apparatus for vaporizing and supplying |
Publications (1)
Publication Number | Publication Date |
---|---|
US20060125129A1 true US20060125129A1 (en) | 2006-06-15 |
Family
ID=29397538
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10/413,204 Expired - Fee Related US7036801B2 (en) | 2002-05-13 | 2003-04-15 | Vaporizer and apparatus for vaporizing and supplying |
US11/345,525 Abandoned US20060125129A1 (en) | 2002-05-13 | 2006-02-02 | Vaporizer and apparatus for vaporizing and supplying |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10/413,204 Expired - Fee Related US7036801B2 (en) | 2002-05-13 | 2003-04-15 | Vaporizer and apparatus for vaporizing and supplying |
Country Status (5)
Country | Link |
---|---|
US (2) | US7036801B2 (en) |
JP (1) | JP3822135B2 (en) |
KR (1) | KR100985656B1 (en) |
CN (1) | CN1305113C (en) |
TW (1) | TW200401840A (en) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20080296791A1 (en) * | 2006-08-31 | 2008-12-04 | Tokyo Electron Limited | Vaporizing apparatus and semiconductor processing system |
US20090014901A1 (en) * | 2006-03-20 | 2009-01-15 | Rasirc | Vaporizer for delivery of low vapor pressure gases |
US20100065972A1 (en) * | 2008-09-12 | 2010-03-18 | Msp Corporation | Method and apparatus for liquid precursor atomization |
WO2011133715A1 (en) * | 2010-04-21 | 2011-10-27 | Rasirc | Apparatus and method for delivery of vapor |
US9695207B2 (en) | 2012-11-19 | 2017-07-04 | Adeka Corporation | Method for producing thin film containing molybdenum |
US11458412B2 (en) * | 2018-01-17 | 2022-10-04 | Rasirc, Inc. | Controlled vapor delivery into low pressure processes |
Families Citing this family (33)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7261118B2 (en) | 2003-08-19 | 2007-08-28 | Air Products And Chemicals, Inc. | Method and vessel for the delivery of precursor materials |
JP2005072195A (en) * | 2003-08-22 | 2005-03-17 | Watanabe Shoko:Kk | Dispersing device for vaporizer, vaporizer for mocvd using the same, and method of vaporizing carrier gas |
JP4595356B2 (en) * | 2004-03-12 | 2010-12-08 | 国立大学法人 奈良先端科学技術大学院大学 | Raw material vaporizer for metalorganic chemical vapor deposition equipment |
US20060207503A1 (en) * | 2005-03-18 | 2006-09-21 | Paul Meneghini | Vaporizer and method of vaporizing a liquid for thin film delivery |
JP2005340405A (en) * | 2004-05-26 | 2005-12-08 | Asahi Denka Kogyo Kk | Raw material for chemical vapor phase growth and manufacturing method of thin film |
KR100543711B1 (en) * | 2004-06-19 | 2006-01-20 | 삼성전자주식회사 | Heat treatment apparatus |
JP2006080374A (en) * | 2004-09-10 | 2006-03-23 | Sharp Corp | Apparatus for manufacturing nitride semiconductor and nitride semiconductor laser element |
JP2006128611A (en) * | 2004-09-30 | 2006-05-18 | Tri Chemical Laboratory Inc | Film forming material and method, and element |
JP4592373B2 (en) * | 2004-09-30 | 2010-12-01 | 株式会社トリケミカル研究所 | Method for forming conductive molybdenum nitride gate electrode film |
JP3896594B2 (en) | 2004-10-01 | 2007-03-22 | 株式会社ユーテック | Vaporizer for CVD, solution vaporization type CVD apparatus, and vaporization method for CVD |
US7465475B2 (en) * | 2004-11-09 | 2008-12-16 | Eastman Kodak Company | Method for controlling the deposition of vaporized organic material |
WO2006098792A2 (en) * | 2004-12-30 | 2006-09-21 | Msp Corporation | High accuracy vapor generation and delivery for thin film deposition |
JPWO2006095772A1 (en) * | 2005-03-10 | 2008-08-14 | 株式会社ユーテック | Zinc oxide layer forming method, zinc oxide layer forming apparatus, and zinc oxide layer |
JP4601535B2 (en) * | 2005-09-09 | 2010-12-22 | 株式会社リンテック | A vaporizer capable of vaporizing liquid raw materials at low temperatures |
JP4299286B2 (en) * | 2005-10-06 | 2009-07-22 | 東京エレクトロン株式会社 | Vaporization apparatus, film forming apparatus, and vaporization method |
US8268078B2 (en) * | 2006-03-16 | 2012-09-18 | Tokyo Electron Limited | Method and apparatus for reducing particle contamination in a deposition system |
JP4605790B2 (en) * | 2006-06-27 | 2011-01-05 | 株式会社フジキン | Raw material vaporization supply device and pressure automatic adjustment device used therefor. |
JP5059371B2 (en) * | 2006-10-18 | 2012-10-24 | 東京エレクトロン株式会社 | Vaporizer and deposition system |
US9109287B2 (en) | 2006-10-19 | 2015-08-18 | Air Products And Chemicals, Inc. | Solid source container with inlet plenum |
JP2008196479A (en) * | 2007-02-09 | 2008-08-28 | Sulzer Chemtech Ag | Exhaust gas cleaning system |
JP4324619B2 (en) * | 2007-03-29 | 2009-09-02 | 東京エレクトロン株式会社 | Vaporization apparatus, film forming apparatus, and vaporization method |
EP2048261A1 (en) * | 2007-10-12 | 2009-04-15 | ArcelorMittal France | Industrial steam generator for depositing an alloy coating on a metal band |
JP5350824B2 (en) * | 2009-02-03 | 2013-11-27 | 株式会社フジキン | Liquid material vaporization supply system |
KR200453186Y1 (en) * | 2009-07-23 | 2011-04-15 | 주식회사 테라세미콘 | Apparatus for uniformly supplying of source gas |
US20130220221A1 (en) * | 2012-02-23 | 2013-08-29 | Applied Materials, Inc. | Method and apparatus for precursor delivery |
US9598766B2 (en) | 2012-05-27 | 2017-03-21 | Air Products And Chemicals, Inc. | Vessel with filter |
KR102104728B1 (en) * | 2015-09-30 | 2020-04-24 | 가부시키가이샤 코쿠사이 엘렉트릭 | Substrate processing device, manufacturing method of semiconductor device and recording medium |
JP6675865B2 (en) * | 2015-12-11 | 2020-04-08 | 株式会社堀場エステック | Liquid material vaporizer |
KR102248120B1 (en) * | 2016-03-24 | 2021-05-04 | 가부시키가이샤 코쿠사이 엘렉트릭 | Vaporizer, substrate processing apparatus and method of manufacturing semiconductor device |
JP6806419B2 (en) * | 2017-09-21 | 2021-01-06 | 株式会社Kokusai Electric | Manufacturing method of storage container, vaporizer, substrate processing device and semiconductor device |
CN108277477B (en) * | 2018-01-25 | 2020-08-28 | 沈阳拓荆科技有限公司 | Liquid vaporizer and semiconductor processing system using the same |
KR102188388B1 (en) * | 2018-12-17 | 2020-12-08 | (주)에이텍솔루션 | A vaporizer having a chemical storage space and a separate vaporization space |
CN111020528B (en) * | 2019-11-20 | 2021-11-19 | 苏州新材料研究所有限公司 | Method for preparing REBCO high-temperature superconducting strip by MOCVD (Metal organic chemical vapor deposition) process |
Citations (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US43215A (en) * | 1864-06-21 | Improvement in vapor-stoves | ||
US4271099A (en) * | 1979-10-01 | 1981-06-02 | Kukla Thomas S | Apparatus for thorough mixture of a liquid with a gas |
US4370304A (en) * | 1978-06-01 | 1983-01-25 | Unie Van Kunstmestfabrieken, B.V. | Two-phase spraying device and reaction chamber for the preparation of a product containing ammonium orthophosphate |
US4379097A (en) * | 1981-04-03 | 1983-04-05 | Leggett Wilbur P | Hydrotherapy jet unit |
US4977785A (en) * | 1988-02-19 | 1990-12-18 | Extrel Corporation | Method and apparatus for introduction of fluid streams into mass spectrometers and other gas phase detectors |
US5372754A (en) * | 1992-03-03 | 1994-12-13 | Lintec Co., Ltd. | Liquid vaporizer/feeder |
US5437784A (en) * | 1993-05-03 | 1995-08-01 | J. M. Voith Gmbh | Injector for a flotation device |
US5901908A (en) * | 1996-11-27 | 1999-05-11 | Ford Motor Company | Spray nozzle for fluid deposition |
US5951923A (en) * | 1996-05-23 | 1999-09-14 | Ebara Corporation | Vaporizer apparatus and film deposition apparatus therewith |
US6110283A (en) * | 1997-03-17 | 2000-08-29 | Mitsubishi Denki Kabushiki Kaisha | Chemical vapor deposition apparatus |
US6155540A (en) * | 1997-09-30 | 2000-12-05 | Japan Pionics Co., Ltd. | Apparatus for vaporizing and supplying a material |
US6195504B1 (en) * | 1996-11-20 | 2001-02-27 | Ebara Corporation | Liquid feed vaporization system and gas injection device |
US6349887B1 (en) * | 1998-12-30 | 2002-02-26 | Hyundai Electronics Industries Co., Ltd. | Liquid delivery system |
US6386466B1 (en) * | 1999-04-19 | 2002-05-14 | Disco Corporation | Cleaning apparatus |
US6473563B2 (en) * | 2000-12-01 | 2002-10-29 | Japan Pionics Co., Ltd. | Vaporizer and apparatus for vaporizing and supplying |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR100507961B1 (en) * | 1996-11-20 | 2005-11-25 | 가부시키가이샤 에바라 세이사꾸쇼 | Liquid raw material gasification system and gas injection device |
US6136725A (en) * | 1998-04-14 | 2000-10-24 | Cvd Systems, Inc. | Method for chemical vapor deposition of a material on a substrate |
JP4018841B2 (en) * | 1999-04-30 | 2007-12-05 | 日本パイオニクス株式会社 | Vaporizer and vaporization supply method |
KR100649852B1 (en) * | 1999-09-09 | 2006-11-24 | 동경 엘렉트론 주식회사 | Semiconductor manufacturing system having a vaporizer which efficiently vaporizes a liquid material |
US6350320B1 (en) * | 2000-02-22 | 2002-02-26 | Applied Materials, Inc. | Heater for processing chamber |
US7163197B2 (en) * | 2000-09-26 | 2007-01-16 | Shimadzu Corporation | Liquid substance supply device for vaporizing system, vaporizer, and vaporization performance appraisal method |
-
2002
- 2002-05-13 JP JP2002136892A patent/JP3822135B2/en not_active Expired - Fee Related
-
2003
- 2003-04-15 US US10/413,204 patent/US7036801B2/en not_active Expired - Fee Related
- 2003-05-08 TW TW092112519A patent/TW200401840A/en unknown
- 2003-05-12 KR KR1020030029762A patent/KR100985656B1/en not_active IP Right Cessation
- 2003-05-12 CN CNB031236499A patent/CN1305113C/en not_active Expired - Fee Related
-
2006
- 2006-02-02 US US11/345,525 patent/US20060125129A1/en not_active Abandoned
Patent Citations (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US43215A (en) * | 1864-06-21 | Improvement in vapor-stoves | ||
US4370304A (en) * | 1978-06-01 | 1983-01-25 | Unie Van Kunstmestfabrieken, B.V. | Two-phase spraying device and reaction chamber for the preparation of a product containing ammonium orthophosphate |
US4271099A (en) * | 1979-10-01 | 1981-06-02 | Kukla Thomas S | Apparatus for thorough mixture of a liquid with a gas |
US4379097A (en) * | 1981-04-03 | 1983-04-05 | Leggett Wilbur P | Hydrotherapy jet unit |
US4977785A (en) * | 1988-02-19 | 1990-12-18 | Extrel Corporation | Method and apparatus for introduction of fluid streams into mass spectrometers and other gas phase detectors |
US5372754A (en) * | 1992-03-03 | 1994-12-13 | Lintec Co., Ltd. | Liquid vaporizer/feeder |
US5437784A (en) * | 1993-05-03 | 1995-08-01 | J. M. Voith Gmbh | Injector for a flotation device |
US5951923A (en) * | 1996-05-23 | 1999-09-14 | Ebara Corporation | Vaporizer apparatus and film deposition apparatus therewith |
US6195504B1 (en) * | 1996-11-20 | 2001-02-27 | Ebara Corporation | Liquid feed vaporization system and gas injection device |
US6269221B1 (en) * | 1996-11-20 | 2001-07-31 | Ebara Corporation | Liquid feed vaporization system and gas injection device |
US5901908A (en) * | 1996-11-27 | 1999-05-11 | Ford Motor Company | Spray nozzle for fluid deposition |
US6110283A (en) * | 1997-03-17 | 2000-08-29 | Mitsubishi Denki Kabushiki Kaisha | Chemical vapor deposition apparatus |
US6155540A (en) * | 1997-09-30 | 2000-12-05 | Japan Pionics Co., Ltd. | Apparatus for vaporizing and supplying a material |
US6349887B1 (en) * | 1998-12-30 | 2002-02-26 | Hyundai Electronics Industries Co., Ltd. | Liquid delivery system |
US6386466B1 (en) * | 1999-04-19 | 2002-05-14 | Disco Corporation | Cleaning apparatus |
US6473563B2 (en) * | 2000-12-01 | 2002-10-29 | Japan Pionics Co., Ltd. | Vaporizer and apparatus for vaporizing and supplying |
Cited By (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20090014901A1 (en) * | 2006-03-20 | 2009-01-15 | Rasirc | Vaporizer for delivery of low vapor pressure gases |
US7618027B2 (en) * | 2006-03-20 | 2009-11-17 | Rasirc | Vaporizer for delivery of low vapor pressure gases |
US20080296791A1 (en) * | 2006-08-31 | 2008-12-04 | Tokyo Electron Limited | Vaporizing apparatus and semiconductor processing system |
US7547003B2 (en) * | 2006-08-31 | 2009-06-16 | Tokyo Electron Limited | Vaporizing apparatus and semiconductor processing system |
US8132793B2 (en) * | 2008-09-12 | 2012-03-13 | Msp Corporation | Method and apparatus for liquid precursor atomization |
US20100065972A1 (en) * | 2008-09-12 | 2010-03-18 | Msp Corporation | Method and apparatus for liquid precursor atomization |
US8393599B2 (en) | 2008-09-12 | 2013-03-12 | Msp Corporation | Apparatus for liquid precursor atomization |
US8529985B2 (en) | 2008-09-12 | 2013-09-10 | Msp Corporation | Method for liquid precursor atomization |
KR101502415B1 (en) * | 2008-09-12 | 2015-03-13 | 엠 에스피 코포레이션 | Method and apparatus for liquid precursor atomization |
WO2011133715A1 (en) * | 2010-04-21 | 2011-10-27 | Rasirc | Apparatus and method for delivery of vapor |
US9695207B2 (en) | 2012-11-19 | 2017-07-04 | Adeka Corporation | Method for producing thin film containing molybdenum |
US9988411B2 (en) | 2012-11-19 | 2018-06-05 | Adeka Corporation | Thin-film-forming material including a molybdenum imide compound |
US10150789B2 (en) | 2012-11-19 | 2018-12-11 | Adeka Corporation | Molybdenum imide compound |
US11458412B2 (en) * | 2018-01-17 | 2022-10-04 | Rasirc, Inc. | Controlled vapor delivery into low pressure processes |
Also Published As
Publication number | Publication date |
---|---|
TW200401840A (en) | 2004-02-01 |
US20030209201A1 (en) | 2003-11-13 |
KR100985656B1 (en) | 2010-10-05 |
JP2003332243A (en) | 2003-11-21 |
US7036801B2 (en) | 2006-05-02 |
CN1458669A (en) | 2003-11-26 |
JP3822135B2 (en) | 2006-09-13 |
CN1305113C (en) | 2007-03-14 |
KR20030088344A (en) | 2003-11-19 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US7036801B2 (en) | Vaporizer and apparatus for vaporizing and supplying | |
US6473563B2 (en) | Vaporizer and apparatus for vaporizing and supplying | |
JP6133954B2 (en) | Method and apparatus to help promote contact between gas and evaporating material | |
US9469898B2 (en) | Method and apparatus to help promote contact of gas with vaporized material | |
US20080092816A1 (en) | Solid Source Container With Inlet Plenum | |
CN101818335A (en) | Method and apparatus for using solution based precursors for atomic layer deposition | |
EP1473384A1 (en) | Vaporizer | |
US6767402B2 (en) | Method for vaporizing and supplying | |
JP4288049B2 (en) | Vaporization supply method | |
JP2003013234A (en) | Vaporizer and device for vaporizing/feeding | |
JP2002173778A (en) | Vaporizer | |
JP4195808B2 (en) | Vaporizer | |
JP2003318170A (en) | Vaporizer | |
JP2000315686A (en) | Vaporizer and vaporizing and supplying method | |
TWI819647B (en) | Containers for evaporating raw materials and solid gasification supply systems | |
JP2003264185A (en) | Gasifying/supplying method | |
JP2004228221A (en) | Vaporizer | |
JP2003309114A (en) | Method and apparatus for vaporizing supply | |
KR100712435B1 (en) | Method of fabricating a BST thin film and vaporizer used therefor | |
JP2004096127A (en) | Method for evaluating vaporization performance of vaporizer | |
JP2006013086A (en) | Vaporizer | |
JP2005150520A (en) | Vaporizer | |
JP2005347598A (en) | Vaporizer and vaporization method |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION |