TWI411662B - Cleaning gas - Google Patents
Cleaning gas Download PDFInfo
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- TWI411662B TWI411662B TW099140847A TW99140847A TWI411662B TW I411662 B TWI411662 B TW I411662B TW 099140847 A TW099140847 A TW 099140847A TW 99140847 A TW99140847 A TW 99140847A TW I411662 B TWI411662 B TW I411662B
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- Taiwan
- Prior art keywords
- cleaning gas
- deposit
- chf
- cof
- cleaning
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- 238000004140 cleaning Methods 0.000 title claims abstract description 61
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 13
- 229910052702 rhenium Inorganic materials 0.000 claims abstract description 13
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 8
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 7
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 7
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 6
- 229910052785 arsenic Inorganic materials 0.000 claims abstract description 6
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 6
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 6
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 6
- 229910052762 osmium Inorganic materials 0.000 claims abstract description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 6
- 229910052709 silver Inorganic materials 0.000 claims abstract description 6
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 6
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 6
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 6
- 229910052786 argon Inorganic materials 0.000 claims abstract description 5
- 229910052734 helium Inorganic materials 0.000 claims abstract description 5
- 229910052743 krypton Inorganic materials 0.000 claims abstract description 5
- 229910052754 neon Inorganic materials 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 29
- 238000005229 chemical vapour deposition Methods 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- 239000000654 additive Substances 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 5
- 229910052735 hafnium Inorganic materials 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 238000003980 solgel method Methods 0.000 claims description 5
- 238000004544 sputter deposition Methods 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical group [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 4
- 125000002524 organometallic group Chemical group 0.000 claims description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims description 4
- 230000003213 activating effect Effects 0.000 claims description 2
- 238000001947 vapour-phase growth Methods 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims 1
- 238000010926 purge Methods 0.000 claims 1
- 239000007789 gas Substances 0.000 description 51
- 239000010408 film Substances 0.000 description 18
- 239000000243 solution Substances 0.000 description 10
- 239000006227 byproduct Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 230000007797 corrosion Effects 0.000 description 7
- 238000005260 corrosion Methods 0.000 description 7
- 238000005530 etching Methods 0.000 description 7
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- CCGKOQOJPYTBIH-UHFFFAOYSA-N ketene group Chemical group C=C=O CCGKOQOJPYTBIH-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000006378 damage Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 229910052594 sapphire Inorganic materials 0.000 description 3
- 239000010980 sapphire Substances 0.000 description 3
- YQQHEHMVPLLOKE-UHFFFAOYSA-N 1,1,2,2-tetrafluoro-1-methoxyethane Chemical compound COC(F)(F)C(F)F YQQHEHMVPLLOKE-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 239000012459 cleaning agent Substances 0.000 description 2
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 238000000927 vapour-phase epitaxy Methods 0.000 description 2
- CRLSHTZUJTXOEL-UHFFFAOYSA-N 2,2-difluoroacetyl fluoride Chemical compound FC(F)C(F)=O CRLSHTZUJTXOEL-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 238000004057 DFT-B3LYP calculation Methods 0.000 description 1
- QFAMWBVXSHCNQX-UHFFFAOYSA-N F.C(C)(=O)O.F Chemical compound F.C(C)(=O)O.F QFAMWBVXSHCNQX-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- -1 WSix Inorganic materials 0.000 description 1
- DFPWNNNCJDHVEY-UHFFFAOYSA-N [F].FC(C(=O)O)(F)F Chemical compound [F].FC(C(=O)O)(F)F DFPWNNNCJDHVEY-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001622 bismuth compounds Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000001784 detoxification Methods 0.000 description 1
- PBWZKZYHONABLN-UHFFFAOYSA-N difluoroacetic acid Chemical compound OC(=O)C(F)F PBWZKZYHONABLN-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- WMIYKQLTONQJES-UHFFFAOYSA-N hexafluoroethane Chemical compound FC(F)(F)C(F)(F)F WMIYKQLTONQJES-UHFFFAOYSA-N 0.000 description 1
- 238000011086 high cleaning Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
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
- C23C16/4401—Means for minimising impurities, e.g. dust, moisture or residual gas, in the reaction chamber
- C23C16/4405—Cleaning of reactor or parts inside the reactor by using reactive gases
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
-
- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
-
- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
-
- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/56—Apparatus specially adapted for continuous coating; Arrangements for maintaining the vacuum, e.g. vacuum locks
- C23C14/564—Means for minimising impurities in the coating chamber such as dust, moisture, residual gases
-
- 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
- C23C16/06—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 deposition of metallic material
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Physics & Mathematics (AREA)
- Chemical Vapour Deposition (AREA)
- Drying Of Semiconductors (AREA)
- Physical Vapour Deposition (AREA)
Description
本發明係關於一種在利用化學氣相沉積法(CVD法)、有機金屬氣相生長法(MOCVD)、濺射法、溶膠-凝膠法及蒸鍍法等之方法製造薄膜、厚膜、粉體及晶鬚等時,用以除去沉積於裝置內壁、治具、配管等上之不必要的沉積物之清洗氣體。
在半導體薄膜裝置製造製程或光學裝置製造製程、超硬材料製造製程中,係利用CVD法、濺射法、溶膠-凝膠法及蒸鍍法等之方法製造各種薄膜、厚膜、粉體及晶鬚等。此時,亦會有沉積物生成於不應沉積膜或晶鬚、粉體之部位的反應器內壁或保持物品之治具等上。生成如此之不必要之沉積物會成為微粒產生的原因,從而難以製造優質的膜、粒子及晶鬚,故必須隨時除去。
先前,為除去如此之不必要的沉積物,一直是使用CF4
、C2
F6
、C3
F8
等之全氟化碳(PFC)的清洗氣體。但,由於該等氣體會長期安定地存在於環境中,故被評估為地球溫暖化係數較高,對環境有不良影響之問題。例如,根據第4次IPCC報告書所言,該等之GWP(100年值)為CF4
:7390、C2
F6
:12200、C3
F8
:8830。
再者,C2
F6
或C3
F8
等之具有CF3
基之部分構造之清洗氣體,雖在沉積室(腔室)內會產生CF3
自由基或離子等之活性種而發揮清洗效果,但當CF3
活性種與F自由基或離子的F活性種接觸時,將會做再結合而副生CF4
。根據環境部地球環境局環境保全對策課氟氯碳化物等對策推進室發行(平成21年3月發行)的PFC破壞處理準則記載,CF4
係在環境中最難分解的PFC,若僅以與其他氟氯碳化物類之破壞處理同等之條件,將有無法進行充分之破壞處理之可能性。
作為代替該等PFC之地球温暖化係數較低之含氟的清洗氣體,經人提出的有COF2
、CHF2
OF(專利文獻1)、CF3
COF(專利文獻2、3)等。針對該等而記載有:例如,CF3
COF可藉由將蝕刻條件最適化,而使CF4
之副生減少。
專利文獻1:日本特開2000-63826
專利文獻2:日本特開2000-265275
專利文獻3:日本特開2002-158181
如前述,根據專利文獻1、2,雖記載有CF3
COF可藉由將清洗條件最適化,而使CF4
之副生減少,但換而言之,CF3
COF與氧之比等之清洗條件並非由清洗性能,而是不得不由CF4
副產物生成率而受到限制。實際上根據腔室之形狀或耐蝕性、所期望之清洗速度等之制約條件,可推測存在難以經常將CF4
之副生減少之情形。
通常在高温、高清洗氣體濃度之過苛的條件下,由於副生之CF4
會進行再分解,因此亦存在表觀上無法確認到CF4
之副生之情形,但若因受限於裝置之耐蝕性而以更溫和的條件實施清洗時,則存在有CF4
副生之情形。因此,只要使用具有CF3
基之部分構造之清洗氣體,就無法徹底避免CF3
活性種與F活性種的再結合。
又,同樣地,作為代替PFC之地球温暖化係數較低的清洗氣體而被提案的COF2
或CF3
COF之情形,係以危險的CO、F2
氣體作為起始原料,需要耐腐蝕性優異之高價的製造設備。
因此,本發明之課題係提供一種不僅清洗性能優異,而且容易獲得,實質上不會副生對環境產生負荷之CF4
之新穎的清洗氣體。
本發明人等經銳意研討之結果,發現藉由使用二氟醋酸氟(CHF2
COF)可完全克服前述問題,終而完成本發明。
亦即,本發明係如下所述。
[技術方案1]一種清洗氣體,其係在利用化學氣相沉積法(CVD法)、有機金屬氣相生長法(MOCCD)、濺射法、溶膠-凝膠法或蒸鍍法製造薄膜、厚膜、粉體或晶鬚時,用以除去附帶地沉積於製造裝置的內壁或其附屬裝置上之沉積物的包含CHF2
COF而成者。
[技術方案2]如技術方案1之清洗氣體,其中沉積物係沉積於成膜裝置上之沉積物。
[技術方案3]如技術方案1或2之清洗氣體,其中沉積物係包含W、Ti、Mo、Re、Ge、P、Si、V、Nb、Ta、Se、Te、Mo、Re、Os、Ir、Sb、Ge、Au、Ag、As、Cr、Hf、Zr、Ni、Co及其化合物的沉積物。
[技術方案4]如技術方案1至3之清洗氣體,其中沉積物係含矽附著物。
[技術方案5]如技術方案1至4之清洗氣體,其中清洗氣體係包含選自O2
、O3
、CO、CO2
、F2
、NF3
、Cl2
、Br2
、I2
、XFn
(式中,X表示Cl、I或Br,n表示1≦n≦7的整數)、CH4
、CH3
F、CH2
F2
、CHF3
、N2
、He、Ar、Ne及Kr中之至少1種氣體作為添加物。
[技術方案6]如技術方案1至5之清洗氣體,其中清洗氣體至少包含CHF2
COF與O2
。
[技術方案7]如技術方案1至6之清洗氣體,其中清洗氣體至少包含CHF2
COF、O2
及CO。
[技術方案8]一種沉積物的除去方法,其係使用如技術方案5至7之清洗氣體。
[技術方案9]如技術方案8之沉積物的除去方法,其中沉積物係沉積於成膜裝置上之沉積物者。
[技術方案10]如技術方案8或9之沉積物的除去方法,其中沉積物為包含W、Ti、Mo、Re、Ge、P、Si、V、Nb、Ta、Se、Te、Mo、Re、Os、Ir、Sb、Ge、Au、Ag、As、Cr、Hf、Zr、Ni、Co及其化合物之沉積物。
[技術方案11]如技術方案8至10之沉積物的除去方法,其中沉積物為含矽附著物。
[技術方案12]一種沉積物的除去方法,其係利用由遠距電漿所引起的高頻或微波使如技術方案5至7之清洗氣體活性化而予使用。
本發明之清洗氣體不僅具有因含有CHF2
COF而對環境產生的負荷較輕此一特徵,而且可發揮具有蝕刻速度快、且不會引起裝置腐蝕等之對於半導體製膜裝置等之優異的清洗性能此一效果。又,使用該清洗氣體之清洗方法同樣可發揮優異的清洗性能。因而,本發明之清洗氣體可用於除去CVD法等之薄膜製造裝置的沉積物。
以下,詳細說明本發明。
藉由作為清潔劑、發泡劑等所使用的HFE-254pc(CHF2
CF2
OMe)或HFE-374pc-f(CHF2
CF2
OEt)等之CHF2
CF2
OR(R為Me、Et、n-Pr、iso-Pr、n-Bu、sec-Bu、iso-Bu、tert-Bu等之烷基)的1-烷氧基-1,1,2,2-四氟乙烷之接觸分解,可容易且定量地合成CHF2
COF。又,由於HFE-254pc或HFE-374pc-f可藉由在工業上可大量生產的四氟乙烯上加成甲醇或乙醇而合成,故為非常容易獲得的化合物。
由於CHF2
COF的沸點為0℃,故可成為無論是作為液體還是氣體皆為處理便利性較高的清洗氣體。又,由於CHF2
COF與水反應會分解成二氟醋酸(CHF2
COOH)與氟化氫(HF),故通常可利用水洗滌器去除,使用鹼性水洗滌器亦較佳、即使萬一未實施除害步驟而被排放至大氣中,亦會與大氣中的雨或水蒸氣發生反應而容易地分解,故對地球温暖化的影響亦微乎其微。
既存之CF3
COF與本發明之CHF2
COF在性質上顯著不同之點可舉出有烯酮構造的容易獲取度。已知CHF2
COF係以如下述反應式,獲取CF2
=C=O之烯酮構造。在CF3
COF之情形下,根據計算可獲得烯酮構造之反應係165.9 kcal之吸熱反應,為促進反應,除了該自由能外還進而需要活化能,故可以說實際發生之可能性非常低。
CHF2
COF→CF2
=C=O+HF +48.9 kcal/mol
CF3
COF→CF2
=C=O+F2
+165.9 kcal/mol
反應熱為B3LYP/6-311G+**之計算值。
如實施例中所示,在將CHF2
COF作為清洗氣體使用之情形下,從於各種條件下均未完全檢測出CF4
來看,可推斷係利用與CF3
COF完全不同的機制進行清洗者。
又,在CF3
COF之情形下,於使用例如電漿之清洗步驟中,一旦所產生的CF3
活性種以某機率與F活性種接觸而再結合,將會副生CF4
。相對於此,在CHF2
COF之情形下,即使CHF2
活性種與F活性種接觸,亦是副生出比較容易分解之CHF3
。在機率上亦可認為有CHF3
會進一步分解,而產生CF3
活性種,經其與F活性種再結合而副生CF4
之情形,但可容易推斷的是,其機率相較於具有CF3
基的部分構造之CF3
COF等之清洗氣體,有顯著之降低。根據該等理由可認為CHF2
COF實質上不會副生CF4
,而實際上,於各實施例中亦未確認到有CF4
副生。
本發明清洗氣體清洗之作為對象之沉積物,係在利用化學氣相沉積法(CVD法)、有機金屬氣相生長法(MOCCD)、濺射法、溶膠-凝膠法及蒸鍍法等之方法製造薄膜、厚膜、粉體及晶鬚等時,附帶地沉積於製造裝置的內壁或治具、配管等之附屬裝置上之不必要的沉積物。在本說明書中,「沉積物」只要未作另行定義,則將其稱為此處所言之「不必要的沉積物」。
作為可利用本發明之清洗氣體進行清洗之沉積物,可舉出有W、Ti、Mo、Re、Ge、P、Si、V、Nb、Ta、Se、Te、Mo、Re、Os、Ir、Sb、Ge、Au、Ag、As、Cr、Hf、Zr、Ni、Co及其化合物,具體而言,可舉出有SiO2
、WSix、TiN、Ta2
O5
、Si3
N4
及SiB等之氧化物、氮化物、碳化物、硼化物及該等之複合物。其中,較佳的是W、WSix、Ti、TiN、Ta2
O5
、Mo、Re、Ge、Si3
N4
、Si及SiO2
等,特別是至少包含矽或其化合物之沉積物之含矽沉積物適於作為除去的對象物。
考慮到應除去之沉積物之種類及厚度、以及使用於製造薄膜等之裝置上之材料的種類,本發明之清洗氣體,作為添加物,可添加O2
、O3
、CO、CO2
、F2
、NF3
、Cl2
、Br2
、I2
、XFn
(式中,X表示Cl、I或Br,n表示1≦n≦7的整數。具體而言,可例示ClF、ClF3
、BrF、BrF3
、IF5
、IF7
。)、CH4
、CH3
F、CH2
F2
、CHF3
、N2
、He、Ar、Ne及Kr中任一者。添加氧對清洗速度提高有效。具體而言,較佳的是CHF2
COF:O2
(摩爾比)為10:1~1:5,更佳的是5:1~1:3。又,在進而添加除氧以外的添加劑之情形下,亦可超出該範圍進行添加。其範圍係依CH4
等之含氫添加劑的添加量而定,較佳的是CH2
COF:O2
(摩爾比)大致為20:1至1:20。
又,O2
與前述碳數目為1的化合物(CO、CO2
、CH4
、CH3
F、CH2
F2
及CHF3
)之組合較佳,尤佳的是O2
與CO之添加。CO會以HCOF的形式捕獲烯酮生成時等副生的HF,以自身作為清洗劑發揮作用,故而有效。CO之添加量為CHF2
COF:CO(摩爾比)=10:1~1:5,較佳為5:1~1:1。N2
、He、Ne、Ar、Kr、Xe等之惰性氣體不僅具有稀釋效果,特別是Ar亦對電漿之安定有效,且根據其與CHF2
COF之相乘效果可使清洗速度提高。F2
、NF3
、Cl2
、Br2
、I2
、XFn
(X=Cl、I、Br,1≦n≦7)、CH4
、CH3
F、CH2
F2
及CHF3
之添加,對因應除去對象沉積物之種類之清洗速度的控制有效。
又,有關反應條件,雖可考量被處理裝置之材質進行適宜選擇而並無特別限制,但較佳的是,温度在裝置材質為石英之情形下為800℃以下,作為一部分或整體材質,在使用陶瓷、鋁等金屬之情形下為500℃以下。若為該等之温度以上則會引起腐蝕,故而不佳。接著,有關壓力,若超過500℃,則以將其設為13.3 kPa(100 Torr)以下為佳,設為6.6 kPa(50 Torr)以下則更佳。若超過100 Torr則會引起腐蝕,故而不佳。
利用本發明清洗氣體之清洗可利用熱分解法、光分解法及電漿法中任一者,但以電漿法較佳。電漿法可使用高頻或微波使其在腔室內產生,但使其在腔室外產生並朝腔室內導入之遠程電漿法亦可較佳地被採用。作為本發明清洗方法之被處理裝置,可適用於利用CVD法而形成半導體裝置、液晶裝置、光學裝置、塗敷工具等之薄膜之製膜裝置或製造晶鬚、粉末等之製造裝置中。其中,尤佳的是適用於製膜裝置中,更佳的是適用於半導體裝置、液晶裝置等之使用有矽化合物之製膜裝置中。
以下,利用實施例詳細說明本發明。
實施例1~4、比較例1~5
於圖1顯示實驗中使用之裝置的概略圖。使用高頻電源3(13.56 MHz、50 W),使自氣體導入口以表1所示之流量所供給的試料氣體(二氟醋酸氟(CHF2
COF)、氧(O2
)、一氧化碳(CO))在安裝於反應腔室1之上部之藍寶石管7內激發,並將生成的活性種利用氣流供給至腔室內,對固定於試料支架11上之試料12(摻雜有P之Si基板)進行蝕刻。
試料氣體中,CHF2
COF、CF3
COF、CF4
、C2
F6
係自第一氣體導入口4,O2
係自第二氣體導入口5,CO係自第三氣體導入口6,分別經由質量流量控制器(未圖示)而被導入。設定基板(試料支架11)温度為25℃、壓力為13.3 Pa(0.1 torr)。排出氣體在機械增壓泵的排氣側加入2升/分鐘的氮進行稀釋,並以FT-IR利用檢量線法測量CF4
濃度。
在實施例1~4結束後,對裝置內進行檢查,並未確認到腐蝕等。為與CHF2
COF進行比較,亦測定了既存之清洗氣體(CF3
COF、CF4
、C2
F6
)之蝕刻速度而作為比較例。將其等結果顯示於表1中。另,表中的ND表示檢測下限以下。蝕刻速度係用蝕刻前後的膜厚除以蝕刻時間而求得。
CHF2
COF:二氟醋酸氟
CF3
COF:三氟醋酸氟
O2
:氧
CO:一氧化碳
CF4
:四氟化碳
C2
F6
:六氟乙烷
0...腔室
2...接地
3...高頻電源
4...第一氣體導入口
5...第二氣體導入口
6...第三氣體導入口
7...藍寶石管
8...感應線圈
9...電子式壓力計
10...排氣氣體管線
11...試料支架
12...試料
圖1係在實施例、比較例中使用之遠程電漿裝置的概略圖。
1...腔室
2...接地
3...高頻電源
4...第一氣體導入口
5...第二氣體導入口
6...第三氣體導入口
7...藍寶石管
8...感應線圈
9...電子式壓力計
10...排氣氣體管線
11...試料支架
12...試料
Claims (12)
- 一種清洗氣體,其係用以利用化學氣相沉積法(CVD法)、有機金屬氣相生長法(MOCCD)、濺射法、溶膠-凝膠法或蒸鍍法製造薄膜、厚膜、粉體或晶鬚時,用以除去附帶地沉積於製造裝置的內壁或其附屬裝置上之沉積物的包含CHF2 COF而成者。
- 如請求項1之清洗氣體,其中沉積物係沉積於成膜裝置上之沉積物。
- 如請求項1或2之清洗氣體,其中沉積物係包含W、Ti、Mo、Re、Ge、P、Si、V、Nb、Ta、Se、Te、Mo、Re、Os、Ir、Sb、Ge、Au、Ag、As、Cr、Hf、Zr、Ni、Co及其化合物的沉積物。
- 如請求項1或2之清洗氣體,其中沉積物為含矽附著物。
- 如請求項1或2之清洗氣體,其中清洗氣體係包含選自O2 、O3 、CO、CO2 、F2 、NF3 、Cl2 、Br2 、I2 、XFn (式中,X表示Cl、I或Br,n表示1≦n≦7的整數)、CH4 、CH3 F、CH2 F2 、CHF3 、N2 、He、Ar、Ne、Kr中之至少1種氣體作為添加物。
- 如請求項1或2之清洗氣體,其中清洗氣體至少包含CHF2 COF與O2 。
- 如請求項1或2之清洗氣體,其中清洗氣體至少包含CHF2 COF、O2 及CO。
- 一種沉積物的除去方法,其係使用如請求項5至7中任一項之清洗氣體。
- 如請求項8之沉積物的除去方法,其中沉積物係沉積於成膜裝置上之沉積物者。
- 如請求項8或9之沉積物的除去方法,其中沉積物為包含W、Ti、Mo、Re、Ge、P、Si、V、Nb、Ta、Se、Te、Mo、Re、Os、Ir、Sb、Ge、Au、Ag、As、Cr、Hf、Zr、Ni、Co及其化合物之沉積物。
- 如請求項8或9之沉積物的除去方法,其中沉積物為含矽附著物。
- 一種沉積物的除去方法,其係利用由遠距電漿所引起的高頻或微波使如請求項5至7中任一項之清洗氣體活性化而予使用。
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2009
- 2009-12-01 JP JP2009273030A patent/JP5691163B2/ja not_active Expired - Fee Related
-
2010
- 2010-11-19 CN CN2010800547530A patent/CN102639748A/zh active Pending
- 2010-11-19 EP EP10834490.4A patent/EP2505687A4/en not_active Withdrawn
- 2010-11-19 KR KR1020127009401A patent/KR101363440B1/ko active IP Right Grant
- 2010-11-19 US US13/513,042 patent/US20120234351A1/en not_active Abandoned
- 2010-11-19 WO PCT/JP2010/070655 patent/WO2011068038A1/ja active Application Filing
- 2010-11-25 TW TW099140847A patent/TWI411662B/zh not_active IP Right Cessation
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JP2000265275A (ja) * | 1999-03-15 | 2000-09-26 | Central Glass Co Ltd | クリーニング方法 |
TW200808656A (en) * | 2006-04-27 | 2008-02-16 | Solvay Fluor Gmbh | Reversible water-free process for the separation of acid-containing gas mixtures |
Also Published As
Publication number | Publication date |
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TW201139622A (en) | 2011-11-16 |
JP2011117014A (ja) | 2011-06-16 |
WO2011068038A1 (ja) | 2011-06-09 |
KR20120056295A (ko) | 2012-06-01 |
EP2505687A1 (en) | 2012-10-03 |
EP2505687A4 (en) | 2013-07-24 |
KR101363440B1 (ko) | 2014-02-14 |
JP5691163B2 (ja) | 2015-04-01 |
US20120234351A1 (en) | 2012-09-20 |
CN102639748A (zh) | 2012-08-15 |
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