TWI514094B - 厚膜負性光致抗蝕劑剝離劑組成成分 - Google Patents
厚膜負性光致抗蝕劑剝離劑組成成分 Download PDFInfo
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- TWI514094B TWI514094B TW102131341A TW102131341A TWI514094B TW I514094 B TWI514094 B TW I514094B TW 102131341 A TW102131341 A TW 102131341A TW 102131341 A TW102131341 A TW 102131341A TW I514094 B TWI514094 B TW I514094B
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- Prior art keywords
- photoresist
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- photoresist stripper
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- 229920002120 photoresistant polymer Polymers 0.000 title claims description 76
- 150000001875 compounds Chemical class 0.000 claims description 17
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Substances [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 12
- 239000003495 polar organic solvent Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 7
- -1 tetramethylammonium hydroxide compound Chemical class 0.000 claims description 7
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 claims description 6
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 claims description 6
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 claims description 3
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 3
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 claims description 3
- DIIIISSCIXVANO-UHFFFAOYSA-N 1,2-Dimethylhydrazine Chemical group CNNC DIIIISSCIXVANO-UHFFFAOYSA-N 0.000 claims description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- LSHROXHEILXKHM-UHFFFAOYSA-N n'-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCN LSHROXHEILXKHM-UHFFFAOYSA-N 0.000 claims description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 2
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 2
- 238000000034 method Methods 0.000 description 32
- 206010040844 Skin exfoliation Diseases 0.000 description 20
- 239000003795 chemical substances by application Substances 0.000 description 19
- 239000002184 metal Substances 0.000 description 15
- 229910052751 metal Inorganic materials 0.000 description 15
- 239000003755 preservative agent Substances 0.000 description 13
- 230000002335 preservative effect Effects 0.000 description 12
- 230000007797 corrosion Effects 0.000 description 11
- 238000005260 corrosion Methods 0.000 description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 11
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 8
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000001312 dry etching Methods 0.000 description 4
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 238000001039 wet etching Methods 0.000 description 3
- IHWDSEPNZDYMNF-UHFFFAOYSA-N 1H-indol-2-amine Chemical compound C1=CC=C2NC(N)=CC2=C1 IHWDSEPNZDYMNF-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 2
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 238000005468 ion implantation Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 238000000206 photolithography Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- RHUYHJGZWVXEHW-UHFFFAOYSA-N 1,1-Dimethyhydrazine Chemical compound CN(C)N RHUYHJGZWVXEHW-UHFFFAOYSA-N 0.000 description 1
- IFZHGQSUNAKKSN-UHFFFAOYSA-N 1,1-diethylhydrazine Chemical compound CCN(N)CC IFZHGQSUNAKKSN-UHFFFAOYSA-N 0.000 description 1
- NYCCIHSMVNRABA-UHFFFAOYSA-N 1,3-diethylimidazolidin-2-one Chemical compound CCN1CCN(CC)C1=O NYCCIHSMVNRABA-UHFFFAOYSA-N 0.000 description 1
- WDQFELCEOPFLCZ-UHFFFAOYSA-N 1-(2-hydroxyethyl)pyrrolidin-2-one Chemical compound OCCN1CCCC1=O WDQFELCEOPFLCZ-UHFFFAOYSA-N 0.000 description 1
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 description 1
- DCALJVULAGICIX-UHFFFAOYSA-N 1-propylpyrrolidin-2-one Chemical compound CCCN1CCCC1=O DCALJVULAGICIX-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- MVPRCWFLPDNGNR-UHFFFAOYSA-N 2-[amino(2-hydroxyethyl)amino]ethanol Chemical compound OCCN(N)CCO MVPRCWFLPDNGNR-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- OHLUUHNLEMFGTQ-UHFFFAOYSA-N N-methylacetamide Chemical compound CNC(C)=O OHLUUHNLEMFGTQ-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000004925 denaturation Methods 0.000 description 1
- 230000036425 denaturation Effects 0.000 description 1
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- YAMHXTCMCPHKLN-UHFFFAOYSA-N imidazolidin-2-one Chemical compound O=C1NCCN1 YAMHXTCMCPHKLN-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 1
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 1
- 230000007257 malfunction Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- AQGNVWRYTKPRMR-UHFFFAOYSA-N n'-[2-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCNCCN AQGNVWRYTKPRMR-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- 230000007903 penetration ability Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000001020 plasma etching Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
Classifications
-
- 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
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
- G03F7/0382—Macromolecular compounds which are rendered insoluble or differentially wettable the macromolecular compound being present in a chemically amplified negative photoresist composition
-
- 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
- G03F7/42—Stripping or agents therefor
-
- 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
- G03F7/42—Stripping or agents therefor
- G03F7/422—Stripping or agents therefor using liquids only
-
- 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
- G03F7/42—Stripping or agents therefor
- G03F7/422—Stripping or agents therefor using liquids only
- G03F7/423—Stripping or agents therefor using liquids only containing mineral acids or salts thereof, containing mineral oxidizing substances, e.g. peroxy compounds
-
- 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
- G03F7/42—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
-
- 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
- G03F7/42—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
-
- 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
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/10—Objects to be cleaned
- C11D2111/14—Hard surfaces
- C11D2111/22—Electronic devices, e.g. PCBs or semiconductors
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
- Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
Description
本發明涉及一種能夠將厚膜負性光致抗蝕劑有效清除的剝離劑的組成成分。
通常情況下,半導體/LED/LCD元件的微回路經過一系列的光刻工藝來完成。光刻工藝需要在基板上均勻地塗覆金屬膜或絕緣膜,在其上均勻塗覆光致抗蝕劑後,讓光照透過刻有圖案的範本,完成顯像工藝後,最終形成所需樣式的光致抗蝕劑。此時,通過乾式/濕式蝕刻,在位於光致抗蝕劑下部的金屬膜及絕緣膜上轉寫圖樣,然後實施剝離工藝,除去不必要的光致抗蝕劑。
光致抗蝕劑根據在放射線的照射下顯像劑溶解度的差異而分為正性光致抗蝕劑和負性光致抗蝕劑。正性光致抗蝕劑因曝光部分溶解度增加,形成顯像,而負性光致抗蝕劑則利用曝光部分硬化造成的溶解度降低進行顯像,從而留下範本圖樣。
對於正性光致抗蝕劑來說,在一般的濕式蝕刻工藝中,通常可以用剝離劑輕鬆清除。但經乾式蝕刻或離子注入工藝進行硬化或變性後,便難以清除。乾式蝕刻工藝與濕式蝕刻相比,便於清除,且能夠獲得各向異性範本,因此是微範本形成的主要使用方式。但由於乾式蝕刻是通過等離子氣體
和導電層等物質膜之間的蒸汽-固相反應完成的,因此等離子蝕刻氣體的離子及原子團會與光致抗蝕劑發生化學反應,導致光致抗蝕劑層硬化、變性,從而難以清除。另外,離子注入工藝作為半導體/LED/LCD元件的製造工藝,為了在基板的特定部分加入導電性,因此對磷、砷、硼元素進行擴散,會使得離子與正性光致抗蝕劑發生化學反應並變性,導致難以清除。
負性光致抗蝕劑則是使用剝離等工藝,通過曝光產生架橋反映,無法利用溶媒充分清除,即使能夠清除,也需要100℃以上的高溫和長時間浸漬,因此工藝過程難以保證穩定性。
另外,一般來說,蝕刻工藝使用的光致抗蝕劑膜厚度在2μm以內,而用於凸塊電極形成工藝或再分佈層工藝(RDL:ReDistribution Line)的電極上的光致抗蝕劑膜厚度超過5μm,可達數十μm,因此清除光致抗蝕劑的剝離工藝必須長時間進行,導致工程效率低下。
若光致抗蝕劑因剝離劑使用不均而未清除,可能造成半導體元件的故障,因此,在光致抗蝕劑清除工藝中使用的剝離劑的組成成分必須能夠同時兼顧均勻的剝離和溶解作用。
目前已有多種光致抗蝕劑剝離劑。例如,專利申請公開2004-0104033號發明介紹了包含單乙醇胺、乙二醇類化合物、極性溶媒及防腐劑的光致抗蝕劑剝離劑組成成分。上述組成成分雖然能夠剝離正性光致抗蝕劑,但無法剝離負性光致抗蝕劑。
專利申請公開2007-0019897號發明介紹了由聯氨、極性有機溶劑及鹽基性化合物組成的負性光致抗蝕劑用剝離劑組成成分。但因其中包含環境管理物質聯氨,因此難以適用於實際工藝之中。
專利申請公開2006-117219號發明介紹了由氫氧化物類化合物、乙二醇類及二甲亞碸組成的負性光致抗蝕劑剝離劑組成成分。上述成分能夠剝離負性光致抗蝕劑,但若需去除厚度超過120μm的厚膜光致抗蝕劑,需要至少60分鐘時間,工程效率低下。
專利註冊10-0770217號發明介紹了由四甲基氫氧化銨(TMAH)、鏈烷醇胺及極性有機溶媒組成的凸塊電極形成用厚膜光致抗蝕劑清除劑的組成成分。上述組成成分對厚膜負性光致抗蝕劑的剝離效果良好,且能夠將對聚醯亞胺薄膜的損傷降至最低。但因對金屬電極的腐蝕性較大,在沒有對凸塊電極實施保護的工藝中難以適用。
專利申請公開1997-016836號發明介紹了由羥胺、水、酸離解常數(pKa)在7.5-13範圍內的胺類、水溶性有機溶媒以及防腐劑組成的剝離劑組成成分。但因其中包含環境管理物質羥胺,具有污水處理困難的缺點。同時,因該發明使用防腐劑,導致物質組成複雜,在作業過程中容易吸附,可能造成後續工藝蒸發不良。
現有技術文獻
專利文獻
(專利文獻1)專利申請公開2004-0104033號
(專利文獻2)專利申請公開2007-0019897號
(專利文獻3)專利申請公開2006-117219號
(專利文獻4)專利註冊10-0770217號
(專利文獻5)專利申請公開1997-016836號
為瞭解決以上問題,本發明想要提供能在短時間內有效剝離厚膜負性光致抗蝕劑的剝離劑組成成分。
本發明解決其技術問題所採用的技術方案是:本發明提供了由重量比1-5%的化學式(1)所標示的化合物、重量比70-95%的極性有機溶媒、重量比0.1-5%的四甲基氫氧化銨類化合物,以及剩餘重量比的水構成的光致抗蝕劑剝離劑。
上述化學式中,n為2-8範圍內的整數。
本發明的光致抗蝕劑剝離劑組成成分即使在短時間內剝離,也能夠有效清除厚膜光致抗蝕劑,壓縮工藝流程時間,節省費用。與其他工藝相比,本發明能夠在相對較高的工程溫度下進行,確保剝離工藝中成分變化最小化。另外,本發明不包括防腐劑,所以可避免因吸附非水溶性防腐劑造成的蒸發不良等後續工藝出現的問題,防止電極損傷。
圖示1為根據依照本發明進行的實例1剝離劑成分評價的凸塊電極表面的FE-SEM照片。
圖示2為根據未依照本發明進行的比較例1剝離劑成分性能評價的凸塊電極表面的FE-SEM照片。
圖示3為根據未依照本發明進行的比較例1剝離劑成分進行金屬膜腐蝕性評價的凸塊電極表面的FE-SEM照片
為了使本發明的目的、技術方案及優點更加清楚明白,以下結合附圖及實施例,對本發明進行進一步詳細說明。應當理解,此處所描述的具體實施例僅用以解釋本發明,並不用於限定本發明。
本發明提供一種能夠有效去除、分解厚膜負性光致抗蝕劑的剝離劑組成成分。在本發明中,厚膜是指在一般光刻工藝中,厚度超過1~2μm的層疊光致抗蝕劑膜。
本發明提供了由1-5wt%的化學式(1)所標示的化合物、70-95wt%的極性有機溶媒、0.1-5wt%的四甲基氫氧化銨類化合物,以及水構成的光致抗蝕劑剝離劑。
剝離劑組成成分內不含防腐劑。因含有化學式(1)表示的化合物,本發明能夠在短時間內有效完成剝離工藝。與其他工藝相比,本發明能夠在相對較高的工程溫度下進行,確保剝離工藝中成分變化最小化。另外,本發明不包括防腐劑,所以可避免因吸附非水溶性防腐劑造成的蒸發不良等後續工藝出現的問題,防止電極損傷。
一般來說,防腐劑是一種附著在金屬表面,用來抑制腐蝕的表層保護劑。防腐劑的作用原理是極性基附著在金屬表面,按非極性基排列生成的被膜改變電荷移動,或阻止與腐蝕有關物質的移動。因此,本發明中使用的化學式(1)所示的化合物為由多個N(氮原子)構成的胺成分,其鹼(alkali)度可將剝離性能極大化,而多個-N基則可保護金屬表面,將金屬電極損傷降到最低。
本發明中使用的化學式(1)所示的化合物因具有水溶性,與其
他防腐劑不同,可以防止後續工藝中不良情況的出現。比如二乙三胺、三乙烯四胺、四乙烯五胺、五乙撐六胺、六乙七胺等,這些物質可以單獨使用或兩種以上組合使用。在化學式(1)中,建議選擇n為2-8的乙醇胺類物質。n為1的化合物為乙二胺,化合物內包含的N(氮原子)不足,沒有防止腐蝕的效果;當n超過9時,隨著分子量的增加,光致抗蝕劑的滲透能力低下,造成剝離性能降低。
對於本發明的剝離劑,建議其中化學式(1)的化合物含量占組成物質總重量的1-5%。當重量比不足1%時,防腐效果較低;而當重量比超過5%時,極性有機溶劑的含量減少,從而導致剝離性能低下。
對於本發明所示剝離劑的組成成分中含有的極性有機溶劑來說,若為剝離劑組成成分中使用的極性有機溶劑,可無限制地使用。具體來說有,包括二甲化碸等的亞碸類;包括二甲基碸、二乙基碸、雙(2-羥乙基)碸、四亞甲基碸等的碸類;包括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-二乙基乙醯胺等的醯胺類;包括N,N-二甲內醯胺、2-吡咯烷酮、N-甲基-2-吡咯烷酮、N-乙基-2-吡咯烷酮、N-丙基-2-吡咯烷酮、N-羥甲基-2-吡咯烷酮、N-羥乙基-2-吡咯烷酮等的內醯胺類;包括1,3-二甲基-2-咪唑烷酮、1,3-二乙基-2-咪唑烷酮、1,3-二異丙基-2-咪唑烷酮等的咪唑烷酮類;包括乙二醇、乙二醇單甲醚、乙二醇單乙醚、乙二醇單丁醚、乙二醇單甲醚乙酸酯、乙二醇單乙醚乙酸酯、二甘醇、二乙二醇單甲醚、二乙二醇單乙醚、二乙二醇單丁醚等的多價乙二醇類及其衍生物。
這些物質可單獨使用,也可選擇兩種以上組合使用。若在二
甲化碸、N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N,N-二乙基乙醯胺、N-甲基甲醯胺、N,N-二甲內醯胺、1,3-二甲基-2-咪唑烷酮、乙二醇單甲醚、乙二醇單乙醚、N-甲基吡咯烷酮、N-以及吡咯烷酮、2-吡咯烷酮中選擇一種以上使用,則會表現出更優越的剝離性。
本發明所示剝離劑的組成成分中含有的極性有機溶劑重量比為70-95%,若為80-95%更加。若上述含量的重量比不足70%,光致抗蝕劑溶解度降低,導致防腐劑無法完全清除乾淨;若上述含量的重量比超過95%,其他成分的含量就會相對減少,剝離性能減弱,可能出現腐蝕現象等問題。
本發明所示的剝離劑中含有的四甲基氫氧化銨類化合物是為了進一步提高負性光致抗蝕劑剝離性能而添加,推薦使用季胺陽離子氫氧化物,這時烴基應在C1-C5的烴基中選擇。
建議四甲基氫氧化銨類化合物的含量占剝離劑總組成成分的0.1-5%的重量,重量比為1-4%最佳。若上述含量的重量比不足0.1%,可能會導致剝離性能低下;若上述含量的重量比超過5%時,則可能出現腐蝕下部金屬膜的可能。
本發明組成成分中的水無特別限制,但應使用去離子水。建議使用阻率值在18MΩ/cm以上的去離子水。
下面的內容為本發明實例。雖要對內容詳細說明,但這些實例僅為對本發明的演示,並不單單限定在下述實例中。
<實例1至13與比較例1至7>
將化學式(1)化合物、極性有機溶劑、四甲基氫氧化銨類和水如表1所示情況配合,製作出負性光致抗蝕劑剝離劑。
<光致抗蝕劑剝離性能評價>
對按照上述表1製作的光致抗蝕劑剝離液組成成分進行光致抗蝕劑剝離性能評價。
為了評價具有上述組成成分的光致抗蝕劑的剝離性能,在鍍銅的圓片上形成一層厚約50~60μm的光致抗蝕劑和錫制凸塊電極。具體來說,先在由銅形成的UBM(Under Bump Metallurgy)層圓片上構成一層厚約50~60μm的光致抗蝕劑膜。在上述光致抗蝕劑上通過曝光工序形成範本後,經過顯像工藝,利用電鍍法形成錫材質的凸塊電極。
接著,把由光致抗蝕劑和凸塊電極構成的圓片切割成3cm x 3cm大小,製作評估樣板。將上述樣本在60℃溫度下,浸入按照表1製成的各剝
離劑組成成分中放置3分鐘,從而去除光致抗蝕劑膜。把被去除光致抗蝕劑膜的上述樣本放入超純水中洗滌約1分鐘後,用氮使其乾燥。用FE-SEM確認乾燥後的樣本是否已去除光致抗蝕劑(參照圖示1和圖示2)。圖示1為根據依照本發明進行的實例1剝離劑成分評價的凸塊電極表面的FE-SEM照片,圖示2為根據未依照本發明進行的比較實例1剝離劑成分性能評價的凸塊電極表面的FE-SEM照片。
上述試驗條件與常規凸塊電極光致抗蝕劑的剝離工序需要10分鐘以上相比更為簡便,且與普通剝離劑的剝離效果相比有較大提升。結果如表2所示。
◎:光致抗蝕劑去除100%,無殘留物
○:光致抗蝕劑去除80%以上,基本無殘留物
△:光致抗蝕劑去除50%以上,有一定量的殘留物
×:光致抗蝕劑去除量不足50%,有大量光致抗蝕劑殘留物
<金屬膜腐蝕性評價>
與上述表1一樣,將製作的光致抗蝕劑剝離液組成成分對凸塊電極金屬的腐蝕性進行了評價。
為了評價上述組成成分對凸塊電極金屬的腐蝕性,在鍍銅的圓片上形成一層厚約50~60μm的光致抗蝕劑和錫制凸塊電極。接著,把光致抗蝕劑和凸塊電極構成的圓片切割成3 x 3cm大小的測試樣本。
將上述樣本在60℃溫度下,浸入按照表1製成的各剝離劑組成成分中放置3分鐘,從而去除光致抗蝕劑膜。把被去除光致抗蝕劑膜的上述樣本放入超純水中洗滌約1分鐘後,用氮使其乾燥。用FE-SEM確認乾燥後的
樣本是否已去除光致抗蝕劑。圖示3為根據未依照本發明進行的比較實例1剝離劑成分進行金屬膜腐蝕性評價的凸塊電極表面的FE-SEM照片。
上述試驗條件與常規凸塊電極光致抗蝕劑的剝離工序需要10分鐘以上相比更為簡便,且與普通剝離劑的剝離效果相比有較大提升。結果如表2所示。
◎:未觀察到對銅和錫的腐蝕
○:觀察到少許對銅和錫的腐蝕
△:觀察到對銅和錫部分金屬的腐蝕
×:觀察到對銅和錫全部金屬的腐蝕
通過上述結果可知,本發明光致抗蝕劑剝離劑組成成分不含防腐劑,含有適量的化學式(1)所示化合物,即使在短時間內剝離,也能夠有效清除厚膜光致抗蝕劑,壓縮工藝流程時間,節省費用。
Claims (5)
- 一種光致抗蝕劑剝離劑,其中,由1-5wt%的化學式(1)所標示的化合物、70-95wt%的極性有機溶媒、0.1-5wt%的四甲基氫氧化銨類化合物,以及水構成:
- 如申請專利範圍第1項所述的光致抗蝕劑剝離劑,其中,化學式(1)所示的化合物可在二乙三胺、三乙烯四胺、四乙烯五胺、五乙撐六胺、六乙七胺及其化合物中選擇。
- 如申請專利範圍第1項所述的光致抗蝕劑剝離劑,其中,所述極性有機溶媒可以在二甲化碸、N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N,N-二乙基乙醯胺、N-甲基甲醯胺、N,N-二甲內醯胺、1,3-二甲基-2-咪唑烷酮、乙二醇單甲醚、乙二醇單乙醚、N-甲基吡咯烷酮、N-以及吡咯烷酮、2-吡咯烷酮及其化合物中選擇。
- 如申請專利範圍第1項所述的光致抗蝕劑剝離劑,其中,四甲基氫氧化銨類化合物為季胺陽離子氫氧化物,烴基為C1-C5的烴基。
- 如申請專利範圍第1項所述的光致抗蝕劑剝離劑,其中,其組成成分可用於清除厚膜負性光致抗蝕劑。
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KR20020042490A (ko) * | 2000-11-30 | 2002-06-05 | 토소가부시키가이샤 | 레지스트 박리제 |
JP2003140364A (ja) * | 2001-11-02 | 2003-05-14 | Mitsubishi Gas Chem Co Inc | 銅配線基板向けレジスト剥離液 |
KR20060010366A (ko) * | 2004-07-28 | 2006-02-02 | 주식회사 삼양이엠에스 | 레지스트 수계 박리액 조성물 |
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KR20020042490A (ko) * | 2000-11-30 | 2002-06-05 | 토소가부시키가이샤 | 레지스트 박리제 |
JP2003140364A (ja) * | 2001-11-02 | 2003-05-14 | Mitsubishi Gas Chem Co Inc | 銅配線基板向けレジスト剥離液 |
KR20060010366A (ko) * | 2004-07-28 | 2006-02-02 | 주식회사 삼양이엠에스 | 레지스트 수계 박리액 조성물 |
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JP2014048667A (ja) | 2014-03-17 |
KR101375100B1 (ko) | 2014-03-17 |
CN103676502A (zh) | 2014-03-26 |
KR20140028962A (ko) | 2014-03-10 |
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