KR101856149B1 - Aqueous clean solution, method for mamufacturing a semiconductor device using the same, and semiconductor device - Google Patents
Aqueous clean solution, method for mamufacturing a semiconductor device using the same, and semiconductor device Download PDFInfo
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- KR101856149B1 KR101856149B1 KR1020160042225A KR20160042225A KR101856149B1 KR 101856149 B1 KR101856149 B1 KR 101856149B1 KR 1020160042225 A KR1020160042225 A KR 1020160042225A KR 20160042225 A KR20160042225 A KR 20160042225A KR 101856149 B1 KR101856149 B1 KR 101856149B1
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- 239000004065 semiconductor Substances 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 title claims description 24
- 238000004140 cleaning Methods 0.000 claims abstract description 65
- 239000000203 mixture Substances 0.000 claims abstract description 59
- 239000007788 liquid Substances 0.000 claims abstract description 31
- -1 alkylamino alcohol Chemical compound 0.000 claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 claims abstract description 10
- 239000000908 ammonium hydroxide Substances 0.000 claims abstract description 7
- 125000001453 quaternary ammonium group Chemical group 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 230000007797 corrosion Effects 0.000 claims description 22
- 238000005260 corrosion Methods 0.000 claims description 22
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 21
- 125000003282 alkyl amino group Chemical group 0.000 claims description 18
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 claims description 13
- 239000003112 inhibitor Substances 0.000 claims description 11
- 239000003960 organic solvent Substances 0.000 claims description 9
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 6
- 238000005498 polishing Methods 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 6
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 claims description 5
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 5
- SNAQINZKMQFYFV-UHFFFAOYSA-N 1-[2-[2-(2-methoxyethoxy)ethoxy]ethoxy]butane Chemical compound CCCCOCCOCCOCCOC SNAQINZKMQFYFV-UHFFFAOYSA-N 0.000 claims description 3
- WFSMVVDJSNMRAR-UHFFFAOYSA-N 2-[2-(2-ethoxyethoxy)ethoxy]ethanol Chemical compound CCOCCOCCOCCO WFSMVVDJSNMRAR-UHFFFAOYSA-N 0.000 claims description 3
- 229920001174 Diethylhydroxylamine Polymers 0.000 claims description 3
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 claims description 3
- 229960005070 ascorbic acid Drugs 0.000 claims description 3
- 235000010323 ascorbic acid Nutrition 0.000 claims description 3
- 239000011668 ascorbic acid Substances 0.000 claims description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 3
- 229940043237 diethanolamine Drugs 0.000 claims description 3
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 claims description 3
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 claims description 3
- FVCOIAYSJZGECG-UHFFFAOYSA-N diethylhydroxylamine Chemical compound CCN(O)CC FVCOIAYSJZGECG-UHFFFAOYSA-N 0.000 claims description 3
- KYWXRBNOYGGPIZ-UHFFFAOYSA-N 1-morpholin-4-ylethanone Chemical compound CC(=O)N1CCOCC1 KYWXRBNOYGGPIZ-UHFFFAOYSA-N 0.000 claims description 2
- IWSZDQRGNFLMJS-UHFFFAOYSA-N 2-(dibutylamino)ethanol Chemical compound CCCCN(CCO)CCCC IWSZDQRGNFLMJS-UHFFFAOYSA-N 0.000 claims description 2
- KKFDCBRMNNSAAW-UHFFFAOYSA-N 2-(morpholin-4-yl)ethanol Chemical compound OCCN1CCOCC1 KKFDCBRMNNSAAW-UHFFFAOYSA-N 0.000 claims description 2
- GVNHOISKXMSMPX-UHFFFAOYSA-N 2-[butyl(2-hydroxyethyl)amino]ethanol Chemical compound CCCCN(CCO)CCO GVNHOISKXMSMPX-UHFFFAOYSA-N 0.000 claims description 2
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 claims description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 2
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 2
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims description 2
- 239000000600 sorbitol Substances 0.000 claims description 2
- LJDSTRZHPWMDPG-UHFFFAOYSA-N 2-(butylamino)ethanol Chemical compound CCCCNCCO LJDSTRZHPWMDPG-UHFFFAOYSA-N 0.000 claims 1
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 28
- 230000000052 comparative effect Effects 0.000 description 24
- 239000010949 copper Substances 0.000 description 16
- 239000002245 particle Substances 0.000 description 11
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 6
- 239000012964 benzotriazole Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000003599 detergent Substances 0.000 description 5
- 238000010790 dilution Methods 0.000 description 5
- 239000012895 dilution Substances 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- LCEDQNDDFOCWGG-UHFFFAOYSA-N morpholine-4-carbaldehyde Chemical compound O=CN1CCOCC1 LCEDQNDDFOCWGG-UHFFFAOYSA-N 0.000 description 4
- 235000012431 wafers Nutrition 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000005416 organic matter Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 150000005622 tetraalkylammonium hydroxides Chemical class 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 208000000059 Dyspnea Diseases 0.000 description 1
- 206010013975 Dyspnoeas Diseases 0.000 description 1
- 206010033799 Paralysis Diseases 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 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
- 239000007864 aqueous solution Substances 0.000 description 1
- SAOKZLXYCUGLFA-UHFFFAOYSA-N bis(2-ethylhexyl) adipate Chemical compound CCCCC(CC)COC(=O)CCCCC(=O)OCC(CC)CCCC SAOKZLXYCUGLFA-UHFFFAOYSA-N 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229940031098 ethanolamine Drugs 0.000 description 1
- LIWAQLJGPBVORC-UHFFFAOYSA-N ethylmethylamine Chemical compound CCNC LIWAQLJGPBVORC-UHFFFAOYSA-N 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N monoethanolamine hydrochloride Natural products NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- 210000003205 muscle Anatomy 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000001007 puffing effect Effects 0.000 description 1
- 238000004439 roughness measurement Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
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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
- C11D7/26—Organic compounds containing oxygen
- C11D7/261—Alcohols; Phenols
-
- C11D11/0047—
-
- 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
- C11D11/00—Special methods for preparing compositions containing mixtures of detergents
- C11D11/0094—Process for making liquid detergent compositions, e.g. slurries, pastes or gels
-
- 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
-
- 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
- H01L21/02041—Cleaning
- H01L21/02043—Cleaning before device manufacture, i.e. Begin-Of-Line process
- H01L21/02052—Wet cleaning only
-
- 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
-
- 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
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
- H01L21/30625—With simultaneous mechanical treatment, e.g. mechanico-chemical polishing
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/10—Objects to be cleaned
- C11D2111/14—Hard surfaces
- C11D2111/22—Electronic devices, e.g. PCBs or semiconductors
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- Life Sciences & Earth Sciences (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Cleaning Or Drying Semiconductors (AREA)
- Detergent Compositions (AREA)
Abstract
본 발명은 4차 암모늄 하이드록사이드를 포함하지 않으며, 알킬아미노알코올 1 ~ 15 중량%, 모폴린 0.1 ~ 5 중량%, 및 잔량의 물을 포함하는 세정액 조성물 및 그 세정액 조성물을 사용하는 반도체 소자의 제조방법 및 반도체 소자에 관하 것이다. The present invention relates to a cleaning liquid composition which does not contain quaternary ammonium hydroxide and which contains 1 to 15% by weight of an alkylamino alcohol, 0.1 to 5% by weight of a mofoline, and a residual amount of water, and a cleaning liquid composition comprising the cleaning liquid composition A manufacturing method thereof, and a semiconductor device.
Description
본 발명은 반도체 소자의 제조 공정에서 사용되는 세정액 조성물, 그 세정액 조성물을 사용하는 반도체 소자의 제조방법, 및 반도체 소자에 관한 것이다. The present invention relates to a cleaning liquid composition used in a manufacturing process of a semiconductor device, a method of manufacturing a semiconductor device using the cleaning liquid composition, and a semiconductor device.
반도체 공정에서 소자의 고집적화에 따른 RC delay, electromigration 등의 문제점이 발생 되며 이러한 문제를 해결하기 위해 금속 배선형성 재료가 알루미늄(Al)에서 구리(Cu)로 대체되고 있다.There are problems such as RC delay and electromigration due to high integration of devices in a semiconductor process. In order to solve this problem, a metal wiring forming material is replaced by aluminum (Al) to copper (Cu).
구리 배선을 형성하기 위해 다마신(damascene) 공정이 사용되며 증착 시킨 후 잔존하거나 과 증착된 구리막질을 제거하기 위하여 연마제, 산화제, 착물 형성제 및 부식 방지제등으로 구성된 슬러리를 사용하여, 일정 압력과 회전 속도로 화학-기계적 연마(CMP) 공정을 통해 기판의 평탄화를 진행하고 있다.A damascene process is used to form the copper interconnects and a slurry composed of an abrasive, an oxidizing agent, a complexing agent and a corrosion inhibitor is used to remove remaining or over-deposited copper film after deposition, The substrate is being planarized through a chemical-mechanical polishing (CMP) process at a rotational speed.
화학-기계적 연마(CMP) 공정 진행 후 유기 잔사, 슬러리 입자 등의 불순물이 기판 표면에 잔류하여 패턴 결합 불량 등의 심각한 문제를 일으킬 수 있다. 따라서 이들 공정 후 불순물을 제거하고 후속 공정의 진행을 위해서 Post CMP cleaning 공정이 필수적으로 진행되고 있다.Impurities such as organic residues and slurry particles remain on the surface of the substrate after the chemical mechanical polishing (CMP) process, which can cause serious problems such as poor pattern bonding. Therefore, Post CMP cleaning process is essential for removing impurities after these processes and proceeding the subsequent process.
Post CMP cleaning 공정에 사용되는 종래의 세정액 조성물로서 국제출원번호 “PCT/US2001/018402”는 테트라알킬암모늄 하이드록사이드로 등의 4차 암모늄 하이드록사이드, 유기 아민 및 물, 부식 억제제를 함유하는 세정 조성물을 기재하고 있다.International application number " PCT / US2001 / 018402 " as a conventional cleaning fluid composition used in a post CMP cleaning process includes cleaning with a quaternary ammonium hydroxide such as tetraalkylammonium hydroxide, organic amine and water, ≪ / RTI >
또한, 국제출원번호 “PCT/US2013/031299”는 TMAH, 아민, 아졸 부식 억제제, 환원제, 하나 이상의용매로 이루어진 세정 조성물을 기재하고 있다.In addition, international application number " PCT / US2013 / 031299 " describes a cleaning composition comprising TMAH, amine, azole corrosion inhibitor, reducing agent and at least one solvent.
또한, 국제출원번호 “PCT/US2013/041634”에서는 4급 염기, 아민, 부식 억제제, 하나 이상의 용매로 이루어진 세정 조성물을 기재하고 있다.In addition, international application number " PCT / US2013 / 041634 " describes a cleaning composition consisting of quaternary base, amine, corrosion inhibitor and at least one solvent.
그러나, 이러한 종래의 Post CMP cleaning 제품들의 경우 모두 테트라메틸 암모늄 하이드록 사이드(TMAH)를 포함하고 있는데, TMAH는 호흡 곤란이나 근육마비를 유발시킨다고 보고되고 있다. 그러므로 TMAH를 포함하지 않는 제품의 개발이 요구되고 있다.However, all of these conventional post CMP cleaning products include tetramethylammonium hydroxide (TMAH), which is reported to cause dyspnea and muscle paralysis. Therefore, development of a product that does not include TMAH is required.
본 발명은 상기와 같은 종래기술의 문제를 해소하기 위하여 안출된 것으로서,테트라알킬암모늄 하이드록사이드로 등의 4차 암모늄 하이드록사이드를 포함하지 않아서 인체에 안전하면서도, 오염 물질을 세정능력이 우수하고, 금속과 베리어 금속 간의 갈바닉 부식에 안정적이며, 부식방지성능이 우수하며, 희석에 따르는 pH의 변화 및 제타전위의 변화도 크지 않은 세정액 조성물을 제공하는 것을 목적으로 한다.Disclosure of Invention Technical Problem [8] Accordingly, the present invention has been made in order to solve the problems of the prior art as described above, and it is an object of the present invention to provide a cleaning composition which does not contain quaternary ammonium hydroxide such as tetraalkylammonium hydroxide, , Which is stable to galvanic corrosion between a metal and a barrier metal, has excellent corrosion resistance, and does not change pH or change zeta potential with dilution.
또한, 본 발명은 상기 세정액 조성물을 사용하여 제조되는 반도체 소자의 제조방법을 제공하는 것을 목적으로 한다.It is another object of the present invention to provide a method of manufacturing a semiconductor device manufactured using the cleaning composition.
또한, 본 발명은 상기 제조방법에 의해 제조되는 반도체 소자를 제공한다.The present invention also provides a semiconductor device manufactured by the above manufacturing method.
본 발명은 4차 암모늄 하이드록사이드를 포함하지 않으며,The present invention does not include quaternary ammonium hydroxide,
알킬아미노알코올 1 ~ 15 중량%, 모폴린 0.1 ~ 5 중량%, 및 잔량의 물을 포함하는 세정액 조성물을 제공한다. 1 to 15% by weight of alkylamino alcohol, 0.1 to 5% by weight of morpholine, and the balance water.
또한, 본 발명은In addition,
화학-기계적 연마(CMP) 공정을 수행한 기판을 상기의 세정액 조성물로 세정하는 공정을 포함하는 반도체 소자의 제조방법을 제공한다.And a step of cleaning the substrate subjected to the chemical mechanical polishing (CMP) process with the cleaning liquid composition described above.
또한, 본 발명은In addition,
상기의 제조방법에 의해 제조되는 반도체 소자를 제공한다.A semiconductor device manufactured by the above manufacturing method is provided.
본 발명에 따른 세정액 조성물은 유해 물질로 규정된 테트라메틸 암모늄 하이드록 사이드(TMAH)를 사용하지 않아 인체에 안전하며, 유기물 및 파티클 등을 효과적으로 세정하며, 세정액에 노출되는 막질(Cu, Ta, Ti, TaN, TiN, Low-K, Co)에 대한 부식방지성능(금속과 베리어 금속 간의 갈바닉 부식 포함)이 우수한 효과를 제공한다. The cleaning liquid composition according to the present invention does not use tetramethylammonium hydroxide (TMAH) defined as a harmful substance, so it is safe for a human body, effectively cleans organic matters and particles, , TaN, TiN, Low-K, Co) (including galvanic corrosion between metal and barrier metal).
또한, 희석에 따르는 pH의 변화 및 제타전위의 변화도 크지 않은 넓은 범위에서 사용할 수 있으며, 파티클의 재 흡착 방지를 통해 반도체 소자 제조 수율을 향상 시키는 효과를 제공한다. In addition, it can be used in a wide range in which the change in pH and the change in zeta potential according to dilution is not large, and the yield of semiconductor device manufacture is improved through prevention of re-adsorption of particles.
도 1 은 본 발명의 실시예 9의 세정액 조성물을 사용하는 Cu 시편에 대한 30 min 처리 전, 후에 대한 AFM Roughness(10X10㎛)를 측정한 이미지이다.
도 2 는 TMAH가 혼합된 비교예 5의 세정액 조성물을 사용하는 Cu 시편 30 min 처리 전, 후에 대한 AFM Roughness(10X10㎛)를 측정한 이미지이다.
도 3은 본 발명의 실시예 8로 세정한 웨이퍼에 대하여 Defect 측정 장비를 이용하여 파티클을 측정한 이미지이다.
도 4는 본 발명의 실시예 8의 세정액 조성물에 의한 유기물 세정 전, 후에 대한 FT-IR 측정 이미지이다.FIG. 1 is an image of AFM roughness (10 × 10 μm) measured before and after 30 min treatment of a Cu specimen using the cleaning liquid composition of Example 9 of the present invention.
FIG. 2 is an image of AFM roughness (10 × 10 μm) measured before and after 30 min of Cu specimen using the cleaning composition of Comparative Example 5 in which TMAH was mixed.
FIG. 3 is an image of particles measured using a defect measuring apparatus for a wafer cleaned in Example 8 of the present invention. FIG.
4 is an FT-IR measurement image of the cleaning liquid composition of Example 8 of the present invention before and after cleaning the organic material.
본 발명은 4차 암모늄 하이드록사이드를 포함하지 않으며, 알킬아미노알코올 1 ~ 15 중량%, 모폴린 0.1 ~ 5 중량%, 및 잔량의 물을 포함하는 세정액 조성물에 관한 것이다.The present invention relates to a cleaning composition which does not contain quaternary ammonium hydroxide, but which comprises from 1 to 15% by weight of alkylamino alcohol, from 0.1 to 5% by weight of mofoline, and a balance of water.
상기 세정액 조성물은 특히, 화학-기계적 연마(CMP) 공정 후의 세정용으로 바람직하게 사용될 수 있다. The cleaning composition may preferably be used particularly for cleaning after a chemical-mechanical polishing (CMP) process.
4차 암모늄 하이드록사이드로는 대표적으로 테트라메틸 암모늄 하이드록 사이드(TMAH) 등을 들 수 있으며, 이러한 물질은 인체에 유해하기 때문에 본 발명의 세정제 조성물에 포함하지 않는다. 본 발명의 세정제 조성물은 상기와 같은 인체 유해성분을 포함하지 않으면서도 우수한 세정특성을 나타내는 것을 특징으로 한다. As the quaternary ammonium hydroxide, tetramethylammonium hydroxide (TMAH) and the like may be exemplified. These substances are not included in the detergent composition of the present invention because they are harmful to human body. The detergent composition of the present invention is characterized in that it exhibits excellent cleaning characteristics without containing such harmful components.
본 발명의 세정제 조성물은 0.05 ~ 5 중량%의 유기용매 및 0.1 ~ 5 중량%의 부식 억제제 중에서 선택되는 1종 이상을 더 포함할 수 있다. The detergent composition of the present invention may further include at least one selected from 0.05 to 5 wt% of organic solvent and 0.1 to 5 wt% of corrosion inhibitor.
이하에서, 세정제 조성물을 구성하는 각각의 성분에 대항 자세히 설명한다.In the following, each component constituting the detergent composition will be described in detail.
(a) (a) 알킬아미노알코올Alkyl amino alcohol
상기 알킬아미노알코올은 본 발명 유기물 및 파티클을 제거하는 주성분으로서 본 발명에 포함된다. 상기 알킬아미노알코올은 1 ~ 15 중량%로 사용될 수 있으며, 더욱 바람직하게는 5~11 중량%로 사용될 수 있다. 상기 알킬아미노알코올이 1 중량% 미만으로 포함되면 유기물 및 파티클에 대한 세정력이 너무 약해지며, 15 중량%를 초과하면 부식력이 너무 강해지기 때문에 바람직하지 않다.The alkylamino alcohol is included in the present invention as a main component for removing the organics and particles of the present invention. The alkylamino alcohol may be used in an amount of 1 to 15% by weight, more preferably 5 to 11% by weight. If the alkyl amino alcohol is contained in an amount of less than 1% by weight, the detergency against organic substances and particles becomes too weak, and if it exceeds 15% by weight, the corrosion power becomes too strong.
상기 알킬아미노알코올로는 2차 알킬아미노알코올 및 3차 알킬아미노알코올로 이루어진 군으로부터 선택되는 2종 이상의 알킬아미노알코올이 바람직하게 사용될 수 있다. 그리고, 1차 알킬아미노알코올은 부식력이 너무 강하므로 사용하지 않는 것이 바람직하다.As the alkyl amino alcohol, two or more kinds of alkyl amino alcohols selected from the group consisting of secondary alkyl amino alcohols and tertiary alkyl amino alcohols can be preferably used. It is preferable that the primary alkyl amino alcohol is not used because it has too strong a corrosive power.
상기와 같이 2종 이상의 알킬아미노알코올이 사용되는 경우 일정한 알칼리 세기를 유지하여 세정 및 부식의 안정성을 가져올 수 있기 때문에 바람직하다. When two or more kinds of alkylamino alcohols are used as described above, they are preferable because they can maintain a constant alkaline strength and provide stability of washing and corrosion.
상기 알킬아미노알코올은 2차 알킬아미노알코올 1종 이상 및 3차 알킬아미노알코올로 1종 이상을 포함하는 것이 더욱 바람직하다. 왜냐하면 2차 알킬아미노알코올은 세정성이 우수한 반면 너무 과량으로 사용되면 부식성이 증가하여 바람직하지 않기 때문이다. 따라서 2차 알킬아미노알코올은 세정성 및 부식 방지성이 모두 우수한 3차 알킬아미노알코올과 함께 사용되는 것이 바람직하다.It is more preferable that the alkylamino alcohol includes at least one kind of secondary alkyl amino alcohol and at least one tertiary alkyl amino alcohol. This is because secondary alkyl amino alcohols are excellent in cleansing properties, whereas when they are used in too much amounts, they are not desirable because of increased corrosiveness. It is therefore preferred that the secondary alkyl amino alcohol be used in combination with tertiary alkyl amino alcohols which are both excellent in cleansing and corrosion inhibition.
상기에서 2차 알킬아미노알코올과 3차 알킬아미노알코올은 중량비로 1:5 ~ 5:1로 포함될 수 있으며, 더욱 바람직하게는 4:1~2:1의 중량비로 사용될 수 있다. The weight ratio of the secondary alkyl amino alcohol to the tertiary alkyl amino alcohol may be 1: 5 to 5: 1, more preferably 4: 1 to 2: 1.
상기 2차 알킬아미노알코올로는 부틸에탄올아민, 메틸에탄올아민, 다이에탄올아민 등이 사용될 수 있으며, 특히, 메틸에탄올아민이 바람직하게 사용될 수 있다. As the secondary alkyl amino alcohol, butyl ethanol amine, methyl ethanol amine, diethanol amine and the like can be used. In particular, methyl ethanol amine is preferably used.
상기 3차 알킬아미노알코올로는 부틸다이에탄올아민, 다이부틸에탄올아민, 다이에틸에탄올아민, 메틸다이에탄올아민, 메틸다이이소프로판올아민, 트리에탄올아민 등이 사용될 수 있으며, 특히, 트리에탄올아민, 메틸다이이소프로파놀아민이 바람직하게 사용될 수 있다. Examples of the tertiary alkylamino alcohol include butyldiethanolamine, dibutylethanolamine, diethylethanolamine, methyldiethanolamine, methyldiisopropanolamine, triethanolamine, and the like. Particularly, triethanolamine, methyldiisopropyl Phenolamine can be preferably used.
(b) (b) 모폴린Morpholine
본 발명의 세정액 조성물에서 모폴린은 pH 조정제 기능 및 약액의 Bubble을 소포하는 역할을 수행한다. 상기 모폴린은 0.1 ~ 5 중량%로 포함되며, 더욱 바람직하게는 0.5~3 중량%로 포함될 수 있다. 모폴린이 0.1 중량% 미만으로 포함되는 경우_pH 조정 및 소포가능이 미비하여 문제가 발생할 수 있으며, 5 중량%를 초과하는 경우 비 경제적인 문제가 발생될 수 있다. In the cleaning liquid composition of the present invention, morpholine functions to purify the pH adjuster function and the bubble of the chemical liquid. The morpholine may be contained in an amount of 0.1 to 5% by weight, more preferably 0.5 to 3% by weight. If the content of mofoline is less than 0.1% by weight, the adjustment of the pH can be difficult and the problem of puffing may occur. If the content exceeds 5% by weight, uneconomical problems may occur.
상기 모폴린으로는 N-메틸 모폴린, 모폴린, N-아세틸 모폴린, 4-(2-하이드록시에틸)모폴린, 2,2'-다이모폴리노다이에틸에테르, N-포름밀 모폴린 등을 들 수 있으며, N-메틸 모폴린, 모폴린, N-포름밀 모폴린 등이 더욱 바람직하게 사용될 수 있다Examples of the morpholine include N-methylmorpholine, morpholine, N-acetylmorpholine, 4- (2-hydroxyethyl) morpholine, 2,2'-diphosphoronodiethylether, , And N-methylmorpholine, morpholine, N-formylmorpholine and the like can be more preferably used
(c) (c) 유기용매Organic solvent
상기 유기용매는 공정에서 발생하는 Bubble을 소포하는 역할을 수행한다. 상기 유기용매는 0.05 ~ 5 중량%로 포함될 수 있으며, 0.1~0.5 중량%로 포함되는 것이 더욱 바람직하다. 유기용매가 0.05 중량% 미만으로 포함되는 경우 Bubble 소포 성능이 떨어지는 문제가 발생할 수 있으며, 5 중량%를 초과하는 경우 비경제적인 문제가 발생될 수 있다. The organic solvent plays a role of expelling bubbles generated in the process. The organic solvent may be contained in an amount of 0.05 to 5% by weight, more preferably 0.1 to 0.5% by weight. If the amount of the organic solvent is less than 0.05% by weight, the performance of the bubble vesicle may be deteriorated. If the amount of the organic solvent is more than 5% by weight, uneconomical problems may occur.
상기 유기용매로는 디에틸렌글리콜모노에틸에테르, 트리에틸렌글리콜부틸메틸에테르, 트리에틸렌글리콜에틸에테르 등이 사용될 수 있으며, 이들로 한정되는 것은 아니다.Examples of the organic solvent include diethylene glycol monoethyl ether, triethylene glycol butyl methyl ether, triethylene glycol ethyl ether, and the like, but are not limited thereto.
(d) 부식 억제제(d) Corrosion inhibitor
상기 부식 억제제로는 N,N-다이에틸하이드록실아민, 아스코르브산, 피라졸, 솔비톨 등이 사용될 수 있다. 상기 부식 억제제는 0.1 ~ 5 중량%로 포함될 수 있으며, 더욱 바람직하게는 0.1~2 중량%로 포함될 수 있다. 부식 방지제가 0.1 중량% 미만으로 포함되는 경우_부식 방지 성능이 떨어지는 문제가 발생할 수 있으며, 5 중량%를 초과하는 경우 막질 표면에 침착되는 문제가 발생될 수 있다.As the corrosion inhibitor, N, N-diethylhydroxylamine, ascorbic acid, pyrazole, sorbitol and the like can be used. The corrosion inhibitor may be contained in an amount of 0.1 to 5% by weight, more preferably 0.1 to 2% by weight. When the corrosion inhibitor is contained in an amount of less than 0.1% by weight, corrosion resistance may be deteriorated. If the corrosion inhibitor is added in an amount exceeding 5% by weight, deposition on the surface of the membrane may occur.
(e) 물(e) Water
상기 물로는 탈이온수가 바람직하게 사용될 수 있으며, 상기 성분들의 함량을 포함하는 조성물의 총 중량이 100 중량%가 되게 하는 잔량으로 포함될 수 있다.As the water, deionized water may be preferably used, and may be included as a residual amount such that the total weight of the composition including the content of the components becomes 100% by weight.
본 발명의 세정제 조성물은 상기 성분들 이외에 이 분야에서 통상적으로 사용되는 첨가제들을 더 포함할 수 있다.The detergent composition of the present invention may further comprise additives commonly used in this field in addition to the above components.
또한, 본 발명은In addition,
기판에 대한 화학-기계적 연마(CMP) 공정을 수행한 후에 청구항 1의 세정액 조성물로 상기 기판을 세정하는 공정을 포함하는 반도체 소자의 제조방법에 관한 것이다.(CMP) process for the substrate, followed by cleaning the substrate with the cleaning composition of
또한, 본 발명은 상기 제조방법에 의해 제조되는 반도체 소자에 관한 것이다.The present invention also relates to a semiconductor device manufactured by the above manufacturing method.
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. 하기의 실시예는 본 발명의 범위 내에서 당업자에 의해 적절히 수정, 변경될 수 있다. 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. The following examples can be appropriately modified and changed by those skilled in the art within the scope of the present invention.
실시예Example 1~11 및 1 to 11 and 비교예Comparative Example 1~6: 세정액 조성물의 제조 1 to 6: Preparation of cleaning liquid composition
하기 표 1, 표2에 기재된 성분을 해당 조성비로 혼합하여 실시예 1~11 및 비교예 1~6의 세정액 조성물을 제조하였다.The cleaning liquid compositions of Examples 1 to 11 and Comparative Examples 1 to 6 were prepared by mixing the components listed in Tables 1 and 2 at the composition ratios.
주) week)
BEA: ButhylethanolamineBEA: Buthylethanolamine
NMEA: N-methylethanolamineNMEA: N-methylethanolamine
MDIA: MethyldiisopropanolamimeMDIA: Methyldiisopropanolamime
TEA: TriethanolamineTEA: Triethanolamine
DEA: DiethanolamineDEA: Diethanolamine
NMM: N-methylmorpholineNMM: N-methylmorpholine
MP: MorpholineMP: Morpholine
NFM: N-formylmorpholineNFM: N-formylmorpholine
EDG: Diethylene glycol monoethyl etherEDG: Diethylene glycol monoethyl ether
MBTG: Triethyleneglycol butyl methyl etherMBTG: Triethyleneglycol butyl methyl ether
ETG: Triethylene glycol ethyl etherETG: Triethylene glycol ethyl ether
DEHA: DiethylhydroxylamineDEHA: Diethylhydroxylamine
AC: AscorbicacidAC: Ascorbicacid
PRZ: PyrazolePRZ: Pyrazole
시험예Test Example 1: 세정 성능 평가 1: Evaluation of cleaning performance
(1) Particle 세정 성능(1) Particle cleaning performance
Cu 웨이퍼, T-oxide 웨이퍼에 대하여 ILD 슬러리와 Cu 슬러리를 이용하여 CMP 공정을 진행한 후, 세정 전 Particle 개수를 측정하였다.Cu and T-oxide wafers were subjected to a CMP process using an ILD slurry and a Cu slurry, and then the number of particles before cleaning was measured.
GnP-Brochure-Cleaner812L 장비를 이용하여 표1의 실시예 1~8 및 비교예 1~5의 세정액 조성물로 상기 웨이퍼들을 세정한 후, 세정 성능을 평가하였다. 상기 평가결과는 하기 표 2에 나타내었다. 하기 표 2의 세정 결과는 상대적인 비교 결과를 나타낸다. 또한, 실시예 8로 세정한 웨이퍼에 대하여 Defect 측정 장비를 이용하여 Particle을 측정한 이미지를 도 3에 도시하였다.The wafers were cleaned with the cleaning liquid compositions of Examples 1 to 8 and Comparative Examples 1 to 5 of Table 1 using GnP-Brochure-Cleaner 812L equipment, and then the cleaning performance was evaluated. The evaluation results are shown in Table 2 below. The cleaning results in Table 2 below show the relative comparison results. 3 shows an image obtained by measuring a particle using a Defect measurement equipment for a wafer cleaned in Example 8. FIG.
(2)(2) 유기물 제거 성능Organic matter removal performance
CMP Slurry에 포함되어 있는 벤조트리아졸의 경우 Cu와 결합하여 매우 강한 Complex를 형성하며, 후속 공정을 어렵게 만든다. 따라서, 표1의 실시예 1~8 및 비교예 1~5의 세정액 조성물의 벤조트리아졸에 대한 제거 성능의 평가를 다음과 같이 실시하였다.In the case of benzotriazole contained in CMP slurry, it forms a very strong complex with Cu and makes subsequent process difficult. Therefore, the removal performance of the cleaning liquid compositions of Examples 1 to 8 and Comparative Examples 1 to 5 in Table 1 for benzotriazole was evaluated as follows.
Cu 시편에 형성된 oxide 막질을 제거하기 위하여 아세트산 수용액에 30sec dipping 처리를 한 후 DIW 린스를 60sec 동안 수행하였다. 표면 처리한 Cu 시편을 벤조트리아졸 수용액에 60sec dipping시키고 DIW 린스를 30sec 처리한 후 FT-IR 장비를 이용하여 Cu 표면에 형성된 벤조트리아졸을 측정하였다.In order to remove the oxide film formed on the Cu specimen, an aqueous acetic acid solution was dipped for 30 seconds and then DIW rinsing was performed for 60 seconds. The surface-treated Cu specimens were dipped in a benzotriazole aqueous solution for 60 seconds, treated with a DIW rinse for 30 seconds, and the benzotriazole formed on the Cu surface was measured using FT-IR equipment.
벤조트리아졸로 오염시킨 시편을 상기 실시예 1~8 및 비교예 1~5의 각의 세정액 조성물에 각 60sec dipping한 후 DIW로 린스하고 N2로 건조하여 벤조트리아졸의 제거 유무를 FT-IR 측정을 통해 확인 한 후, 그 결과를 하기 표 3에 기재하였다. 또한, 도 4에 실시예 8의 세정액 조성물로 유기물을 세정하기 전과 후의 FT-IR 측정 이미지를 나타내었다.The specimens contaminated with benzotriazole were each dipped in the cleaning composition compositions of Examples 1 to 8 and Comparative Examples 1 to 5 for 60 seconds, rinsed with DIW, and dried with
(상대적 결과)Remove Particle
(Relative result)
<평가기준><Evaluation Criteria>
◎: 완전 제거, ○: 0.0005% 이하 잔존, △: 0.001% 이하 잔존, X: 0.001% 초과 잔존?: Completely removed,?: Not more than 0.0005%,?: Not more than 0.001%, X: not more than 0.001% Remaining
상기 표 1에서 확인되는 바와 같이, 본 발명의 세정액 조성물(실시예 1~8)은 TMAH가 포함된 비교예 1~5의 세정액 조성보다 파티클 제거 및 유기물 제거 능력에서 더 우수한 효과를 나타내었다. As can be seen in Table 1, the cleaning liquid compositions of the present invention (Examples 1 to 8) showed better effects on particle removal and organic matter removal than the cleaning liquid compositions of Comparative Examples 1 to 5 containing TMAH.
시험예Test Example 2: 부식 성능 평가 2: Corrosion performance evaluation
(1) Roughness 측정(1) Roughness measurement
실시예 8~11의 세정액 조성물과 비교예 5의 세정액 조성물의 부식 성능 평가를 통해 본 발명의 세정액 조성물의 부식 억제 성능을 평가하였다.Corrosion inhibiting performance of the cleaning liquid composition of the present invention was evaluated through evaluation of corrosion performance of the cleaning liquid compositions of Examples 8 to 11 and Comparative Example 5.
2,000Å의 두께로 증착된 Cu 시편을 실시예 8~11의 세정액 조성물과 비교예 5의 각 세정액 조성물에 1min, 10min, 20min, 30min간 dipping하고 DIW로 린스 한 후, AFM Roughness를 측정하고, 그 결과를 하기 표 3에 나타내었다. 상기에서 실시예 8에 Cu 시편을 30 min 간 dipping한 결과를 도 1에 나타내고, 비교예 5에 Cu 시편을 30 min 간 dipping한 결과를 도 2에 나타내었다. The Cu specimens deposited at a thickness of 2,000 ANGSTROM were dipped in the cleaning liquid compositions of Examples 8 to 11 and the cleaning liquid compositions of Comparative Example 5 for 1 min, 10 min, 20 min and 30 min, rinsed with DIW, and AFM roughness was measured. The results are shown in Table 3 below. FIG. 1 shows the result of dipping the Cu specimen in Example 8 for 30 min, and FIG. 2 shows the results of dipping the Cu specimen in Comparative Example 5 for 30 min.
상기 표 3에서 확인되는 바와 같이, 본 발명의 세정액 조성물(실시예 8~11)은 TMAH가 포함된 비교예 5의 세정액 조성물과 비교하여 동등 이상의 부식억제성능을 가짐을 알 수 있다. As can be seen from the above Table 3, it can be seen that the cleaning liquid compositions of the present invention (Examples 8 to 11) have corrosion inhibition performance equal to or greater than that of the cleaning liquid composition of Comparative Example 5 containing TMAH.
(2) Etch rate 측정(2) Etch rate measurement
실시예 8~11의 세정액 조성물과 비교예 5의 세정액 조성물의 Metal 막질에 대한 Etch rate를 측정하기 위하여 각각의 Metal 시편을 25℃ 30min간 dipping하고, DIW로 린스 후, 4 point probe와 Nano spec 장비를 통해 min당 Etch rate를 측정하고 그 결과를 하기 표 3에 나타내었다. To measure the etch rate of the cleaning liquid compositions of Examples 8 to 11 and the cleaning liquid composition of Comparative Example 5, each metal specimen was dipped at 25 ° C for 30 minutes, rinsed with DIW, And the results are shown in Table 3 below.
또한, 실시예 8 세정액 조성물과 비교예 5의 세정액 조성물(TMAH 포함)에 대하여 경시에 따른 Etch rate 변화를 측정하고, 그 결과를 하기 표 4에 나타내었다.The etch rate changes of the cleaning composition of Example 8 and the cleaning composition of Comparative Example 5 (including TMAH) over time were measured, and the results are shown in Table 4 below.
상기 표 4에서 확인되는 바와 같이, 본 발명의 세정액 조성물(실시예 8~10)은 TMAH가 포함된 비교예 5의 세정액 조성보다 낮은 Etch rate를 나타내었다. 또한, 경시에 따르는 Etch rate에 있어서도 본 발명의 세정액 조성물(실시예 9)은 TMAH가 포함된 비교예 5의 세정액 조성보다 낮은 Etch rate를 나타내었다. As can be seen in Table 4 above, the cleaning composition compositions of the present invention (Examples 8-10) exhibited lower etch rates than the cleaning composition compositions of Comparative Example 5 containing TMAH. Also, at the etch rate according to time, the cleaning composition of the present invention (Example 9) showed lower etch rate than the cleaning composition of Comparative Example 5 containing TMAH.
시험예Test Example 3: 희석 비율별 pH와 Zeta 전위 변화 평가 3: Evaluation of pH and Zeta potential change by dilution ratio
Operating range를 평가하기 위하여 희석에 따른 pH 변화와 Zeta 전위 값을 측정 하였다. 즉, 세정액 조성물을 희석하는 경우에 pH의 변화를 줄여 Repulsive force를 유지하는지를 확인하기 위하여 실시예 1의 세정액 조성물 원액을 0 내지 120배로 희석하면서 그에 따르는 pH변화 및 Zeta 전위 값을 측정 하고, 그 결과를 하기 표 5에 나타내었다.To evaluate the operating range, we measured the pH change and Zeta potential according to dilution. That is, in order to confirm whether the pH of the cleaning liquid composition was reduced by decreasing the pH and maintaining the repulsive force, the pH of the washing liquid composition was diluted to 0 to 120 times, and the Zeta potential value was measured. Are shown in Table 5 below.
(mV)Zeta potential
(mV)
상기 표 5로부터 확인되는 바와 같이, 본 발명의 세정액 조성물은 희석에 따르는 pH의 변화가 작으며 제타전위의 변화도 크지 않으므로, 넓은 범위에서 사용할 수 있는 것으로 확인되었다. As can be seen from the above Table 5, it was confirmed that the cleaning composition of the present invention can be used in a wide range since the change in pH with dilution is small and the change in zeta potential is not so large.
Claims (13)
알킬아미노알코올 1 ~ 15 중량%, 모폴린 0.1 ~ 5 중량%, 및 잔량의 물을 포함하는 세정액 조성물로서,
상기 세정액 조성물은 0.05 ~ 5 중량%의 유기용매 및 0.1 ~ 5 중량%의 부식 억제제 중에서 선택되는 1종 이상을 더 포함하며,
상기 알킬아미노알코올은 2차 알킬아미노알코올 1종 이상 및 3차 알킬아미노알코올로 1종 이상을 포함하는 것을 특징으로 하며,
상기 세정액 조성물은 화학-기계적 연마(CMP) 공정 후의 세정용으로 사용되는 것을 특징으로 하는 세정액 조성물.It does not contain quaternary ammonium hydroxide,
1 to 15% by weight of alkylamino alcohol, 0.1 to 5% by weight of morpholine, and the balance water,
The cleaning liquid composition may further include at least one selected from 0.05 to 5% by weight of an organic solvent and 0.1 to 5% by weight of a corrosion inhibitor,
Wherein the alkylamino alcohol comprises at least one secondary alkyl amino alcohol and at least one tertiary alkyl amino alcohol,
Wherein the cleaning composition is used for cleaning after a chemical-mechanical polishing (CMP) process.
상기 2차 알킬아미노알코올은 부틸에탄올아민, 메틸에탄올아민, 및 다이에탄올아민으로 이루어진 군으로부터 선택되는 것을 특징으로 하는 세정액 조성물.The method according to claim 1,
Wherein said secondary alkyl amino alcohol is selected from the group consisting of butyl ethanolamine, methyl ethanol amine, and diethanol amine.
상기 2차 알킬아미노알코올은 메틸에탄올아민을 포함하는 것을 특징으로 하는 세정액 조성물.The method of claim 6,
Wherein the secondary alkyl amino alcohol comprises methyl ethanol amine.
상기 3차 알킬아미노알코올은 부틸다이에탄올아민, 다이부틸에탄올아민, 다이에틸에탄올아민, 메틸다이에탄올아민, 메틸다이이소프로판올아민, 및 트리에탄올아민으로 이루어진 군으로부터 선택되는 것을 특징으로 하는 세정액 조성물.The method according to claim 1,
Wherein said tertiary alkylamino alcohol is selected from the group consisting of butyldiethanolamine, dibutylethanolamine, diethylethanolamine, methyldiethanolamine, methyldiisopropanolamine, and triethanolamine.
상기 모폴린은 N-메틸 모폴린, 모폴린, N-아세틸 모폴린, 4-(2-하이드록시에틸)모폴린, 2,2'-다이모폴리노다이에틸에테르, 및 N-포름밀 모폴린으로 이루어진 군으로부터 선택되는 1종 이상의 것임을 특징으로 하는 세정액 조성물.The method according to claim 1,
The morpholine may be selected from the group consisting of N-methylmorpholine, morpholine, N-acetylmorpholine, 4- (2-hydroxyethyl) morpholine, 2,2'-diphosphoronodiethylether, Wherein the cleaning liquid composition is at least one selected from the group consisting of:
상기 유기용매는 디에틸렌글리콜모노에틸에테르, 트리에틸렌글리콜부틸메틸에테르, 및 트리에틸렌글리콜에틸에테르로 이루어진 군으로부터 선택되는 1종 이상의 것임을 특징으로 하는 세정액 조성물.The method according to claim 1,
Wherein the organic solvent is at least one selected from the group consisting of diethylene glycol monoethyl ether, triethylene glycol butyl methyl ether, and triethylene glycol ethyl ether.
상기 부식 억제제는 N,N-다이에틸하이드록실아민, 아스코르브산, 피라졸, 및솔비톨로 이루어진 군으로부터 선택되는 1종 이상의 것임을 특징으로 하는 세정액 조성물.The method according to claim 1,
Wherein the corrosion inhibitor is at least one selected from the group consisting of N, N-diethylhydroxylamine, ascorbic acid, pyrazole, and sorbitol.
상기 세정액 조성물은 pH 11.86 내지 12.73 범위인 것을 특징으로 하는, 세정액 조성물.The method according to claim 1,
Wherein the cleaning composition has a pH in the range of from about 11.86 to about 12.73.
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