TWI426362B - 用於製造液晶顯示器(lcd)之光阻剝離組合物 - Google Patents
用於製造液晶顯示器(lcd)之光阻剝離組合物 Download PDFInfo
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- TWI426362B TWI426362B TW099128466A TW99128466A TWI426362B TW I426362 B TWI426362 B TW I426362B TW 099128466 A TW099128466 A TW 099128466A TW 99128466 A TW99128466 A TW 99128466A TW I426362 B TWI426362 B TW I426362B
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- 229920002120 photoresistant polymer Polymers 0.000 title claims description 59
- 239000000203 mixture Substances 0.000 title claims description 54
- 238000004519 manufacturing process Methods 0.000 title description 8
- 239000003960 organic solvent Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000002798 polar solvent Substances 0.000 claims description 12
- -1 methyl ethyl Chemical group 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 9
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 6
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 6
- 229920006395 saturated elastomer Polymers 0.000 claims description 6
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 6
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 5
- 125000001424 substituent group Chemical group 0.000 claims description 5
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims 4
- KERBAAIBDHEFDD-UHFFFAOYSA-N n-ethylformamide Chemical compound CCNC=O KERBAAIBDHEFDD-UHFFFAOYSA-N 0.000 claims 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims 2
- 125000003161 (C1-C6) alkylene group Chemical group 0.000 claims 1
- 239000004973 liquid crystal related substance Substances 0.000 claims 1
- 239000002904 solvent Substances 0.000 claims 1
- 238000000034 method Methods 0.000 description 34
- 230000008569 process Effects 0.000 description 34
- 239000010949 copper Substances 0.000 description 20
- 239000000758 substrate Substances 0.000 description 19
- 230000007797 corrosion Effects 0.000 description 13
- 238000005260 corrosion Methods 0.000 description 13
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 5
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 5
- PRBXPAHXMGDVNQ-UHFFFAOYSA-N 2-[2-(2-hydroxyethoxy)ethoxy]acetic acid Chemical compound OCCOCCOCC(O)=O PRBXPAHXMGDVNQ-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 150000003141 primary amines Chemical class 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 3
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 3
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 3
- 150000003335 secondary amines Chemical class 0.000 description 3
- DIIIISSCIXVANO-UHFFFAOYSA-N 1,2-Dimethylhydrazine Chemical compound CNNC DIIIISSCIXVANO-UHFFFAOYSA-N 0.000 description 2
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 238000001312 dry etching Methods 0.000 description 2
- 230000009977 dual effect Effects 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 238000000206 photolithography Methods 0.000 description 2
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 description 2
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 description 1
- PVXVWWANJIWJOO-UHFFFAOYSA-N 1-(1,3-benzodioxol-5-yl)-N-ethylpropan-2-amine Chemical compound CCNC(C)CC1=CC=C2OCOC2=C1 PVXVWWANJIWJOO-UHFFFAOYSA-N 0.000 description 1
- IHWDSEPNZDYMNF-UHFFFAOYSA-N 1H-indol-2-amine Chemical compound C1=CC=C2NC(N)=CC2=C1 IHWDSEPNZDYMNF-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- SHXWCVYOXRDMCX-UHFFFAOYSA-N 3,4-methylenedioxymethamphetamine Chemical compound CNC(C)CC1=CC=C2OCOC2=C1 SHXWCVYOXRDMCX-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- QMMZSJPSPRTHGB-UHFFFAOYSA-N MDEA Natural products CC(C)CCCCC=CCC=CC(O)=O QMMZSJPSPRTHGB-UHFFFAOYSA-N 0.000 description 1
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 1
- 239000001089 [(2R)-oxolan-2-yl]methanol Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004380 ashing Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- HQFQTTNMBUPQAY-UHFFFAOYSA-N cyclobutylhydrazine Chemical compound NNC1CCC1 HQFQTTNMBUPQAY-UHFFFAOYSA-N 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229940113088 dimethylacetamide Drugs 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229940102253 isopropanolamine Drugs 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000001039 wet etching Methods 0.000 description 1
Classifications
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- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/08—Preparation by ring-closure
- C07D213/09—Preparation by ring-closure involving the use of ammonia, amines, amine salts, or nitriles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
- C07D307/48—Furfural
-
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
- Cleaning Or Drying Semiconductors (AREA)
- Liquid Crystal (AREA)
Description
本發明是關於一種欲用於所有製造LCD之製程的光阻剝離組合物,更特定言之是關於呈鹼性複合物之良好環保的光阻剝離組合物,其具有水以及三級烷醇胺。所述組合物具有良好的抑制銅以及鋁線腐蝕之能力以及良好的移除光阻之能力。
在平板顯示器(flat-panel display;FPD)製造製程中,光微影製程廣泛用於在基板上形成均勻圖案。此光微影製程由一系列製程組成,包括暴露製程、乾式或濕式蝕刻製程以及灰化製程。通常,藉由將光阻塗覆於基板上且使其暴露,接著進行乾式或濕式蝕刻製程來形成圖案。此時,使用光阻剝離劑移除留在金屬線上之光阻。
迄今為止,一級胺或二級胺與極性溶劑或二醇之混合物已主要用作製造LCD之光阻剝離組合物。具體而言,單乙醇胺(Monoethanolamine;MEA)用作一級胺,異丙醇胺(Isopropanolamine;MIPA)等用作二級胺,且N-甲基吡咯啶酮(N-methyllpyrollidone;NMP)、環丁烯碸(Sulfolene)或二甲亞碸(Dmethylsulfoxide;DMSO)等用作極性溶劑。而且,二乙二醇單乙醚(Diethyleneglycolmonoethylether;EDG)、二乙二醇單丁醚(Diethyleneglycolmonobutylether;BDG)、三乙二醇醚(Triethyleneglycolether;TEG)等用作二醇。
通常,使用剝離劑剝離在蝕刻製程後留下之光阻,接著使用水洗滌。然而,此製程產生一個問題,即由於光阻之再黏著而產生雜質。
此原因是烷醇胺與水混合,接著產生氫氧離子,因此對具有鋁之金屬的腐蝕顯著增加。從而需要用於防止金屬線腐蝕之特殊腐蝕抑制劑。然而,先前腐蝕抑制劑之問題在於由於其生產成本高而經濟效率低。特定言之,近來,在製造如LCD之平板顯示器時,面板之正面尺寸變得愈來愈大,使得剝離劑之使用增加,從而不可避免加工成本之升高。
當面板正面尺寸變得愈來愈大時,用銅取代鋁作為金屬線之材料。然而,由此產生的問題為即先前剝離劑無法塗覆於銅與鋁兩者上。換言之,在TFT-LCD製程中,迄今為止,任何光阻剝離劑均不能夠應用於所有Al製程、Cu製程、閘極製程以及COA製程。
為解決所述問題,發明者嘗試藉由使用三級烷醇胺來開發全水性光阻剝離劑,由於三級烷醇胺極弱的剝離光阻之效能而尚未用作剝離劑。水性光阻剝離劑可防止Al以及Cu金屬線腐蝕,具有良好的移除光阻之能力且可用於所有Al製程、Cu製程、有機膜製程以及COA製程。
為解決上述問題,提供本發明。本發明之一技術目的在於藉由使用三級烷醇胺來開發全水性光阻剝離劑,其可防止Al以及Cu金屬線腐蝕,具有良好的移除光阻之能力且可用於所有Al製程、Cu製程、有機膜製程以及COA製程。
本發明之一目的是提供一種光阻剝離組合物,其使用由於極弱剝離效能而尚未用作剝離劑之三級烷醇胺與水以及適當有機溶劑。剝離劑之組合物不會腐蝕銅線且絕對不會損壞在濾色器陣列(Color filter On Array;COA)製程中暴露之彩色光阻,且可應用於現有製程(Al製程以及閘極製程),亦即可用於所有製程。
詳言之,本發明之光阻剝離組合物包括(a)1重量%至20重量%之式(I)三級烷醇胺;(b)1重量%至60重量%之水;以及(c)20重量%至98重量%之有機溶劑,其係為具有飽和或不飽和烴鏈之4至6員環,所述烴鏈具有一或多個氧原子且經羥基-C1
-C5
烷基之取代基取代:
其中,R為直鏈或分支鏈C1
-C6
伸烷基,且X為OH或H。
本發明提供一種用於製造LCD之光阻剝離組合物,所述組合物包括:(a)1重量%至20重量%之式(I)三級烷醇胺化合物;(b)1重量%至60重量%之水;以及(c)20重量%至98重量%之有機溶劑,其係為具有飽和或
不飽和烴鏈之4至6員環,所述烴鏈具有一或多個氧原子且經羥基-C1
-C5
烷基之取代基取代:
其中,R為直鏈或分支鏈C1
-C6
伸烷基,且X為OH或H。
可用於本發明中之三級烷醇胺能夠取代現有光阻剝離劑中所含之會腐蝕且損壞金屬線以及有機膜或彩色光阻的一級、二級胺化合物。
詳言之,可用於本發明中之三級烷醇胺(例如甲基二乙醇胺)為弱鹼,對金屬線的腐蝕極小,此歸因於其自身獨特結構。舉例而言,銅線通常因與一級、二級胺形成配位鍵而腐蝕,此作用機制由以下化學方程式表示。
形成氫氧離子:RNH2
+H2
O→RNH3 +
+OH-
(損失電子對)
反應:Cu+6RNH2
→Cu(RNH2
)6 2
。
同時,三級烷醇胺(例如甲基二乙醇胺或甲基二甲醇胺)由以下化學方程式表示。
形成氫氧離子:R3
N+H2
O→R3
NH+
+OH-
(損失電子對)
反應:Cu+6R3
N→Cu(R3
N)6 2
。
然而,在三級烷醇胺中,由於R(烷基)之實體障礙而不易發生Cu與R3
N之反應,因此經由此反應,對銅線之腐蝕極小。
可用於本發明中之所需三級烷醇胺為選自甲基二乙醇胺、甲基二甲醇胺以及此等化合物之混合物的族群的化合物。詳言之,包括水(1重量%至60重量%)之上述所需三級烷醇胺不會腐蝕金屬線,特定言之對於銅線具有極好選擇性,此不同於強鹼一級或二級烷醇胺。另外,其大大增強用於本發明中之有機溶劑(c)組分對光阻的溶解力。而且,一級烷醇胺以及二級烷醇胺因為其產生醯胺而使得剝離液變質且因其氫能夠脫離而產生副反應,而三級烷醇胺具有以下優點:基本上不存在所述問題,因為其不具有能夠脫離之氫。
三級烷醇胺與整個剝離劑之組合物的比率較佳為1重量%至20重量%。在三級烷醇胺之比率小於1重量%的情況下,光阻剝離能力較低,在所述比率超過20重量%之情況下,其增加剝離液之黏度,使得在噴霧工作期間可能存在問題。
水與整個剝離劑之組合物的比率較佳為1重量%至60重量%,更佳為10重量%至40重量%。在水之比率小於1重量%的情況下,由於三級烷醇胺自身之鹼度極低而光阻剝離能力較低。在所述比率超過60重量%之情況下,金屬線可能會被腐蝕且光阻剝離效果亦降低。
同時,通常已知呈極弱鹼性胺之三級烷醇胺的光阻剝離能力與一級烷醇胺以及二級烷醇胺相比相對較弱。但發明者發現,使用與經羥烷基取代且環中包括醚基之有機溶劑(c)混合的三級烷醇胺由於協同效應而具有良好光阻剝離能力。
而且,由於金屬表面上化學結構中之配位鍵,故此極性有機溶劑(c)可更為增強防止金屬線腐蝕之效果,且具有良好清潔力,在用於製造LCD之光阻剝離後移除離子水清潔製程中之雜質。
可用於本發明中之有機溶劑(c)係為具有飽和或不飽和烴鏈之4至6員環,所述烴鏈具有一或多個氧原子且經羥基(C1
-C5
)烷基之取代基取代。有機溶劑(c)較佳由以下化合物以及其混合物所構成的族群中選出:以及。
可用於本發明中之有機溶劑(c)的比率較佳為20重量%至98重量%,更佳為20重量%至80重量%。極少含量之有機溶劑(c)會降低光阻溶解性。亦即,在進行長時間噴霧加工之情況下,因消耗而降低其重量比率,使得其無法充分溶解光阻。僅因為可用於本發明中之有機溶劑(c)具有相對高的價格,所以存在以下缺點:有機溶劑(c)之含量愈小,整個製程所需之成本愈高。
同時,在乾式蝕刻所引起之極嚴重硬化光阻的情況下,本發明之複合物無法充分膨脹。因此,為了補償此缺點,可另外添加以下極性溶劑。本發明中之所需極性溶劑可由以下所構成的族群中選出(但不限於):N-甲基吡咯啶酮、環丁碸、二甲亞碸、二甲基乙醯胺(Dimehylacetamide)、單甲基甲醯胺(Monomethylformamide;MMF)以及其混合物。
極性溶劑之比率較佳為5重量%至80重量%。在極性溶劑之比率小於5重量%的情況下,硬化光阻無法充分溶解,且存在以下缺點:極性溶劑使用愈多,整個製程所需之成本愈高。
而且,根據本發明之一詳細實例的所需組合物如下:光阻剝離組合物,所述組合物包括:
(a)1重量%至20重量%之式(I)三級烷醇胺化合物;
(b)1重量%至60重量%之水;以及
(c)10重量%至98重量%之有機溶劑,其形成4至6員環之飽和或不飽和烴鏈,所述烴鏈具有一或多個氧原子且經羥基(C1
-C5
)烷基之取代基取代,且以重量計之剩餘量為極性溶劑:
其中,R為直鏈或分支鏈C1
-C6
伸烷基,且X為OH或H。
而且,在將上述有機溶劑(c)與一或多種二醇醚化合物混合時,能夠更有效地剝離光阻。此等二醇醚有助於藉由使溶解之光阻充分散佈於剝離劑中而將其快速移除。上述二醇醚化合物具有以R'-O(CH2
CH2
O)H表示之化學結構式,其中R'為直鏈、分支鏈或環烴,亦即分支鏈烴或環烴。
可用於本發明中之所需二醇醚化合物能夠由以下所構成的族群中選出(但不限於):二乙二醇單甲醚(Diethylenglycolmonomethylether;MDG)、二乙二醇單乙醚(EDG)、二乙二醇單丁醚(BDG)以及三乙二醇醚(TEG)以及其混合物。
二醇醚之比率較佳為所有含量之5重量%至80重量%。
第一,在平面顯示面板之製程中,本發明之光阻剝離組合物具有良好的移除乾式蝕刻以及濕式蝕刻後留下之光阻的能力。
第二,其同時塗覆於現有剝離液無法塗覆之鋁線以及銅線,甚至可引入有機膜以及COA製程中。
第三,其為環保剝離劑,其與其他烷醇胺光阻剝離液相比相對無毒性。
現在,本發明之各種實施例將參考附圖作具體描述。說明書以及申請專利範圍中所用之術語或詞語不應以限於一般或詞彙意義之解釋方式理解,而應基於發明者可定義術語之概念從而用最好方式解釋其發明之原則,理解為與本發明之技術觀點一致的意義以及概念。
因此,說明書中所述之圖式以及實施例中所繪製之結構僅為一實例且並不完全表示本發明之技術觀點,因此,應瞭解,在申請本發明時許多可替代的替代物以及等效物意欲包含在本發明之範疇內。
下表1是藉由使用光阻剝離液之許多可能組合物剝離真實光阻來鑑別其有效性的數據。
FA:糠醇(Furfuryl alcohol)
MDEA:甲基二乙醇胺
MDG:二乙二醇單甲醚
EDG:二乙二醇單乙醚
BDG:二乙二醇單丁醚
NMP:N-甲基吡咯啶酮
DMSO:二甲亞碸
DMAC:二甲基乙醯胺
DMF:二甲基甲醯胺
MMF:單甲基甲醯胺
THFA:四氫康醇(Tetrahydrofurfurylalcohol)
MDMA:甲基二乙醇胺
圖1為處理Al/Mo雙線基材前後之掃描電子顯微鏡(SEM)照片,在40℃下用表1中之組合物1至10處理所述基材2分鐘。在使用組合物1至10之所有實施例中,Al無任何腐蝕且完全移除光阻。
圖2為處理Mo/Al/Mo三線基材前後之SEM照片,在70℃下用表1中之組合物1至10處理所述基材30分鐘。在長時間使用組合物1至10之情況下,Al線無任何腐蝕。
圖3為處理具有弱硬化光阻之乾式蝕刻基材前後之SEM照片,在40℃下用表1中之組合物1至10處理所述基材2分鐘。在使用組合物1至10之所有情況下,完全移除所述弱硬化光阻。
圖4為處理Mo/Cu/Mo三膜基材前後之SEM照片,在40℃下用表1中之組合物1至10處理所述基材一次以及三次,各歷時2分鐘。在長時間使用組合物1至10之情況下,Cu線無任何腐蝕。
圖5為處理具有嚴重硬化光阻之乾式蝕刻基材前後之SEM照片,在40℃下用表1中之組合物1至10處理所述基材2分鐘。在使用組合物1至10處理之情況下,光阻完全移除。
圖6為Cu/Ti雙膜基材之SEM照片,其中已用市售Al線LCD光阻剝離劑以及表1中之組合物1至10剝離光阻。在使用市售Al線LCD光阻剝離劑的情況下,Cu/Ti膜被腐蝕。但在使用表1中之組合物1至10的實施例中,Cu/Ti膜無任何腐蝕。
經由上述實施例,雖然使用三級烷醇胺、水以及糠醇,但在FPD製造製程中蝕刻之後完全移除光阻。而且,在添加二醇醚與極性溶劑之混合物的情況下,光阻剝離劑移除光阻之能力強得多且整個製程成本降低。
熟習相關技術者將認識到,在不脫離本發明之範疇內的許多其他等效物或替代物是可能存在的。因此,本發明之技術範疇由隨附申請專利範圍而非先前揭露內容界定。
圖1為處理Al/Mo雙線基材前後之掃描電鏡(SEM)照片,在40℃下用表1中之組合物1至10處理所述基材2分鐘。
圖2為處理Mo/Al/Mo三線基材前後之SEM照片,在70℃下用表1中之組合物1至10處理所述基材30分鐘。
圖3為處理具有弱硬化光阻之乾式蝕刻基材前後的SEM照片,在40℃下用表1中之組合物1至10處理所述基材2分鐘。
圖4為處理Mo/Cu/Mo三膜基材前後之SEM照片,在40℃下用表1中之組合物1至10處理所述基材一次以及三次,各歷時2分鐘。
圖5為處理具有嚴重硬化光阻之乾式蝕刻基材前後的SEM照片,在40℃下用表1中之組合物1至10處理所述基材2分鐘。
圖6為Cu/Ti雙膜基材之SEM照片,其中已用市售Al線LCD光阻剝離劑以及表1中之組合物1至10剝離光阻。
Claims (6)
- 一種用於製造液晶顯示器(LCD)之光阻剝離組合物,所述組合物包括:(a)1重量%至20重量%之式(I)三級烷醇胺化合物;(b)1重量%至60重量%之水;以及(c)20重量%至98重量%之有機溶劑,其係為具有飽和或不飽和烴鏈之4至6員環,所述烴鏈具有一或多個氧原子且經羥基-C1 -C5 烷基之取代基取代:
- 如申請專利範圍第1項所述之光阻剝離組合物,其中所述三級烷醇胺是由以下所構成的族群中選出:甲基二乙醇胺(Methyldiethanolamine)、甲基二甲醇胺(Methyldimethanolamine)以及其混合物。
- 如申請專利範圍第1項所述之光阻剝離組合物,其中所述有機溶劑是由以下化合物以及其混合物所構成的族群中選出:以及。
- 如申請專利範圍第1項所述之光阻剝離組合物,其進一步 包括以所述組合物計5重量%至80重量%之二醇醚,所述二醇醚具有式R'-O(CH2 CH2 O)H之化合物,其中R'為直鏈、分支鏈或環烴。
- 如申請專利範圍第4項所述之光阻剝離組合物,其進一步包括以所述組合物計5至80重量%之極性溶劑,所述極性溶劑是由以下所構成的族群中選出:N-甲基吡咯啶酮(N-methylpyrollidone)、環丁碸(Sulfolane)、二甲亞碸(Dimethylsulfoxide)、二甲基乙醯胺(Dimethylacetamide)、單乙基甲醯胺(Monoethylformamide;MMF)以及其混合物。
- 一種光阻剝離組合物,所述組合物包括:(a)1重量%至20重量%之式(I)三級烷醇胺化合物:
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- 2009-08-25 KR KR1020090078867A patent/KR100950779B1/ko active IP Right Grant
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2010
- 2010-08-19 US US13/993,278 patent/US9360761B2/en active Active
- 2010-08-19 JP JP2011528961A patent/JP5089808B2/ja active Active
- 2010-08-19 CN CN2010800015187A patent/CN102216855B/zh active Active
- 2010-08-19 WO PCT/KR2010/005494 patent/WO2011025180A2/en active Application Filing
- 2010-08-25 TW TW099128466A patent/TWI426362B/zh not_active IP Right Cessation
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WO2011025180A3 (en) | 2011-07-07 |
KR100950779B1 (ko) | 2010-04-02 |
US20130345106A1 (en) | 2013-12-26 |
JP5089808B2 (ja) | 2012-12-05 |
US9360761B2 (en) | 2016-06-07 |
CN102216855B (zh) | 2013-11-13 |
TW201107908A (en) | 2011-03-01 |
CN102216855A (zh) | 2011-10-12 |
JP2012500421A (ja) | 2012-01-05 |
WO2011025180A2 (en) | 2011-03-03 |
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