TW201606072A - 供乾燥半導體圖案之用的置換溶液,及乾燥半導體圖案的方法 - Google Patents
供乾燥半導體圖案之用的置換溶液,及乾燥半導體圖案的方法 Download PDFInfo
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- 239000004065 semiconductor Substances 0.000 title claims abstract description 44
- 238000001035 drying Methods 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 29
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 82
- 238000009835 boiling Methods 0.000 claims abstract description 16
- 238000006073 displacement reaction Methods 0.000 claims description 27
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 5
- -1 methoxy perfluoroheptene Chemical compound 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract description 3
- 230000015556 catabolic process Effects 0.000 abstract description 2
- 238000005406 washing Methods 0.000 abstract description 2
- 238000007688 edging Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 238000005530 etching Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
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- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
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- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- OKIYQFLILPKULA-UHFFFAOYSA-N 1,1,1,2,2,3,3,4,4-nonafluoro-4-methoxybutane Chemical compound COC(F)(F)C(F)(F)C(F)(F)C(F)(F)F OKIYQFLILPKULA-UHFFFAOYSA-N 0.000 description 1
- RIQRGMUSBYGDBL-UHFFFAOYSA-N 1,1,1,2,2,3,4,5,5,5-decafluoropentane Chemical compound FC(F)(F)C(F)C(F)C(F)(F)C(F)(F)F RIQRGMUSBYGDBL-UHFFFAOYSA-N 0.000 description 1
- WZLFPVPRZGTCKP-UHFFFAOYSA-N 1,1,1,3,3-pentafluorobutane Chemical compound CC(F)(F)CC(F)(F)F WZLFPVPRZGTCKP-UHFFFAOYSA-N 0.000 description 1
- IDBYQQQHBYGLEQ-UHFFFAOYSA-N 1,1,2,2,3,3,4-heptafluorocyclopentane Chemical compound FC1CC(F)(F)C(F)(F)C1(F)F IDBYQQQHBYGLEQ-UHFFFAOYSA-N 0.000 description 1
- OOWAARMDMOWGDJ-UHFFFAOYSA-N 1,1,2,2,4,4,4-heptafluoro-1-(1,1,2,2,4,4,4-heptafluorobutoxy)butane Chemical compound FC(F)(F)CC(F)(F)C(F)(F)OC(F)(F)C(F)(F)CC(F)(F)F OOWAARMDMOWGDJ-UHFFFAOYSA-N 0.000 description 1
- SXKNYNUXUHCUHX-UHFFFAOYSA-N 1,1,2,3,3,4-hexafluorobut-1-ene Chemical compound FCC(F)(F)C(F)=C(F)F SXKNYNUXUHCUHX-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical group ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- FTHNVRLZJZUAMQ-UHFFFAOYSA-N 1-propoxyethane-1,1-diol Chemical compound CCCOC(C)(O)O FTHNVRLZJZUAMQ-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- LPEKGGXMPWTOCB-UHFFFAOYSA-N 8beta-(2,3-epoxy-2-methylbutyryloxy)-14-acetoxytithifolin Natural products COC(=O)C(C)O LPEKGGXMPWTOCB-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- MRABAEUHTLLEML-UHFFFAOYSA-N Butyl lactate Chemical compound CCCCOC(=O)C(C)O MRABAEUHTLLEML-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical class [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 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
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- CQNUVRLDYLUAJS-UHFFFAOYSA-N acetic acid;pentane Chemical compound CC(O)=O.CCCCC CQNUVRLDYLUAJS-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000001191 butyl (2R)-2-hydroxypropanoate Substances 0.000 description 1
- IWPATTDMSUYMJV-UHFFFAOYSA-N butyl 2-methoxyacetate Chemical compound CCCCOC(=O)COC IWPATTDMSUYMJV-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- ODQWQRRAPPTVAG-GZTJUZNOSA-N doxepin Chemical compound C1OC2=CC=CC=C2C(=C/CCN(C)C)/C2=CC=CC=C21 ODQWQRRAPPTVAG-GZTJUZNOSA-N 0.000 description 1
- 229940116333 ethyl lactate Drugs 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 description 1
- 229940011051 isopropyl acetate Drugs 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229940057867 methyl lactate Drugs 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- MSSNHSVIGIHOJA-UHFFFAOYSA-N pentafluoropropane Chemical compound FC(F)CC(F)(F)F MSSNHSVIGIHOJA-UHFFFAOYSA-N 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
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- 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
- H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
- H01L21/67005—Apparatus not specifically provided for elsewhere
- H01L21/67011—Apparatus for manufacture or treatment
- H01L21/67017—Apparatus for fluid treatment
- H01L21/67028—Apparatus for fluid treatment for cleaning followed by drying, rinsing, stripping, blasting or the like
- H01L21/67034—Apparatus for fluid treatment for cleaning followed by drying, rinsing, stripping, blasting or the like for drying
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/30—Imagewise removal using liquid means
- G03F7/32—Liquid compositions therefor, e.g. developers
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/40—Treatment after imagewise removal, e.g. baking
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B3/00—Cleaning by methods involving the use or presence of liquid or steam
- B08B3/04—Cleaning involving contact with liquid
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0046—Photosensitive materials with perfluoro compounds, e.g. for dry lithography
-
- 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
- H01L21/02041—Cleaning
- H01L21/02043—Cleaning before device manufacture, i.e. Begin-Of-Line process
- H01L21/02046—Dry cleaning only
-
- 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
- H01L21/02041—Cleaning
- H01L21/02043—Cleaning before device manufacture, i.e. Begin-Of-Line process
- H01L21/02052—Wet cleaning only
-
- 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
- H01L21/324—Thermal treatment for modifying the properties of semiconductor bodies, e.g. annealing, sintering
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- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Cleaning Or Drying Semiconductors (AREA)
Abstract
本發明的目的係提供用於乾燥半導體圖案的置換溶液,及用於乾燥半導體圖案之方法,其等可在半導體製造過程中的磨邊完成後之清洗過程後的乾燥期間,避免有高深寬比的複雜半導體圖案之損壞。
本發明提供用於乾燥半導體圖案的置換溶液與方法,包含與異丙醇完全互溶的氫氟醚及/或氫氟碳,前述氫氟醚及/或氫氟碳具有70℃或更高的沸點,且當加熱至低於沸點的溫度時,於大氣條件下具有10mN/m或更低之表面張力。
Description
本發明係關於用於乾燥半導體圖案的置換溶液,及用於乾燥半導體圖案的方法,其可避免半導體圖案的損壞(breakdown)。
近年來,半導體元件的微型化進展顯著,且因此有以高深寬比(high aspect ratio)形塑複雜半導體圖案的需求。
半導體圖案在半導體製造過程中,藉由平版印刷步驟與蝕刻步驟在半導體晶圓上形塑而成,但有高深寬比的複雜半導體圖案,該圖案有可能會在蝕刻步驟完成後的清洗(washing)過程後,當進行乾燥時損壞。
蝕刻步驟後,化學溶液會用於晶圓表面,以移除蝕刻溶液及蝕刻殘留物。使用以水為基底的沖洗劑沖洗掉(沖洗)該化學溶液,該以水為基底的沖洗劑諸如純水或類似物,接著乾燥通常藉由以異丙醇(此後亦稱為「IPA」)及類似物置換停留在晶圓表面之以水為基底的沖洗劑來進行,該等異丙醇及類似物具有低表面張力,且可與以水為基底的沖洗劑互溶。然而,因為近年來在半導體
圖案微型化上的進展,類似於直接乾燥水份的情況,由於表面張力,當使用IPA或類似物時,有導致半導體圖案損壞的擔憂。
為了避免半導體圖案的損壞,用零表面張力的超臨界液體進行置換的乾燥方法為人所知,但是這個方法的問題在於所使用的設備昂貴且不適合大量生產,且如果水氣(moisture)或類似物進入到已達超臨界環境的腔室,圖案的損壞無法避免(專利文件1)。
另一方面,一方法為人所知,其中防水保護膜形成於半導體晶圓表面上,以避免乾燥時的圖案損壞,但這個方法的問題在於形成防水保護膜之部分表面處理劑變成殘留物,且造成半導體圖案的缺陷(專利文件2)。(造成這種類型半導體元件缺陷的超細異物材料通常稱為粒子。)
此外,一方法亦為人所知,其使用包括含有氟化合物與以氟為基底的界面活性劑的溶劑之溶劑組成做為對沖洗劑之置換溶液,但這個方法的問題在於殘留組成物形成粒子,且不是充分的解決方案方法(專利文件3)。
專利文件1:日本未審查專利申請2011-187570
專利文件2:國際公開第No.2012/002346號
專利文件3:專利#4442324
本發明的目的係提供用於乾燥半導體圖案的置換溶液,及用於乾燥半導體圖案之方法,其等可在沖洗過程後的乾燥期間避免有高深寬比的複雜半導體圖案之損壞。
經努力研究的結果,本發明人發現前述的目的可藉由在沖洗半導體晶圓後的乾燥時,以異丙醇(IPA)置換以水為基底的沖洗劑(諸如純水或類似物)來達成,且接著以特定氫氟醚(以下亦稱為「HFE」)及/或氫氟碳(以下亦稱為「HFC」)進行IPA之置換,因而實現本發明。
換言之,本發明包括以下幾點。
1.一種用於乾燥半導體圖案的置換溶液,其進行異丙醇之置換,其包含氫氟醚及/或氫氟碳,其中前述氫氟醚及/或氫氟碳於異丙醇中可完全互溶,具有70℃或更高之沸點,且當加熱至該沸點以下的溫度時,於大氣條件下的表面張力為10mN/m或更低。
2.如1之置換溶液,其中該沸點為83℃或更高。
3.如1或2之置換溶液,其中該氫氟醚係甲氧基全氟庚烯。
4.如1或2之置換溶液,其中該氫氟碳係十三氟辛烷(tridecafluorooctane)。
5.如4之置換溶液,其中該十三氟辛烷為1,1,1,2,2,3,3,4,4,5,5,6,6,-十三氟辛烷。
6.一種乾燥半導體圖案之方法,包含:在清洗該半導體圖案後沖洗,接著以異丙醇進行該沖洗劑的置換,接著以如1至5的置換溶液進行置換,且接著熱乾燥。
7.如6之乾燥半導體圖案之方法,其中乾燥係藉由加熱至70℃或更高進行。
當沖洗半導體晶圓後乾燥時,以本發明則半導體晶圓可經乾燥而不造成複雜半導體圖案的損壞。再者,可避免乾燥後粒子的發生。
本發明在下文詳細說明。
在本發明的置換溶液中,作為置換溶液的氫氟醚(HFE)及/或氫氟碳(HFC)係於IPA中可完全互溶。用於置換的溶液IPA可有效地被移除,因為該置換溶液於IPA中可完全互溶。於本發明中,可完全互溶意味二液體皆係可互溶,且在任何組成比率都沒有相分離(phase separation)。
在本發明的置換溶液中,HFE/HFC具有70℃之沸點。其中,如果HFE/HFC之沸點為83℃或更高(高於IPA的沸點),HFE/HFC不會先於殘留的IPA蒸發,因此可避免HFE/HFC置換後IPA濃度上升。此外,由於置換溶液的沸點上升,乾燥可在更高的
溫度進行,且置換溶液的表面張力會更低。此外,在更高的溫度,殘留沖洗劑(主要是水)及IPA的潛熱會更低,乾燥效率會改善,且乾燥時間會縮短。因此,HFE/HFC的沸點較佳地為83℃或更高,更佳地為100℃或更高,甚至更佳地為105℃或更高,且特別佳地為110℃或更高。
用本發明的置換溶液,HFE/HFC在大氣條件下可達到10mN/m或更低的表面張力。表面張力可用多種類型的方法測量,諸如Wilhelmy法或最大氣泡壓力法(maximum bubble pressure method)、或類似方法、或可由方程式所計算。表面張力隨著溫度上升而降低,且被稱為Brock-Bird方程式的下列方程式為精確表達溫度依存度的方程式。用本發明,HFE/HFC的表面張力藉由Brock-Bird方程式計算。
σ:表面張力(mN/m)
Pc:臨界壓力(MPa)
Tc:臨界溫度(K)
T:溫度(K)
Tr:溫度對臨界溫度的比率,Tr=T/Tc
Tbr:沸點(Tb)對臨界溫度的比率,Tbr=Tb/Tc
在本發明的置換溶液中,HFE/HFC較佳地可以溶解微量的水氣。因此,由於使圖案更複雜而無法被IPA沖洗完全移除的微量之水氣可被移除。水氣溶解度較佳地是使得在25℃時可溶解50ppm的水氣。
用本發明的置換溶液,HFE/HFC較佳地具有低全球暖化潛勢(global warming potential,GWP)。具體而言,GWP係100或更低,更佳地為50或更低,且特別佳地為10或更低。再者,臭氧耗乏係數(ozone depletion coefficient)較佳地為零。
用本發明的置換溶液,HFE/HFC可經個別使用,或二種或多種類型可被組合使用。
被用於本發明的置換溶液的HFC可為飽和或不飽和,且係僅包含3至9個碳原子的化合物,較佳地係4至8個碳原子,亦包含氟及氫原子。HFC的具體實例包括1,1,1,2,2,3,3,4,4,5,5,6,6-十三氟辛烷、1,1,1,2,2,3,4,5,5,5-十氟戊烷、1,1,1,3,3-五氟丁烷、1,1,2,2,3,3,4-七氟環戊烷、1H-全氟庚烷、1,1,1,3,3-五氟丙烷、六氟丁烯、及類似物,較佳地為十三氟辛烷,且特別佳地為沸點為114.7℃的1,1,1,2,2,3,3,4,4,5,5,6,6-十三氟辛烷。
一個適合使用的HFC實例係由Asahi Glass Co.,Ltd所生產的Asahiklin(註冊商標)AC-6000。
被用於本發明的置換溶液的HFE可為飽和或不飽和,且係有醚鍵及僅包含3至9個碳原子的化合物,較佳地是4至
8個碳原子,亦包含氫、氟、及氧原子。HFE的具體實例包括1,1,1-三氟乙基-1,1,2,2-四氟乙基醚、九氟丁基甲基醚、甲氧全氟庚烯、及類似物,但沸點110.5℃且GWP為5的甲氧基全氟庚烯係較佳,但是上述之各種同分異構物或混合物亦係可接受。
適合使用的HFC之實例包括由Mitsui Dupont Fluorochemical Co.,Ltd所生產的Vertrel(註冊商標)Suprion;及由Sumitomo 3M所生產的NoVec(註冊商標)7200、Novec(註冊商標)7500、及Novec(註冊商標)7600。
再者,在本發明的置換溶液中,HFC/HFE較佳地不與另一溶劑(諸如IPA)混合使用,以避免增加表面張力與水氣含量,但小量的有機溶劑可被混入以調整乾燥溫度。混入的有機溶劑實例包括烴類、氯化烴類、醇、酮、酯,及上述之混合物。烴類實例包括戊烷、己烷、庚烷,及類似物;氯化烴類之實例包括二氯乙烯及類似物;醇之實例包括甲醇、乙醇、丙醇,及類似物;酮之實例包括丙酮、甲基異丁基酮,及類似物;及酯之實例包括乙酸乙酯、乙酸甲酯、乙酸丁酯、甲氧基乙酸丁酯、賽珞蘇乙酸酯(Cellosolve acetate)、乙酸戊酯、正乙酸丙酯、乙酸異丙酯、乳酸甲酯、乳酸乙酯、乳酸丁酯,及類似物。混入的有機溶劑可適當地設定為不超過5質量%的範圍。
對根據本發明的用於乾燥半導體圖案的置換溶液與方法,半導體圖案的乾燥是指藉由加熱乾燥,該加熱乾燥係在正常的半導體製造過程中,於蝕刻步驟後之提供化學溶液至晶圓表面後
沖洗掉該化學溶劑之後進行。沖洗過程使用正常純水作為沖洗劑,但是包含添加劑(諸如界面活性劑或類似物)的水溶液也可被使用。沖洗之後,沖洗劑(諸如純水或類似物)被IPA置換,且接著被由HFC/HFE所製成的置換溶液所置換。沖洗過程、IPA置換、及HFC/HFE置換步驟皆可藉由所屬技術領域中具有通常知識者所普遍習知的方法進行,但是這些方法的實例包括把半導體晶圓浸入溶液的方法、或像淋浴(shower)般滴落溶液的方法,及類似方法。
根據本發明之在以HFC/HFE所製成的置換溶液置換後的藉由加熱的乾燥,可藉由所屬技術領域中具有通常知識者所普遍習知的方法進行,但是加熱溫度較佳地為70℃或更高、更佳地為80℃或更高、甚至更佳地為90℃或更高、且特別佳地為100℃或更高。
透過Brock-Bird方程式所計算的表面溫度為10mN/m的溫度,已為於表1中所顯示的化合物(皆與IPA完全互溶)計算,表1中所顯示的化合物為氫氟醚或氫氟碳(HFC)中任一者。
結果示於表2。
本發明的置換溶液含有氫氟醚(HFE)及/或氫氟碳(HFC),在半導體晶圓的沖洗過程後的乾燥時,被置換異丙醇(IPA)所使用,該異丙醇已置換以水為基底的沖洗劑(諸如純水或類似
物),且因此與IPA相較,在乾燥溫度的表面張力可大幅降低,而因此能夠避免損壞有高深寬比的複雜半導體圖案,且如此本發明可適合被用於半導體製造過程。
Claims (7)
- 一種用於乾燥半導體圖案的置換溶液,其進行異丙醇之置換,其包含氫氟醚及/或氫氟碳;其中前述氫氟醚及/或氫氟碳於異丙醇中可完全互溶,具有70℃或更高之沸點,且當加熱至該沸點以下的溫度時,於大氣條件下的表面張力為10mN/m或更低。
- 如請求項1之置換溶液,其中該沸點為83℃或更高。
- 如請求項1或2之置換溶液,其中該氫氟醚係甲氧基全氟庚烯。
- 如請求項1或2之置換溶液,其中該氫氟碳係十三氟辛烷(tridecafluorooctane)。
- 如請求項4之置換溶液,其中該十三氟辛烷為1,1,1,2,2,3,3,4,4,5,5,6,6,-十三氟辛烷。
- 一種乾燥半導體圖案之方法,包含:在清洗該半導體圖案後沖洗,接著以異丙醇進行該沖洗劑的置換,接著以如請求項1至請求項5中任一項所述的置換溶液進行置換,且接著熱乾燥。
- 如請求項6之乾燥半導體圖案之方法,其中乾燥係藉由加熱至70℃或更高進行。
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