KR101696390B1 - A cleaning composition for TFT-LCD or semiconductor displays - Google Patents
A cleaning composition for TFT-LCD or semiconductor displays Download PDFInfo
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- KR101696390B1 KR101696390B1 KR1020100054033A KR20100054033A KR101696390B1 KR 101696390 B1 KR101696390 B1 KR 101696390B1 KR 1020100054033 A KR1020100054033 A KR 1020100054033A KR 20100054033 A KR20100054033 A KR 20100054033A KR 101696390 B1 KR101696390 B1 KR 101696390B1
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- 239000000203 mixture Substances 0.000 title claims abstract description 50
- 239000004065 semiconductor Substances 0.000 title claims abstract description 16
- 238000004140 cleaning Methods 0.000 title abstract description 14
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims abstract description 44
- 239000003599 detergent Substances 0.000 claims abstract description 27
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000004642 Polyimide Substances 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 12
- 229920001721 polyimide Polymers 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 8
- 239000012459 cleaning agent Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- FQXRXTUXSODUFZ-UHFFFAOYSA-N 1h-imidazol-2-ylmethanethiol Chemical compound SCC1=NC=CN1 FQXRXTUXSODUFZ-UHFFFAOYSA-N 0.000 claims description 4
- PMNLUUOXGOOLSP-UHFFFAOYSA-N 2-mercaptopropanoic acid Chemical compound CC(S)C(O)=O PMNLUUOXGOOLSP-UHFFFAOYSA-N 0.000 claims description 4
- 229920002120 photoresistant polymer Polymers 0.000 claims description 4
- -1 mercapto compound Chemical class 0.000 claims description 3
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 claims description 3
- OSLOXIRGUNMLII-UHFFFAOYSA-N 2-(1h-imidazol-2-yl)ethanethiol Chemical compound SCCC1=NC=CN1 OSLOXIRGUNMLII-UHFFFAOYSA-N 0.000 claims description 2
- PJUIMOJAAPLTRJ-UHFFFAOYSA-N monothioglycerol Chemical compound OCC(O)CS PJUIMOJAAPLTRJ-UHFFFAOYSA-N 0.000 claims description 2
- 229940035024 thioglycerol Drugs 0.000 claims description 2
- 239000002184 metal Substances 0.000 abstract description 20
- 229910052751 metal Inorganic materials 0.000 abstract description 20
- 230000007797 corrosion Effects 0.000 abstract description 15
- 238000005260 corrosion Methods 0.000 abstract description 15
- 230000000694 effects Effects 0.000 abstract description 7
- 230000007613 environmental effect Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000000654 additive Substances 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
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910021642 ultra pure water Inorganic materials 0.000 description 4
- 239000012498 ultrapure water Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000003085 diluting agent Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 229910004205 SiNX Inorganic materials 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- DEXFNLNNUZKHNO-UHFFFAOYSA-N 6-[3-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-3-oxopropyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)C(CCC1=CC2=C(NC(O2)=O)C=C1)=O DEXFNLNNUZKHNO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 229910016547 CuNx Inorganic materials 0.000 description 1
- 229910001182 Mo alloy Inorganic materials 0.000 description 1
- 229910016027 MoTi Inorganic materials 0.000 description 1
- VCUFZILGIRCDQQ-KRWDZBQOSA-N N-[[(5S)-2-oxo-3-(2-oxo-3H-1,3-benzoxazol-6-yl)-1,3-oxazolidin-5-yl]methyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C1O[C@H](CN1C1=CC2=C(NC(O2)=O)C=C1)CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F VCUFZILGIRCDQQ-KRWDZBQOSA-N 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
Classifications
-
- 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
- C11D7/22—Organic compounds
- C11D7/34—Organic compounds containing sulfur
-
- 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
-
- 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
- C11D7/22—Organic compounds
- C11D7/32—Organic compounds containing nitrogen
-
- 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
- H01L21/302—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
- H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Detergent Compositions (AREA)
- Cleaning Or Drying Semiconductors (AREA)
Abstract
본 발명은 TFT-LCD 또는 반도체 소자용 세정제 조성물에 관한 것으로, 보다 상세하게는 테트라메틸암모늄하이드록사이드 10-15 중량부, 모노에탄올아민 10-15 중량부, 및 잔부의 물을 포함하여, 모든 막에 대한 세정효과가 우수하고, 금속막질에 대한 부식방지와 작업성이 향상되고, 안정성 및 환경친화성을 확보할 수 있는 TFT-LCD 또는 반도체 소자용 세정제 조성물에 관한 것이다.The present invention relates to a detergent composition for a TFT-LCD or semiconductor device, and more particularly to a detergent composition for a TFT-LCD or a semiconductor device, which comprises 10-15 parts by weight of tetramethylammonium hydroxide, 10-15 parts by weight of monoethanolamine, The present invention relates to a cleaning composition for a TFT-LCD or a semiconductor device, which is excellent in a cleaning effect on a film, can prevent corrosion on a metal film, improve workability, and ensure stability and environmental friendliness.
Description
본 발명은 TFT-LCD 또는 반도체 소자용 세정제 조성물에 관한 것으로, 더욱 상세하게는 우수한 세정력을 가짐과 동시에, 금속막질의 부식을 방지하고, 인화성, 저장성 및 환경에 있어서도 문제가 없으며, 특히 기존 세정공정에서 쓰이는 알코올류, KOH, TMAH 희석액 화학물질을 대체할 수 있으며, 모든 막에서 탁월한 세정효과를 가지는 TFT-LCD 또는 반도체 소자용 세정제 조성물에 관한 것이다.
The present invention relates to a detergent composition for a TFT-LCD or a semiconductor device, and more particularly to a detergent composition for a TFT-LCD or a semiconductor device which has excellent detergency, prevents corrosion of metal film, And a cleaning agent composition for a TFT-LCD or a semiconductor device, which can replace the alcohol, KOH, and TMAH diluent chemicals used in the present invention, and has an excellent cleaning effect in all the films.
종래에 TFT-LCD 또는 반도체 소자의 제조공정에서 사용되고 있는 세정제의 종류는 많으나, 크게는 알코올류를 사용하는 케미칼 린스 조성물과 초기 글래스 세정이나 PI(Polyimide) Rework또는 금속 산화막 제거, 기타 입자(particle)성 이물의 제거를 위해 사용되는 단순물질인 KOH나 TMAH (Tetra methyl ammonium hydroxide) 희석액으로 나눌 수 있다.Conventionally, there are many kinds of cleaning agents used in the manufacturing process of TFT-LCD or semiconductor devices, but there are many kinds of cleaning agents, such as a chemical rinse composition using alcohol, an initial glass cleaning, a polyimide rework or metal oxide film removal, It can be divided into KOH or TMAH (Tetra methyl ammonium hydroxide) diluent, which is a simple substance used to remove foreign matter.
또한 케미칼 린스 조성물에는 메탄올, 에탄올, 이소프로필알콜, 아세톤, 디메틸설폭사이드 (Dimethylsulfoxide) 등이 사용되고 있었으나, 상기 용매로서는 충분한 세정력을 기대할 수 없으며, 특히 미세 회로 부위의 세정이 곤란하다. 또한 상기 알코올류는 인화성 또는 저장성에 문제점을 갖고 있기 때문에 취급시 각별한 주의를 요하므로 작업능률이 떨어지는 문제점이 있으며, 공정단가의 상승 및 특정 배선재료에 대한 유기잔사 문제를 해결해 주지 못하는 단점이 있다.Methanol, ethanol, isopropyl alcohol, acetone, dimethyl sulfoxide and the like have been used for the chemical rinse composition. However, sufficient washing power can not be expected as the solvent, and it is difficult to clean the micro circuit area. In addition, since the alcohols have problems in flammability or shelf life, special care is required in handling, which results in poor work efficiency, and does not solve the problem of increase in the process cost and organic residues of specific wiring materials.
또한, 상기 KOH나 TMAH 희석액은 특정 막에서만 사용이 가능하고 일반 Mo 또는 그 화합물, Cu 또는 그 화합물, ITO, IZO, SiNx 등의 모든 막에는 적용이 불가능하다. 왜냐하면, Mo 또는 그 화합물, Cu 또는 그 화합물 등의 금속배선에는 심각한 침식을 발생시키고, ITO, IZO, Mo등에는 표면변화를 발생시키므로 공정에 맞추어 세정제를 선택해서 사용되고 있다.
In addition, the KOH or TMAH diluent can be used only for a specific film and is not applicable to all films such as general Mo or a compound thereof, Cu or a compound thereof, ITO, IZO, or SiNx. This is because serious corrosion occurs in metal wiring such as Mo or a compound thereof, Cu or a compound thereof, and a surface change occurs in ITO, IZO, Mo, etc. Therefore, a cleaning agent is selected and used according to the process.
상기 종래 기술의 문제점을 해결하기 위해, 본 발명의 목적은 TFT-LCD 또는 반도체 소자 제조공정에서 사용될 수 있는 린스 조성물, 특히 폴리이미드의 코팅전의 린스 조성물로서 사용될 수 있는 세정제 조성물을 제공하고자 한다.In order to solve the problems of the prior art, it is an object of the present invention to provide a rinse composition that can be used in a TFT-LCD or semiconductor device manufacturing process, particularly a rinse composition that can be used as a rinse composition before coating a polyimide.
또한, 본 발명의 다른 목적은 미세 회로 부위에 대한 충분한 세정효과는 물론, 모든 금속막질에 대하여 매우 우수한 세정효과를 가지며, 금속막질의 부식을 방지하고, 인화성, 저장성 및 환경에 있어서도 문제가 없는 세정제 조성물을 제공하고자 한다.
Another object of the present invention is to provide a cleaning agent which has an excellent cleaning effect on all metal membranes as well as a sufficient cleaning effect on a microcircuit site and which prevents corrosion of metal film and has no problem in terms of flammability, Composition.
상기 목적을 달성하기 위하여, 본 발명은In order to achieve the above object,
테트라메틸암모늄하이드록사이드 10-15 중량부,10-15 parts by weight of tetramethylammonium hydroxide,
모노에탄올아민 10-15 중량부, 및10-15 parts by weight of monoethanolamine, and
잔부의 물을 포함하는 TFT-LCD 또는 반도체 소자용 세정제 조성물을 제공한다.And a cleaning agent composition for a TFT-LCD or a semiconductor device comprising water of the remainder.
본 발명의 세정제 조성물은, 테트라메틸암모늄하이드록사이드 10-15 중량부, 모노에탄올아민 10-15 중량부, 및 물 70 내지 80 중량부를 포함하는 것이 바람직하다.The detergent composition of the present invention preferably comprises 10-15 parts by weight of tetramethylammonium hydroxide, 10-15 parts by weight of monoethanolamine, and 70-80 parts by weight of water.
또한 본 발명의 세정제 조성물은 테트라메틸암모늄하이드록사이드 10-15 중량부, 모노에탄올아민 10-15 중량부, 및 물 70 내지 80 중량부의 총합 100 중량부에 대하여 0.01-0.1 중량부의 머캅토계열의 화합물을 더 포함하는 것이 바람직하다.
Also, the detergent composition of the present invention may contain 0.01-0.1 parts by weight of a mercapto-based compound, based on 100 parts by weight of the total amount of tetramethylammonium hydroxide, 10-15 parts by weight of monoethanolamine, and 70-80 parts by weight of water. It is preferable to further include a compound.
이하에서 본 발명을 상세하게 설명한다.Hereinafter, the present invention will be described in detail.
본 발명에서는 기존에 사용되고 있는KOH등을 대체할 수 있으며, 특히 Mo 또는 그 화합물이나 Cu 또는 그 화합물, ITO, IZO 등의 금속배선에 침식을 발생시키지 않는 TFT-LCD 또는 반도체 소자용 세정제 조성물에 관한 것이다.In the present invention, it is possible to replace KOH which has been used in the past, and particularly to a detergent composition for a TFT-LCD or a semiconductor device which does not cause erosion in a metal wiring such as Mo or a compound thereof, Cu or a compound thereof, ITO or IZO will be.
또한, 본 발명은 폴리이미드 코팅 전에 사용하는 세정제 조성물을 제공하는 특징이 있다.In addition, the present invention is characterized by providing a detergent composition for use prior to polyimide coating.
즉, 본 발명은 KOH 성분을 사용하지 않으면서, 테트라메틸암모늄 하이드록사이드(TMAH)와 함께 특정 성분의 조합으로 이루어진 세정제 조성물을 제공함으로써, TFT-LCD 또는 반도체 소자를 제조하는 과정의 모든 막 및 패턴의 미세회로에 대하여 우수한 세정력을 가지고, 금속막질의 부식을 방지할 수 있다. 또한, 본 발명의 세정제 조성물은 인화성, 저장성 및 환경에 대한 문제도 없어서 안전하게 사용할 수 있다. 특히, 본 발명에서는 화소층의 표면 특성을 향상시키기 때문에 폴리이미드의 퍼짐성을 우수하게 한다. 따라서, 본 발명의 세정제 조성물은 폴리이미드의 코팅전의 패턴의 세정에 사용하는 것이 더 효과적일 수 있다. 또한, 본 발명의 세정제 조성물은 CuNx, MoTi, SiNx, a-ITO 등의 모든 금속막에 대한 세정력을 향상시킬 수 있다.That is, the present invention provides a detergent composition comprising a combination of specific components together with tetramethylammonium hydroxide (TMAH), without using a KOH component, to provide a detergent composition comprising all the membranes of the process of manufacturing a TFT- It has excellent detergency against the microcircuit of the pattern, and corrosion of the metal film can be prevented. Further, the detergent composition of the present invention can be safely used because it has no problems with respect to flammability, shelf life and environment. Particularly, in the present invention, since the surface characteristics of the pixel layer are improved, the spreadability of the polyimide is improved. Accordingly, the detergent composition of the present invention may be more effectively used for cleaning the pattern before coating of the polyimide. In addition, the detergent composition of the present invention can improve the detergency against all metal films such as CuNx, MoTi, SiNx, and a-ITO.
이러한 본 발명의 세정제 조성물은, 특정하게 테트라메틸암모늄하이드록사이드(TMAH) 10-15 중량부, 모노에탄올아민(MEA) 10-15 중량부, 및 잔부의 물을 포함하는 3성분계로 이루어진 특징이 있다.Such detergent compositions of the present invention are characterized by a three-component system comprising 10-15 parts by weight of tetramethylammonium hydroxide (TMAH), 10-15 parts by weight of monoethanolamine (MEA), and the balance water have.
상기 테트라메틸암모늄 하이드록사이드의 함량이 10 중량부 미만이면 린스력 저하로 인하여 세정 공정에 적합하지 않고, 그 함량이 15 중량부를 초과하면 하부 금속층 (Metal layer)에 대한 부식을 초래할 수 있으며, 과량 포함시 세정후 흡착될 수 있는 문제가 있다.If the content of the tetramethylammonium hydroxide is less than 10 parts by weight, it is not suitable for the cleaning process due to a decrease in the rinsing power. If the content exceeds 15 parts by weight, corrosion to the metal layer may occur, There is a problem that it can be adsorbed after washing when it is contained.
또한 상기 모노에탄올아민의 함량이 10 중량부 미만이면 적당한 세정공정을 진행할 수 없고, 그 함량이 15 중량부를 초과하면 하부 금속 배선에 부식을 초래할 문제가 있다.If the content of the monoethanolamine is less than 10 parts by weight, a proper washing process can not be carried out. If the content of the monoethanolamine is more than 15 parts by weight, there is a problem that the bottom metal wiring is corroded.
더욱이, 상기 여기서 테트라메틸암모늄하이드록사이드의 함량과 모노에탄올아민 함량이 과량 첨가될 경우에는 첨가제로 부식방지를 하기 어렵게 된다. 따라서, 그만큼 구리 막질에 대한 손상(damage)을 최소화해야 하는 세정제(Rinser)로 사용해야 하므로, 상기 TMAH 함량과 MEA 함량의 범위가 중요하다.Moreover, when the content of tetramethylammonium hydroxide and the amount of monoethanolamine are excessively added, it is difficult to prevent corrosion by additives. Therefore, the TMAH content and the range of the MEA content are important because they must be used as a rinser to minimize the damage to the copper film.
또한, 상기 물은 밸런스 성분으로 잔부로 사용될 수 있으며, 바람직하게 70 내지 80 중량부로 사용한다. 또한, 물은 통상의 이온교환수지를 통한 초순수를 사용하는 것이 바람직하다.In addition, the water may be used as the remainder as a balance component, preferably 70 to 80 parts by weight. In addition, it is preferable to use ultrapure water through a conventional ion exchange resin.
또한 본 발명의 세정제 조성물은 전체 조성물 100 중량부에 대하여 0.01-0.1 중량부의 머캅토계열의 화합물을 첨가제로 더 포함하여 4성분계로 이루어질 수 있다. 상기 첨가제의 추가에 의해서 하부 금속에 대한 부식성을 떨어뜨리는 효과를 부여할 수 있다. 이때, 상기 머캅토계열의 화합물은 머캅토 메틸 이미다졸, 머캅토 에틸 이미다졸, 머캅토 프로필 이미다졸, 티오글리세롤 및 티오락틱산로 이루어진 군에서 선택된 1종 이상을 사용할 수 있다.Further, the detergent composition of the present invention may be composed of four components by further containing 0.01-0.1 parts by weight of a mercapto compound as an additive, based on 100 parts by weight of the total composition. By adding the additive, the effect of lowering the corrosiveness to the lower metal can be given. At this time, the mercapto-based compound may be at least one selected from the group consisting of mercaptomethylimidazole, mercaptoethylimidazole, mercaptopropimidazole, thioglycerol, and thiolactic acid.
이와 같은 본 발명의 세정제 조성물의 제1실시예에 따르면, 테트라메틸암모늄하이드록사이드 10-15 중량부, 모노에탄올아민 10-15 중량부, 및 물 70 내지 80 중량부를 포함한다. 또한, 본 발명의 제2실시예에 따른 세정제 조성물은 테트라메틸암모늄하이드록사이드 10-15 중량부, 모노에탄올아민 10-15 중량부, 및 물 70 내지 80 중량부의 총합 100 중량부에 대하여 0.01-0.1 중량부의 머캅토계열의 화합물을 포함한다. 가장 바람직하게, 상기 세정제 조성물은 TMAH 10 중량부, MEA 중량부 및 물 80 중량부로 이루어질 수 있다. 또한 상기 조성에는 머캅토 메틸 이미다졸이 0.01-0.1 중량부로 추가로 포함될 수 있다.According to the first embodiment of the detergent composition of the present invention, 10-15 parts by weight of tetramethylammonium hydroxide, 10-15 parts by weight of monoethanolamine, and 70-80 parts by weight of water. In addition, the detergent composition according to the second embodiment of the present invention may contain 0.01 to 10 parts by weight per 100 parts by weight of the total of tetramethylammonium hydroxide 10-15 parts by weight, monoethanolamine 10-15 parts by weight, and water 70-80 parts by weight, 0.1 part by weight of a mercapto compound. Most preferably, the detergent composition may comprise 10 parts by weight of TMAH, parts by weight of MEA and 80 parts by weight of water. The composition may further include 0.01 to 0.1 parts by weight of mercaptomethylimidazole.
이때, 세정제 조성물이 상기의 특정의 3성분 또는 4성분의 조성으로 이루어지지 않으면, 세정후 PI(Polyimide) 코팅할 때, PI가 퍼지지 않아 액정 구동에 문제가 있다. 다시 말해, 상기 세정제 조성물의 조성과 함량 범위가 본 발명의 범위를 벗어날 경우, PI 접촉각 및 퍼짐섬을 향상시킬 수 없다.If the detergent composition does not have the composition of the specific three or four components as described above, the PI does not spread when the PI (polyimide) coating is applied after cleaning, which causes a problem in liquid crystal driving. In other words, when the composition and content range of the detergent composition is out of the range of the present invention, the PI contact angle and spread island can not be improved.
또한, 본 발명에 따른 세정제 조성물은 TFT-LCD 또는 반도체 소자를 제조하는 과정에서 포토레지스트를 제거한 후, 폴리이미드의 코팅 전에 사용할 수 있다.Further, the detergent composition according to the present invention may be used after removing the photoresist in the process of manufacturing a TFT-LCD or a semiconductor device, and then coating the polyimide.
따라서, 상기 세정제 조성물을 이용하여, 기판을 세정 후, 폴리이미드를 코팅하여 막을 형성한 다음, 접촉각을 측정하면 15도 이하를 나타내어, 폴리이미드의 퍼짐성을 향상시켜 액정의 불균일한 배열을 바로잡는 효과를 부여할 수 있다. 또한, 본 발명은 모든 금속 배선에 대한 부식을 방지할 수 있고 배선재료의 유기잔사 문제를 해결할 수 있다.Accordingly, after the substrate is cleaned using the above-described detergent composition, the film is formed by coating the polyimide, and then the contact angle is measured to be 15 degrees or less, thereby improving the spreadability of the polyimide to correct the uneven arrangement of the liquid crystal Can be given. Further, the present invention can prevent corrosion to all the metal wiring and solve the organic residue problem of the wiring material.
이때, 본 발명에서 TFT-LCD 또는 반도체 소자의 제조공정은 이 분야의 당업자들에게 잘 알려진 것이므로, 구체적인 설명은 생략하기로 한다.
At this time, the manufacturing process of the TFT-LCD or the semiconductor device in the present invention is well known to those skilled in the art, so a detailed description thereof will be omitted.
본 발명에 따른 세정제 조성물은 TFT-LCD 또는 반도체 소자 제조공정에서 형성된 모든 단계의 막(layer)을 세정하는데 사용이 가능할 뿐 아니라, 특히 화소층(Pixel layer)의 표면 특성을 향상시켜 폴리이미드의 퍼짐성을 우수하게 하므로, 폴리이미드를 코팅하기 전의 패턴을 세정하기에 더욱 효과적으로 사용할 수 있다. 또한, 본 발명의 세정제 조성물은 기존에 주로 사용하는 0.05% KOH와 비교하여 탁월한 린스 성능을 발휘할 수 있다. 또한 본 발명의 세정제 조성물은 화소로 사용되는 ITO, a-ITO, IZO, Mo 화합물, Cu 화합물에 대한 부식이 없으며 세정효과도 뛰어나다.
The detergent composition according to the present invention can be used not only for cleaning the TFT-LCD or any layer formed in a semiconductor device manufacturing process, but also for improving the surface characteristics of the pixel layer, It can be more effectively used to clean the pattern before coating the polyimide. In addition, the detergent composition of the present invention can exert excellent rinsing performance compared with 0.05% KOH which is mainly used. Further, the detergent composition of the present invention is free from corrosion of ITO, a-ITO, IZO, Mo compound, and Cu compound used as a pixel, and has excellent cleaning effect.
이하, 발명의 구체적인 실시예를 통해, 발명의 작용 및 효과를 보다 상술하기로 한다. 다만, 이러한 실시예는 발명의 예시로 제시된 것에 불과하며, 이에 의해 발명의 권리범위가 정해지는 것은 아니다.Best Mode for Carrying Out the Invention Hereinafter, the function and effect of the present invention will be described in more detail through specific examples of the present invention. It is to be understood, however, that these embodiments are merely illustrative of the invention and are not intended to limit the scope of the invention.
실시예Example 1 내지 4 및 1 to 4 and 비교예Comparative Example 1 내지 2 1 to 2
다음 표 1과 같은 조성과 함량으로, 실시예 1-4 및 비교예 1-2의 세정제 조성물을 제조하였다. 이때, 첨가제는 머캅토 메틸 이미다졸을 사용하였다.The cleaning composition of Examples 1-4 and Comparative Example 1-2 was prepared with the compositions and contents shown in Table 1 below. At this time, mercaptomethylimidazole was used as an additive.
(중량부)TMAH
(Parts by weight)
(중량부)KOH
(Parts by weight)
(중량부)MEA
(Parts by weight)
(중량부)Ultrapure water
(Parts by weight)
(중량부)additive
(Parts by weight)
[실험예][Experimental Example]
상기 실시예 1-4 및 비교예 1-2에서 제조한 세정제 조성물에 대한 성능평가를 위해, 하기 공정의 금속막(metal Layer) 및 유리기판(Glass)에 대하여 접촉각 측정 시험 및 부식 평가 시험을 실시하였다. 또한 그 결과는 다음 표 2에 나타내었다.In order to evaluate the performance of the cleaning composition prepared in Examples 1-4 and Comparative Example 1-2, a contact angle measurement test and a corrosion evaluation test were conducted on a metal layer (metal layer) and a glass substrate in the following steps Respectively. The results are also shown in Table 2 below.
1. 시편 제조1. Specimen Manufacturing
글래스 전면에 현재 사용되고 있는 ITO, Mo합금 및 Cu합금 Layer를 통상의 방법으로 증착하였다. 이후, 금속막을 식각하여 패턴을 형성하였다. 상기 금속막 상부에 있는 PR(Photo Resist, 감광제)을 지운 후 시편을 준비하였다.The ITO, Mo alloy and Cu alloy layer currently used on the glass surface were deposited by a conventional method. Thereafter, the metal film was etched to form a pattern. A photoresist (PR) on the metal film was erased and a specimen was prepared.
2. 접촉각 측정 시험2. Contact angle measurement test
상기 제조된 시편에 상기 실시예 1-4 및 비교예 1-2의 세정제 조성물을 상온(25℃)에서 1분간 스프레이 평가 후, 초순수로 세정하고 질소로 건조하였다. 세정후의 기판에, 접촉각 측정 장비를 이용하여 PI(Polyimide) 0.5 uL를 떨어뜨려서 접촉각을 측정하였다. 이때, 평가 기준은 다음과 같다.The detergent compositions of Examples 1-4 and 1-2 were spray-coated on the prepared specimens at room temperature (25 ° C) for 1 minute, then washed with ultrapure water and dried with nitrogen. On the cleaned substrate, a contact angle was measured by dropping 0.5 uL of PI (polyimide) using a contact angle measuring instrument. At this time, the evaluation criteria are as follows.
금속배선 부식정도: X(배선 제거), △(Metal의 심각한 손상), ○(미세 손상-사용 가능), ◎(손상 없음)Degree of corrosion of metal wiring: X (wiring removal), Δ (serious damage to metal), ○ (fine damage - usable), ◎ (no damage)
3. 부식 평가 시험3. Corrosion test
상기 제조된 시편에 상기 실시예 1-4 및 비교예 1-2의 세정제 조성물을 상온(25℃)에서 3회 Rework Spray진행한 후, 초순수로 세정하고 질소로 건조하였다. SEM(주사전자현미경)을 이용하여 표면 및 다중막의 부식을 평가하였다. 이때, 평가 기준은 다음과 같다.The cleaner compositions of Examples 1-4 and Comparative Example 1-2 were subjected to rework spraying three times at room temperature (25 ° C), cleaned with ultrapure water, and dried with nitrogen. SEM (Scanning Electron Microscope) was used to evaluate the corrosion of the surface and multilayers. At this time, the evaluation criteria are as follows.
* 접촉각 측정 결과 : X(15도 이상), ◎(15도 이하)* Contact angle measurement result: X (15 degrees or more), ◎ (15 degrees or less)
상기 표 2의 결과를 통해, 본 발명의 실시예 1-4는 비교예 1-2에 비해, 접촉각이 15도 이하여서 PI의 퍼짐성이 좋고, 금속 배선의 부식이 일어나지 않아, TFT-LCF 또는 반도체 소자 제조의 린스액으로 사용하기 적합하였다.
The results of Table 2 show that the embodiment 1-4 of the present invention has a contact angle of 15 degrees or less as compared with the comparative example 1-2 so that the spreadability of the PI is good and the corrosion of the metal wiring does not occur, It was suitable for use as a rinse liquid for device manufacture.
Claims (6)
모노에탄올아민 10-15 중량부, 및
물 70 내지 80중량부를 포함하는 조성물의 총합 100 중량부에 대하여 0.01-0.1 중량부의 머캅토계열의 화합물을 더 포함하고,
상기 머캅토계열의 화합물은 머캅토 메틸 이미다졸, 머캅토 에틸 이미다졸, 머캅토 프로필 이미다졸 및 티오글리세롤, 및 티오락틱산으로 이루어진 군에서 선택된 1종 이상인,
TFT-LCD 또는 반도체 소자용 세정제 조성물.10-15 parts by weight of tetramethylammonium hydroxide,
10-15 parts by weight of monoethanolamine, and
Further comprising 0.01-0.1 parts by weight of a mercapto compound based on 100 parts by weight of the total composition comprising 70 to 80 parts by weight of water,
Wherein the mercapto-based compound is at least one selected from the group consisting of mercaptomethylimidazole, mercaptoethylimidazole, mercaptopropimidazole, and thioglycerol, and thiolactic acid.
TFT-LCD or a cleaning agent composition for a semiconductor device.
테트라메틸암모늄하이드록사이드 10 중량부, 모노에탄올아민 10 중량부, 및 물 80 중량부를 포함하는 TFT-LCD 또는 반도체 소자용 세정제 조성물.The composition of claim 1, wherein the composition comprises tetramethylammonium hydroxide, monoethanolamine and water,
10 parts by weight of tetramethylammonium hydroxide, 10 parts by weight of monoethanolamine, and 80 parts by weight of water.
2. The detergent composition according to claim 1, wherein the composition is used prior to coating the polyimide after removing the photoresist in the process of manufacturing the TFT-LCD or semiconductor device.
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