TWI595330B - Non-aqueous cleaning solution and silicon substrate etching processing method - Google Patents
Non-aqueous cleaning solution and silicon substrate etching processing method Download PDFInfo
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- TWI595330B TWI595330B TW102124918A TW102124918A TWI595330B TW I595330 B TWI595330 B TW I595330B TW 102124918 A TW102124918 A TW 102124918A TW 102124918 A TW102124918 A TW 102124918A TW I595330 B TWI595330 B TW I595330B
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- Prior art keywords
- etching
- forming
- substrate
- cleaning solution
- mask layer
- Prior art date
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- 238000005530 etching Methods 0.000 title claims description 200
- 238000004140 cleaning Methods 0.000 title claims description 153
- 239000000758 substrate Substances 0.000 title claims description 114
- 238000003672 processing method Methods 0.000 title claims description 9
- 229910052710 silicon Inorganic materials 0.000 title description 2
- 239000010703 silicon Substances 0.000 title description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims description 112
- 238000000034 method Methods 0.000 claims description 80
- 239000007788 liquid Substances 0.000 claims description 57
- -1 fluoroalkyl alcohol Chemical compound 0.000 claims description 48
- 239000003960 organic solvent Substances 0.000 claims description 47
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 27
- 150000002291 germanium compounds Chemical class 0.000 claims description 24
- 150000001875 compounds Chemical class 0.000 claims description 23
- 229910052732 germanium Inorganic materials 0.000 claims description 22
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 22
- 238000005406 washing Methods 0.000 claims description 17
- 229910052731 fluorine Inorganic materials 0.000 claims description 16
- 239000000908 ammonium hydroxide Substances 0.000 claims description 13
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 13
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- 229910052715 tantalum Inorganic materials 0.000 claims description 11
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 11
- 125000001153 fluoro group Chemical group F* 0.000 claims description 10
- 150000001412 amines Chemical class 0.000 claims description 6
- 239000003495 polar organic solvent Substances 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 150000002009 diols Chemical class 0.000 claims description 3
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- 239000000243 solution Substances 0.000 description 95
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- 238000012360 testing method Methods 0.000 description 22
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- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 17
- 229910052707 ruthenium Inorganic materials 0.000 description 17
- 125000000217 alkyl group Chemical group 0.000 description 15
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- 230000000694 effects Effects 0.000 description 11
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- 230000000052 comparative effect Effects 0.000 description 7
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- RHRTWGPLEDNKEO-UHFFFAOYSA-N n,n-diethyl-1h-indol-2-amine Chemical class C1=CC=C2NC(N(CC)CC)=CC2=C1 RHRTWGPLEDNKEO-UHFFFAOYSA-N 0.000 description 1
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- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 150000005846 sugar alcohols Chemical class 0.000 description 1
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
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- QVOFCQBZXGLNAA-UHFFFAOYSA-M tributyl(methyl)azanium;hydroxide Chemical compound [OH-].CCCC[N+](C)(CCCC)CCCC QVOFCQBZXGLNAA-UHFFFAOYSA-M 0.000 description 1
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Classifications
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- 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
- G03F7/42—Stripping or agents therefor
- G03F7/422—Stripping or agents therefor using liquids only
- G03F7/426—Stripping or agents therefor using liquids only containing organic halogen compounds; containing organic sulfonic acids or salts thereof; containing sulfoxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B81—MICROSTRUCTURAL TECHNOLOGY
- B81C—PROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
- B81C1/00—Manufacture or treatment of devices or systems in or on a substrate
- B81C1/00841—Cleaning during or after manufacture
- B81C1/00849—Cleaning during or after manufacture during manufacture
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/02—Inorganic compounds
- C11D7/04—Water-soluble compounds
- C11D7/06—Hydroxides
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
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- C11D7/28—Organic compounds containing halogen
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
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- C11D7/32—Organic compounds containing nitrogen
- C11D7/3209—Amines or imines with one to four nitrogen atoms; Quaternized amines
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
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- 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
- G03F7/42—Stripping or agents therefor
- G03F7/422—Stripping or agents therefor using liquids only
- G03F7/425—Stripping or agents therefor using liquids only containing mineral alkaline compounds; containing organic basic compounds, e.g. quaternary ammonium compounds; containing heterocyclic basic compounds containing nitrogen
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- H—ELECTRICITY
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- 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
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
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- H01L21/30604—Chemical etching
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- 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
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- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
- H01L21/3065—Plasma etching; Reactive-ion etching
- H01L21/30655—Plasma etching; Reactive-ion etching comprising alternated and repeated etching and passivation steps, e.g. Bosch process
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- 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
- H01L21/3105—After-treatment
- H01L21/311—Etching the insulating layers by chemical or physical means
- H01L21/31127—Etching organic layers
- H01L21/31133—Etching organic layers by chemical means
-
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- 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
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- 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
- H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
- H01L21/321—After treatment
- H01L21/32115—Planarisation
- H01L21/3212—Planarisation by chemical mechanical polishing [CMP]
-
- H—ELECTRICITY
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- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76898—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics formed through a semiconductor substrate
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- C—CHEMISTRY; METALLURGY
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- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
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- C11D2111/10—Objects to be cleaned
- C11D2111/14—Hard surfaces
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
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Description
本發明係關於以BOSCH法進行之矽基板的蝕刻加工方法中所適合使用之非水系洗淨液、與使用前述非水系洗淨液之矽基板之加工方法。
例如,MEMS(Micro Electro Mechanical Systems)之加工製程、或矽貫通電極(TSV,through-silicon via)之加工製程等當中,係有需要藉由蝕刻,深度挖入矽基板的情況。如此情況時,因容易控制蝕刻速度、或由蝕刻所形成之孔洞的縱橫比的原因,多採用稱為BOSCH法之蝕刻製程。
BOSCH法,係在藉由蝕刻所挖下之部分的內表面,一邊以氟碳氣體形成氟碳層,同時蝕刻挖進矽基板的方法。因此,形成於矽基板之孔洞的內表面係堆積有氟碳層。因而藉由BOSCH法於矽基板形成孔洞的情況時,最終必須將堆積於孔洞內表面之氟碳層去除。
因此,提出有將堆積於藉由BOSCH法所形成之孔洞內表面的氟碳層去除的數個方法。作為具體的方
法,可列舉例如使用乙基全氟丁基醚(HFE-7200、住友3M股份有限公司製)作為專用的藥液,將氟碳層洗淨去除的方法(非專利文獻1)、或藉由過氧化氫水、四甲基銨氫氧化物等鹼性藥液、與水之混合液,來洗淨去除氟碳層的方法(專利文獻1)。
[專利文獻1]日本特開2012-023339號公報
[非專利文獻1]江刺正喜、“Electronic Journal第98回Technical Seminar MEMS之基礎與應用徹底解說”、第44~第45頁、[online]、電子期刊股份有限公司、[平成24(2012)年6月13日檢索]、網際網路(URL:http://www.electronicjournal.co.jp/pdf/t_seminer/t098/01.pdf)
但是,非專利文獻1記載之洗淨液,揮發性非常高,使用於洗淨製程時的揮發損失尚待改良。又,MEMS或TSV之加工製程中,矽基板之深挖蝕刻以外的部分亦進行使用了阻劑材料之加工,因此若亦可藉由去除以BOSCH法形成之孔洞內的氟碳層之洗淨液,來進行阻
劑材料之去除,則會成為製程上之大優點。但是,非專利文獻1記載之洗淨液,其阻劑材料之去除性能不佳。
關於專利文獻1記載之洗淨液,即使可去除氟碳層,亦有難以去除阻劑材料、特別是負型阻劑材料之問題。
本發明係鑑於上述課題所為者,其目的為提供可去除氟碳層與阻劑材料雙方,且抑制了使用於洗淨製程時之洗淨液成分的揮發損失之洗淨液。又,本發明之目的為提供以使用前述洗淨液之BOSCH法所進行之矽基板之蝕刻加工方法。
本發明者等發現藉由於非水系洗淨液中摻合氟烷醇、與依需要之四級銨氫氧化物,可解決上述課題,而完成了本發明。具體而言,本發明係提供以下者。
本發明之第一態樣,係一種非水系洗淨液,其係含有(A)氟烷醇、(B)四級銨氫氧化物、與(C1)有機溶劑。
本發明之第二態樣,係一種非水系洗淨液,其係含有(A)氟烷醇、與(C2)有機溶劑,且(C2)有機溶劑不含有氟原子之非胺系有機溶劑。
本發明之第三態樣,係一種矽基板之蝕刻加工方法,其係包含:(A-I)於矽基板之表面,形成指定圖型之蝕刻遮罩層之蝕刻
遮罩層形成步驟;(A-II)蝕刻由蝕刻遮罩層露出之基板的表面之第一蝕刻步驟;(A-III)重複指定次數之下述步驟(i)及(ii),於矽基板形成指定深度之凹部的凹部形成步驟(i)於藉由蝕刻所形成之基板表面的凹部之側壁及底面形成氟碳層之氟碳層形成步驟、及(ii)蝕刻凹部之底面的第二蝕刻步驟;與(A-IV)於形成指定深度的凹部後,藉由洗淨液去除氟碳層之氟碳層去除步驟,其中於氟碳層去除步驟中,係使用第一態樣之非水系洗淨液、或第二態樣之非水系洗淨液,作為洗淨液。
本發明之第四態樣,係一種矽基板之蝕刻加工方法,其係包含:(B-I)於矽基板表面塗佈阻劑組成物而形成阻劑膜之阻劑膜形成步驟;(B-II)將阻劑膜曝光及顯影,而形成指定圖型之蝕刻遮罩層的蝕刻遮罩層形成步驟;(B-III)蝕刻由蝕刻遮罩層露出之基板的表面之第一蝕刻步驟;(B-IV)重複指定次數之下述步驟(i)及(ii),於矽基板形成指定深度之凹部的凹部形成步驟(i)於藉由蝕刻所形成之基板表面之凹部的側壁形成氟碳層之氟碳層形成步驟、及
(ii)蝕刻凹部之底面的第二蝕刻步驟;(B-V)於形成指定深度之凹部後,藉由洗淨液去除蝕刻遮罩層之蝕刻遮罩層去除步驟;與(B-VI)於形成指定深度的凹部後,藉由洗淨液去除氟碳層之氟碳層去除步驟,其中於蝕刻遮罩層去除步驟及/或氟碳層去除步驟中,係使用第一態樣之非水系洗淨液、或第二態樣之非水系洗淨液,作為洗淨液。
本發明之第五態樣,係一種矽基板之蝕刻加工方法,其係包含:(C-I)於矽基板表面形成無機矽化合物膜之無機矽化合物膜形成步驟;(C-II)於無機矽化合物膜上塗佈阻劑組成物而形成阻劑膜之阻劑膜形成步驟;(C-III)將阻劑膜曝光及顯影而形成指定圖型之阻劑圖型的阻劑圖型形成步驟;(C-IV)蝕刻由阻劑圖型之開口部露出之無機矽化合物膜,形成由指定圖型之矽化合物所構成之蝕刻遮罩層後,藉由洗淨液去除阻劑圖型之蝕刻遮罩層形成步驟;(C-V)蝕刻由蝕刻遮罩層露出之基板的表面之第一蝕刻步驟;(C-VI)重複指定次數之下述步驟(i)及(ii),於矽基板形成指定深度之凹部的凹部形成步驟(i)於藉由蝕刻所形成之基板表面之凹部的側壁形成氟
碳層之氟碳層形成步驟、及(ii)蝕刻凹部之底面的第二蝕刻步驟;與(C-VII)於形成指定深度的凹部後,藉由洗淨液去除氟碳層之氟碳層去除步驟,其中於蝕刻遮罩層形成步驟及/或氟碳層去除步驟中,使用第一態樣之非水系洗淨液、或第二態樣之非水系洗淨液,作為洗淨液。
依照本發明,可提供可去除氟碳層與阻劑材料雙方,且抑制了使用於洗淨製程時之洗淨液成分的揮發損失之洗淨液。又,依照本發明,可提供以使用前述洗淨液之BOSCH法所進行之矽基板之蝕刻加工方法。
10‧‧‧矽基板
11‧‧‧蝕刻遮罩層
12‧‧‧凹部
13‧‧‧側壁
14‧‧‧底面
15‧‧‧氟碳層
16‧‧‧非水系洗淨液
[圖1]顯示本發明之第三態樣之矽基板之蝕刻加工方法的概略圖。
[圖1-a]顯示蝕刻加工前之矽基板的圖。
[圖1-b]顯示於表面具備具有指定圖型之開口部的蝕刻遮罩層之矽基板的圖。
[圖1-c]顯示具備藉由第一蝕刻步驟而形成之凹部的矽基板之圖。
[圖1-d]顯示具備藉由第一蝕刻步驟而形成之凹部,
且於凹部內之側壁及底面形成有氟碳層之矽基板的圖。
[圖1-e]顯示藉由第二蝕刻步驟,具備氟碳層之凹部的底面被挖入之矽基板的圖。
[圖1-f]顯示具備藉由第二蝕刻步驟而深化的凹部,且於凹部內之側壁及底面形成有氟碳層之矽基板的圖。
[圖1-g]顯示具備藉由重複蝕刻與形成氟碳層,而深化至指定深度之凹部,且於凹部內之側壁及底面形成有氟碳層之矽基板的圖。
[圖1-h]顯示將於深化至指定深度之凹部內的側壁及底面所形成之氟碳層,使用第一或第二態樣之非水系洗淨液去除之步驟的圖。
[圖1-i]顯示具備經去除側壁及底面之氟碳層的指定深度之凹部、與蝕刻遮罩層之矽基板的圖。
[圖1-j]顯示經去除蝕刻遮罩層、且具備經去除側壁及底面之氟碳層的指定深度之凹部的矽基板之圖。
以下,說明本發明之第一態樣之非水系洗淨液。第一態樣之非水系洗淨液,係含有(A)氟烷醇、(B)四級銨氫氧化物、與(C1)有機溶劑。以下,依序說明(A)氟烷醇、(B)四級銨鹽、(C1)有機溶劑、(D)其他成分、與非水系洗淨液之製造方法。
第一態樣之非水系洗淨液,係含有鍵結於烷醇中之碳的氫原子之至少1個係經氟原子取代之(A)氟烷醇(以下亦記為(A)成分)。
(A)氟烷醇之構造,只要在不阻礙本發明之目的的範圍內,則無特殊限定,直鏈狀、分支鏈狀、環狀、及組合該等構造之構造的任一者均可。作為(A)氟烷醇之構造,就獲得容易,且所得之洗淨液的氟碳層去除性能優良而言,較佳為直鏈狀。
(A)氟烷醇所具有之羥基的數目,只要在不阻礙本發明之目的的範圍內,則無特殊限定。作為(A)氟烷醇,較佳為氟烷單醇或氟烷二醇、更佳為氟烷單醇。
(A)氟烷醇之碳原子數,只要在不阻礙本發明之目的的範圍內,則無特殊限定。(A)氟烷醇之碳原子數,較佳為3~20、更佳為3~12、特佳為3~8。
氟烷醇係含有經氟取代之1價以上之烴基。氟烷醇中所包含之經氟取代之烴基之氟原子的取代率,只要在不阻礙本發明之目的的範圍內,則無特殊限定,較佳為50%以上。
以上說明之(A)成分中,較佳為以下述式(1)或式(2)表示之化合物。
H(CF2)aCH2-OH...(1)
F(CF2)b(CH2)c-OH...(2)
(式(1)及(2)中,a及b分別為2~6之整數,c為1~2之整數)。
上述式(1)表示之化合物之適合的具體例,可列舉以下之式(1-1)~(1-3)之化合物。
H(CF2)2CH2-OH...(1-1)
H(CF2)4CH2-OH...(1-2)
H(CF2)6CH2-OH...(1-3)
又,上述以式(2)表示之化合物之適合的具體例,可列舉以下之式(2-1)或式(2-2)表示之化合物。
F(CF2)2(CH2)1-OH...(2-1)
F(CF2)4(CH2)2-OH...(2-1)
以上說明之氟烷醇,可組合2種以上來使用。第一態樣之非水系洗淨液中(A)成分之含量,只要係可調製各成分均勻溶解的非水系洗淨液,則無特殊限定。第一態樣之非水系洗淨液中(A)成分之含量,相對於非水系洗淨液之質量,較佳為0.1~50質量%、更佳為0.5~10質量%。
第一態樣之非水系洗淨液,係含有(B)四級銨氫氧化物(以下亦記為(B)成分)。(B)四級銨氫氧化物,只要在不阻礙本發明之目的的範圍內,則無特殊限定。(B)四級銨氫氧化物,可由習知之使用阻劑材料之各種之基板的加工方法、或以蝕刻所進行之基板的加工方法中使用之洗淨液
所使用者當中適當選擇。
適合的(B)四級銨氫氧化物,可列舉以下式(3)表示之化合物。
上述式(3)表示之化合物之中,就容易獲得的觀點而言,更佳為四甲基銨氫氧化物、四乙基銨氫氧化物、四丙基銨氫氧化物、四丁基銨氫氧化物、甲基三丙基銨氫氧化物、甲基三丁基銨氫氧化物、及(2-羥基乙基)三甲基銨氫氧化物。進而,就容易得到可良好地洗淨阻劑材料或氟碳之非水系洗淨液的觀點,特佳為四甲基銨氫氧化物、及四乙基銨氫氧化物。
第一態樣之非水系洗淨液中(B)成分之含量,只要係可調製各成分均勻溶解的非水系洗淨液,則無特殊限定。第一態樣之非水系洗淨液中(B)成分之含量,相對於非水系洗淨液之質量,較佳為0.5~10質量%、更佳為1~5質量%、又更佳為1~3質量%。
第一態樣之非水系洗淨液,係含有(C1)有機溶劑(以下亦記為(C1)成分)。(C1)有機溶劑,只要在不阻礙本發明之目的的範圍內,則無特殊限定。(C1)有機溶劑,可由習知之使用阻劑材料之各種之基板的加工方法、或以蝕刻所進行之基板的加工方法中使用之非水系洗淨液中所用者當中適當選擇。(C1)有機溶劑,較佳為二醇類、二醇醚類、及非質子性極性有機溶劑。
二醇類較佳為乙二醇、二乙二醇、及丙二醇。二醇醚類較佳為乙二醇醚類、二乙二醇醚類、及丙二醇醚類。又,二醇醚類較佳為二醇類之烷基醚、更佳為二醇類之碳原子數1~6之烷基醚、特佳為二醇類之碳原子數1~4之烷基醚。
二醇類及二醇醚類之適合的例子,可列舉乙二醇、乙二醇單甲基醚、乙二醇單乙基醚、乙二醇單丁基醚、乙二醇單甲基醚乙酸酯、乙二醇單乙基醚乙酸酯、二乙二醇、二乙二醇單甲基醚、二乙二醇單乙基醚、二乙二醇單丙基醚、二乙二醇單丁基醚、及丙二醇等。該等之中更佳為乙二醇、丙二醇、及二乙二醇單丁基醚。
非質子性極性有機溶劑之適合的例子,可列舉二甲基亞碸等之亞碸類;二甲基碸、二乙基碸、雙(2-羥基乙基)碸、四亞甲基碸等之碸類;N,N-二甲基甲醯胺、N-甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基乙醯胺、N,N-二乙基乙醯胺等之醯胺類;N-甲基-2-吡咯啶酮、N-乙基-2-吡咯啶酮、N-丙基-2-吡咯啶酮、N-羥基甲基-2-吡
咯啶酮、N-羥基乙基-2-吡咯啶酮等之內醯胺類;1,3-二甲基-2-咪唑啉酮、1,3-二乙基-2-咪唑啉酮、1,3-二異丙基-2-咪唑啉酮等之咪唑啉酮類等。該等之中,更佳為二甲基亞碸、環丁碸、N-甲基-2-吡咯啶酮、及N-乙基-2-吡咯啶酮。
(C1)有機溶劑,可組合2種以上來使用。又,使用2種以上之(C1)有機溶劑時,較佳為組合二醇類及二醇醚類、與非質子性極性有機溶劑來使用。
第一態樣之非水系洗淨液,在不阻礙本案發明之目的的範圍內,亦可含有界面活性劑、防蝕劑等之(D)其他成分(以下,亦記為(D)成分)。界面活性劑之種類並無特殊限定。適合的界面活性劑,可列舉至少取代有碳原子數10以上之烷基或氧基烷基的胺系活性劑、炔屬醇系活性劑、及至少取代有1個以上之碳原子數7以上之烷基的二苯基醚系活性劑等。
防蝕劑係為了抑制形成於矽基板上之銅等金屬材料被非水系洗淨液腐蝕所使用。防蝕劑之適合的例子,可列舉芳香族羥基化合物(例如、焦兒茶酚、tert-丁基兒茶酚、五倍子酚、沒食子酸等)、三唑系化合物(例如苯并三唑等)、含有巰基之化合物、糖醇(例如、木糖醇、山梨糖醇等)等。該等之中,就對金屬等之防蝕效果的觀點而言,較佳為含有巰基之化合物。含有巰基之化合物,
較佳為以下式(4)及(5)表示之化合物。
HS-(CH2)x-OH...(5)(式(5)中,x為3以上之整數)。
式(4)中R為可具有碳原子數1~4之羥基的烷基的情況的具體例,可列舉甲基、乙基、n-丙基、iso-丙基、n-丁基、iso-丁基、sec-丁基、及tert-丁基。該等烷基之中,因為對(C1)有機溶劑之溶解性為適宜的理由,較佳為甲基、羥基甲基、或乙基;因為更提高防蝕效果的理由,更佳為甲基或羥基甲基。
式(4)中R為碳原子數1~4之烷氧基的情況的具體例,可列舉甲氧基、乙氧基、n-丙氧基、iso-丙氧
基、n-丁氧基、iso-丁氧基、sec-丁氧基、及tert-丁氧基。該等烷氧基之中,因為對(C1)有機溶劑之溶解性為適宜的理由,較佳為甲氧基、或乙氧基;因為更提高防蝕效果的理由,更佳為甲氧基。
式(4)中,R為碳原子數1~4之烷基硫基的情況的具體例,可列舉甲基硫基、乙基硫基、n-丙基硫基、iso-丙基硫基、n-丁基硫基、iso-丁基硫基、sec-丁基硫基、及tert-丁基硫基。該等烷基硫基之中,因為對(C1)有機溶劑之溶解性為適宜的理由,較佳為甲基硫基、或乙基硫基;因為更提高防蝕效果的理由,更佳為甲基硫基。
式(4)中R為碳原子數1~4之羥基烷基的情況的具體例,可列舉羥基甲基、2-羥基乙基、1-羥基乙基、3-羥基-n-丙基、4-羥基-n-丁基等。該等羥基烷基之中,因為對(C1)有機溶劑之溶解性為適宜的理由,較佳為羥基甲基、2-羥基乙基、或1-羥基乙基;因為更提高防蝕效果的理由,更佳為羥基甲基。
式(4)中R為碳原子數1~4之巰基烷基的情況的具體例,可列舉巰基甲基、2-巰基乙基、1-巰基乙基、3-巰基-n-丙基、4-巰基-n-丁基等。該等巰基烷基之中,因為對(C1)有機溶劑之溶解性為適宜的理由,較佳為巰基甲基、2-巰基乙基、或1-巰基乙基;因為更提高防蝕效果的理由,更佳為巰基甲基。
式(4)中R為碳原子數1~4之鹵化烷基的情況時,作為鹵化烷基中所含的鹵素原子,可列舉氟、氯、
溴、碘等。R為碳原子數1~4之鹵化烷基的情況的具體例,可列舉氯甲基、溴甲基、碘甲基、氟甲基、二氯甲基、二溴甲基、二氟甲基、三氯甲基、三溴甲基、三氟甲基、2-氯乙基、2-溴乙基、2-氟乙基、1,2-二氯乙基、2,2-二氟乙基、1-氯-2-氟乙基、3-氯-n-丙基、3-溴-n-丙基、3-氟-n-丙基、及4-氯-n-丁基等。該等鹵化烷基之中,較佳為氯甲基、溴甲基、碘甲基、氟甲基、二氯甲基、二溴甲基、二氟甲基、三氯甲基、三溴甲基、或三氟甲基;因為更提高防蝕效果的理由,更佳為氯甲基、二氯甲基、三氯甲基、或三氟甲基。
R為鹵素原子的情況的具體例,可列舉氟、氯、溴、或碘。
式(4)中,m為1~3之整數,更佳為1。m為2或3時,R可相同亦可相異。
式(4)表示之化合物中,苯環上之R的取代位置並無特殊限定。就容易得到高的防蝕效果的觀點而言,苯環上之R的取代位置較佳相對於-(CH2)n-SH之鍵結位置,係間位或對位。
式(4)表示之化合物,就對銅等金屬之防蝕性優良、且於非水系洗淨液中之安定性優良而言,作為R,較佳為具有至少1個之選自由烷基、羥基烷基、及巰基烷基所構成群組之基的化合物;作為R,更佳為具有1個之選自由烷基、羥基烷基、及巰基烷基所構成群組之基的化合物。式(4)表示之化合物,作為R,具有1個之選自由烷
基、羥基烷基、及巰基烷基所構成群組之基時,烷基、羥基烷基、或巰基烷基在苯環上之取代位置,較佳相對於-(CH2)n-SH之鍵結位置,係間位或對位、更佳為對位。
式(4)中,n為0~3之整數。就容易調製化合物、或容易獲得而言,n較佳為0或1、更佳為0。
式(4)表示之化合物之具體例,可列舉p-巰基酚、p-甲硫酚、m-甲硫酚、4-(甲基硫基)苯硫醇、4-甲氧基苯硫醇、3-甲氧基苯硫醇、4-乙氧基苯硫醇、4-異丙氧基苯硫醇、4-tert-丁氧基苯硫醇、3,4-二甲氧基苯硫醇、3,4,5-三甲氧基苯硫醇、4-乙基苯硫醇、4-異丙基苯硫醇、4-n-丁基苯硫醇、4-tert-丁基苯硫醇、3-乙基苯硫醇、3-異丙基苯硫醇、3-n-丁基苯硫醇、3-tert-丁基苯硫醇、3,5-二甲基苯硫醇、3,4-二甲基苯硫醇、3-tert-丁基-4-甲基苯硫醇、3-tert-4-甲基苯硫醇、3-tert-丁基-5-甲基苯硫醇、4-tert-丁基-3-甲基苯硫醇、4-巰基苄基醇、3-巰基苄基醇、4-(巰基甲基)酚、3-(巰基甲基)酚、4-氟苯硫醇、3-氟苯硫醇、4-氯苯硫醇、3-氯苯硫醇、4-溴苯硫醇、4-碘苯硫醇、3-溴苯硫醇、3,4-二氯苯硫醇、3,5-二氯苯硫醇、3,4-二氟苯硫醇、3,5-二氟苯硫醇、4-巰基兒茶酚、2,6-二-tert-丁基-4-巰基酚、3,5-二-tert-丁基-4-甲氧基苯硫醇、4-溴-3-甲基苯硫醇、4-(三氟甲基)苯硫醇、3-(三氟甲基)苯硫醇、3,5-雙(三氟甲基)苯硫醇、4-甲基硫基苯硫醇、4-乙基硫基苯硫醇、4-n-丁基硫基苯硫醇、及4-tert-丁基硫基苯硫醇等。該等化合物之中,就對銅等金屬
之防蝕效果高、且容易獲得而言,更佳為p-巰基酚、p-甲硫酚、m-甲硫酚、4-(甲基硫基)苯硫醇、4-甲氧基苯硫醇、4-乙基苯硫醇、4-異丙基苯硫醇、4-氟苯硫醇、4-氯苯硫醇、及4-溴苯硫醇。又,就對銅等金屬之防蝕效果高、且於洗淨液中之安定性優良而言,亦佳為4-巰基苄基醇、及4-(巰基甲基)酚。
式(5)中,x為3以上之整數,只要在不阻礙本發明之目的的範圍內,其上限則無特殊限定。就可良好地抑制非水系洗淨液對銅等金屬的腐蝕之觀點而言,x較佳為3以上、10以下之整數;更佳為3以上、9以下之整數。
式(5)表示之化合物之適合的例子,可列舉HS-(CH2)3-OH;HS-(CH2)4-OH;HS-(CH2)5-OH;HS-(CH2)6-OH;HS-(CH2)7-OH;HS-(CH2)8-OH;HS-(CH2)9-OH;、及HS-(CH2)10-OH。
非水系洗淨液中,防蝕劑之含量,相對於非水系洗淨液之質量,較佳為0.05~5.0質量%、更佳為0.1~1.0質量%。
第一態樣之非水系洗淨液之製造方法並無特殊限定。第一態樣之非水系洗淨液可將(A)氟烷醇、(B)四級銨鹽、(C1)有機溶劑、與(D)其他成分混合後,藉由攪拌裝置混合,使各成分均勻地溶解而調製。
以上說明之第一態樣之非水系洗淨液,能夠去除以BOSCH法形成之氟碳層、與阻劑材料之兩者,使用於洗淨製程時的洗淨液成分之揮發損失係被抑制。第一態樣之非水系洗淨液,特別可有利地使用於對含有負型及正型光阻而能夠以鹼水溶液顯影之阻劑材料的洗淨。
又,第一態樣之非水系洗淨液,亦有對藉由銅等金屬而形成有配線等之基板來使用的情況。此時,例如習知之混合有過氧化氫水、鹼性藥液與水之洗淨液,容易使金屬腐蝕。另一方面,第一態樣之非水系洗淨液,相較於混合有過氧化氫水、鹼性藥液與水之洗淨液,更不易使金屬腐蝕。
本發明之第二態樣之非水系洗淨液,係含有(A)氟烷醇、與(C2)有機溶劑,且(C2)有機溶劑不含有氟原子之非胺系有機溶劑的非水系洗淨液。以下,依序說明(A)氟烷醇、(C2)有機溶劑、與(D)其他成分。
第二態樣之非水系洗淨液,係含有與第一態樣之非水系洗淨液所含有的(A)氟烷醇同樣的氟烷醇。第二態樣之非水系洗淨液中,(A)氟烷醇之含量,係與第一態樣之非水系洗淨液相同。
第二態樣之非水系洗淨液,係含有不含有氟原子之非胺系有機溶劑,作為(C2)有機溶劑(以下,亦記為(C2)成分)。(C2)有機溶劑,只要係不含有氟原子之非胺系有機溶劑、且只要在不阻礙本發明之目的的範圍內,則無特殊限定。不含有氟原子之非胺系有機溶劑的適合的例子,可列舉於第一態樣之非水系洗淨液當中,作為(C1)有機溶劑所適合使用之二醇類、二醇醚類、及非質子性極性有機溶劑。該等有機溶劑之適合的具體例,亦與(C1)有機溶劑之適合的具體例相同。
第二態樣之非水系洗淨液,亦可依照需要,含有第一態樣之非水系洗淨液所含有之(D)其他成分。
第二態樣之非水系洗淨液之製造方法並無特殊限定。第二態樣之非水系洗淨液,可將(A)氟烷醇、(C2)有機溶劑、與(D)其他成分混合後,藉由攪拌裝置混合,使各成
分均勻地溶解來調製。
以上說明之第二態樣之非水系洗淨液,可去除以BOSCH法形成之氟碳層、與阻劑材料之兩者,使用於洗淨製程時的洗淨液成分之揮發損失係被抑制。第二態樣之非水系洗淨液,特別可有利地使用於對含有負型及正型光阻而能夠以有機溶劑顯影之阻劑材料的洗淨。
又,第二態樣之非水系洗淨液,與第一態樣之非水系洗淨液同樣地,相較於混合有過氧化氫水、鹼性藥液與水之習知洗淨液,更不易使金屬腐蝕。
本發明之第三態樣,係一種矽基板之蝕刻加工方法,其係包含:(A-I)於矽基板之表面,形成指定圖型之蝕刻遮罩層之蝕刻遮罩層形成步驟;(A-II)蝕刻由蝕刻遮罩層露出之基板的表面之第一蝕刻步驟;(A-III)重複指定次數之下述步驟(i)及(ii),於矽基板形成指定深度之凹部的凹部形成步驟(i)於藉由蝕刻而形成之基板表面的凹部之側壁及底面形成氟碳層之氟碳層形成步驟、及(ii)蝕刻凹部之底面的第二蝕刻步驟;與(A-IV)於形成指定深度的凹部後,藉由洗淨液去除氟碳層之氟碳層去除步驟,其中
於氟碳層去除步驟中,係使用第一態樣之非水系洗淨液、或第二態樣之非水系洗淨液,作為洗淨液。
以下,參照圖1-a~圖1-j,說明第三態樣之蝕刻加工方法。
(A-I)蝕刻遮罩層形成步驟中,如圖1-a及圖1-b所示,係於矽基板10之表面,形成具有指定圖型之開口部的蝕刻遮罩層11。蝕刻遮罩層11之材料並無特殊限定。蝕刻遮罩層11之適合的材料,可為各種之阻劑材料、或SiO2或SiN等無機矽化合物。蝕刻遮罩層11由阻劑材料所構成時,蝕刻遮罩層11係由習知之光微影法而形成。蝕刻遮罩層11為無機矽化合物時,蝕刻遮罩層11可藉由於矽基板10之表面形成無機矽化合物之薄膜後,於無機矽化合物之薄膜上形成在相當於蝕刻遮罩層之開口部處具有開口的阻劑圖型,藉由蝕刻自阻劑圖型之開口部露出的無機矽化合物之薄膜而剝離,接著將阻劑圖型去除,藉以形成。
又,蝕刻遮罩層11,亦可藉由形成在相當於蝕刻遮罩層11處具有開口之阻劑圖型後,藉由CVD法將無機矽化合物堆積在阻劑圖型之開口部,接著將阻劑圖型去除的方法來形成。
(A-I)蝕刻遮罩層形成步驟中,將由阻劑材料所構成之阻劑圖型作為蝕刻遮罩層11時,由阻劑材料所
構成之蝕刻遮罩層11,可使用第一或第二態樣之非水系洗淨液去除。此時,非水系洗淨液之組成,係依照阻劑材料之種類作適當選擇。
(A-II)第一蝕刻步驟中,如圖1-b及圖1-c所示,係蝕刻由蝕刻遮罩層11露出之矽基板10之表面,而形成凹部12。第一蝕刻步驟中,蝕刻由蝕刻遮罩層11露出之矽基板10之表面的方法並無特殊限定。BOSCH法中,通常係藉由使用SF6氣體之等方性的電漿蝕刻,進行矽基板10之蝕刻。
(A-III)凹部形成步驟中,如圖1-c及圖1-d所示,係重複指定次數之(A-II)於在第一蝕刻步驟形成之凹部12的側壁13及底面14,形成氟碳層15之(i)氟碳層形成步驟;與如圖1-d及圖1-e所示之蝕刻形成有氟碳層15之凹部12的底面14之(ii)第二蝕刻步驟,以於矽基板10形成指定深度之凹部12。
(i)氟碳層形成步驟中,於凹部12之內表面形成氟碳層15的方法並無特殊限定。BOSCH法中,通常藉由將C4F8氣體流通於凹部內並電漿聚合,而於凹部12之內表面形成氟碳層15。
(ii)第二蝕刻步驟中之蝕刻方法並無特殊限
定。通常,(ii)第二蝕刻步驟中,係藉由與第一蝕刻步驟同樣的方法,蝕刻凹部12之底面14。
(A-III)凹部形成步驟中,如圖1-e、圖1-f、及圖1-g所示,係重複指定次數之於凹部12之側壁13形成氟碳層,使得側壁13不易受到蝕刻後,進行底面14之蝕刻的步驟(i)及(ii),藉此可在不使凹部12之直徑擴大之下,形成深的凹部12。
(A-IV)氟碳層去除步驟中,如圖1-g、圖1-h、及圖1-i所示,係使用第一或第二態樣之非水系洗淨液16,將形成於凹部12之側壁13及底面14的氟碳層15去除。藉由非水系洗淨液16去除氟碳層之方法並無特殊限定,由容易使非水系洗淨液16接觸於凹部12全體而言,較佳為將基板10浸漬於非水系洗淨液16之方法。
再者,氟碳層15之去除,可在蝕刻遮罩層11之去除前進行,亦可在之後進行。圖1-h中,係顯示於蝕刻遮罩層11去除前去除氟碳層15之態樣。蝕刻遮罩層11由SiO2或SiN等之無機矽化合物所構成時,例如可藉由含有氫氟酸之洗淨液來去除蝕刻遮罩層11。又,蝕刻遮罩層11由阻劑材料所構成時,可藉由使用第一或第二態樣之非水系洗淨液,將氟碳層15與蝕刻遮罩層同時去除。
藉由進行蝕刻遮罩層11之去除、與(A-IV)氟
碳層去除步驟中氟碳層15之去除,可得到如圖1-j所示之具備指定深度之凹部12的矽基板10。
本發明之第四態樣,係一種矽基板之蝕刻加工方法,其係包含:(B-I)於矽基板表面塗佈阻劑組成物而形成阻劑膜之阻劑膜形成步驟;(B-II)將阻劑膜曝光及顯影,而形成指定圖型之蝕刻遮罩層的蝕刻遮罩層形成步驟;(B-III)蝕刻由蝕刻遮罩層露出之基板的表面之第一蝕刻步驟;(B-IV)重複指定次數之下述步驟(i)及(ii),而於矽基板形成指定深度之凹部的凹部形成步驟(i)於藉由蝕刻而形成之基板表面的凹部之側壁及底面形成氟碳層之氟碳層形成步驟、及(ii)蝕刻凹部之底面的第二蝕刻步驟;(B-V)於形成指定深度之凹部後,藉由洗淨液去除蝕刻遮罩層之蝕刻遮罩層去除步驟;與(B-VI)於形成指定深度的凹部後,藉由洗淨液去除氟碳層之氟碳層去除步驟,其中,於蝕刻遮罩層去除步驟及/或氟碳層去除步驟中,係使用第一態樣之非水系洗淨液、或第二態樣之非水系洗淨液,作為洗淨液。
第四態樣之蝕刻加工方法中,藉由(B-I)阻劑膜形成步驟、及(B-II)蝕刻遮罩層形成步驟,於矽基板10之表面,使用阻劑材料形成蝕刻遮罩層11。使用阻劑材料形成蝕刻遮罩層11之方法,無特殊限定,係遵照周知之光微影法進行。
第四態樣之蝕刻加工方法,係以與第三態樣之蝕刻加工方法中之(A-II)第一蝕刻步驟同樣方式,於(B-III)第一蝕刻步驟中,蝕刻由蝕刻遮罩層11露出之矽基板10之表面,形成凹部12。
第四態樣之蝕刻加工方法中,係以與第三態樣之蝕刻加工方法中之(A-III)凹部形成步驟同樣方式,於(B-IV)凹部形成步驟中,於(B-III)第一蝕刻步驟形成之凹部12的側壁13及底面14,重複指定次數之形成氟碳層15的(i)氟碳層形成步驟、與蝕刻形成有氟碳層15之凹部12的底面14之(ii)第二蝕刻步驟,於矽基板10形成指定深度之凹部12。
第四態樣之蝕刻加工方法中,係將由形成於矽基板10之表面的阻劑材料所構成之蝕刻遮罩層11去除。將蝕刻遮罩層11去除之方法並無特殊限定,較佳為藉由第一或第二態樣之非水系洗淨液來去除的方法。藉由非水系洗淨液來去除蝕刻遮罩層11的情況時,其方法並無特殊限定,係由周知方法中適當選擇。適合的方法之具體例,可列舉浸漬法、及噴灑法等。
第四態樣之蝕刻加工方法中,係將形成於指定深度之凹部12的側壁13及底面14之氟碳層15去除。將氟碳層15去除之方法並無特殊限定,較佳為藉由第一或第二態樣之非水系洗淨液16來去除之方法。將氟碳層15藉由第一或第二態樣之非水系洗淨液16去除的情況時,其方法並無特殊限定,就使非水系洗淨液16容易接觸於凹部12全體而言,較佳為將基板10浸漬於非水系洗淨液16之方法。(B-V)蝕刻遮罩去除步驟、與(B-VI)氟碳層去除步驟,可同時進行。例如,使用第一或第二態樣之非水系洗淨液16的情況時,若藉由前述浸漬法來去除蝕刻遮罩層11,則氟碳層15亦同時被去除。
再者,(B-V)蝕刻遮罩去除步驟及(B-VI)氟碳層去除步驟中,至少任一步驟中,使用第一態樣或第二態樣之非水系洗淨液,較佳為於雙方之步驟中使用第一態樣或第二態樣之非水系洗淨液。
本發明之第五態樣,係一種矽基板之蝕刻加工方法,其係包含(C-I)於矽基板表面形成無機矽化合物膜之無機矽化合物膜形成步驟;(C-II)於無機矽化合物膜上塗佈阻劑組成物而形成阻劑膜之阻劑膜形成步驟;(C-III)將阻劑膜曝光及顯影而形成指定圖型之阻劑圖型的阻劑圖型形成步驟;(C-IV)蝕刻由阻劑圖型之開口部露出之無機矽化合物膜,形成由指定圖型之無機矽化合物所構成的蝕刻遮罩層後,藉由洗淨液去除阻劑圖型之蝕刻遮罩層形成步驟;(C-V)蝕刻由蝕刻遮罩層露出之基板的表面之第一蝕刻步驟;(C-VI)重複指定次數之下述步驟(i)及(ii),於矽基板形成指定深度之凹部的凹部形成步驟(i)於藉由蝕刻所形成之基板表面之凹部的側壁形成氟碳層之氟碳層形成步驟、及(ii)蝕刻凹部之底面的第二蝕刻步驟;與(C-VII)於形成指定深度的凹部後,藉由洗淨液去除氟碳層之氟碳層去除步驟,其中於蝕刻遮罩層去除步驟及/或氟碳層去除步驟中,係使用第一態樣之非水系洗淨液、或第二態樣之非水系洗淨
液,作為洗淨液。
第五態樣之蝕刻加工方法中,於(C-I)無機矽化合物膜形成步驟中,係於矽基板10之表面,形成由作為蝕刻遮罩層11之材料的SiO2或SiN等所構成之無機矽化合物膜。於矽基板10之表面形成無機矽化合物膜之方法並無特殊限定,可列舉例如CVD法等。
(C-II)阻劑膜形成步驟及(C-III)阻劑圖型形成步驟中,係遵照周知之光微影法,於無機矽化合物膜上,形成於相當於蝕刻遮罩層11之開口部處具有開口部之阻劑圖型。
(C-IV)蝕刻遮罩層形成步驟中,係蝕刻由於(C-III)阻劑圖型形成步驟形成之阻劑圖型的開口部露出之無機矽化合物膜,接著,去除阻劑圖型。去除阻劑圖型之方法並無特殊限定,較佳為藉由第一或第二態樣之非水系洗淨液來去除。藉由第一或第二態樣之非水系洗淨液來去除阻劑圖型的情況時,阻劑圖型之去除,係與第四態樣之蝕刻加工方法之(B-V)蝕刻遮罩去除步驟同樣地方式進行。
第五態樣之蝕刻加工方法中,係以與第三態樣之蝕刻加工方法中之(A-II)第一蝕刻步驟同樣方式,於(C-V)第一蝕刻步驟中,蝕刻由蝕刻遮罩層11露出之矽基板10之表面,而形成凹部12。
第五態樣之蝕刻加工方法中,係以與第三態樣之蝕刻加工方法中之(A-III)凹部形成步驟同樣的方式,於(C-VI)凹部形成步驟中,係對(C-V)第一蝕刻步驟中形成之凹部12的側壁13及底面14,重複指定次數之形成氟碳層15的(i)氟碳層形成步驟、與蝕刻形成有氟碳層15之凹部12的底面14之(ii)第二蝕刻步驟,於矽基板10形成指定深度之凹部12。
第五態樣之蝕刻加工方法中,係以與第四態樣之蝕刻加工方法中之(B-VI)氟碳層去除步驟同樣方式,將形成於指定深度之凹部12的側壁13及底面14之氟碳層15去除。第五態樣之蝕刻加工方法中,係以與第三態樣之蝕刻加工方法同樣方式,來去除蝕刻遮罩層11。
再者,(C-IV)蝕刻遮罩層形成步驟及(C-VII)氟碳層去除步驟中,係於至少任一步驟中,使用第一態樣或第二態樣之非水系洗淨液,較佳為於雙方之步驟中使用
第一態樣或第二態樣之非水系洗淨液。
以下,藉由實施例更詳細地說明本發明,但本發明不受該等實施例限定。
實施例及比較例中,係使用以下者,作為(A)氟烷醇(A-1~A-5)、類似於(A)氟烷醇之成分(A’)含氟溶劑(A-6~A-10)、(B)四級銨氫氧化物、及(C)有機溶劑。表1及2中記載各非水系洗淨液之組成。表1及表2中各成分之含量,係相對於非水系洗淨液之質量的質量%。
A-1:H(CF)2CH2-OH
A-2:H(CF)4CH2-OH
A-3:H(CF)6CH2-OH
A-4:F(CF2)2CH2-OH
A-5:F(CF2)4CH2CH2-OH
A-6:C4F9OCH3
A-7:C4F9OC2H5
A-8:C6F13OCH3
A-9:F-(CF2CF2O)n-C2F5(質量平均分子量:2700)
A-10:N(C3F7)3
四甲基銨氫氧化物
PG:丙二醇
SF:環丁碸
DMSO:二甲基亞碸
NMP:N-甲基-2-吡咯啶酮
NEP:N-乙基-2-吡咯啶酮
遵照表1記載之組成,調製實施例1~14、及比較例1~6之非水系洗淨液。對實施例1~14、及比較例1~6之非水系洗淨液,遵照下述方法,確認氟碳層之去除性、與阻劑材料之去除性。以下試驗結果記載於表1。
遵照一般方法,藉由BOSCH法蝕刻矽基板,於矽基板形成於側壁堆積有厚度100nm之氟碳層的孔洞。將此形成有孔洞之基板使用作為氟碳層去除試驗用之試驗基板。將洗淨液加溫至80℃後,將試驗基板片(2cm×4cm)浸漬於經加溫之洗淨液30分鐘。浸漬後,將試驗基板片由洗淨液取出,以異丙基醇將試驗基板片洗淨後,以純水將試驗基板片洗淨。以純水洗淨後,對基板表面吹送氮氣以去除水,接著,將試驗基板片載置於100℃之加熱板,使試驗基板片完全乾燥。
藉由掃描型電子顯微鏡觀察經乾燥之試驗基
板的孔洞側壁之表面,評估洗淨液之氟碳層去除性。將氟碳層完全去除者評估為○。又,將氟碳層未完全去除者評估為×。
作為摻合於阻劑組成物之樹脂,係使用下式表示之樹脂。下式中各單位之右下的數字為樹脂100質量份中各單位之質量份數。又,下式表示之樹脂之質量平均分子量為20,000。
將上述式表示之樹脂100質量份、2,2-二甲氧基-1,2-二苯基乙烷-1-酮(光聚合起始劑、製品名Irgacure 651、Ciba Japan股份有限公司製)8質量份、2-(o-氯苯基)-4,5-二苯基咪唑2聚體4質量份、環氧乙烷改質三羥甲基丙烷三丙烯酸酯(製品名Aronix M-350、東亞合成股份有限公司製)30質量份、聚乙二醇二丙烯酸酯(製品名NK ESTER A-200、新中村化學工業股份有限公司製)10質
量份、N-乙烯基吡咯啶酮(製品名Aronix M-150、東亞合成股份有限公司製)10質量份、甲基氫醌(聚合抑制劑)0.1質量份,溶解於丙二醇單甲基醚乙酸酯與甲基異丁基酮之質量比1:1的混合溶劑100質量份中,得到阻劑組成物。
使用2cm×4cm之銅基板作為基板。於基板上塗佈上述阻劑組成物後,將基板於110℃加熱10分鐘,形成膜厚40μm之阻劑膜。將所形成之阻劑膜,藉由曝光裝置、Canon PLA501F Hardcontact(佳能股份有限公司製)以曝光量1000mJ/cm2曝光。使用所得到之具備經曝光之阻劑膜的銅基板作為試驗基板。
將洗淨液加溫至60℃後,將試驗基板片(2cm×4cm)浸漬於經加溫之洗淨液15分鐘。浸漬後,將試驗基板片由洗淨液取出,以異丙基醇將試驗基板片洗淨後,以純水將試驗基板片洗淨。以純水洗淨後,對基板表面吹送氮氣,將水去除,接著,將試驗基板片載置於100℃之加熱板,使試驗基板片完全乾燥。
藉由掃描型電子顯微鏡觀察經乾燥之試驗基板的表面,評估洗淨液之阻劑材料去除性。將阻劑膜完全去除者評估為○。又,將阻劑膜未完全去除者評估為×。
依照實施例1~14,可知只要係含有(A)氟烷醇、(B)四級銨氫氧化物、與(C)有機溶劑之非水系洗淨液,則可良好地去除氟碳層與阻劑材料兩者。
依照比較例1,可知非水系洗淨液不含有(A)氟烷醇時,難以去除氟碳層。
比較例2~6中,無法調製均勻溶解之非水系洗淨液。因此,比較例2~6中,未進行氟碳層去除試驗、與阻劑材料去除試驗。
10‧‧‧矽基板
11‧‧‧蝕刻遮罩層
12‧‧‧凹部
13‧‧‧側壁
14‧‧‧底面
15‧‧‧氟碳層
16‧‧‧非水系洗淨液
Claims (11)
- 一種非水系洗淨液,其係含有(A)氟烷醇、(B)四級銨氫氧化物、與(C1)有機溶劑,且前述(C1)有機溶劑,係含有由二醇類及二醇醚類中選擇之有機溶劑、與非質子性極性有機溶劑。
- 一種非水系洗淨液,其係含有(A)氟烷醇、(B)四級銨氫氧化物、與(C1)有機溶劑,且前述(C1)有機溶劑,係含有二醇類。
- 如申請專利範圍第1或2項之非水系洗淨液,其中前述(A)氟烷醇為以下式(1)或(2)表示之化合物,H(CF2)aCH2-OH...(1) F(CF2)b(CH2)c-OH...(2)(式(1)及(2)中,a及b分別為2~6之整數,c為1~2之整數)。
- 一種非水系洗淨液,其係含有(A)氟烷醇、與(C2)有機溶劑,且前述(C2)有機溶劑為不含有氟原子之非胺系有機溶劑,且含有由二醇類及二醇醚類中選擇之有機溶劑、與非質子性極性有機溶劑。
- 一種非水系洗淨液,其係含有(A)氟烷醇、與(C2)有機溶劑,且前述(C2)有機溶劑為不含有氟原子之非胺系有機溶劑,且含有二醇類。
- 如申請專利範圍第4或5項之非水系洗淨液,其中 前述(A)氟烷醇為以下式(1)或(2)表示之化合物,H(CF2)aCH2-OH...(1) F(CF2)b(CH2)c-OH...(2)(式(1)及(2)中,a及b分別為2~6之整數,c為1~2之整數)。
- 一種如申請專利範圍第1~6項中任一項之非水系洗淨液之使用,其係用於洗淨。
- 一種如申請專利範圍第1~6項中任一項之非水系洗淨液之使用,其係使用於氟碳層之去除。
- 一種矽基板之蝕刻加工方法,其係包含:(A-I)於矽基板之表面,形成指定圖型之蝕刻遮罩層之蝕刻遮罩層形成步驟;(A-II)蝕刻由前述蝕刻遮罩層露出之前述基板的表面之第一蝕刻步驟;(A-III)重複指定次數之下述步驟(i)及(ii),於矽基板形成指定深度之凹部的凹部形成步驟(i)於藉由蝕刻所形成之前述基板表面之凹部的側壁形成氟碳層之氟碳層形成步驟、及(ii)蝕刻前述凹部之底面的第二蝕刻步驟;與(A-IV)於前述指定深度之凹部形成後,藉由洗淨液去除前述氟碳層之氟碳層去除步驟,且於前述氟碳層去除步驟中,係使用如申請專利範圍第1~6項中任一項之洗淨液,作為前述洗淨液。
- 一種矽基板之蝕刻加工方法,其係包含: (B-I)於矽基板表面塗佈阻劑組成物而形成阻劑膜之阻劑膜形成步驟;(B-II)將前述阻劑膜曝光及顯影,而形成指定圖型之蝕刻遮罩層的蝕刻遮罩層形成步驟;(B-III)蝕刻由前述蝕刻遮罩層露出之前述基板的表面之第一蝕刻步驟;(B-IV)重複指定次數之下述步驟(i)及(ii),於矽基板形成指定深度之凹部的凹部形成步驟(i)於藉由蝕刻所形成之前述基板表面之凹部的側壁形成氟碳層之氟碳層形成步驟、及(ii)蝕刻前述凹部之底面的第二蝕刻步驟;(B-V)於前述指定深度之凹部形成後,藉由洗淨液去除前述蝕刻遮罩層之蝕刻遮罩層去除步驟;與(B-VI)於前述指定深度之凹部形成後,藉由洗淨液去除前述氟碳層之氟碳層去除步驟,且於前述蝕刻遮罩層去除步驟及/或前述氟碳層去除步驟中,係使用如申請專利範圍第1~6項中任一項之洗淨液,作為前述洗淨液。
- 一種矽基板之蝕刻加工方法,其係包含:(C-I)於矽基板表面形成無機矽化合物膜之無機矽化合物膜形成步驟;(C-II)於前述無機矽化合物膜上塗佈阻劑組成物而形成阻劑膜之阻劑膜形成步驟;(C-III)將前述阻劑膜曝光及顯影而形成指定圖型之阻劑圖 型的阻劑圖型形成步驟;(C-IV)蝕刻由前述阻劑圖型之開口部露出之前述無機矽化合物膜,形成由指定圖型之無機矽化合物所構成之蝕刻遮罩層後,藉由洗淨液將前述阻劑圖型去除之蝕刻遮罩層形成步驟;(C-V)蝕刻由前述蝕刻遮罩層露出之前述基板的表面之第一蝕刻步驟;(C-VI)重複指定次數之下述步驟(i)及(ii),於矽基板形成指定深度之凹部的凹部形成步驟(i)於藉由蝕刻所形成之前述基板表面之凹部的側壁形成氟碳層之氟碳層形成步驟、及(ii)蝕刻前述凹部之底面的第二蝕刻步驟;與(C-VII)於前述指定深度之凹部形成後,藉由洗淨液去除前述氟碳層之氟碳層去除步驟,且於前述蝕刻遮罩層形成步驟及/或前述氟碳層去除步驟中,係使用如申請專利範圍第1~6項中任一項之洗淨液,作為前述洗淨液。
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