KR20130092096A - Chemical mechanical polishing cleaning coposition and the cleaning method therewith - Google Patents
Chemical mechanical polishing cleaning coposition and the cleaning method therewith Download PDFInfo
- Publication number
- KR20130092096A KR20130092096A KR1020120013601A KR20120013601A KR20130092096A KR 20130092096 A KR20130092096 A KR 20130092096A KR 1020120013601 A KR1020120013601 A KR 1020120013601A KR 20120013601 A KR20120013601 A KR 20120013601A KR 20130092096 A KR20130092096 A KR 20130092096A
- Authority
- KR
- South Korea
- Prior art keywords
- cleaning
- copper
- liquid composition
- mechanical polishing
- cleaning liquid
- Prior art date
Links
- 238000004140 cleaning Methods 0.000 title claims abstract description 116
- 238000000034 method Methods 0.000 title claims abstract description 56
- 238000005498 polishing Methods 0.000 title claims abstract description 34
- 239000000126 substance Substances 0.000 title claims description 33
- 239000010949 copper Substances 0.000 claims abstract description 59
- 239000000203 mixture Substances 0.000 claims abstract description 57
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 55
- 229910052802 copper Inorganic materials 0.000 claims abstract description 55
- 239000007788 liquid Substances 0.000 claims abstract description 49
- 230000008569 process Effects 0.000 claims abstract description 45
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims abstract description 24
- 239000003960 organic solvent Substances 0.000 claims abstract description 14
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 10
- 239000004475 Arginine Substances 0.000 claims abstract description 7
- ODKSFYDXXFIFQN-UHFFFAOYSA-N arginine Natural products OC(=O)C(N)CCCNC(N)=N ODKSFYDXXFIFQN-UHFFFAOYSA-N 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 19
- 238000010790 dilution Methods 0.000 claims description 11
- 239000012895 dilution Substances 0.000 claims description 11
- 238000005260 corrosion Methods 0.000 claims description 9
- 230000007797 corrosion Effects 0.000 claims description 9
- 239000003112 inhibitor Substances 0.000 claims description 9
- ODKSFYDXXFIFQN-BYPYZUCNSA-P L-argininium(2+) Chemical compound NC(=[NH2+])NCCC[C@H]([NH3+])C(O)=O ODKSFYDXXFIFQN-BYPYZUCNSA-P 0.000 claims description 3
- 239000003755 preservative agent Substances 0.000 claims 1
- 238000007517 polishing process Methods 0.000 abstract description 7
- 239000013522 chelant Substances 0.000 abstract description 3
- 239000011368 organic material Substances 0.000 abstract description 2
- 239000003599 detergent Substances 0.000 abstract 4
- 239000003795 chemical substances by application Substances 0.000 abstract 2
- 230000000052 comparative effect Effects 0.000 description 21
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 18
- SHGAZHPCJJPHSC-YCNIQYBTSA-N all-trans-retinoic acid Chemical compound OC(=O)\C=C(/C)\C=C\C=C(/C)\C=C\C1=C(C)CCCC1(C)C SHGAZHPCJJPHSC-YCNIQYBTSA-N 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 5
- 238000005530 etching Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000003917 TEM image Methods 0.000 description 4
- 239000000356 contaminant Substances 0.000 description 4
- 238000002845 discoloration Methods 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 3
- 239000005751 Copper oxide Substances 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
- 229910000431 copper oxide Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 230000009467 reduction Effects 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
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 1
- ULRPISSMEBPJLN-UHFFFAOYSA-N 2h-tetrazol-5-amine Chemical compound NC1=NN=NN1 ULRPISSMEBPJLN-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- LYVWMIHLNQLWAC-UHFFFAOYSA-N [Cl].[Cu] Chemical compound [Cl].[Cu] LYVWMIHLNQLWAC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- SFMJNHNUOVADRW-UHFFFAOYSA-N n-[5-[9-[4-(methanesulfonamido)phenyl]-2-oxobenzo[h][1,6]naphthyridin-1-yl]-2-methylphenyl]prop-2-enamide Chemical compound C1=C(NC(=O)C=C)C(C)=CC=C1N1C(=O)C=CC2=C1C1=CC(C=3C=CC(NS(C)(=O)=O)=CC=3)=CC=C1N=C2 SFMJNHNUOVADRW-UHFFFAOYSA-N 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000004441 surface measurement Methods 0.000 description 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
Images
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
- C11D7/50—Solvents
- C11D7/5004—Organic solvents
- C11D7/5022—Organic solvents containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
-
- 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
- C11D7/3245—Aminoacids
-
- 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
- C11D7/50—Solvents
- C11D7/5004—Organic solvents
- C11D7/5013—Organic solvents 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
- C11D2111/16—Metals
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Materials Engineering (AREA)
- Cleaning Or Drying Semiconductors (AREA)
- Detergent Compositions (AREA)
Abstract
Description
본 발명은 화학적 기계적 연마 공정에 사용되는 세정액 및 세정방법에 관한 것으로서, 보다 상세하게는 구리 배선의 화학적 기계적 연마 후 세정 시 사용되는 구리 화학적 기계적 연마 후 세정 공정용 세정액 및 이를 이용한 세정방법에 관한 것이다.
The present invention relates to a cleaning liquid and a cleaning method used in a chemical mechanical polishing process, and more particularly, to a cleaning liquid for a copper chemical mechanical polishing post cleaning process used for cleaning after chemical mechanical polishing of copper wiring and a cleaning method using the same. .
반도체 공정에서 배선의 선폭이 점차 감소함에 따라, 배선의 단면적 감소로 인해 저항이 증가되고 배선간 간격 감소로 인해 신호의 지연이 발생한다. 이러한 신호 지연을 줄이기 위해서, 배선의 소재는 낮은 비저항 특성을 가지는 구리 (Cu)로, 절연층 (dielectric)은 더 낮은 유전 상수를 갖는 물질로 대체되고 있다.As the line width of the wiring gradually decreases in the semiconductor process, the resistance is increased due to the reduction of the cross-sectional area of the wiring, and the signal is delayed due to the reduction of the wiring interval. In order to reduce this signal delay, the material of the wiring is replaced by copper (Cu) with low specific resistivity and the dielectric is replaced by a material with a lower dielectric constant.
그런데, 기존의 텅스텐(W)과 알루미늄 (Al) 배선 형성 공정에서 사용되던 건식 식각 (dry etch back) 공정을 구리 배선 형성 과정에 적용하면, 구리와 염소 (Cl)가 반응하여 휘발성이 낮은 구리-염소 착물 (complex)이 형성된다. 상기 구리-염소 착물은 기판 표면에 잔류하여 식각을 방해하는 장애물로 작용함으로써 패턴을 형성하는데 문제를 야기한다.However, when a dry etch back process used in a conventional tungsten (W) and aluminum (Al) wiring forming process is applied to a copper wiring forming process, copper reacts with chlorine (Cl) A chlorine complex is formed. The copper-chlorine complex remains on the surface of the substrate and acts as an obstacle that interferes with the etching, thereby causing a problem in forming a pattern.
이를 극복하기 위해, 화학적 기계적 연마 (Chemical Mechanical Polishing: CMP) 공정이 도입되었다. 즉, 상기 화학적 기계적 연마 공정을 이용한 다마신 공정 (damascene process)을 통해 반도체 기판 상에 구리 배선을 형성한다. 상기 화학적 기계적 연마를 이용한 구리 배선 형성 과정 시, 물질간 제거 선택비 차이로 인한 산화막 침하 및 구리 침하 때문에, 구리 제거는 2단계에 걸쳐 이루어진다. To overcome this, a chemical mechanical polishing (CMP) process was introduced. That is, a copper wiring is formed on a semiconductor substrate through a damascene process using the chemical mechanical polishing process. In the copper wiring formation process using the chemical mechanical polishing, copper removal is performed in two steps because of oxide settlement and copper settlement due to the difference in removal selectivity between materials.
상기 화학적 기계적 연마 공정 후에는 구리 표면은 슬러리 내 포함된 입자와 유기 첨가제가 표면에 존재한다. 구리 화학기계적 연마 (CMP) 공정 시 슬러리 내 입자의 표면 흡착은 염기성 세정액 조성물을 사용함으로써 음의 제타전위 구현을 통하여 제거 및 재흡착 방지를 달성할 수 있다.After the chemical mechanical polishing process, the copper surface is present on the surface with particles and organic additives contained in the slurry. Surface adsorption of the particles in the slurry during the copper chemical mechanical polishing (CMP) process can achieve removal and re-adsorption prevention through the implementation of negative zeta potential by using a basic cleaning composition.
그러나 구리 화학기계적 연마 (CMP) 공정 시 사용되는 산화-부식방지 메커니즘에 의해서 형성된 불안정한 구리 산화막과 그 위에 형성되는 유기물 오염은 제거하는 것이 용이하지 않다. 그러므로 구리 화학기계적 연마 (CMP) 후 세정 공정에서는 유기물 오염층을 완전히 제거하고, 후속하는 공정까지 안정한 산화막을 형성을 통하여 구리막을 보호하는 것이 요구된다.However, it is not easy to remove the unstable copper oxide film formed by the oxidation-corrosion prevention mechanism used in the copper chemical mechanical polishing (CMP) process and the organic material contamination formed thereon. Therefore, in the cleaning process after copper chemical mechanical polishing (CMP), it is required to completely remove the organic contaminant layer, and to protect the copper film through formation of a stable oxide film to a subsequent process.
종래의 Lift off 방식 세정은 구리 산화막을 에칭함에 따라서 안정한 구리 산화막 형성을 통한 구리막 보호에 문제점이 있어, 구리 화학기계적 연마 (CMP) 후 유기물 오염을 완전하게 제거하고, 안정한 산화막 형성을 통해 구리막을 변질 없이 후속하는 공정까지 보호하는 세정액 조성물에 대한 요구가 있다.
Conventional lift off cleaning has a problem in protecting the copper film by forming a stable copper oxide film by etching the copper oxide film, thereby completely removing organic contamination after copper chemical mechanical polishing (CMP), and removing the copper film by forming a stable oxide film. There is a need for a cleaning liquid composition that protects subsequent processes without alteration.
본 발명은 상기의 문제점을 해결하기 위하여 발명된 것으로서, 화학기계적 연마 (CMP) 공정 후 세정 과정, 특히 구리 화학기계적 연마 (CMP) 공정 후 표면 세정 과정에서 유기물 오염층을 완전히 제거하고, 후속 공정까지 안정적으로 유지되는 산화막을 형성할 수 있는 세정액 조성물 및 이를 이용한 화학기계적 연마 (CMP) 공정 후 세정방법을 제공하는 것이다. The present invention has been invented to solve the above problems, and the organic contaminant layer is completely removed from the cleaning process after the chemical mechanical polishing (CMP) process, particularly the surface cleaning process after the copper chemical mechanical polishing (CMP) process, and then to the subsequent process. The present invention provides a cleaning liquid composition capable of forming a stable oxide film and a cleaning method after a chemical mechanical polishing (CMP) process using the same.
본 발명은 희석 시에 조성물의 pH의 변화폭이 크지 않고, 세정 전후 표면의 접촉각 변화가 작고, 장시간 담지의 경우에도 표면의 화학적 결함이 발생하지 않는 안정적인 세정액 조성물 및 이를 이용한 화학기계적 연마 (CMP) 공정 후 세정방법을 제공하는 것이다.
The present invention provides a stable cleaning liquid composition and a chemical mechanical polishing (CMP) process using the same. It is to provide a post-cleaning method.
본 발명의 일 측면에 따른 세정액 조성물은 KOH, TMAH 또는 이 둘을 포함하는 유기 용매; EDTA, 아르기닌 (arginine) 또는 이 둘을 포함하는 킬레이트 시약; 부식방지제; 및 순수 (純水);를 포함한다.Cleaning liquid composition according to an aspect of the present invention KOH, TMAH or an organic solvent comprising both; Chelating reagents comprising EDTA, arginine or both; Corrosion inhibitors; And pure water.
상기 유기 용매는 상기 세정액 조성물 중 1 내지 10 중량%일 수 있고, 상기 킬레이트 시약은 상기 세정액 조성물 중 1 내지 10 중량%일 수 있고, 상기 부식방지제는 상기 세정액 조성물 중 0.2 내지 2 중량%일 수 있다.The organic solvent may be 1 to 10% by weight in the cleaning liquid composition, the chelating reagent may be 1 to 10% by weight in the cleaning liquid composition, and the corrosion inhibitor may be 0.2 to 2% by weight in the cleaning liquid composition. .
상기 세정액 조성물은 pH가 10 내지 12.5일 수 있다.The cleaning liquid composition may have a pH of 10 to 12.5.
상기 세정액 조성물은, 구리 화학기계적 연마 (CMP) 공정 후 상기 세정액 조성물로 세정한 구리 표면의 접촉각이 45 이하인 것일 수 있다.The cleaning liquid composition may have a contact angle of 45 or less on the copper surface cleaned with the cleaning liquid composition after a copper chemical mechanical polishing (CMP) process.
상기 세정액 조성물은, 구리 화학기계적 연마 (CMP) 공정 후 구리 표면 세정시, 희석비 1:10 ~ 1:100으로 사용하는 것일 수 있다.The cleaning liquid composition may be used at a dilution ratio of 1:10 to 1: 100 when cleaning the copper surface after the copper chemical mechanical polishing (CMP) process.
본 발명의 다른 일 측면으로서, 구리 화학기계적 연마 (CMP) 공정 세정방법은, 구리 표면을 화학기계적 연마 (CMP) 연마하는 단계; 및 연마된 구리 표면을 본 발명의 세정액 조성물을 이용하여 세정하는 단계;를 포함한다.
In another aspect of the present invention, a copper chemical mechanical polishing (CMP) process cleaning method comprises the steps of: chemical mechanical polishing (CMP) polishing a copper surface; And cleaning the polished copper surface using the cleaning liquid composition of the present invention.
본 발명의 세정액 조성물은 구리 화학기계적 연마 (CMP) 공정 후 세정 과정에서 구리 표면 상의 유기물 오염층을 완전히 제거하고, 후속 공정까지 안정적으로 유지되는 산화막을 얻을 수 있다.The cleaning liquid composition of the present invention can completely remove the organic contaminant layer on the copper surface in the cleaning process after the copper chemical mechanical polishing (CMP) process, and obtain an oxide film which is stably maintained until the subsequent process.
또한, 세정 공정에서 희석액으로 사용하는 경우에도 조성물의 pH가 안정적으로 유지되고, 세정 전후 표면의 접촉각 변화를 최소화할 수 있다.In addition, even when used as a diluting solution in the cleaning step, the pH of the composition is stably maintained, and the change in the contact angle of the surface before and after cleaning can be minimized.
또한, 본 발명의 세정액 조성물은 장시간 담지의 경우에도 구리 표면의 디스칼라 (discolor)와 같은 표면 변화가 일어나지 않으므로, 세정 시간의 조절 등 공정 운영이 유리하다.
In addition, since the cleaning liquid composition of the present invention does not cause a surface change such as discolor of the copper surface even in the case of being supported for a long time, process operation such as adjustment of cleaning time is advantageous.
도 1은 본 발명의 실시예 1-1, 2-1 및 3-1의 세정액 조성물 및 비교예 1 내지 3의 상용 세정제의 희석비에 따른 pH 변화를 나타낸 그래프이다.
도 2는 본 발명의 실시예 2-1의 세정액 조성물로 세정 공정을 수행한 후의 구리 표면의 TEM 이미지이다.
도 3은 비교예 의 상용 세정액으로 세정 공정을 수행한 후의 구리 표면의 TEM 이미지이다.1 is a graph showing the pH change according to the dilution ratio of the cleaning liquid compositions of Examples 1-1, 2-1 and 3-1 and the commercial cleaning agents of Comparative Examples 1 to 3 of the present invention.
2 is a TEM image of a copper surface after performing a cleaning process with the cleaning liquid composition of Example 2-1 of the present invention.
3 is a TEM image of a copper surface after performing a cleaning process with a commercial cleaning solution of Comparative Example.
본 발명의 일 측면에 따른 세정액 조성물은 KOH, TMAH 또는 이 둘을 포함하는 유기 용매; EDTA, 아르기닌 (arginine) 또는 이 둘을 포함하는 킬레이트 시약; 부식방지제; 및 순수 (純水);를 포함한다. Cleaning liquid composition according to an aspect of the present invention KOH, TMAH or an organic solvent comprising both; Chelating reagents comprising EDTA, arginine or both; Corrosion inhibitors; And pure water.
본 발명의 세정액 조성물은 유기 용매 (organic base)로 KOH (수산화칼륨)나 TMAH (Tetramethyl ammounium hydroxide, 테트라 메틸 암모니움 하이드로 옥사이드)를 포함하고, 킬레이트 시약으로서 EDTA (ethylenediamine tetraacetic acid, 에틸렌디아민테트라아세트산, 화학식: (HOOCCH2)2NCH2CH2N(CH2COOH)2) 또는 아르기닌을 포함하고, 5-아미노 테트라졸 (5-amino-1H-Tetrazole)과 같은 부식방지제를 포함하고, 잔량에 대하여는 순수, 바람직하게는 초순수 (DI water)를 포함한다.The cleaning liquid composition of the present invention contains KOH (potassium hydroxide) or TMAH (Tetramethyl ammounium hydroxide, tetramethyl ammonium hydroxide) as an organic solvent, EDTA (ethylenediamine tetraacetic acid, ethylenediamine tetraacetic acid, Formula: (HOOCCH 2 ) 2 NCH 2 CH 2 N (CH 2 COOH) 2 ) or arginine, including a corrosion inhibitor such as 5-amino-1H-Tetrazole, with respect to the remaining amount Pure water, preferably ultrapure water (DI water).
상기 유기 용매는 상기 세정액 조성물 중 1 ~ 10 중량%일 수 있고, 4 ~ 10 중량%가 더욱 바람직할 수 있고, 상기 킬레이트 시약은 상기 세정액 조성물 중 1 ~ 10 중량%일 수 있고, 4 ~ 8 중량%가 더욱 바람직할 수 있다. The organic solvent may be 1 to 10% by weight of the cleaning liquid composition, 4 to 10% by weight may be more preferable, and the chelating reagent may be 1 to 10% by weight of the cleaning liquid composition, 4 to 8% by weight % May be more preferred.
상기 부식방지제는 상기 세정액 조성물 중 0.2 ~ 2 중량%일 수 있다.The corrosion inhibitor may be 0.2 to 2% by weight of the cleaning liquid composition.
유기 용매로 사용된 TMAH (테트라메틸암모늄 하이드록사이드) 등은 반도체 PR 스트리퍼 등을 제거하는 세정액으로 사용되고 있으며, Cleaning 효과가 탁월하다. 특히 염기성 용매로 용액 내 음의 제타전위를 구현하여 정전기적 반발력을 통해서 세정 후 Particle 재흡착 방지를 할 수 있다. TMAH (tetramethylammonium hydroxide) used as an organic solvent is used as a cleaning liquid for removing semiconductor PR strippers and the like, and has an excellent cleaning effect. In particular, by implementing a negative zeta potential in the solution with a basic solvent it can prevent the re-adsorption of particles after washing through electrostatic repulsion.
Cu Slurry내 연마제 파티클은 음의 제타전위를 띄고 있으며, CMP 공정 후 금속이온이 포함되지 않은 염기성 유기 용매를 사용하면 파티클을 용이하게 제거하고, 또한 재흡착 방지가 가능하다. 유기 용매는 최종 pH 조절제로서의 역할을 수행하기 때문에 그 함량은 적절한 성능을 나타내는 pH 수준으로 결정된다.The abrasive particles in the Cu slurry have a negative zeta potential, and using a basic organic solvent containing no metal ions after the CMP process can easily remove the particles and prevent resorption. Since the organic solvent plays a role as a final pH adjuster, its content is determined at a pH level which shows adequate performance.
킬레이트 시약의 경우, 세정 공정이 진행될 때 발생하는 금속 이온의 착화제로 작용을 한다. 또한 약산을 띠게 됨으로서 염기성 유기 용매와 약산-강염기의 버퍼 용액을 형성함으로서 희석비에 관계없이 적절한 pH 영역이 유지되게 한다.In the case of a chelating reagent, it acts as a complexing agent for the metal ion that occurs when the cleaning process proceeds. It also has a weak acid to form a buffer solution of basic organic solvent and weak acid-strong base so that the appropriate pH range is maintained regardless of the dilution ratio.
부식방지제의 경우, 세정 작용시 금속 표면을 보호하는 작용하며, 과량 첨가시 웨이퍼 표면에 잔류하여 오히려 유기물 오염을 유발할 수 있다.In the case of a corrosion inhibitor, it acts to protect the metal surface during the cleaning action, and may remain on the wafer surface when excessively added, causing organic contamination.
본 발명의 세정액 조성물은, 상기 세정액 조성물을 이용하여 구리 화학기계적 연마 (CMP) 공정을 수행한 구리 표면의 접촉각이 45 이하일 수 있다.In the cleaning liquid composition of the present invention, the contact angle of the copper surface, which has been subjected to the copper chemical mechanical polishing (CMP) process using the cleaning liquid composition, may be 45 or less.
화학기계적 연마 (CMP) 공정 및 세정 후 접촉각이 증가하는 것은 표면이 소수성으로 변환된 것을 의미한다. 초순수에 담지한 후 세척하고 질소 가스로 완전 세척한 상태의 구리 (fresh Cu)의 표면의 접촉각이 41.6 정도이므로, 화학기계적 연마 (CMP) 공정 및 세정 후 접촉각이 45 이하로 유지되어야 한다. 접촉각이 45를 넘게 되면 상기 검토대로 표면이 부식방지제에 의하여 소수성으로 변환된 것임을 나타낸다. 화학기계적 연마 (CMP) 후 세정 공정은 연마 후 표면에 잔류하는 유기물 오염층을 제거하는 것이 목적이므로, 세정 작용 외에는 표면에 영향을 미치지 않는 것이 바람직하다. 그러므로 세정 후 접촉각에 있어서도 세정 전 접촉가을 기준으로 표면의 특성 변화가 없는 것으로 평가 가능한 수준인 45도 이하를 유지하는 것이 바람직하다. Increasing the contact angle after the chemical mechanical polishing (CMP) process and cleaning means that the surface has been converted to hydrophobic. Since the contact angle of the surface of fresh Cu, which is washed after being supported in ultrapure water and thoroughly cleaned with nitrogen gas, is about 41.6, the contact angle after the chemical mechanical polishing (CMP) process and cleaning should be maintained at 45 or less. When the contact angle exceeds 45, it indicates that the surface has been converted to a hydrophobic property by the corrosion inhibitor as described above. Since the cleaning process after chemical mechanical polishing (CMP) is intended to remove the organic contaminant layer remaining on the surface after polishing, it is preferable not to affect the surface except for the cleaning action. Therefore, it is preferable to maintain the degree of 45 degrees or less, which can be estimated that there is no change in the characteristics of the surface on the basis of the contact value before cleaning even in the contact angle after cleaning.
상기 세정액 조성물은, 구리 화학기계적 연마 (CMP) 공정 후 구리 표면 세정 시, 희석비 1:10 ~ 1:100으로 사용하는 것일 수 있다. 희석비가 1:10보다 작으면, 제조되는 세정액 조성물의 함량이 낮아서 조성물의 특성을 평가하기가 어렵고, 생산성이 저조한 문제가 있을 수 있고, 1:100 보다 크면 조성물 함량이 너무 높아서 저장안정성 및 경시안정성에서 문제가 있을 수 있다. The cleaning liquid composition may be used in a dilution ratio of 1:10 to 1: 100 when cleaning the copper surface after the copper chemical mechanical polishing (CMP) process. If the dilution ratio is less than 1:10, it is difficult to evaluate the characteristics of the composition due to the low content of the cleaning liquid composition to be prepared, there may be a problem of poor productivity, and if it is greater than 1: 100, the storage content and stability over time There may be a problem.
본 발명의 구리 화학기계적 연마 (CMP) 공정 세정방법은, 구리 표면을 화학기계적 연마 (CMP)하는 단계; 및 연마된 구리 표면을 상기의 세정액 조성물을 이용하여 세정하는 단계;를 포함한다.
The copper chemical mechanical polishing (CMP) process cleaning method of the present invention comprises the steps of chemical mechanical polishing (CMP) of the copper surface; And cleaning the polished copper surface using the cleaning liquid composition.
이하 실시예 및 비교예를 통하여 본 발명을 더욱 상세히 설명한다. 다만, 이는 설명을 위한 것일 뿐, 본 발명이 이에 한정되는 것은 아니다.
Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, this is for illustrative purposes only, and the present invention is not limited thereto.
실시예Example 1-1 내지 1-1 to 실시예Example 3-2 3-2
아래의 표 1과 같은 조성의 세정액 조성물을 제조하였다.To prepare a cleaning solution composition of the composition shown in Table 1 below.
(중량%)Organic solvent
(weight%)
(중량%)Chelate reagents
(weight%)
(중량%)Corrosion inhibitor
(weight%)
이렇게 준비된 세정액 조성물 및 상용 세정액의 pH를 측정하고, 구리 웨이퍼를 1 시간 동안 담지하여 구리 웨이퍼 표면의 디스 칼라 (discolor) 여부를 확인하였다. The pH of the cleaning solution composition and the commercial cleaning solution thus prepared was measured, and the copper wafer was supported for 1 hour to check whether the copper wafer surface was discolored.
또한, 실시예 1-1 내지 3-2의 세정액 조성물을 이용하여 연마 화학기계적 연마 공정을 거친 구리 웨이퍼 표면을 세정한 후, 접촉각을 측정하였고, 표면의 세정 정도를 확인하기 위하여 FE-SEM (Field emission Electron microscope, 전계방출형 주사전자 현미경) 및 현미경 관찰을 수행하고 표면을 확인하였다.In addition, after cleaning the surface of the copper wafer subjected to the polishing chemical mechanical polishing process using the cleaning liquid composition of Examples 1-1 to 3-2, the contact angle was measured, and in order to check the degree of cleaning of the surface, FE-SEM (Field emission Electron microscope, field emission scanning electron microscope) and microscopic observation were performed to confirm the surface.
한편, 실시예 1-1, 2-1의 세정액 조성물을 1:50으로 희석하여 세정 과정을 수행하고, 4-point probe로 세정 전후 측정하여 그 차를 기초로 제거된 양을 나타내어 시간당 제거량을 확인함으로써 에칭율을 측정하였다.
On the other hand, the cleaning liquid composition of Example 1-1, 2-1 was diluted 1:50 to perform the cleaning process, and measured before and after washing with a 4-point probe to indicate the amount removed based on the difference to confirm the amount removed per hour. The etching rate was measured by doing this.
비교예Comparative example 1 내지 3 1 to 3
비교예로는 3 가지 상용 세정액을 사용하였다. 물성 측정 및 연마 공정 후 세정은 실시예와 동일한 방법으로 수행하였다.
Three commercial cleaning liquids were used as a comparative example. Measurement of physical properties and cleaning after the polishing process were performed in the same manner as in Example.
아래의 표 2는 실시예 1-1 내지 3-2의 세정액 조성물 및 비교예 1 내지 3의 상용 세정액의 물성과 이를 이용한 세정 후 표면 측정 결과를 정리한 것이다.Table 2 below summarizes the physical properties of the cleaning solution compositions of Examples 1-1 to 3-2 and the commercial cleaning solutions of Comparative Examples 1 to 3 and the surface measurement results after cleaning using the same.
접촉각After cleaning
Contact angle
(Å/min, 1:50희석)Etching rate
(Min / min, 1:50 dilution)
표 2에서 확인되듯이, pH에 있어서, 비교예 1 및 3의 상용 세정액 원액은 14 및 13의 강염기성을 나타내었으나, 본 발명의 실시예 1-1 내지 3-2의 세정액 조성물은 10.5 ~ 12 범위를 나타내었다. As confirmed in Table 2, in pH, the commercial wash solutions of Comparative Examples 1 and 3 exhibited strong bases of 14 and 13, but the cleaning solution compositions of Examples 1-1 to 3-2 of the present invention were 10.5 to 12. The range is shown.
한편, 실제 세정액의 사용에 있어서는 상당한 비율로 희석하여 사용함을 고려하여 희석 시의 pH의 변화가 작은 pH 안정성이 요구된다. 도 1은 본 발명의 실시예 1-1, 2-1 및 3-1의 세정액 조성물 및 비교예 1 내지 3의 상용 세정액의 희석비에 따른 pH 변화를 나타낸 그래프이다. 도 1에서 보듯이, 실시예 1-1 및 실시예 2-1의 경우, 희석비에 따른 pH 안정성이 매우 뛰어난 것을 확인할 수 있었다.On the other hand, in the use of the actual washing | cleaning liquid, in consideration of diluting in considerable ratio and using it, pH stability with small change of pH at the time of dilution is calculated | required. 1 is a graph showing the pH change according to the dilution ratio of the cleaning solution compositions of Examples 1-1, 2-1 and 3-1 of the present invention and the commercial cleaning solutions of Comparative Examples 1 to 3. As shown in Figure 1, in the case of Example 1-1 and Example 2-1, it was confirmed that the pH stability according to the dilution ratio is very excellent.
구리 웨이퍼를 1분간 담지한 후 접촉각을 측정한 결과, 본 발명의 실시예 1-1 내지 3-2는 44.5가 최대값이었으나, 비교예 1은 80.3의 큰 값을 나타내었다. As a result of measuring the contact angle after supporting the copper wafer for 1 minute, Examples 1-1 to 3-2 of the present invention had a maximum value of 44.5, but Comparative Example 1 showed a large value of 80.3.
한편, 구리 웨이퍼를 1시간 동안 담지한 후 관찰한 결과, 비교예 3은 변색 (discolor)이 심하게 발생하는 문제점이 발견되었으나, 본 발명의 실시예 1-1 내지 3-2는 이러한 변색이 발생하지 않았다. 비교예 3의 상용 세정액은 여타 물성에 있어서는 매우 우수하고, 실제로 가장 널리 사용되는 제품이나 상기와 같이 장시간 담지 시에 변색 발생의 문제가 있는데 반하여, 본 발명은 여타 물성에 있어서는 비교예 3의 우수한 상용 세정액과 동등 이상의 특성을 가지면서도 장시간 담지 시에도 변색이 발생하지 않아, 세정 공정의 운영에 있어서 탄력적, 효율적으로 적용 가능한 장점이 있음을 확인할 수 있었다.On the other hand, as a result of observing the copper wafer for one hour and observed, Comparative Example 3 was found to have a severe discolor (discolor) problem, Examples 1-1 to 3-2 of the present invention does not occur such a discoloration Did. The commercial cleaning solution of Comparative Example 3 is very excellent in the other physical properties, there is a problem of discoloration occurs in the case of the most widely used product or the long-term support as described above, the present invention is excellent commercial of Comparative Example 3 in other physical properties Discoloration does not occur even if it has a characteristic equivalent to that of the cleaning solution for a long time, it can be seen that there is an advantage that can be applied elastically and efficiently in the operation of the cleaning process.
화학기계적 연마 및 세정 후 표면을 현미경으로 관찰한 결과 표면 상태는 모두다 우수 또는 양호한 상태였으나, 표면을 FE-SEM 측정한 결과 비교예 2의 경우에는 결함이 발견되었다. After the surface was examined under a microscope after chemical mechanical polishing and cleaning, all of the surface conditions were excellent or good. However, when the surface was measured by FE-SEM, defects were found in Comparative Example 2.
도 2는 본 발명의 실시예 2-1의 세정액 조성물로 세정 공정을 수행한 후의 구리 표면의 TEM 이미지이고, 도 3은 비교예의 상용 세정액으로 세정 공정을 수행한 후의 구리 표면의 TEM 이미지이다.FIG. 2 is a TEM image of a copper surface after performing a cleaning process with the cleaning solution composition of Example 2-1 of the present invention, and FIG. 3 is a TEM image of a copper surface after performing a cleaning process with a commercial cleaning solution of Comparative Example.
상기와 같이 본 발명의 6가지 실시예 및 상용 세정액을 비교하여 측정 한 결과, 원액의 pH 및 희석 시의 pH 안정성, 접촉각, 장시간 담지 시의 변색 여부, 세정 후 표면의 세정 완성도, 표면 결함 여부, 에칭율에 있어서, 비교예에 비하여 본 발명의 세정액 조성물이 우수한 특성을 나타냄을 확인할 수 있었다.As a result of comparing and measuring the six embodiments of the present invention and the commercial cleaning solution as described above, the pH of the stock solution and pH stability when dilution, contact angle, whether or not discoloration when supporting for a long time, the cleanliness of the surface after cleaning, surface defects, In the etching rate, it was confirmed that the cleaning liquid composition of the present invention showed superior characteristics as compared with the comparative example.
Claims (8)
EDTA, 아르기닌 (arginine) 또는 이 둘을 포함하는 킬레이트 시약;
부식방지제; 및
순수 (純水);
를 포함하는 세정액 조성물.
Organic solvents comprising KOH, TMAH or both;
Chelating reagents comprising EDTA, arginine or both;
Preservatives; And
Pure water;
≪ / RTI >
상기 유기 용매는 상기 세정액 조성물 중 1 내지 10 중량%인 것을 특징으로 하는 세정액 조성물.
The method of claim 1,
The organic solvent is a cleaning liquid composition, characterized in that 1 to 10% by weight of the cleaning liquid composition.
상기 킬레이트 시약은 상기 세정액 조성물 중 1 내지 10 중량%인 것을 특징으로 하는 세정액 조성물.
The method of claim 1,
The chelating reagent is a cleaning liquid composition, characterized in that 1 to 10% by weight of the cleaning liquid composition.
According to claim 1, wherein the corrosion inhibitor is a cleaning liquid composition, characterized in that 0.2 to 2% by weight of the cleaning liquid composition.
The cleaning solution composition of claim 1, wherein the cleaning solution composition has a pH of 10 to 12.5.
The cleaning liquid composition according to claim 1, wherein the cleaning liquid composition has a contact angle of 45 or less on the copper surface cleaned with the cleaning liquid composition after a copper chemical mechanical polishing (CMP) process.
The cleaning liquid composition according to claim 1, wherein the cleaning liquid composition is used at a dilution ratio of 1:10 to 1: 100 when cleaning the copper surface after a copper chemical mechanical polishing (CMP) process.
연마된 구리 표면을 제1항 내지 제7항 중 한 항의 세정액 조성물을 이용하여 세정하는 단계;
를 포함하는 구리 화학기계적 연마 (CMP) 공정 세정방법.Chemical mechanical polishing (CMP) of the copper surface; And
Cleaning the polished copper surface using the cleaning liquid composition of claim 1;
(CMP) process. ≪ / RTI >
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020120013601A KR20130092096A (en) | 2012-02-10 | 2012-02-10 | Chemical mechanical polishing cleaning coposition and the cleaning method therewith |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020120013601A KR20130092096A (en) | 2012-02-10 | 2012-02-10 | Chemical mechanical polishing cleaning coposition and the cleaning method therewith |
Publications (1)
Publication Number | Publication Date |
---|---|
KR20130092096A true KR20130092096A (en) | 2013-08-20 |
Family
ID=49217016
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
KR1020120013601A KR20130092096A (en) | 2012-02-10 | 2012-02-10 | Chemical mechanical polishing cleaning coposition and the cleaning method therewith |
Country Status (1)
Country | Link |
---|---|
KR (1) | KR20130092096A (en) |
Cited By (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10988718B2 (en) | 2016-03-09 | 2021-04-27 | Entegris, Inc. | Tungsten post-CMP cleaning composition |
KR20210062543A (en) | 2019-11-21 | 2021-05-31 | 엘지전자 주식회사 | Treadmill |
KR20210062539A (en) | 2019-11-21 | 2021-05-31 | 엘지전자 주식회사 | Treadmill |
KR20210062540A (en) | 2019-11-21 | 2021-05-31 | 엘지전자 주식회사 | Treadmill |
KR20210062541A (en) | 2019-11-21 | 2021-05-31 | 엘지전자 주식회사 | Treadmill |
KR20210062538A (en) | 2019-11-21 | 2021-05-31 | 엘지전자 주식회사 | Treadmill |
KR20210062542A (en) | 2019-11-21 | 2021-05-31 | 엘지전자 주식회사 | Treadmill |
KR20210062537A (en) | 2019-11-21 | 2021-05-31 | 엘지전자 주식회사 | Treadmill |
KR20210063193A (en) | 2019-11-22 | 2021-06-01 | 엘지전자 주식회사 | Treadmill |
KR20210063192A (en) | 2019-11-22 | 2021-06-01 | 엘지전자 주식회사 | Treadmill |
KR20210063191A (en) | 2019-11-22 | 2021-06-01 | 엘지전자 주식회사 | Treadmill |
KR20210063190A (en) | 2019-11-21 | 2021-06-01 | 엘지전자 주식회사 | Treadmill |
KR20210063189A (en) | 2019-11-22 | 2021-06-01 | 엘지전자 주식회사 | Treadmill |
KR20210063194A (en) | 2019-11-22 | 2021-06-01 | 엘지전자 주식회사 | Treadmill |
KR20210064017A (en) | 2019-11-22 | 2021-06-02 | 엘지전자 주식회사 | Treadmill |
KR20210064014A (en) | 2019-11-22 | 2021-06-02 | 엘지전자 주식회사 | Treadmill |
-
2012
- 2012-02-10 KR KR1020120013601A patent/KR20130092096A/en active Search and Examination
Cited By (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10988718B2 (en) | 2016-03-09 | 2021-04-27 | Entegris, Inc. | Tungsten post-CMP cleaning composition |
KR20210063190A (en) | 2019-11-21 | 2021-06-01 | 엘지전자 주식회사 | Treadmill |
KR20210062543A (en) | 2019-11-21 | 2021-05-31 | 엘지전자 주식회사 | Treadmill |
KR20210062539A (en) | 2019-11-21 | 2021-05-31 | 엘지전자 주식회사 | Treadmill |
KR20210062540A (en) | 2019-11-21 | 2021-05-31 | 엘지전자 주식회사 | Treadmill |
KR20210062541A (en) | 2019-11-21 | 2021-05-31 | 엘지전자 주식회사 | Treadmill |
KR20210062538A (en) | 2019-11-21 | 2021-05-31 | 엘지전자 주식회사 | Treadmill |
KR20210062542A (en) | 2019-11-21 | 2021-05-31 | 엘지전자 주식회사 | Treadmill |
KR20210062537A (en) | 2019-11-21 | 2021-05-31 | 엘지전자 주식회사 | Treadmill |
KR20210063193A (en) | 2019-11-22 | 2021-06-01 | 엘지전자 주식회사 | Treadmill |
KR20210063191A (en) | 2019-11-22 | 2021-06-01 | 엘지전자 주식회사 | Treadmill |
KR20210063192A (en) | 2019-11-22 | 2021-06-01 | 엘지전자 주식회사 | Treadmill |
KR20210063189A (en) | 2019-11-22 | 2021-06-01 | 엘지전자 주식회사 | Treadmill |
KR20210063194A (en) | 2019-11-22 | 2021-06-01 | 엘지전자 주식회사 | Treadmill |
KR20210064017A (en) | 2019-11-22 | 2021-06-02 | 엘지전자 주식회사 | Treadmill |
KR20210064014A (en) | 2019-11-22 | 2021-06-02 | 엘지전자 주식회사 | Treadmill |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
KR20130092096A (en) | Chemical mechanical polishing cleaning coposition and the cleaning method therewith | |
TWI299885B (en) | Post chemical-mechanical planarization (cmp) cleaning composition | |
US6492308B1 (en) | Post chemical-mechanical planarization (CMP) cleaning composition | |
TWI507521B (en) | Copper passivating post-chemical mechanical polishing cleaning composition and method of use | |
US6546939B1 (en) | Post clean treatment | |
JP5561914B2 (en) | Semiconductor substrate cleaning liquid composition | |
KR101140970B1 (en) | Improved acidic chemistry for post-cmp cleaning | |
JP4550838B2 (en) | Improved alkaline chemical product for post-cleaning of chemical mechanical planarization | |
US9458415B2 (en) | Post chemical-mechanical-polishing (post-CMP) cleaning composition comprising a specific sulfur-containing compound and a sugar alcohol or a polycarboxylic acid | |
WO2003065433A1 (en) | Liquid detergent for semiconductor device substrate and method of cleaning | |
JP2008210990A (en) | Cleaning agent for semiconductor device, and cleaning method of semiconductor device using the same | |
JP2019502802A (en) | Cleaning composition after chemical mechanical polishing | |
KR20180091928A (en) | Chemical-mechanical-composition for cleaning after polishing | |
US20120080053A1 (en) | Method for cleaning of semiconductor substrate and acidic solution | |
US20040204329A1 (en) | Cleaning liquid composition for semiconductor substrate | |
US11066627B2 (en) | Cleaning agent composition for semiconductor device substrate, method of cleaning semiconductor device substrate, method of manufacturing semiconductor device substrate, and semiconductor device substrate | |
KR101572639B1 (en) | Post-cmp washiing liquid composition | |
US10844335B2 (en) | Composition for performing cleaning after chemical/ mechanical polishing | |
KR101323040B1 (en) | Cleaning solution composition and the cleaning method therewith | |
JP2015203047A (en) | Substrate cleaning liquid for semiconductor device and method for cleaning substrate for semiconductor device | |
KR102399811B1 (en) | Post metal film chemical mechanical polishing cleaning solution | |
KR101406761B1 (en) | Cleaning solution composition and the cleaning method therewith | |
US20230106132A1 (en) | Cleaning Composition for Post Chemical Mechanical Planarization And Method Of Using The Same |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A201 | Request for examination | ||
E902 | Notification of reason for refusal | ||
AMND | Amendment | ||
E601 | Decision to refuse application | ||
AMND | Amendment |