JP2023169845A - Semiconductor substrate cleaning solution composition - Google Patents
Semiconductor substrate cleaning solution composition Download PDFInfo
- Publication number
- JP2023169845A JP2023169845A JP2022118605A JP2022118605A JP2023169845A JP 2023169845 A JP2023169845 A JP 2023169845A JP 2022118605 A JP2022118605 A JP 2022118605A JP 2022118605 A JP2022118605 A JP 2022118605A JP 2023169845 A JP2023169845 A JP 2023169845A
- Authority
- JP
- Japan
- Prior art keywords
- semiconductor substrate
- acid
- hydroxide
- cleaning liquid
- liquid composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 238000004140 cleaning Methods 0.000 title claims abstract description 94
- 239000000203 mixture Substances 0.000 title claims abstract description 86
- 239000000758 substrate Substances 0.000 title claims abstract description 81
- 239000004065 semiconductor Substances 0.000 title claims abstract description 77
- 239000010949 copper Substances 0.000 claims abstract description 55
- 229910052802 copper Inorganic materials 0.000 claims abstract description 41
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000005260 corrosion Methods 0.000 claims abstract description 28
- 230000007797 corrosion Effects 0.000 claims abstract description 28
- 125000001453 quaternary ammonium group Chemical group 0.000 claims abstract description 23
- 239000000908 ammonium hydroxide Substances 0.000 claims abstract description 22
- 239000008139 complexing agent Substances 0.000 claims abstract description 20
- 229910052751 metal Inorganic materials 0.000 claims abstract description 19
- 239000002184 metal Substances 0.000 claims abstract description 19
- 239000000126 substance Substances 0.000 claims abstract description 16
- 238000005498 polishing Methods 0.000 claims abstract description 15
- 239000007788 liquid Substances 0.000 claims description 53
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 37
- 238000000034 method Methods 0.000 claims description 35
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 32
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 32
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 27
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 22
- NDKBVBUGCNGSJJ-UHFFFAOYSA-M benzyltrimethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)CC1=CC=CC=C1 NDKBVBUGCNGSJJ-UHFFFAOYSA-M 0.000 claims description 18
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 17
- 239000003112 inhibitor Substances 0.000 claims description 15
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 claims description 14
- 150000001412 amines Chemical class 0.000 claims description 13
- 150000007524 organic acids Chemical class 0.000 claims description 12
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 12
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 11
- 235000001014 amino acid Nutrition 0.000 claims description 10
- 150000001413 amino acids Chemical class 0.000 claims description 10
- 239000004094 surface-active agent Substances 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 235000015165 citric acid Nutrition 0.000 claims description 9
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 claims description 8
- 239000004471 Glycine Substances 0.000 claims description 7
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 claims description 6
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 6
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 6
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 6
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 6
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 6
- QCOGKXLOEWLIDC-UHFFFAOYSA-N N-methylbutylamine Chemical compound CCCCNC QCOGKXLOEWLIDC-UHFFFAOYSA-N 0.000 claims description 6
- SEQKRHFRPICQDD-UHFFFAOYSA-N N-tris(hydroxymethyl)methylglycine Chemical compound OCC(CO)(CO)[NH2+]CC([O-])=O SEQKRHFRPICQDD-UHFFFAOYSA-N 0.000 claims description 6
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 claims description 6
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 6
- KVFVBPYVNUCWJX-UHFFFAOYSA-M ethyl(trimethyl)azanium;hydroxide Chemical compound [OH-].CC[N+](C)(C)C KVFVBPYVNUCWJX-UHFFFAOYSA-M 0.000 claims description 6
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- 235000005985 organic acids Nutrition 0.000 claims description 6
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 6
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 6
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 6
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 6
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 claims description 4
- MTCFGRXMJLQNBG-REOHCLBHSA-N (2S)-2-Amino-3-hydroxypropansäure Chemical compound OC[C@H](N)C(O)=O MTCFGRXMJLQNBG-REOHCLBHSA-N 0.000 claims description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 3
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 claims description 3
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 claims description 3
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 claims description 3
- HMBHAQMOBKLWRX-UHFFFAOYSA-N 2,3-dihydro-1,4-benzodioxine-3-carboxylic acid Chemical compound C1=CC=C2OC(C(=O)O)COC2=C1 HMBHAQMOBKLWRX-UHFFFAOYSA-N 0.000 claims description 3
- YINZGXSSYYFXEY-UHFFFAOYSA-N 2-(diethylaminomethoxy)ethanol Chemical compound CCN(CC)COCCO YINZGXSSYYFXEY-UHFFFAOYSA-N 0.000 claims description 3
- ZFDNAYFXBJPPEB-UHFFFAOYSA-M 2-hydroxyethyl(tripropyl)azanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCO ZFDNAYFXBJPPEB-UHFFFAOYSA-M 0.000 claims description 3
- ULRPISSMEBPJLN-UHFFFAOYSA-N 2h-tetrazol-5-amine Chemical compound NC1=NN=NN1 ULRPISSMEBPJLN-UHFFFAOYSA-N 0.000 claims description 3
- AJEUSSNTTSVFIZ-UHFFFAOYSA-M 3-hydroxypropyl(trimethyl)azanium;hydroxide Chemical compound [OH-].C[N+](C)(C)CCCO AJEUSSNTTSVFIZ-UHFFFAOYSA-M 0.000 claims description 3
- FAXDZWQIWUSWJH-UHFFFAOYSA-N 3-methoxypropan-1-amine Chemical compound COCCCN FAXDZWQIWUSWJH-UHFFFAOYSA-N 0.000 claims description 3
- UIKUBYKUYUSRSM-UHFFFAOYSA-N 3-morpholinopropylamine Chemical compound NCCCN1CCOCC1 UIKUBYKUYUSRSM-UHFFFAOYSA-N 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 3
- 229920001174 Diethylhydroxylamine Polymers 0.000 claims description 3
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 claims description 3
- AYFVYJQAPQTCCC-GBXIJSLDSA-N L-threonine Chemical compound C[C@@H](O)[C@H](N)C(O)=O AYFVYJQAPQTCCC-GBXIJSLDSA-N 0.000 claims description 3
- KZSNJWFQEVHDMF-BYPYZUCNSA-N L-valine Chemical compound CC(C)[C@H](N)C(O)=O KZSNJWFQEVHDMF-BYPYZUCNSA-N 0.000 claims description 3
- FSVCELGFZIQNCK-UHFFFAOYSA-N N,N-bis(2-hydroxyethyl)glycine Chemical compound OCCN(CCO)CC(O)=O FSVCELGFZIQNCK-UHFFFAOYSA-N 0.000 claims description 3
- YFCDLVPYFMHRQZ-UHFFFAOYSA-N N-Nitrosodiethanolamine Chemical compound OCCN(N=O)CCO YFCDLVPYFMHRQZ-UHFFFAOYSA-N 0.000 claims description 3
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 claims description 3
- MTCFGRXMJLQNBG-UHFFFAOYSA-N Serine Natural products OCC(N)C(O)=O MTCFGRXMJLQNBG-UHFFFAOYSA-N 0.000 claims description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 3
- UZMAPBJVXOGOFT-UHFFFAOYSA-N Syringetin Natural products COC1=C(O)C(OC)=CC(C2=C(C(=O)C3=C(O)C=C(O)C=C3O2)O)=C1 UZMAPBJVXOGOFT-UHFFFAOYSA-N 0.000 claims description 3
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 3
- AYFVYJQAPQTCCC-UHFFFAOYSA-N Threonine Natural products CC(O)C(N)C(O)=O AYFVYJQAPQTCCC-UHFFFAOYSA-N 0.000 claims description 3
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- 239000007997 Tricine buffer Substances 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
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- 235000004279 alanine Nutrition 0.000 claims description 3
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 3
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- GFHYNILUYZMFAM-UHFFFAOYSA-N 1H-1,2,4-triazol-5-amine Chemical compound NC1=NC=NN1.NC1=NC=NN1 GFHYNILUYZMFAM-UHFFFAOYSA-N 0.000 description 1
- WFYASTPQDOUBSW-UHFFFAOYSA-N 1h-1,2,4-triazole Chemical compound C=1N=CNN=1.C1=NN=CN1 WFYASTPQDOUBSW-UHFFFAOYSA-N 0.000 description 1
- KIZQNNOULOCVDM-UHFFFAOYSA-M 2-hydroxyethyl(trimethyl)azanium;hydroxide Chemical compound [OH-].C[N+](C)(C)CCO KIZQNNOULOCVDM-UHFFFAOYSA-M 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 206010033799 Paralysis Diseases 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- -1 and in this case Chemical compound 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 210000005036 nerve Anatomy 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000029058 respiratory gaseous exchange Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 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
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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0073—Anticorrosion compositions
-
- 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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2075—Carboxylic acids-salts thereof
- C11D3/2086—Hydroxy carboxylic acids-salts thereof
-
- 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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/26—Organic compounds containing nitrogen
- C11D3/28—Heterocyclic compounds containing nitrogen in the ring
-
- 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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/26—Organic compounds containing nitrogen
- C11D3/30—Amines; Substituted amines ; Quaternized amines
-
- 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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/26—Organic compounds containing nitrogen
- C11D3/33—Amino carboxylic acids
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (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)
- Mechanical Treatment Of Semiconductor (AREA)
- Detergent Compositions (AREA)
Abstract
Description
本発明は、半導体基板洗浄液組成物に関し、より具体的には、銅（Ｃｕ）配線を含む半導体ウェーハの化学機械研磨（ＣＭＰ）後、ウェーハ表面を洗浄するための組成物に関し、ウェーハ基板表面に存在する研磨剤及び各種有機汚染物質を有効に除去でき、銅配線の腐食を防止できる。 The present invention relates to a semiconductor substrate cleaning liquid composition, and more specifically, to a composition for cleaning the wafer surface after chemical mechanical polishing (CMP) of a semiconductor wafer containing copper (Cu) wiring. Existing abrasives and various organic contaminants can be effectively removed, and corrosion of copper wiring can be prevented.
最近、半導体は高集積化によって配線の線幅が継続的に減少している傾向にある。かかる配線微細化が進むにつれ、配線抵抗が増加することになるが、これを解決するために銅を使用する工程が増加している。 2. Description of the Related Art Recently, the line width of interconnections in semiconductors has been decreasing due to higher integration. As such interconnect miniaturization progresses, interconnect resistance increases, and in order to solve this problem, the number of processes using copper is increasing.
このような銅配線を形成するためにはダマシン工程（Ｄａｍａｓｃｅｎｅ ｐｒｏｃｅｓｓ）が必須であり、蒸着された銅膜質を除去して平坦化するために化学機械研磨（ｃｈｅｍｉｃａｌ ｍｅｃｈａｎｉｃａｌ ｐｏｌｉｓｈｉｎｇ、ＣＭＰ）工程が行われる。 In order to form such copper wiring, a Damascene process is essential, and a chemical mechanical polishing (CMP) process is performed to remove and planarize the deposited copper film. .
ＣＭＰ工程は半導体材料の薄く平たい基板を適正の圧力及び温度条件下でウェットポリッシングされた表面に対して固定させて回転させるステップを含む。また、研磨剤としてはアルミナ又はシリカのような粒子を含有する化学スラリ－を使用できる。このような化学スラリ－は選択された化学物質を含有し、これは加工中に基板の様々な表面をエッチングさせることができる。このような研磨工程で材料の機械的除去と化学的除去の組み合わせは表面の優れた平坦化を達成するために適している。 The CMP process involves holding and rotating a thin, flat substrate of semiconductor material against a wet polished surface under appropriate pressure and temperature conditions. Additionally, a chemical slurry containing particles such as alumina or silica can be used as the abrasive. Such chemical slurries contain selected chemicals that can etch various surfaces of the substrate during processing. A combination of mechanical and chemical removal of material in such polishing steps is suitable for achieving excellent planarization of the surface.
しかし、ＣＭＰ工程は半導体基板の表向上に汚染物質を残す場合があり、この汚染物質はアルミナ又はシリカと研磨スラリ－に添加される反応性化学物質からなる研磨粒子がほとんどである。ＣＭＰ工程に使用される上記研磨スラリ－は研磨剤、酸化剤、腐食防止剤などのような化学薬品で構成されている。 However, the CMP process can leave contaminants on the surface of the semiconductor substrate, and these contaminants are mostly polishing particles consisting of alumina or silica and reactive chemicals added to the polishing slurry. The polishing slurry used in the CMP process is composed of chemicals such as abrasives, oxidizers, corrosion inhibitors, and the like.
このような汚染層は研磨スラリ－と研磨表面の間の反応生成物を含むことができ、また、研磨粒子や有機物などがウェーハ表面を汚染させてパターン欠陥などの深刻な問題を引き起こし得る。したがって、半導体装置の信頼性の低下及び製造工程の歩留まりを減少させる欠陥の導入を回避するために、半導体基板の以降の工程を行う前に汚染源の除去は必須である。 Such a contamination layer may include reaction products between the polishing slurry and the polishing surface, and abrasive particles, organic matter, etc. may contaminate the wafer surface and cause serious problems such as pattern defects. Therefore, in order to avoid introducing defects that reduce the reliability of the semiconductor device and the yield of the manufacturing process, it is essential to remove the contamination source before performing subsequent processes on the semiconductor substrate.
すなわち、ＣＭＰ工程後、汚染物質を除去するためにはＣＭＰ後洗浄工程が必ず必要である。一般にＣＭＰ後洗浄工程は洗浄液の塗布後、ポリビニルアルコール系スポンジのようなブラシを用いて行われる。また、ＣＭＰ残留物が存在する基板表面を洗浄するためにポスト－ＣＭＰ洗浄溶液が開発された。 That is, after the CMP process, a post-CMP cleaning process is always necessary to remove contaminants. Generally, the post-CMP cleaning step is performed using a brush such as a polyvinyl alcohol sponge after applying a cleaning solution. Post-CMP cleaning solutions have also been developed to clean substrate surfaces where CMP residue is present.
このようなポスト－ＣＭＰ洗浄液として、従来は水酸化アンモニウムベースのアルカリ溶液が通常用いられていたが、これらのほとんどはアルミニウム、タングステン、タンタル及び酸化物含有表面に使用されるＣＭＰ洗浄液である。 In the past, ammonium hydroxide-based alkaline solutions were commonly used as such post-CMP cleaning solutions, and most of these are CMP cleaning solutions used for aluminum, tungsten, tantalum, and oxide-containing surfaces.
最近、インターコネクトの製造に最適の物質として銅がアルミニウムの代わりに使用されている。銅を使用する基板のＣＭＰ工程以降は銅、酸化銅及び研磨液のスラリ－粒子が銅表面に存在し得る。このような銅表面はケイ素及び二酸化硅素の中で速やかに拡散できるため、装置故障を防止するために全てのウェーハ表面から除去すべきである。 Recently, copper has replaced aluminum as the material of choice for interconnect manufacturing. After a CMP process for a substrate using copper, slurry particles of copper, copper oxide, and polishing liquid may be present on the copper surface. Such copper surfaces can quickly diffuse into silicon and silicon dioxide and should be removed from all wafer surfaces to prevent equipment failure.
しかし、通常、アルミナ及びシリカベースのＣＭＰ工程に有効なポスト－ＣＭＰ洗浄溶液は銅含有表面には効果的ではない。また、銅は上記洗浄溶液によって容易に損傷を受ける可能性があり、上記ポスト－ＣＭＰ洗浄溶液の洗浄効率は容認できないものと立証された。 However, post-CMP cleaning solutions that are typically effective for alumina and silica-based CMP processes are not effective for copper-containing surfaces. Also, copper can be easily damaged by the cleaning solution and the cleaning efficiency of the post-CMP cleaning solution has proven to be unacceptable.
これと関連して、特許文献１はピラゾロン又はピラゾロン誘導体を含む半導体基板用洗浄液組成物について開示している。 In connection with this, Patent Document 1 discloses a cleaning liquid composition for semiconductor substrates containing a pyrazolone or a pyrazolone derivative.
本発明の目的は、上記従来の技術の問題点を解決するために案出されたものであり、ＣＭＰ工程後、ウェーハ基板表面に存在する研磨剤及び各種有機汚染物質を有効に除去できる半導体基板洗浄液組成物を提供することにある。 The object of the present invention was devised to solve the above-mentioned problems of the conventional technology, and provides a semiconductor substrate that can effectively remove abrasives and various organic contaminants present on the surface of a wafer substrate after a CMP process. An object of the present invention is to provide a cleaning liquid composition.
また、本発明は、銅配線の腐食を防止できる半導体基板洗浄液組成物を提供することにある。 Another object of the present invention is to provide a semiconductor substrate cleaning liquid composition that can prevent corrosion of copper wiring.
前述した技術的課題を達成するための技術的手段として、本発明の一側面は、 As a technical means for achieving the above-mentioned technical problem, one aspect of the present invention is as follows:
第四級アンモニウムヒドロキシド及び金属錯化剤；を含む半導体基板洗浄液組成物であって、上記組成物全体重量に対して、上記第四級アンモニウムヒドロキシド１乃至２０重量％及び上記金属錯化剤０．１乃至１０重量％を含む半導体基板洗浄液組成物が提供される。 A semiconductor substrate cleaning liquid composition comprising: quaternary ammonium hydroxide and a metal complexing agent; 1 to 20% by weight of the quaternary ammonium hydroxide and the metal complexing agent based on the total weight of the composition; A semiconductor substrate cleaning liquid composition containing 0.1 to 10% by weight is provided.
上記第四級アンモニウムヒドロキシドはテトラエチルアンモニウムヒドロキシド（ＴＥＡＨ）、テトラブチルアンモニウムヒドロキシド（ＴＢＡＨ）、テトラプロピルアンモニウムヒドロキシド、トリメチルエチルアンモニウムヒドロキシド、ベンジルトリメチルアンモニウムヒドロキシド（ＢＴＭＡＨ）、（ヒドロキシエチル）トリメチルアンモニウムヒドロキシド、（ヒドロキシエチル）トリエチルアンモニウムヒドロキシド、（ヒドロキシエチル）トリプロピルアンモニウムヒドロキシド、（ヒドロキシプロピル）トリメチルアンモニウムヒドロキシド、エチルトリメチルアンモニウムヒドロキシド、ジエチルジメチルアンモニウムヒドロキシド及びコリンヒドロキシドからなる群より選択された１種以上を含むことができる。 The above quaternary ammonium hydroxides include tetraethylammonium hydroxide (TEAH), tetrabutylammonium hydroxide (TBAH), tetrapropylammonium hydroxide, trimethylethylammonium hydroxide, benzyltrimethylammonium hydroxide (BTMAH), (hydroxyethyl) Consisting of trimethylammonium hydroxide, (hydroxyethyl)triethylammonium hydroxide, (hydroxyethyl)tripropylammonium hydroxide, (hydroxypropyl)trimethylammonium hydroxide, ethyltrimethylammonium hydroxide, diethyldimethylammonium hydroxide and choline hydroxide It can contain one or more selected from the group.
上記第四級アンモニウムヒドロキシドはテトラエチルアンモニウムヒドロキシド（ＴＥＡＨ）及びベンジルトリメチルアンモニウムヒドロキシド（ＢＴＭＡＨ）からなる群より選択された１種以上を含むことができる。 The quaternary ammonium hydroxide may include one or more selected from the group consisting of tetraethylammonium hydroxide (TEAH) and benzyltrimethylammonium hydroxide (BTMAH).
上記金属錯化剤は有機酸及びアミノ酸からなる群より選択された１種以上を含むことができる。 The metal complexing agent may include one or more selected from the group consisting of organic acids and amino acids.
上記有機酸はクエン酸、乳酸、ギ酸、シュウ酸、酢酸、プロピオン酸、マロン酸、コハク酸、グルタル酸、マレイン酸、フマル酸、フタル酸、グリコール酸、グルコン酸、サリチル酸、酒石酸及びリンゴ酸からなる群より選択された１種以上を含むことができる。 The above organic acids include citric acid, lactic acid, formic acid, oxalic acid, acetic acid, propionic acid, malonic acid, succinic acid, glutaric acid, maleic acid, fumaric acid, phthalic acid, glycolic acid, gluconic acid, salicylic acid, tartaric acid and malic acid. One or more types selected from the group consisting of:
上記組成物全体重量に対して、上記有機酸１乃至７重量％を含むことができる。 The composition may contain 1 to 7% by weight of the organic acid based on the total weight of the composition.
上記アミノ酸はグリシン（ｇｌｙｃｉｎｅ）、セリン（ｓｅｒｉｎｅ）、トレオニン（ｔｈｒｅｏｎｉｎｅ）、アラニン（ａｌａｎｉｎｅ）、バリン（ｖａｌｉｎｅ）、ビシン（ｂｉｃｉｎｅ）及びトリシン（ｔｒｉｃｉｎｅ）からなる群より選択された１種以上を含むことができる。 The above amino acids include one or more selected from the group consisting of glycine, serine, threonine, alanine, valine, bicine, and tricine. I can do it.
上記組成物全体重量に対して、上記アミノ酸０．１乃至１重量％を含むことができる。 The amino acid may contain 0.1 to 1% by weight based on the total weight of the composition.
上記組成物は有機アミン、腐食防止剤及び界面活性剤からなる群より選択された１種以上をさらに含むことができる。 The composition may further include one or more selected from the group consisting of organic amines, corrosion inhibitors, and surfactants.
上記有機アミンはモノエタノールアミン（ＭＥＡ）、エチルヘキシルアミン、メチルアミン、ジメチルアミン、エチルアミン、ジエチルアミン、エタノールアミン、ジエタノールアミン、メチルジエタノールアミン、トリエチルアミン、トリメチルアミン、トリエタノールアミン、イソプロパノールアミン、ジイソプロパノールアミン、トリイソプロパノールアミン、ニトロソジエタノールアミン、ブチルアミン、３－メトキシプロピルアミン、ｔｅｒｔ－ブチルアミン、ベンジルアミン、ヘキシルアミン、シクロヘキシルアミン、オクチルアミン、Ｎ－メチル－Ｎ－ブチルアミン、Ｎ－（３－アミノプロピル）モルホリン、アミノエタノール、キシリレンジアミン、ドデシルアミン、（ヒドロキシエチルオキシメチル）ジエチルアミン、ジメチルヒドロキシルアミン、ジエチルヒドロキシルアミン及びジブチルヒドロキシルアミンからなる群より選択された１種以上を含むことができる。 The above organic amines include monoethanolamine (MEA), ethylhexylamine, methylamine, dimethylamine, ethylamine, diethylamine, ethanolamine, diethanolamine, methyldiethanolamine, triethylamine, trimethylamine, triethanolamine, isopropanolamine, diisopropanolamine, triisopropanolamine. , nitrosodiethanolamine, butylamine, 3-methoxypropylamine, tert-butylamine, benzylamine, hexylamine, cyclohexylamine, octylamine, N-methyl-N-butylamine, N-(3-aminopropyl)morpholine, aminoethanol, xylene It can contain one or more selected from the group consisting of diamine, dodecylamine, (hydroxyethyloxymethyl)diethylamine, dimethylhydroxylamine, diethylhydroxylamine, and dibutylhydroxylamine.
上記腐食防止剤は１，２，４－トリアゾール、ベンゾトリアゾール、ピラゾール、５－アミノテトラゾール及び３－アミノ－１，２，４－トリアゾールからなる群より選択された１種以上を含むことができる。 The corrosion inhibitor may include one or more selected from the group consisting of 1,2,4-triazole, benzotriazole, pyrazole, 5-aminotetrazole, and 3-amino-1,2,4-triazole.
上記界面活性剤はジエチレングリコール（ＤＥＧ）を含むことができる。 The surfactant may include diethylene glycol (DEG).
本発明の他の一側面は、銅配線を含む半導体基板に対して化学機械研磨（ＣＭＰ）工程を行うステップ；及び上記半導体基板に 本発明に記載の半導体基板洗浄液組成物を加えて洗浄を行うステップ；を含む銅配線を含む半導体基板のＣＭＰ工程後洗浄方法が提供される。 Another aspect of the present invention is to perform a chemical mechanical polishing (CMP) process on a semiconductor substrate including copper wiring; and to perform cleaning by adding a semiconductor substrate cleaning liquid composition according to the present invention to the semiconductor substrate. A method for cleaning a semiconductor substrate including copper wiring after a CMP process is provided, the method comprising the steps of:
本発明の半導体基板洗浄液組成物は、ＣＭＰ工程後、ウェーハ基板表面に存在する研磨剤及び各種有機汚染物質を有効に除去できる。 The semiconductor substrate cleaning liquid composition of the present invention can effectively remove abrasives and various organic contaminants present on the surface of a wafer substrate after a CMP process.
また、本発明の半導体基板洗浄液組成物は銅配線の腐食を防止できる効果がある。 Further, the semiconductor substrate cleaning liquid composition of the present invention has the effect of preventing corrosion of copper wiring.
以下、本発明をさらに詳細に説明する。しかし、本発明は様々な異なる形態に実装されることができ、ここで説明する実施例によって本発明が限定されるものではなく、本発明は後述する請求範囲によってのみ定義される。 The present invention will be explained in more detail below. However, the invention may be implemented in a variety of different forms, and the invention is not limited to the embodiments described herein, but rather is defined only by the scope of the claims that follow.
加えて、本発明で用いた用語は単に特定の実施例を説明するために用いられたものであって、本発明を限定することを意図しない。単数の表現は文脈上明白に異なる意味で用いられない限り、複数の表現を含む。本発明の明細書全体においてある構成要素を「含む」ということは特に相反する記載がない限り、他の構成要素を除外するものではなく、他の構成要素をさらに含むことができることを意味する。 Additionally, the terms used in the present invention are merely used to describe particular embodiments and are not intended to limit the invention. A singular expression includes a plural expression unless the context clearly dictates otherwise. Throughout the specification of the present invention, unless there is a statement to the contrary, the term "comprising" a certain component does not exclude other components, and means that other components can be further included.
本願の第１側面は、第四級アンモニウムヒドロキシド及び金属錯化剤；を含む半導体基板洗浄液組成物を提供する。 A first aspect of the present application provides a semiconductor substrate cleaning liquid composition comprising: a quaternary ammonium hydroxide and a metal complexing agent.
以下、本願の第１側面による半導体基板洗浄液組成物について説明する。 Hereinafter, a semiconductor substrate cleaning liquid composition according to the first aspect of the present application will be described.
第四級アンモニウムヒドロキシド Quaternary ammonium hydroxide
本願の一実施例によれば、上記半導体基板洗浄液組成物は第四級アンモニウムヒドロキシドを含むことができる。“第四級アンモニウムヒドロキシド”は窒素原子１個に４個の炭化水素鎖が結合された第四級アンモニウムカチオンとヒドロキシルアニオンがイオン結合で結合された塩を意味する。上記第四級アンモニウムヒドロキシドは静電的反発力によって洗浄後パーティクル（Ｐａｒｔｉｃｌｅ）の再吸着を防止できる。 According to one embodiment of the present application, the semiconductor substrate cleaning liquid composition may include quaternary ammonium hydroxide. "Quaternary ammonium hydroxide" means a salt in which a quaternary ammonium cation, in which four hydrocarbon chains are bonded to one nitrogen atom, and a hydroxyl anion are bonded by an ionic bond. The quaternary ammonium hydroxide can prevent particles from being re-adsorbed after cleaning due to electrostatic repulsion.
本願の一実施例によれば、上記第四級アンモニウムヒドロキシドはテトラエチルアンモニウムヒドロキシド（ＴＥＡＨ）、テトラブチルアンモニウムヒドロキシド（ＴＢＡＨ）、テトラプロピルアンモニウムヒドロキシド、トリメチルエチルアンモニウムヒドロキシド、ベンジルトリメチルアンモニウムヒドロキシド（ＢＴＭＡＨ）、（ヒドロキシエチル）トリメチルアンモニウムヒドロキシド、（ヒドロキシエチル）トリエチルアンモニウムヒドロキシド、（ヒドロキシエチル）トリプロピルアンモニウムヒドロキシド、（ヒドロキシプロピル）トリメチルアンモニウムヒドロキシド、エチルトリメチルアンモニウムヒドロキシド、ジエチルジメチルアンモニウムヒドロキシド及びコリンヒドロキシドからなる群より選択された１種以上を含むことができ、好ましくはテトラエチルアンモニウムヒドロキシド（ＴＥＡＨ）及びベンジルトリメチルアンモニウムヒドロキシド（ＢＴＭＡＨ）からなる群より選択された１種以上を含むことができる。 According to an embodiment of the present application, the quaternary ammonium hydroxide is tetraethylammonium hydroxide (TEAH), tetrabutylammonium hydroxide (TBAH), tetrapropylammonium hydroxide, trimethylethylammonium hydroxide, benzyltrimethylammonium hydroxide. (BTMAH), (hydroxyethyl)trimethylammonium hydroxide, (hydroxyethyl)triethylammonium hydroxide, (hydroxyethyl)tripropylammonium hydroxide, (hydroxypropyl)trimethylammonium hydroxide, ethyltrimethylammonium hydroxide, diethyldimethyl It may contain one or more selected from the group consisting of ammonium hydroxide and choline hydroxide, preferably one selected from the group consisting of tetraethylammonium hydroxide (TEAH) and benzyltrimethylammonium hydroxide (BTMAH). The above can be included.
本願の一実施例によれば、上記組成物全体重量に対して、上記第四級アンモニウムヒドロキシド１乃至２０重量％を含むことができる。好ましくは上記組成物全体重量に対して、上記第四級アンモニウムヒドロキシド１０乃至２０重量％を含むことができる。 According to an embodiment of the present application, the quaternary ammonium hydroxide may be contained in an amount of 1 to 20% by weight based on the total weight of the composition. Preferably, the quaternary ammonium hydroxide may be contained in an amount of 10 to 20% by weight based on the total weight of the composition.
上記第四級アンモニウムヒドロキシドが上記組成物全体重量に対して１重量％未満の場合は汚染物質除去効果が現れない場合があるので好ましくなく、２０重量％を超える場合は工程の経済性に劣る場合があり、却って汚染物質除去効果が低下し得るので好ましくない。 If the amount of the quaternary ammonium hydroxide is less than 1% by weight based on the total weight of the composition, the effect of removing contaminants may not be exhibited, which is not preferable, and if it exceeds 20% by weight, the economic efficiency of the process is poor. This is not preferable because it may actually reduce the pollutant removal effect.
金属錯化剤 metal complexing agent
本願の一実施例によれば、上記半導体基板洗浄液組成物は金属錯化剤（ｍｅｔａｌ ｃｏｍｐｌｅｘｉｎｇ ａｇｅｎｔ）を含むことができる。上記金属錯化剤は洗浄工程が行われる際に発生する金属イオンの錯化剤として作用でき、また、弱酸性を帯びているのでアルカリ性の溶媒と弱酸－強塩基のバッファ溶液を形成して希釈比にかからわず適切なｐＨ領域を維持させることができる。 According to an embodiment of the present application, the semiconductor substrate cleaning liquid composition may include a metal complexing agent. The above metal complexing agent can act as a complexing agent for metal ions generated during the cleaning process, and since it has weak acidity, it can be diluted by forming a weak acid-strong base buffer solution with an alkaline solvent. An appropriate pH range can be maintained regardless of the ratio.
本願の一実施例によれば、上記組成物全体重量に対して、上記金属錯化剤０．１乃至１０重量％を含むことができる。 According to an embodiment of the present application, the metal complexing agent may contain 0.1 to 10% by weight based on the total weight of the composition.
本願の一実施例によれば、上記金属錯化剤は有機酸及びアミノ酸からなる群より選択された１種以上を含むことができる。 According to an embodiment of the present application, the metal complexing agent may include one or more selected from the group consisting of organic acids and amino acids.
本願の一実施例によれば、上記有機酸はクエン酸、乳酸、ギ酸、シュウ酸、酢酸、プロピオン酸、マロン酸、コハク酸、グルタル酸、マレイン酸、フマル酸、フタル酸、グリコール酸、グルコン酸、サリチル酸、酒石酸及びリンゴ酸からなる群より選択された１種以上を含むことができる、好ましくはクエン酸を含むことができる。上記有機酸を含有することにより、半導体基板の腐食抑制性に優れ、また、半導体基板上の各種有機汚染物質の除去性に優れる効果がある。 According to an embodiment of the present application, the organic acids are citric acid, lactic acid, formic acid, oxalic acid, acetic acid, propionic acid, malonic acid, succinic acid, glutaric acid, maleic acid, fumaric acid, phthalic acid, glycolic acid, gluconic acid. The acid may contain one or more selected from the group consisting of salicylic acid, tartaric acid, and malic acid, preferably citric acid. By containing the above-mentioned organic acid, there is an effect that it is excellent in inhibiting corrosion of a semiconductor substrate and is also excellent in removing various organic contaminants on a semiconductor substrate.
本願の一実施例によれば、上記組成物全体重量に対して、上記有機酸１乃至７重量％を含むことができる。好ましくは上記組成物全体重量に対して、上記有機酸４乃至５重量％を含むことができる。 According to an embodiment of the present application, the organic acid may contain 1 to 7% by weight based on the total weight of the composition. Preferably, the organic acid may contain 4 to 5% by weight based on the total weight of the composition.
上記有機酸が上記組成物全体重量に対して１重量％未満の場合は汚染物質除去効果が現れない場合があるので好ましくなく、７重量％を超える場合は銅配線に対する腐食性が増加し得るので好ましくない。 If the amount of the organic acid is less than 1% by weight based on the total weight of the composition, the effect of removing contaminants may not be exhibited, which is undesirable, and if it exceeds 7% by weight, the corrosivity to copper wiring may increase. Undesirable.
本願の一実施例によれば、上記アミノ酸はグリシン（ｇｌｙｃｉｎｅ）、セリン（ｓｅｒｉｎｅ）、トレオニン（ｔｈｒｅｏｎｉｎｅ）、アラニン（ａｌａｎｉｎｅ）、バリン（ｖａｌｉｎｅ）、ビシン（ｂｉｃｉｎｅ）及びトリシン（ｔｒｉｃｉｎｅ）からなる群より選択された１種以上を含むことができ、好ましくはグリシンを含むことができる。 According to one embodiment of the present application, the amino acid is from the group consisting of glycine, serine, threonine, alanine, valine, bicine and tricine. It can contain one or more selected types, preferably glycine.
本願の一実施例によれば、上記組成物全体重量に対して、上記アミノ酸０．１乃至１重量％を含むことができる。好ましくは上記組成物全体重量に対して、上記アミノ酸０．４乃至０．６重量％を含むことができる。 According to an embodiment of the present application, the amino acid may contain 0.1 to 1% by weight based on the total weight of the composition. Preferably, the amino acid may be contained in an amount of 0.4 to 0.6% by weight based on the total weight of the composition.
有機アミン organic amine
本願の一実施例によれば、上記半導体基板洗浄液組成物は有機アミンをさらに含むことができる。上記有機アミンは半導体基板（ウェーハ）に存在する有機残留物及び金属酸化膜を除去する役割を行うことができる。 According to an embodiment of the present application, the semiconductor substrate cleaning liquid composition may further include an organic amine. The organic amine may serve to remove organic residues and metal oxide layers present on the semiconductor substrate (wafer).
本願の一実施例によれば、上記有機アミンはモノエタノールアミン（ｍｏｎｏｅｔｈａｎｏｌａｍｉｎｅ、ＭＥＡ）、エチルヘキシルアミン（ｅｔｈｙｌｈｅｘｙｌａｍｉｎｅ）、メチルアミン（ｍｅｔｈｙｌａｍｉｎｅ）、ジメチルアミン（ｄｉｍｅｔｈｙｌａｍｉｎｅ）、エチルアミン（ｅｔｈｙｌａｍｉｎｅ）、ジエチルアミン（ｄｉｅｔｈｙｌａｍｉｎｅ）、エタノールアミン（ｅｔｈａｎｏｌａｍｉｎｅ）、ジエタノールアミン（ｄｉｅｔｈａｎｏｌａｍｉｎｅ）、メチルジエタノールアミン（ｍｅｔｈｙｌｄｉｅｔｈａｎｏｌａｍｉｎｅ）、トリエチルアミン（ｔｒｉｅｔｈｙｌａｍｉｎｅ）、トリメチルアミン（ｔｒｉｍｅｔｈｙｌａｍｉｎｅ）、トリエタノールアミン（ｔｒｉｅｔｈａｎｏｌａｍｉｎｅ）、イソプロパノールアミン（ｉｓｏｐｒｏｐａｎｏｌａｍｉｎｅ）、ジイソプロパノールアミン（ｄｉｉｓｏｐｒｏｐａｎｏｌａｍｉｎｅ）、トリイソプロパノールアミン（ｔｒｉｉｓｏｐｒｏｐａｎｏｌａｍｉｎｅ）、ニトロソジエタノールアミン（ｎｉｔｒｏｓｏｄｉｅｔｈａｎｏｌａｍｉｎｅ）、ブチルアミン（ｂｕｔｙｌａｍｉｎｅ）、３－メトキシプロピルアミン（３－ｍｅｔｈｏｘｙｐｒｏｐｙｌａｍｉｎｅ）、ｔｅｒｔ－ブチルアミン（ｔｅｒｔ－ｂｕｔｙｌａｍｉｎｅ）、ベンジルアミン（ｂｅｎｚｙｌａｍｉｎｅ）、ヘキシルアミン（ｈｅｘｙｌａｍｉｎｅ）、シクロヘキシルアミン（ｃｙｃｌｏｈｅｘｙｌａｍｉｎｅ）、オクチルアミン（ｏｃｔｙｌａｍｉｎｅ）、Ｎ－メチル－Ｎ－ブチルアミン（Ｎ－ｍｅｔｈｙｌ－Ｎ－ｂｕｔｙｌａｍｉｎｅ）、Ｎ－（３－アミノプロピル）モルホリン（Ｎ－（３－ａｍｉｎｏｐｒｏｐｙｌ）ｍｏｒｐｈｏｌｉｎｅ）、アミノエタノール（ｅｔｈａｎｏｌａｍｉｎｅ）、キシリレンジアミン（ｘｙｌｙｌｅｎｄｉａｍｉｎ）、ドデシルアミン（ｄｏｄｅｃｙｌ ａｍｉｎｅ）、（ヒドロキシエチルオキシメチル）ジエチルアミン（（ｈｙｄｒｏｘｙｅｔｈｙｌｏｘｙｍｅｔｈｙｌ）ｄｉｅｔｈｙｌｅｎａｍｉｎｅ）、ジメチルヒドロキシルアミン（ｄｉｍｅｔｈｙｌｈｙｄｒｏｘｙｌａｍｉｎｅ）、ジエチルヒドロキシルアミン（ｄｉｅｔｈｙｌｈｙｄｒｏｘｙｌａｍｉｎｅ）、ジブチルヒドロキシルアミン（ｄｉｂｕｔｙｌｈｙｄｒｏｘｙｌａｍｉｎｅ）からなる群より選択された１種以上を含むことができ、好ましくはモノエタノールアミン（ｍｏｎｏｅｔｈａｎｏｌａｍｉｎｅ、ＭＥＡ）を含むことができる。 According to an embodiment of the present application, the organic amine is monoethanolamine (MEA), ethylhexylamine, methylamine, dimethylamine, ethylamine, diethylamine. hylamine), Ethanolamine, diethanolamine, methyldiethanolamine, triethylamine, trimethylamine, triethanolamine ne), isopropanolamine, diisopropanolamine, triisopropanolamine (triisopropanolamine), nitrosodiethanolamine, butylamine, 3-methoxypropylamine, tert-butylamine e), benzylamine, hexylamine, cyclohexylamine ( cyclohexylamine), octylamine, N-methyl-N-butylamine, N-(3-aminopropyl)morpholine, aminoethanol ine ), xylylendiamine, dodecyl amine, (hydroxyethyloxymethyl)diethylamine, dimethylhydroxylamine , diethylhydroxylamine, dibutylhydroxylamine It may contain one or more selected from the group consisting of, preferably monoethanolamine (MEA).
本願の一実施例によれば、上記組成物全体重量に対して、上記有機アミン１乃至１０重量％を含むことができる。好ましくは上記組成物全体重量に対して、上記有機アミン４乃至７重量％を含むことができる。 According to one embodiment of the present application, the organic amine may be contained in an amount of 1 to 10% by weight based on the total weight of the composition. Preferably, the organic amine may contain 4 to 7% by weight based on the total weight of the composition.
上記有機アミンが上記組成物全体重量に対して１重量％未満の場合は半導体基板上に存在する有機残留物の除去効果が現れない場合があるので好ましくなく、１０重量％を超える場合は工程の経済性に劣る場合があるので好ましくない。 If the amount of the organic amine is less than 1% by weight based on the total weight of the composition, the effect of removing organic residues present on the semiconductor substrate may not be exhibited, which is not preferable, and if it exceeds 10% by weight, it is not preferable. This is not preferred because it may be less economical.
腐食防止剤 corrosion inhibitor
本願の一実施例によれば、上記半導体基板洗浄液組成物は腐食防止剤をさらに含むことができる。上記腐食防止剤は銅に対する保護膜を形成して銅表面のエッチング抑制及び表面が粗くなることを防止する役割を行うことができる。 According to an embodiment of the present application, the semiconductor substrate cleaning liquid composition may further include a corrosion inhibitor. The corrosion inhibitor may form a protective film against copper, thereby inhibiting etching of the copper surface and preventing the surface from becoming rough.
上記腐食防止剤は１，２，４－トリアゾール（１，２，４－Ｔｒｉａｚｏｌｅ）、ベンゾトリアゾール（Ｂｅｎｚｏｔｒｉａｚｏｌｅ）、ピラゾール（Ｐｙｒａｚｏｌｅ）、５－アミノテトラゾール（５－Ａｍｉｎｏｔｅｔｒａｚｏｌｅ）及び３－アミノ－１，２，４－トリアゾール（３－Ａｍｉｎｏ－１，２，４－ｔｒｉａｚｏｌｅ）からなる群より選択された１種以上を含むことができ、好ましくは１，２，４－トリアゾール（１，２，４－Ｔｒｉａｚｏｌｅ）を含むことができる。 The above corrosion inhibitors include 1,2,4-Triazole, Benzotriazole, Pyrazole, 5-Aminotetrazole and 3-Amino-1,2 , 4-triazole (3-Amino-1,2,4-triazole), preferably 1,2,4-triazole (1,2,4-Triazole). ) can be included.
本願の一実施例によれば、上記組成物全体重量に対して、上記腐食防止剤０．０５乃至０．２重量％を含むことができる。 According to an embodiment of the present application, the corrosion inhibitor may be included in an amount of 0.05 to 0.2% by weight based on the total weight of the composition.
上記腐食防止剤が上記組成物全体重量に対して０．０５重量％未満の場合は腐食防止剤の量が少ないため腐食防止効果が減少するので好ましくなく、０．２重量％を超える場合はエッチング残留物の除去能力が減少したり過量を使用しても同じ腐食防止剤効果が現れるので経済的にも好ましくない。 If the amount of the corrosion inhibitor is less than 0.05% by weight based on the total weight of the composition, the amount of the corrosion inhibitor is so small that the corrosion inhibiting effect will be reduced, which is not preferable, and if it exceeds 0.2% by weight, the etching It is also economically unfavorable because the ability to remove residues decreases or the same corrosion inhibitor effect appears even if an excessive amount is used.
界面活性剤 surfactant
本願の一実施例によれば、上記半導体基板洗浄液組成物は界面活性剤をさらに含むことができる。上記界面活性剤は洗浄液組成物の粘度を調整し、洗浄対象物への濡れ性を改良できる役割を行うことができる。 According to an embodiment of the present application, the semiconductor substrate cleaning liquid composition may further include a surfactant. The surfactant can adjust the viscosity of the cleaning liquid composition and improve wettability to the object to be cleaned.
本願の一実施例によれば、上記界面活性剤はジエチレングリコール（ＤＥＧ）を含むことができる。 According to one embodiment of the present application, the surfactant may include diethylene glycol (DEG).
本願の一実施例によれば、上記組成物全体重量に対して、上記界面活性剤１乃至５重量％を含むことができる。 According to an embodiment of the present application, the surfactant may be contained in an amount of 1 to 5% by weight based on the total weight of the composition.
本願の一実施例によれば、上記半導体基板洗浄液組成物は超純水をさらに含むことができる。上記第四級アンモニウムヒドロキシド、有機アミン、金属錯化剤、腐食防止剤、界面活性剤などを除いた残部が超純水であり得る。 According to an embodiment of the present application, the semiconductor substrate cleaning liquid composition may further include ultrapure water. The remainder after removing the quaternary ammonium hydroxide, organic amine, metal complexing agent, corrosion inhibitor, surfactant, etc. may be ultrapure water.
本願の一実施例によれば、上記半導体基板洗浄液組成物は化学機械研磨（ＣＭＰ）後洗浄に使用するためのものであり得る。 According to one embodiment of the present application, the semiconductor substrate cleaning liquid composition may be for use in chemical mechanical polishing (CMP) post cleaning.
本願の第２側面は、銅配線を含む半導体基板のＣＭＰ工程後洗浄方法を提供する。 A second aspect of the present application provides a method for cleaning a semiconductor substrate including copper wiring after a CMP process.
以下、本願の第２側面による銅配線を含む半導体基板のＣＭＰ工程後洗浄方法について説明する。 Hereinafter, a method for cleaning a semiconductor substrate including copper wiring after a CMP process according to the second aspect of the present application will be described.
具体的には、上記洗浄方法は銅配線を含む半導体基板に対して化学機械研磨（ＣＭＰ）工程を行うステップ；及び上記半導体基板に本願の第１側面による半導体基板洗浄液組成物を加えて洗浄を行うステップ；を含むことができる。 Specifically, the cleaning method includes performing a chemical mechanical polishing (CMP) process on a semiconductor substrate including copper wiring; and cleaning the semiconductor substrate by adding the semiconductor substrate cleaning liquid composition according to the first aspect of the present application to the semiconductor substrate. The steps may include: performing.
本願の一実施例によれば、上記ＣＭＰ工程はアルミナ（Ａｌ２Ｏ３）、コロイダルシリカ（ＳｉＯ２）、フュームドシリカ、セリア（ＣｅＯ２）などをベースとするＣＭＰスラリ－によって行われることができる。 According to an embodiment of the present application, the CMP process may be performed using a CMP slurry based on alumina (Al 2 O 3 ), colloidal silica (SiO 2 ), fumed silica, ceria (CeO 2 ), etc. can.
本願の一実施例によれば、上記方法において、上記洗浄を行うステップはスピン式又はスプレー式洗浄を用いることができ、さらには物理力による洗浄方法、例えば、洗浄ブラシを使用するスクラブ洗浄又は超音波洗浄を併用することによって基板に付着した汚染粒子の除去効率を向上させることができ、洗浄時間を短縮させることができる。 According to an embodiment of the present application, in the method, the step of cleaning can use spin or spray cleaning, and may also include physical cleaning methods, such as scrub cleaning using a cleaning brush or superfluous cleaning. By using sonic cleaning in combination, the removal efficiency of contaminant particles attached to the substrate can be improved, and the cleaning time can be shortened.
本願の一実施例によれば、上記洗浄ブラシは樹脂、例えばポリビニルアルコールを使用して製造されたものを使用できる。 According to one embodiment of the present application, the cleaning brush may be manufactured using a resin, such as polyvinyl alcohol.
化学機械研磨（ＣＭＰ）工程以降に銅粒子と銅配線／表面には銅酸化膜が自然的に生成される。また、研磨工程に使用されるスラリ－無機粒子と残留無機物はこのような銅酸化膜上に汚染源として残留することになる。研磨工程では上記のような銅酸化膜を選択的に除去して洗浄効果を達成することができ、研磨工程で生じる銅酸化物粒子などを容易に除去するとともに、銅膜に対しては損傷が少ない洗浄液が必要である。本発明による半導体基板洗浄液組成物は、基板表面に存在する研磨剤及び各種有機汚染物質を有効に除去できるだけでなく、銅配線の腐食を抑制できる効果を持つものである。 After the chemical mechanical polishing (CMP) process, a copper oxide film is naturally generated on the copper particles and copper wiring/surface. In addition, slurry inorganic particles and residual inorganic substances used in the polishing process remain on the copper oxide film as a source of contamination. In the polishing process, a cleaning effect can be achieved by selectively removing the copper oxide film as described above, and the copper oxide particles generated in the polishing process can be easily removed and the copper film will not be damaged. Less cleaning fluid is required. The semiconductor substrate cleaning liquid composition according to the present invention not only can effectively remove abrasives and various organic contaminants present on the substrate surface, but also has the effect of suppressing corrosion of copper wiring.
本発明者らは従来の銅ＣＭＰ工程後洗浄用組成物に含まれる第四級アンモニウムヒドロキシドとして、神経と筋肉に影響を及ぼし、さらには呼吸困難又は筋肉麻痺を引き起こす場合があると報告された物質であるテトラメチルアンモニウムヒドロキシド（ＴＭＡＨ）の代わりにテトラエチルアンモニウムヒドロキシド（ＴＥＡＨ）を使用し、金属腐食防止剤として従来使用されていたピリジンの代わりに１，２，４－トリアゾールを使用し、金属錯化剤としてアスコルビン酸の代わりにクエン酸を使用した場合、より安全なだけでなく、銅腐食速度及び銅表面粗さの面からより有効に銅ＣＭＰ工程後洗浄工程を行うことができることを確認することにより、本発明の完成に至った。 The present inventors reported that quaternary ammonium hydroxide contained in conventional post-copper CMP process cleaning compositions can affect nerves and muscles and even cause breathing difficulties or muscle paralysis. Tetraethylammonium hydroxide (TEAH) is used instead of the substance tetramethylammonium hydroxide (TMAH), and 1,2,4-triazole is used instead of pyridine, which is traditionally used as a metal corrosion inhibitor. It has been found that when citric acid is used instead of ascorbic acid as a metal complexing agent, it is not only safer but also more effective in terms of copper corrosion rate and copper surface roughness in the post-copper CMP cleaning process. By confirming this, the present invention was completed.
以下、本発明の属する技術分野における通常の知識を有する者が容易に実施できるようにするために、本発明の実施例について詳細に説明する。しかし、本発明は様々な互いに異なる形態に実装されることができ、ここで説明する実施例に限定されない。 DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the present invention will be described in detail so that those having ordinary knowledge in the technical field to which the present invention pertains can easily carry out the embodiments. However, the invention can be implemented in a variety of different forms and is not limited to the embodiments described herein.
実施例：半導体基板洗浄液組成物の製造 Example: Production of semiconductor substrate cleaning liquid composition
実施例１ Example 1
テトラエチルアンモニウムヒドロキシド（ＴＥＡＨ）１５．７ｗｔ％、モノエタノールアミン（ＭＥＡ）４．５ｗｔ％、クエン酸（Ｃｉｔｒｉｃ ａｃｉｄ）５ｗｔ％、１，２，４－Ｔｒｉａｚｏｌｅ ０．１ｗｔ％、ジエチレングリコール（ＤＥＧ）３ｗｔ％を混合して半導体基板洗浄液組成物を製造した。この時、残部は超純水である。 Tetraethylammonium hydroxide (TEAH) 15.7wt%, monoethanolamine (MEA) 4.5wt%, citric acid (Citric acid) 5wt%, 1,2,4-Triazole 0.1wt%, diethylene glycol (DEG) 3wt% A semiconductor substrate cleaning liquid composition was prepared by mixing the following. At this time, the remainder is ultrapure water.
実施例２ Example 2
テトラエチルアンモニウムヒドロキシド（ＴＥＡＨ）１５．７ｗｔ％、モノエタノールアミン（ＭＥＡ）４．５ｗｔ％、クエン酸（Ｃｉｔｒｉｃ ａｃｉｄ）４ｗｔ％、１，２，４－Ｔｒｉａｚｏｌｅ ０．１ｗｔ％、ジエチレングリコール（ＤＥＧ）３ｗｔ％を混合して半導体基板洗浄液組成物を製造した。この時、残部は超純水である。 Tetraethylammonium hydroxide (TEAH) 15.7wt%, monoethanolamine (MEA) 4.5wt%, citric acid (Citric acid) 4wt%, 1,2,4-Triazole 0.1wt%, diethylene glycol (DEG) 3wt% A semiconductor substrate cleaning liquid composition was prepared by mixing the following. At this time, the remainder is ultrapure water.
実施例３ Example 3
テトラエチルアンモニウムヒドロキシド（ＴＥＡＨ）１５．７ｗｔ％、クエン酸（Ｃｉｔｒｉｃ ａｃｉｄ）５ｗｔ％、グリシン（Ｇｌｙ）０．５ｗｔ％、１，２，４－Ｔｒｉａｚｏｌｅ ０．１ｗｔ％、ジエチレングリコール（ＤＥＧ）３ｗｔ％を混合して半導体基板洗浄液組成物を製造した。この時、残部は超純水である。 Mixed with 15.7 wt% of tetraethylammonium hydroxide (TEAH), 5 wt% of citric acid, 0.5 wt% of glycine (Gly), 0.1 wt% of 1,2,4-Triazole, and 3 wt% of diethylene glycol (DEG). A semiconductor substrate cleaning liquid composition was produced. At this time, the remainder is ultrapure water.
実施例４ Example 4
テトラエチルアンモニウムヒドロキシド（ＴＥＡＨ）１５．７ｗｔ％、モノエタノールアミン（ＭＥＡ）６．５ｗｔ％、クエン酸（Ｃｉｔｒｉｃ ａｃｉｄ）５ｗｔ％、１，２，４－Ｔｒｉａｚｏｌｅ ０．１ｗｔ％、ジエチレングリコール（ＤＥＧ）３ｗｔ％を混合して半導体基板洗浄液組成物を製造した。この時、残部は超純水である。 Tetraethylammonium hydroxide (TEAH) 15.7wt%, monoethanolamine (MEA) 6.5wt%, citric acid (Citric acid) 5wt%, 1,2,4-Triazole 0.1wt%, diethylene glycol (DEG) 3wt% A semiconductor substrate cleaning liquid composition was prepared by mixing the following. At this time, the remainder is ultrapure water.
実施例５ Example 5
テトラエチルアンモニウムヒドロキシド（ＴＥＡＨ）１５．７ｗｔ％、クエン酸（Ｃｉｔｒｉｃ ａｃｉｄ）５ｗｔ％、グリシン（Ｇｌｙ）０．５ｗｔ％、１，２，４－Ｔｒｉａｚｏｌｅ ０．１ｗｔ％、ジエチレングリコール（ＤＥＧ）１ｗｔ％を混合して半導体基板洗浄液組成物を製造した。この時、残部は超純水である。 Mixed with 15.7 wt% of tetraethylammonium hydroxide (TEAH), 5 wt% of citric acid, 0.5 wt% of glycine (Gly), 0.1 wt% of 1,2,4-Triazole, and 1 wt% of diethylene glycol (DEG). A semiconductor substrate cleaning liquid composition was produced. At this time, the remainder is ultrapure water.
実施例６ Example 6
テトラエチルアンモニウムヒドロキシド（ＴＥＡＨ）１２．７ｗｔ％、モノエタノールアミン（ＭＥＡ）４．５ｗｔ％、クエン酸（Ｃｉｔｒｉｃ ａｃｉｄ）５ｗｔ％、１，２，４－Ｔｒｉａｚｏｌｅ ０．１ｗｔ％、ジエチレングリコール（ＤＥＧ）３ｗｔ％を混合して半導体基板洗浄液組成物を製造した。この時、残部は超純水である。 Tetraethylammonium hydroxide (TEAH) 12.7wt%, monoethanolamine (MEA) 4.5wt%, citric acid (Citric acid) 5wt%, 1,2,4-Triazole 0.1wt%, diethylene glycol (DEG) 3wt% A semiconductor substrate cleaning liquid composition was prepared by mixing the following. At this time, the remainder is ultrapure water.
実施例７ Example 7
テトラエチルアンモニウムヒドロキシド（ＴＥＡＨ）１８．７ｗｔ％、モノエタノールアミン（ＭＥＡ）４．５ｗｔ％、クエン酸（Ｃｉｔｒｉｃ ａｃｉｄ）５ｗｔ％、１，２，４－Ｔｒｉａｚｏｌｅ ０．１ｗｔ％、ジエチレングリコール（ＤＥＧ）３ｗｔ％を混合して半導体基板洗浄液組成物を製造した。この時、残部は超純水である。 Tetraethylammonium hydroxide (TEAH) 18.7wt%, monoethanolamine (MEA) 4.5wt%, citric acid (Citric acid) 5wt%, 1,2,4-Triazole 0.1wt%, diethylene glycol (DEG) 3wt% A semiconductor substrate cleaning liquid composition was prepared by mixing the following. At this time, the remainder is ultrapure water.
実施例８ Example 8
ベンジルトリメチルアンモニウムヒドロキシド（ＢＴＭＡＨ）１５ｗｔ％、モノエタノールアミン（ＭＥＡ）４．５ｗｔ％、クエン酸（Ｃｉｔｒｉｃ ａｃｉｄ）５ｗｔ％、１，２，４－Ｔｒｉａｚｏｌｅ ０．１ｗｔ％、ジエチレングリコール（ＤＥＧ）３ｗｔ％を混合して半導体基板洗浄液組成物を製造した。この時、残部は超純水である。 Benzyltrimethylammonium hydroxide (BTMAH) 15wt%, monoethanolamine (MEA) 4.5wt%, citric acid (Citric acid) 5wt%, 1,2,4-Triazole 0.1wt%, diethylene glycol (DEG) 3wt%. A semiconductor substrate cleaning liquid composition was prepared by mixing. At this time, the remainder is ultrapure water.
実施例９ Example 9
ベンジルトリメチルアンモニウムヒドロキシド（ＢＴＭＡＨ）１５ｗｔ％、モノエタノールアミン（ＭＥＡ）４．５ｗｔ％、クエン酸（Ｃｉｔｒｉｃ ａｃｉｄ）５ｗｔを混合して半導体基板洗浄液組成物を製造した。この時、残部は超純水である。 A semiconductor substrate cleaning liquid composition was prepared by mixing 15 wt % of benzyltrimethylammonium hydroxide (BTMAH), 4.5 wt % of monoethanolamine (MEA), and 5 wt % of citric acid. At this time, the remainder is ultrapure water.
比較例１ Comparative example 1
テトラメチルアンモニウムヒドロキシド（ＴＭＡＨ）５ｗｔ％、モノエタノールアミン（ＭＥＡ）９ｗｔ％、アスコルビン酸（Ａｓｃｏｒｂｉｃ ａｃｉｄ）３．５ｗｔを混合して半導体基板洗浄液組成物を製造した。この時、残部は超純水である。 A semiconductor substrate cleaning liquid composition was prepared by mixing 5 wt % of tetramethylammonium hydroxide (TMAH), 9 wt % of monoethanolamine (MEA), and 3.5 wt % of ascorbic acid. At this time, the remainder is ultrapure water.
比較例２ Comparative example 2
テトラメチルアンモニウムヒドロキシド（ＴＭＡＨ）５ｗｔ％、モノエタノールアミン（ＭＥＡ）９ｗｔ％、クエン酸（Ｃｉｔｒｉｃ ａｃｉｄ）３．５ｗｔを混合して半導体基板洗浄液組成物を製造した。この時、残部は超純水である。 A semiconductor substrate cleaning liquid composition was prepared by mixing 5wt% of tetramethylammonium hydroxide (TMAH), 9wt% of monoethanolamine (MEA), and 3.5wt of citric acid. At this time, the remainder is ultrapure water.
下記表１に実施例１乃至９並びに比較例１及び２によって製造された半導体基板洗浄液組成物の造成を示した。
実験例１：銅（Ｃｕ）腐食速度評価 Experimental example 1: Copper (Cu) corrosion rate evaluation
実施例１乃至９並びに比較例１及び２によって製造された半導体基板洗浄液組成物の銅（Ｃｕ）腐食速度を評価した。 The copper (Cu) corrosion rate of the semiconductor substrate cleaning liquid compositions prepared in Examples 1 to 9 and Comparative Examples 1 and 2 was evaluated.
具体的には、上記実施例１乃至９並びに比較例１及び２の組成物をそれぞれ超純水に１００倍希釈し、２５℃に温度を調整した後、２０ｍｍ×２０ｍｍサイズのＣｕウェーハを３０分間浸漬した後、取り出してＤＩＷで洗浄し、窒素ガスを使用してウェーハを乾燥した後、シート抵抗測定器（（株）ＡｉＴ社、大韓民国）を用いて腐食程度を測定した。 Specifically, the compositions of Examples 1 to 9 and Comparative Examples 1 and 2 were each diluted 100 times with ultrapure water, the temperature was adjusted to 25°C, and then a Cu wafer of 20 mm x 20 mm size was heated for 30 minutes. After immersion, the wafer was taken out, cleaned with DIW, dried using nitrogen gas, and then the degree of corrosion was measured using a sheet resistance measuring device (AiT Co., Ltd., Republic of Korea).
実験例２：銅（Ｃｕ）表面粗さ評価 Experimental example 2: Copper (Cu) surface roughness evaluation
実施例１乃至９並びに比較例１及び２によって製造された半導体基板洗浄液組成物の銅（Ｃｕ）表面粗さを評価した。 The copper (Cu) surface roughness of the semiconductor substrate cleaning liquid compositions manufactured in Examples 1 to 9 and Comparative Examples 1 and 2 was evaluated.
具体的には、上記実施例１乃至９並びに比較例１及び２の組成物をそれぞれ超純水に１，０００倍希釈し、２５℃に温度を調整した後、２０ｍｍ×２０ｍｍサイズのＣｕウェーハを１０分間浸漬した後、取り出してＤＩＷで洗浄し、窒素ガスを使用してウェーハを乾燥した後、原子間力顕微鏡（ＡＦＭ、パークシステムズ社、大韓民国）を使用して非接触モードでＣｕ表面粗さを測定した。 Specifically, the compositions of Examples 1 to 9 and Comparative Examples 1 and 2 were each diluted 1,000 times with ultrapure water, the temperature was adjusted to 25°C, and then a Cu wafer of 20 mm x 20 mm size was diluted. After immersion for 10 min, the wafer was taken out and cleaned with DIW, dried using nitrogen gas, and then the Cu surface roughness was measured in a non-contact mode using an atomic force microscope (AFM, Park Systems Inc., Republic of Korea). was measured.
実験例３：粒子除去能力評価 Experimental example 3: Evaluation of particle removal ability
実施例１乃至９並びに比較例１及び２によって製造された半導体基板洗浄液組成物の粒子除去能力を評価した。 The particle removal ability of the semiconductor substrate cleaning liquid compositions prepared in Examples 1 to 9 and Comparative Examples 1 and 2 was evaluated.
具体的には、コロイダルシリカ１４ｗｔ％濃度にＫＯＨを使用してｐＨ１３にした後、２０ｍｍ×２０ｍｍサイズのＣｕウェーハを２分浸漬後、取り出してＤＩＷで洗浄し、窒素ガスを使用してウェーハを乾燥した。上記実施例１乃至９並びに比較例１及び２の組成物をそれぞれ超純水に１００倍希釈した洗浄液に上記Ｃｕウェーハを１分浸漬後、取り出してＤＩＷで洗浄し、窒素ガスを使用してウェーハを乾燥した後、走査電子顕微鏡（ＳＥＭ、日立製作所社、日本）を使用して２万倍の倍率でのＣｕウェーハ表面の残余粒子数を測定して粒子除去能力を確認した。この時、評価基準は、○：５個未満、△：５～１０個、Ｘ：１１個以上である。 Specifically, after adjusting the pH to 13 using KOH with colloidal silica at a concentration of 14 wt%, a 20 mm x 20 mm size Cu wafer was immersed for 2 minutes, then taken out and cleaned with DIW, and the wafer was dried using nitrogen gas. did. The Cu wafer was immersed for 1 minute in a cleaning solution prepared by diluting each of the compositions of Examples 1 to 9 and Comparative Examples 1 and 2 100 times with ultrapure water for 1 minute, and then taken out and cleaned with DIW. After drying, the number of residual particles on the surface of the Cu wafer was measured using a scanning electron microscope (SEM, Hitachi, Ltd., Japan) at a magnification of 20,000 times to confirm the particle removal ability. At this time, the evaluation criteria are: ○: less than 5 pieces, Δ: 5 to 10 pieces, X: 11 pieces or more.
実験例４：有機物除去能力評価 Experimental example 4: Evaluation of organic matter removal ability
実施例１乃至９並びに比較例１及び２によって製造された半導体基板洗浄液組成物の有機物除去能力を評価した。 The organic matter removal ability of the semiconductor substrate cleaning liquid compositions produced in Examples 1 to 9 and Comparative Examples 1 and 2 was evaluated.
具体的には、ＤＩＷに１，２，４トリアゾール０．５ｗｔ％濃度に２０ｍｍ×２０ｍｍサイズのＣｕウェーハを３０分間浸漬した後、取り出してＤＩＷで洗浄し、窒素ガスを使用してウェーハを乾燥した。上記実施例１乃至９並びに比較例１及び２の組成物をそれぞれ超純水に１００倍希釈した洗浄液に上記Ｃｕウェーハを２０分間浸漬後、洗浄液１０ｇを採取して高性能液体クロマトグラフィー（ＨＰＬＣ、Ａｇｉｌｅｎｔ社、米国）によって１，２，４トリアゾールの含量を測定した。 Specifically, a 20 mm x 20 mm size Cu wafer was immersed in DIW at a concentration of 0.5 wt% 1,2,4 triazole for 30 minutes, then taken out, cleaned with DIW, and dried using nitrogen gas. . After immersing the Cu wafer in a cleaning solution prepared by diluting each of the compositions of Examples 1 to 9 and Comparative Examples 1 and 2 100 times with ultrapure water for 20 minutes, 10 g of the cleaning solution was collected and subjected to high performance liquid chromatography (HPLC). The content of 1,2,4 triazole was determined by Agilent, USA).
上記実験例１乃至４に対する結果を下記表２に示した。
上記表２を参照すると、第四級アンモニウムヒドロキシドとしてテトラエチルアンモニウムヒドロキシド（ＴＥＡＨ）又はベンジルトリメチルアンモニウムヒドロキシド（ＢＴＭＡＨ）を使用した実施例１乃至９がテトラメチルアンモニウムヒドロキシド（ＴＭＡＨ）を使用した比較例１及び２に比べて銅腐食速度及び銅表面粗さの面からより優れた効果を持つことが確認できた。 Referring to Table 2 above, Examples 1 to 9 which used tetraethylammonium hydroxide (TEAH) or benzyltrimethylammonium hydroxide (BTMAH) as the quaternary ammonium hydroxide, used tetramethylammonium hydroxide (TMAH). It was confirmed that compared to Comparative Examples 1 and 2, it had better effects in terms of copper corrosion rate and copper surface roughness.
テトラエチルアンモニウムヒドロキシド（ＴＥＡＨ）の含量が１２．７ｗｔ％である実施例６の場合、粒子除去能力が他の実施例に比べてやや劣ることが確認できた。 In the case of Example 6, in which the content of tetraethylammonium hydroxide (TEAH) was 12.7 wt%, it was confirmed that the particle removal ability was slightly inferior compared to other Examples.
また、実施例１で有機アミンであるモノエタノールアミン（ＭＥＡ）の代わりに金属錯化剤としてグリシン（Ｇｌｙ）を含む実施例３の場合、銅腐食速度、銅表面粗さだけでなく有機物除去能力により優れることが確認できた。すなわち、実施例１乃至９の中で実施例３が最も優れた効果を示すことが確認できた。 In addition, in the case of Example 3, which contains glycine (Gly) as a metal complexing agent instead of the organic amine monoethanolamine (MEA) in Example 1, not only the copper corrosion rate and copper surface roughness but also the organic matter removal ability It was confirmed that the results were superior. That is, it was confirmed that among Examples 1 to 9, Example 3 exhibited the most excellent effect.
錯化剤としてアスコルビン酸を使用する比較例１の場合、アスコルビン酸の酸化反応によって褐変現象が起こり、この場合、アスコルビン酸は金属錯化剤としての機能を正しく発揮できなくなるので、アスコルビン酸は使用しないことが好ましい。 In the case of Comparative Example 1 in which ascorbic acid is used as a complexing agent, a browning phenomenon occurs due to the oxidation reaction of ascorbic acid, and in this case, ascorbic acid cannot properly function as a metal complexing agent, so ascorbic acid is not used. It is preferable not to do so.
以上、図面を参照して好ましい実施例とともに本発明について詳しく説明したが、このような図面と実施例で本発明の技術的思想の範囲が限定されるわけではない。したがって、本発明の技術的思想の範囲内で多様な変形例又は均等な範囲の実施例が存在し得る。よって、本発明による技術的思想の権利範囲は請求範囲によって解釈され、それと同等又は均等な範囲内の技術思想は本発明の権利範囲に属する。 Although the present invention has been described above in detail along with preferred embodiments with reference to the drawings, the scope of the technical idea of the present invention is not limited by these drawings and embodiments. Therefore, various modifications or equivalent embodiments may exist within the scope of the technical idea of the present invention. Therefore, the scope of the technical ideas according to the present invention shall be interpreted according to the scope of the claims, and technical ideas within the scope equivalent or equivalent thereto belong to the scope of the rights of the present invention.
Claims (13)
前記組成物全体重量に対して、前記第四級アンモニウムヒドロキシド１乃至２０重量％及び前記金属錯化剤０．１乃至１０重量％を含む
ことを特徴とする半導体基板洗浄液組成物。 A semiconductor substrate cleaning liquid composition comprising: a quaternary ammonium hydroxide and a metal complexing agent;
A semiconductor substrate cleaning liquid composition comprising 1 to 20% by weight of the quaternary ammonium hydroxide and 0.1 to 10% by weight of the metal complexing agent based on the total weight of the composition.
請求項１に記載の半導体基板洗浄液組成物。 The quaternary ammonium hydroxides include tetraethylammonium hydroxide (TEAH), tetrabutylammonium hydroxide (TBAH), tetrapropylammonium hydroxide, trimethylethylammonium hydroxide, benzyltrimethylammonium hydroxide (BTMAH), (hydroxyethyl) Consisting of trimethylammonium hydroxide, (hydroxyethyl)triethylammonium hydroxide, (hydroxyethyl)tripropylammonium hydroxide, (hydroxypropyl)trimethylammonium hydroxide, ethyltrimethylammonium hydroxide, diethyldimethylammonium hydroxide and choline hydroxide The semiconductor substrate cleaning liquid composition according to claim 1, comprising one or more selected from the group.
請求項２に記載の半導体基板洗浄液組成物。 3. The semiconductor substrate cleaning liquid composition according to claim 2, wherein the quaternary ammonium hydroxide contains one or more selected from the group consisting of tetraethylammonium hydroxide (TEAH) and benzyltrimethylammonium hydroxide (BTMAH).
請求項１に記載の半導体基板洗浄液組成物。 The semiconductor substrate cleaning liquid composition according to claim 1, wherein the metal complexing agent contains one or more selected from the group consisting of organic acids and amino acids.
請求項４に記載の半導体基板洗浄液組成物。 The organic acids include citric acid, lactic acid, formic acid, oxalic acid, acetic acid, propionic acid, malonic acid, succinic acid, glutaric acid, maleic acid, fumaric acid, phthalic acid, glycolic acid, gluconic acid, salicylic acid, tartaric acid and malic acid. The semiconductor substrate cleaning liquid composition according to claim 4, comprising one or more selected from the group consisting of:
請求項４に記載の半導体基板洗浄液組成物。 The semiconductor substrate cleaning liquid composition according to claim 4, which contains 1 to 7% by weight of the organic acid based on the total weight of the composition.
請求項４に記載の半導体基板洗浄液組成物。 The amino acid includes one or more selected from the group consisting of glycine, serine, threonine, alanine, valine, bicine, and tricine. Item 4. The semiconductor substrate cleaning liquid composition according to item 4.
請求項４に記載の半導体基板洗浄液組成物。 The semiconductor substrate cleaning liquid composition according to claim 4, comprising 0.1 to 1% by weight of the amino acid based on the total weight of the composition.
請求項１に記載の半導体基板洗浄液組成物。 The semiconductor substrate cleaning liquid composition according to claim 1, wherein the composition further contains one or more selected from the group consisting of organic amines, corrosion inhibitors, and surfactants.
請求項９に記載の半導体基板洗浄液組成物。 The organic amines include monoethanolamine (MEA), ethylhexylamine, methylamine, dimethylamine, ethylamine, diethylamine, ethanolamine, diethanolamine, methyldiethanolamine, triethylamine, trimethylamine, triethanolamine, isopropanolamine, diisopropanolamine, triisopropanolamine. , nitrosodiethanolamine, butylamine, 3-methoxypropylamine, tert-butylamine, benzylamine, hexylamine, cyclohexylamine, octylamine, N-methyl-N-butylamine, N-(3-aminopropyl)morpholine, aminoethanol, xylene The semiconductor substrate cleaning liquid composition according to claim 9, comprising one or more selected from the group consisting of diamine, dodecylamine, (hydroxyethyloxymethyl)diethylamine, dimethylhydroxylamine, diethylhydroxylamine, and dibutylhydroxylamine.
請求項９に記載の半導体基板洗浄液組成物。 10. The corrosion inhibitor includes one or more selected from the group consisting of 1,2,4-triazole, benzotriazole, pyrazole, 5-aminotetrazole, and 3-amino-1,2,4-triazole. The semiconductor substrate cleaning liquid composition described above.
請求項９に記載の半導体基板洗浄液組成物。 10. The semiconductor substrate cleaning liquid composition according to claim 9, wherein the surfactant includes diethylene glycol (DEG).
前記半導体基板に請求項１に記載の半導体基板洗浄液組成物を加えて洗浄を行うステップ；とを含む銅配線を含む
ことを特徴とする半導体基板のＣＭＰ工程後洗浄方法。
performing a chemical mechanical polishing (CMP) process on a semiconductor substrate including copper wiring;
A method for cleaning a semiconductor substrate after a CMP process, the method comprising a step of cleaning the semiconductor substrate by adding the semiconductor substrate cleaning liquid composition according to claim 1 to the semiconductor substrate.
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| JP2011243610A (en) * | 2010-05-14 | 2011-12-01 | Fujifilm Corp | Cleaning composition, semiconductor device manufacturing method and cleaning method |
| JP2014154625A (en) * | 2013-02-06 | 2014-08-25 | Mitsubishi Chemicals Corp | Cleaning solvent for semiconductor device substrate, and cleaning method |
| WO2021054010A1 (en) * | 2019-09-18 | 2021-03-25 | 富士フイルムエレクトロニクスマテリアルズ株式会社 | Cleaning solution and cleaning method |
| WO2021230063A1 (en) * | 2020-05-15 | 2021-11-18 | 富士フイルムエレクトロニクスマテリアルズ株式会社 | Cleaning solution and method for cleaning semiconductor substrate |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2011243610A (en) * | 2010-05-14 | 2011-12-01 | Fujifilm Corp | Cleaning composition, semiconductor device manufacturing method and cleaning method |
| JP2014154625A (en) * | 2013-02-06 | 2014-08-25 | Mitsubishi Chemicals Corp | Cleaning solvent for semiconductor device substrate, and cleaning method |
| WO2021054010A1 (en) * | 2019-09-18 | 2021-03-25 | 富士フイルムエレクトロニクスマテリアルズ株式会社 | Cleaning solution and cleaning method |
| WO2021230063A1 (en) * | 2020-05-15 | 2021-11-18 | 富士フイルムエレクトロニクスマテリアルズ株式会社 | Cleaning solution and method for cleaning semiconductor substrate |
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