KR20140113116A - Composition for cleaning flat panel display and cleaning method using the same - Google Patents
Composition for cleaning flat panel display and cleaning method using the same Download PDFInfo
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- KR20140113116A KR20140113116A KR1020130028075A KR20130028075A KR20140113116A KR 20140113116 A KR20140113116 A KR 20140113116A KR 1020130028075 A KR1020130028075 A KR 1020130028075A KR 20130028075 A KR20130028075 A KR 20130028075A KR 20140113116 A KR20140113116 A KR 20140113116A
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- glass substrate
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- ammonium
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- 239000000203 mixture Substances 0.000 title claims abstract description 38
- 238000004140 cleaning Methods 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims description 20
- 239000000758 substrate Substances 0.000 claims abstract description 68
- 239000011521 glass Substances 0.000 claims abstract description 63
- 150000001875 compounds Chemical class 0.000 claims abstract description 11
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 9
- 239000011737 fluorine Substances 0.000 claims abstract description 9
- 239000012748 slip agent Substances 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002245 particle Substances 0.000 claims description 21
- 239000000356 contaminant Substances 0.000 claims description 14
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 11
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 8
- 150000003863 ammonium salts Chemical class 0.000 claims description 7
- 238000005498 polishing Methods 0.000 claims description 6
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 6
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 5
- 239000003599 detergent Substances 0.000 claims description 5
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 claims description 5
- 229910017855 NH 4 F Inorganic materials 0.000 claims description 4
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 4
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 4
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 3
- 239000005695 Ammonium acetate Substances 0.000 claims description 3
- 229940043376 ammonium acetate Drugs 0.000 claims description 3
- 235000019257 ammonium acetate Nutrition 0.000 claims description 3
- 150000002222 fluorine compounds Chemical class 0.000 claims description 3
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 3
- RILZRCJGXSFXNE-UHFFFAOYSA-N 2-[4-(trifluoromethoxy)phenyl]ethanol Chemical compound OCCC1=CC=C(OC(F)(F)F)C=C1 RILZRCJGXSFXNE-UHFFFAOYSA-N 0.000 claims description 2
- MOVBJUGHBJJKOW-UHFFFAOYSA-N methyl 2-amino-5-methoxybenzoate Chemical compound COC(=O)C1=CC(OC)=CC=C1N MOVBJUGHBJJKOW-UHFFFAOYSA-N 0.000 claims description 2
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims 1
- 239000011146 organic particle Substances 0.000 abstract description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 3
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 3
- DVARTQFDIMZBAA-UHFFFAOYSA-O ammonium nitrate Chemical compound [NH4+].[O-][N+]([O-])=O DVARTQFDIMZBAA-UHFFFAOYSA-O 0.000 abstract description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract 2
- 239000004615 ingredient Substances 0.000 abstract 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract 1
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 229910004298 SiO 2 Inorganic materials 0.000 description 8
- 238000011109 contamination Methods 0.000 description 6
- 238000005530 etching Methods 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229910021642 ultra pure water Inorganic materials 0.000 description 4
- 239000012498 ultrapure water Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000004506 ultrasonic cleaning Methods 0.000 description 2
- MIMUSZHMZBJBPO-UHFFFAOYSA-N 6-methoxy-8-nitroquinoline Chemical compound N1=CC=CC2=CC(OC)=CC([N+]([O-])=O)=C21 MIMUSZHMZBJBPO-UHFFFAOYSA-N 0.000 description 1
- UAUDZVJPLUQNMU-UHFFFAOYSA-N Erucasaeureamid Natural products CCCCCCCCC=CCCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- KVBCYCWRDBDGBG-UHFFFAOYSA-N azane;dihydrofluoride Chemical compound [NH4+].F.[F-] KVBCYCWRDBDGBG-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000003550 marker Substances 0.000 description 1
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 description 1
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- QSUJAUYJBJRLKV-UHFFFAOYSA-M tetraethylazanium;fluoride Chemical compound [F-].CC[N+](CC)(CC)CC QSUJAUYJBJRLKV-UHFFFAOYSA-M 0.000 description 1
- WYXIGTJNYDDFFH-UHFFFAOYSA-Q triazanium;borate Chemical compound [NH4+].[NH4+].[NH4+].[O-]B([O-])[O-] WYXIGTJNYDDFFH-UHFFFAOYSA-Q 0.000 description 1
Classifications
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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
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- 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
- 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 at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System 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
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
-
- C11D2111/22—
Abstract
Description
본 발명은 평판표시장치용 기판의 제조공정에서 초기 유리 기판 상의 유기 오염물이나 파티클(particle), 이송이나 스크래치 방지를 위해 유리기판 사이에 적층된 간지 성분인 TiO2 혹은 점착된 이형 필름에서 전사되어 유리 기판 상에 잔존하는 슬립제 성분 및 유리 기판 연마시 발생하는 연마 잔해물 제거에 적합한 세정제 조성물 및 이를 이용한 세정방법에 관한 것이다. In the process for manufacturing a flat panel display, organic contaminants and particles on an initial glass substrate are transferred from TiO 2 or an adhesive release film laminated between glass substrates for transferring or scratch prevention, To a cleaning agent composition suitable for removing a slip agent component remaining on a substrate and polishing debris generated when polishing a glass substrate, and a cleaning method using the same.
액정표시장치로 대표되는 평판표시장치(FPD)는 성막, 노광, 에칭 등의 공정을 거쳐 제조되며, 각 제조공정에서 기판 표면에 각종 유기물이나 무기물 등 크기가 1㎛이하의 매우 작은 파티클(Particle)들이 부착되어 오염이 야기된다. 이러한 파티클에 의한 오염은 디바이스의 수율을 저하시키기 때문에, 후 공정에 들어가기 전에 최대한 저감시킬 필요가 있다.A flat panel display (FPD) typified by a liquid crystal display device is manufactured through processes such as film formation, exposure, and etching. In each manufacturing process, a very small particle having a size of 1 μm or less, So that contamination is caused. Since contamination by such particles lowers the yield of the device, it is required to be reduced as much as possible before entering the post-process.
따라서 오염물을 제거하기 위한 세정이 각 공정간에 행해지고 있고, 이를 위한 세정액에 대해서도 많은 제안이 이루어지고 있다. Therefore, cleaning for removing contaminants is carried out between each process, and many proposals have been made for a cleaning liquid for this purpose.
특히, FPD 제조공정 초기에 유리 기판의 이송 중 오염을 방지하고 유기기판간의 마찰력으로 인한 스크래치를 방지하기 위해 보호필름을 부착하거나 유리기판 사이에 간지를 적층하게 되는데 이 과정에서 보호필름 표면의 슬립제나 간지 중에 포함된 TiO2 성분이 유리 기판 표면에 전사되어, 유리 기판의 추가 오염이 발생하기도 한다. 유리 기판에 전사된 슬립제 전사물은 올레아마이드, 에루카마이드 같은 유기 성분 등으로 이루어져 있고, 이런 슬립제 전사물이나 TiO2와 같은 오염물질은 종래의 유리 기판 세정제 조성물로는 제거가 용이하지 않았다.In particular, in order to prevent contamination during transport of the glass substrate at the initial stage of the FPD manufacturing process and to prevent scratches due to the frictional force between the organic substrates, a protective film is laminated or a sheet of paper is laminated between the glass substrates. In this process, The TiO 2 component contained in the gypsum is transferred to the surface of the glass substrate, and further contamination of the glass substrate occurs. The slip agent transferred to the glass substrate is composed of organic components such as oleamide and erucamide. Such contaminants such as slip agents and TiO 2 are not easily removed by a conventional glass substrate cleaning composition .
예를 들어, 대한민국 등록특허 10-0741991호는 중불화암모늄, 무기산, 유기산, 저극성 유기용매를 주성분으로 하는 실리콘 산화물 식각액 조성물을 개시하고, 대한민국 공개특허 10-2009-0012953호는 유기용매, 1개 이상의 카르복실기를 갖는 유기산, 불소화합물, 무기산을 포함하는 반도체 소자용 식각액 조성물을 개시하는데, 상기 조성물들은 다량의 유기용매 사용으로 경제적, 환경적 문제가 있을 뿐만 아니라 글래스 슬립제 혹은 TiO2에 대한 제거능력이 확인되지 않고 있다. For example, Korean Patent Registration No. 10-0741991 discloses a silicon oxide etchant composition containing as a main component ammonium borate, inorganic acid, organic acid, and low-polarity organic solvent, and Korean Patent Laid-Open No. 10-2009-0012953 discloses an organic solvent, an organic acid, a fluorine compound having at least a carboxyl group, to initiate the etching liquid composition for a semiconductor device including an inorganic acid, the composition may be removed for, as well as glass slip agent or TiO 2 have to use a large amount of organic solvent economic and environmental problems The ability is not confirmed.
이에 본 발명자들은 평판표시장치용 기판의 제조공정에서 유리 기판 표면의 유기물 및 파티클 제거력이 우수하고, 유리 기판의 슬립제의 제거능력이 뛰어난 유리 기판 세정제 조성물을 안출하게 되었다.Therefore, the inventors of the present invention have found a glass substrate cleaning composition excellent in the ability to remove organic substances and particles on the surface of a glass substrate in the manufacturing process of a substrate for a flat panel display, and capable of removing a slip agent of the glass substrate.
본 발명은, 평판표시장치용 기판의 제조공정에서 초기 유리 기판 위의 유기 오염물이나 파티클, 및 유리 기판 연마시 발생하는 연마 잔해물 제거에 적합한 유리 기판 세정제 조성물 및 세정방법을 제공하는 것을 목적으로 한다.An object of the present invention is to provide a glass substrate cleaning composition and a cleaning method suitable for removing organic contaminants and particles on an initial glass substrate in a process for manufacturing a substrate for a flat panel display, and polishing debris generated during polishing of a glass substrate.
상기 목적을 달성하기 위해, 본 발명은 조성물의 총 중량에 대하여, 불소계 화합물 0.05 내지 5 중량%, 질산 0.1 내지 10 중량%, 암모늄염 0.01~10 중량% 및 잔량의 물을 포함하는 유리 기판 세정제 조성물을 제공한다.In order to achieve the above object, the present invention provides a glass substrate cleaner composition comprising 0.05 to 5% by weight of a fluorinated compound, 0.1 to 10% by weight of nitric acid, 0.01 to 10% by weight of an ammonium salt, to provide.
또한 본 발명은, 상기 유리 기판 세정제 조성물을 사용하는 유리 기판 세정방법을 제공한다.The present invention also provides a glass substrate cleaning method using the glass substrate cleaner composition.
본 발명의 유리 기판 세정제 조성물은, 평판표시 장치용 기판의 제조공정에서 초기 유리 기판 표면에 존재하는 오염물 및 파티클 제거력이 우수하고, 유리 기판에 잔존하는 슬립제 성분이나 TiO2에 대한 제거성이 뛰어나 슬립제 혹은 TiO2 잔존물의 제거력이 우수하고, 유리 기판 연마 시 발생하는 SiO2 성분의 연마 잔해물의 제거에 효과적이다.INDUSTRIAL APPLICABILITY The glass substrate cleaner composition of the present invention is excellent in removing contaminants and particles existing on the surface of an initial glass substrate in the process of manufacturing a substrate for a flat panel display device and is excellent in the slip component remaining on the glass substrate and the removability of TiO 2 The removal power of the slip agent or TiO 2 remnant is excellent, and the SiO 2 It is effective in removing abrasive debris of the component.
이하 본 발명을 보다 상세하게 설명한다.Hereinafter, the present invention will be described in more detail.
본 발명의 유리 기판 세정제 조성물은 불소계 화합물, 수용성 극성 용매, 질산 및 물을 포함하는 것을 특징으로 한다.
The glass substrate cleaner composition of the present invention is characterized by containing a fluorine-based compound, a water-soluble polar solvent, nitric acid, and water.
이하, 각 성분에 대하여 구체적으로 설명한다.Hereinafter, each component will be described in detail.
(1) 불소계 화합물(1) Fluorine-based compound
상기 불소계 화합물로 불화수소산(HF), 불화암모늄(NH4F), 산성불화암모늄(NH4F·HF), 테트라메틸 암모늄플루오라이드((CH3)4NF), 테트라에틸 암모늄플루오라이드((CH3CH2)4NF), 불화붕소산(fluoroboric acid) 및 불화벤젠(fluorobenzene)으로 이루어진 군으로부터 선택되는 1종이상의 화합물을 사용하는 것이 바람직하나, 반드시 이에 한정되는 것은 아니다.Examples of the fluorine-based compound include hydrofluoric acid (HF), ammonium fluoride (NH 4 F), acid ammonium fluoride (NH 4 F.HF), tetramethylammonium fluoride ((CH 3 ) 4 NF), tetraethylammonium fluoride CH 3 CH 2 ) 4 NF), fluoroboric acid, and fluorobenzene. However, the present invention is not limited thereto.
상기 불소계 화합물은 조성물 총 중량에 대하여 바람직하게는 0.05 내지 5중량%, 더욱 바람직하게는 0.1 내지 3 중량%로 포함된다.The amount of the fluorine-based compound is preferably 0.05 to 5% by weight, more preferably 0.1 to 3% by weight based on the total weight of the composition.
상기의 불소계 화합물의 함량이 0.05 중량%미만이면 세정제 조성물의 SiO2 또는 TiO2 성분에 기인하는 오염물에 대한 용해력 증가를 기대할 수 없고, 5 중량%를 초과하여 사용할 경우 세정제 사용으로 인한 과도한 글래스 에칭 효과로 인하여 유리 기판의 표면 평활도가 변하는 문제가 발생하게 된다.
If the content of the fluorine-based compound is less than 0.05 wt%, the solubility of the detergent composition due to the SiO 2 or TiO 2 component is not expected to increase. When the fluorine-based compound is used in an amount exceeding 5 wt%, excessive glass etching There arises a problem that the surface smoothness of the glass substrate changes.
(2) 질산(2) Nitric acid
상기 질산은 불소계 화합물의 활성도를 높여 글래스(glass)의 균일 식각 및 무기 오염물의 효과적인 제거를 가능하게 한다. The nitric acid enhances the activity of the fluorine-based compound to enable uniform etching of the glass and effective removal of the inorganic contaminants.
상기 질산의 함량은 바람직하게는 0.1 내지 10중량%, 더욱 바람직하게는 0.1 내지 5중량%이다. 상기 질산의 함량이 0.1중량%미만이면 효과적인 무기물 제거력의 증가를 기대할 수 없고, 10중량%를 초과할 경우 유리기판의 표면 평활도가 변화하는 문제가 발생하고, 세정제 사용으로 인한 경제적, 환경적 이점을 기대할 수 없다.The content of the nitric acid is preferably 0.1 to 10% by weight, more preferably 0.1 to 5% by weight. If the content of nitric acid is less than 0.1% by weight, an increase in the inorganic removing power can not be expected to be increased effectively. If the content of nitric acid exceeds 10% by weight, the surface smoothness of the glass substrate changes, and the economic and environmental advantages I can not expect it.
(3) 암모늄염(3) Ammonium salt
본 발명에서 암모늄염은 수산화테트라메틸암모늄, 수산화테트라에틸암모늄, 수산화테트라프로필암모늄, 수산화테트라부틸암모늄 및 암모늄 아세테이트로 이루어진 군으로부터 선택되는 1종이상인 것이 바람직하나, 반드시 이에 한정되는 것은 아니다.In the present invention, the ammonium salt is preferably in the form of one kind selected from the group consisting of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide and ammonium acetate, but is not limited thereto.
상기 암모늄염의 함량은 바람직하게는 0.01 내지 10 중량%, 더욱 바람직하게는 0.1 내지 3 중량%이다. 암모늄염의 함량이 0.01 중량% 미만이면 효과적인 유기물 제거력의 증가 및 글래스 식각 조절능력을 기대할 수 없고, 10 중량%를 초과할 경우 무기물에 대한 제거성 저하 문제가 발생하고, 세정제 사용으로 인한 경제적, 환경적 이점을 기대할 수 없다.
The content of the ammonium salt is preferably 0.01 to 10% by weight, more preferably 0.1 to 3% by weight. If the content of the ammonium salt is less than 0.01% by weight, it is impossible to expect an increase in the removal efficiency of organic substances and a capability of controlling the glass etching. If the content is more than 10% by weight, I can not expect this.
(4) 물(4) Water
본 발명의 유리 기판 세정제 조성물에 포함되는 물은 특별히 한정되지는 않으나, 반도체 공정용의 물로서, 비저항 값이 18MΩ·cm 이상인 탈 이온수를 사용하는 것이 바람직하다. 상기 물은 전체 조성물의 총 중량이 100 중량%가 되도록 하는 잔량으로 포함되므로, 다른 구성성분의 함량에 따라 조정될 수 있다.
Water contained in the glass substrate cleaner composition of the present invention is not particularly limited, but it is preferable to use deionized water having a specific resistance value of 18 M? · Cm or more as water for semiconductor processing. The water is included in the remaining amount such that the total weight of the entire composition is 100% by weight, so that it can be adjusted according to the contents of other components.
본 발명에 따른 유리 기판 세정제 조성물은 통상적으로 공지된 방법에 의해서 제조가 가능하며, 반도체 공정용의 순도를 가지는 것이 바람직하다.
The glass substrate cleaner composition according to the present invention can be manufactured by a conventionally known method, and preferably has a purity for semiconductor processing.
본 발명의 유리 기판 세정제 조성물은, 평판표시장치용 기판의 제조공정에서 초기 유리 기판 표면에 존재하는 유기물 오염물 및 파티클 제거력이 우수하고, 유기기판에 전사되어 잔존하는 슬립제나 TiO2 성분에 대한 제거성이 뛰어나며, 유리 기판 연마시 발생하는 SiO2성분의 연마 잔해물 제거에 효과적이다.INDUSTRIAL APPLICABILITY The glass substrate cleaner composition of the present invention is excellent in the ability to remove organic contaminants and particles existing on the surface of an initial glass substrate in the process of manufacturing a substrate for a flat panel display device and is excellent in removing slip agent and remaining TiO 2 component And is effective in removing abrasive debris from the SiO 2 component which occurs during the polishing of the glass substrate.
또한 본 발명은, 상기 유리 기판 세정제 조성물을 사용하는 유리 기판 세정방법을 제공한다.The present invention also provides a glass substrate cleaning method using the glass substrate cleaner composition.
본 발명에 따른 유리 기판 세정제 조성물이 적용되는 세정방법은 특별히 한정되지 않으며, 침지 세정법, 요동 세정법, 초음파 세정법, 샤워·스프레이 세정법, 퍼들 세정법, 브러쉬 세정법, 교반 세정법 등의 방법에 적용될 수 있다. 본 발명에서는 특히 침지 세정법 또는 초음파 세정법이 바람직하다.
The cleaning method to which the glass substrate cleaner composition according to the present invention is applied is not particularly limited and can be applied to methods such as immersion cleaning, oscillating cleaning, ultrasonic cleaning, shower spray cleaning, puddle cleaning, brush cleaning and agitation cleaning. In the present invention, an immersion cleaning method or an ultrasonic cleaning method is particularly preferable.
이하에서, 실시예를 통하여 본 발명을 보다 상세히 설명한다. 그러나, 하기의 실시예는 본 발명을 더욱 구체적으로 설명하기 위한 것으로서, 본 발명의 범위가 하기의 실시예에 의하여 한정되는 것은 아니다.
Hereinafter, the present invention will be described in more detail by way of examples. However, the following examples are intended to further illustrate the present invention, and the scope of the present invention is not limited by the following examples.
실시예Example 1 내지 8, 및 1 to 8, and 비교예Comparative Example 1 내지 3 : 유리 기판 세정제 조성물의 제조 1 to 3: Preparation of Glass Substrate Cleaner Composition
하기 표 1에 기재된 구성성분 및 조성으로 혼합하고 교반하여, 세정제 조성물을 제조하였다.
The components and compositions shown in Table 1 were mixed and stirred to prepare a detergent composition.
A-1 : 불화수소산(HF)A-1: Hydrofluoric acid (HF)
A-2 : 불화암모늄(Ammonium fluoride)A-2: Ammonium fluoride
A-3 : 중불화암모늄(Ammonium bifluoride)A-3: Ammonium bifluoride
B-1 : 수산화테트라메틸암모늄(TMAH)B-1: Tetramethylammonium hydroxide (TMAH)
B-2 : 수산화테트라에틸암모늄(TEAH)B-2: tetraethylammonium hydroxide (TEAH)
B-3 : 수산화테트라프로필암모늄B-3: Tetrapropylammonium hydroxide
B-4 : 수산화테트라부틸암모늄B-4: Tetrabutylammonium hydroxide
B-4 : 암모늄 아세테이트
B-4: Ammonium acetate
시험예Test Example : 유리 기판 세정제 조성물의 특성 평가: Characterization of Glass Substrate Cleaner Composition
1) SiO2 제거력 평가1) SiO 2 jegeoryeok evaluation
글래스 성분인 SiO2 파티클 제거력 평가를 위해 2.5㎝ x 2.5㎝ 크기로 유기기판을 준비하고 평균 입자크기가 0.8㎛인 SiO2 입자를 분산시킨 솔루션을 5방울 적하하여 150℃에서 베이킹(baking) 후 오염된 유리 기판을 준비한다. 실시예 1 내지 8 및 비교예 1 내지 3의 유리 기판 세정제 조성물로 침지 세정한 다음 초순수로 30초간 세척 후 질소로 건조하였다.In order to evaluate the removability of SiO 2 particles as a glass component, an organic substrate having a size of 2.5 cm x 2.5 cm was prepared, and 5 drops of SiO 2 particles having an average particle size of 0.8 탆 dispersed therein was dropped and baked at 150 캜 for contamination Thereby preparing a glass substrate. The glass substrate cleaner compositions of Examples 1 to 8 and Comparative Examples 1 to 3, washed with ultrapure water for 30 seconds, and then dried with nitrogen.
이때 하기 표 2에서 파티클의 제거 유무는 제거가 되었을 때 ◎, 대부분 제거 되었을 때 ○, 제거가 되지 않았을 때 ×로 표시하였다.
At this time, in Table 2, the presence or absence of removal of the particles was indicated as? When it was removed,? When it was mostly removed, and when it was not removed.
2) 유기 오염물 제거력 평가(1, 2)2) Evaluation of removal efficiency of organic contaminants (1, 2)
유기 오염물의 제거력 평가를 위해 5㎝ x 5㎝ 크기로 형성된 유리 기판 위에 사람의 지문 자국(1) 및 유기성분 사인펜(2)으로 오염시키고, 오염된 기판을 스프레이식 유리 기판 세정장치를 이용하여 2분 동안 상온에서 실시예 1 내지 8 및 비교예 1 내지 3의 세정제 조성물로 세정하였다. 세정 후 초순수로 30초 세척한 후 질소로 건조하였다.To evaluate the removability of organic contaminants, the substrate was stained with a finger print (1) and an organic constituent pen (2) on a glass substrate having a size of 5 cm x 5 cm, and the contaminated substrate was cleaned with a spray type glass substrate cleaner Lt; RTI ID = 0.0 > 1 < / RTI > to 8 and Comparative Examples 1-3. After washing, it was washed with ultrapure water for 30 seconds and then dried with nitrogen.
이때 하기 표 2에서 유기 오염물의 제거 유무는 제거가 되었을 때 ◎, 대부분 제거 되었을 때 ○, 제거가 되지 않았을 때 ×로 표시하였다.
At this time, the presence or absence of the organic contaminants in the following Table 2 was marked as ⊚ when it was removed, ○ when it was mostly removed, and × when it was not.
3) 유기 오염물 제거력 평가(3)3) Evaluation of organic pollutant removing ability (3)
실시예 1, 실시예 3, 실시예 5, 및 비교예 1 내지 3의 세정제 조성물을 사용하여, 유기 파티클 솔루션으로 오염시킨 유리 기판에 대한 세정을 실시하였다. 즉, 유리 기판을 평균 입자 크기가 0.8㎛인 유기 파티클 솔루션으로 오염시키고 1분간 3000rpm으로 스핀(spin) 드라이한 후 스프레이식 유리 기판 세정장치를 이용하여 2분 동안 실온에서 각각의 세정액으로 세정하였다. 세정 후 초순수로 30초 세척한 후 질소로 건조하였다. 표면입자측정기(Topcon WM-1500)로 세정 전후의 0.1㎛ 이상의 파티클 수를 측정하여, 하기 표 2에 나타내었다.
Using the detergent compositions of Examples 1, 3, 5, and Comparative Examples 1 to 3, the glass substrate contaminated with the organic particle solution was cleaned. That is, the glass substrate was contaminated with an organic particle solution having an average particle size of 0.8 μm, spin-dried at 3000 rpm for 1 minute, and then cleaned with each cleaning liquid at room temperature for 2 minutes using a spray-type glass substrate cleaning apparatus. After washing, it was washed with ultrapure water for 30 seconds and then dried with nitrogen. The number of particles having a particle size of 0.1 mu m or more before and after cleaning was measured with a surface particle analyzer (Topcon WM-1500) and is shown in Table 2 below.
4) TiO2 제거성 평가4) Evaluation of TiO 2 removability
유리 기판의 이송 중 오염을 방지하기 위한 간지를 적층하여 유리 기판 표면에 TiO2가 전사된 유리 기판을 준비한 후 스프레이식 유리 기판 세정장치를 이용하여 1분 동안 상온에서 실시예 1 내지 8 및 비교예 1 내지 3의 세정제 조성물로 세정하였다. 세정 후 초순수로 30초 세척한 후 질소로 건조하였다. 이때 하기 표 2에서 유기/무기 오염물의 제거 유무는 제거가 되었을 때 ◎, 대부분 제거되었을 때 ○, 제거가 되지 않았을 때 ×로 표시하였다.
A glass substrate on which TiO 2 was transferred onto the surface of a glass substrate was laminated to prevent contamination during transportation of the glass substrate, and then a glass substrate was cleaned with a spray type glass substrate cleaning apparatus for 1 minute at room temperature, 1 to 3 detergent compositions. After washing, it was washed with ultrapure water for 30 seconds and then dried with nitrogen. At this time, the presence or absence of organic / inorganic contaminants in the following Table 2 was marked as ⊚ when it was removed, ○ when it was mostly removed, and × when it was not removed.
사인펜abandonment
Marker pen
상기 표 2에서 보는 바와 같이, 실시예 1 내지 8의 조성물은 비교예 1 내지 3의 조성물에 비해, SiO2 파티클, 유기오염물, 유기파티클 및 Ti02 제거력이 우수함을 알 수 있다. As shown in Table 2, the compositions of Examples 1 to 8 are superior to the compositions of Comparative Examples 1 to 3 in removing SiO 2 particles, organic contaminants, organic particles and TiO 2 .
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| US11618710B2 (en) | 2016-08-08 | 2023-04-04 | Sep, Inc. | Nano protrusion surface forming method and base material having nano protrusion surface formed by method |
| KR20200054688A (en) * | 2018-11-12 | 2020-05-20 | (주)합동하이텍그라스 | Cleaner composition for glass substrate for waste solar cell and method for cleaning the glass substrate for solar cell using thereof |
| CN111825480A (en) * | 2020-08-13 | 2020-10-27 | 西藏大学 | Ultraviolet-resistant super-hydrophobic anti-freezing material and preparation method thereof |
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| KR101932774B1 (en) | 2018-12-26 |
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