TWI434929B - 清潔半導體基材用的組成物與方法 - Google Patents
清潔半導體基材用的組成物與方法 Download PDFInfo
- Publication number
- TWI434929B TWI434929B TW099132618A TW99132618A TWI434929B TW I434929 B TWI434929 B TW I434929B TW 099132618 A TW099132618 A TW 099132618A TW 99132618 A TW99132618 A TW 99132618A TW I434929 B TWI434929 B TW I434929B
- Authority
- TW
- Taiwan
- Prior art keywords
- acid
- hydroxide
- diphosphonic
- cleaning solution
- alkyl
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims description 60
- 238000004140 cleaning Methods 0.000 title claims description 24
- 238000000034 method Methods 0.000 title claims description 24
- 239000000758 substrate Substances 0.000 title claims description 13
- 239000004065 semiconductor Substances 0.000 title claims description 9
- -1 alkyl diphosphonic acid Chemical compound 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 23
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 21
- 150000007513 acids Chemical class 0.000 claims description 18
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 15
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 claims description 14
- 150000007514 bases Chemical class 0.000 claims description 14
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 14
- 239000004094 surface-active agent Substances 0.000 claims description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 11
- 229920002125 Sokalan® Polymers 0.000 claims description 10
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 10
- 239000000460 chlorine Substances 0.000 claims description 10
- 229910021645 metal ion Inorganic materials 0.000 claims description 10
- 239000004584 polyacrylic acid Substances 0.000 claims description 10
- 239000002253 acid 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 8
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 8
- 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 8
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 8
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 8
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 8
- 239000012458 free base Substances 0.000 claims description 8
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 claims description 8
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 8
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 150000005622 tetraalkylammonium hydroxides Chemical class 0.000 claims description 8
- 235000015165 citric acid Nutrition 0.000 claims description 7
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- XOAAWQZATWQOTB-UHFFFAOYSA-N taurine Chemical compound NCCS(O)(=O)=O XOAAWQZATWQOTB-UHFFFAOYSA-N 0.000 claims description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 150000003973 alkyl amines Chemical class 0.000 claims description 5
- 150000004982 aromatic amines Chemical class 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- 239000012895 dilution Substances 0.000 claims description 5
- 238000010790 dilution Methods 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 235000006408 oxalic acid Nutrition 0.000 claims description 5
- JIRHAGAOHOYLNO-UHFFFAOYSA-N (3-cyclopentyloxy-4-methoxyphenyl)methanol Chemical compound COC1=CC=C(CO)C=C1OC1CCCC1 JIRHAGAOHOYLNO-UHFFFAOYSA-N 0.000 claims description 4
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 4
- YMOJUZRGXNRXAD-UHFFFAOYSA-N (cyclohexyl-hydroxy-phosphonomethyl)phosphonic acid Chemical compound OP(=O)(O)C(P(O)(O)=O)(O)C1CCCCC1 YMOJUZRGXNRXAD-UHFFFAOYSA-N 0.000 claims description 4
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- GIAFURWZWWWBQT-UHFFFAOYSA-N 2-(2-aminoethoxy)ethanol Chemical compound NCCOCCO GIAFURWZWWWBQT-UHFFFAOYSA-N 0.000 claims description 4
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 4
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 claims description 4
- RILZRCJGXSFXNE-UHFFFAOYSA-N 2-[4-(trifluoromethoxy)phenyl]ethanol Chemical compound OCCC1=CC=C(OC(F)(F)F)C=C1 RILZRCJGXSFXNE-UHFFFAOYSA-N 0.000 claims description 4
- BKMMTJMQCTUHRP-UHFFFAOYSA-N 2-aminopropan-1-ol Chemical compound CC(N)CO BKMMTJMQCTUHRP-UHFFFAOYSA-N 0.000 claims description 4
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- 239000005711 Benzoic acid Substances 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 4
- 239000005751 Copper oxide Substances 0.000 claims description 4
- 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 4
- 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 4
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims description 4
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 claims description 4
- WUGQZFFCHPXWKQ-UHFFFAOYSA-N Propanolamine Chemical compound NCCCO WUGQZFFCHPXWKQ-UHFFFAOYSA-N 0.000 claims description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 4
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 claims description 4
- 125000000129 anionic group Chemical group 0.000 claims description 4
- 235000010323 ascorbic acid Nutrition 0.000 claims description 4
- 239000011668 ascorbic acid Substances 0.000 claims description 4
- 229960005070 ascorbic acid Drugs 0.000 claims description 4
- 229960001716 benzalkonium Drugs 0.000 claims description 4
- CYDRXTMLKJDRQH-UHFFFAOYSA-N benzododecinium Chemical compound CCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 CYDRXTMLKJDRQH-UHFFFAOYSA-N 0.000 claims description 4
- 235000010233 benzoic acid Nutrition 0.000 claims description 4
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 4
- 125000002091 cationic group Chemical group 0.000 claims description 4
- 229940075419 choline hydroxide Drugs 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 229910000431 copper oxide Inorganic materials 0.000 claims description 4
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 4
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 claims description 4
- 235000019253 formic acid Nutrition 0.000 claims description 4
- GSTNAAOCEHQZDY-UHFFFAOYSA-N formic acid phosphane Chemical compound [PH4+].[O-]C=O GSTNAAOCEHQZDY-UHFFFAOYSA-N 0.000 claims description 4
- 229940074391 gallic acid Drugs 0.000 claims description 4
- 235000004515 gallic acid Nutrition 0.000 claims description 4
- 239000000174 gluconic acid Substances 0.000 claims description 4
- 235000012208 gluconic acid Nutrition 0.000 claims description 4
- 150000002443 hydroxylamines Chemical class 0.000 claims description 4
- 229940102253 isopropanolamine Drugs 0.000 claims description 4
- 239000004310 lactic acid Substances 0.000 claims description 4
- 235000014655 lactic acid Nutrition 0.000 claims description 4
- MBKDYNNUVRNNRF-UHFFFAOYSA-N medronic acid Chemical compound OP(O)(=O)CP(O)(O)=O MBKDYNNUVRNNRF-UHFFFAOYSA-N 0.000 claims description 4
- HJZKOAYDRQLPME-UHFFFAOYSA-N oxidronic acid Chemical compound OP(=O)(O)C(O)P(O)(O)=O HJZKOAYDRQLPME-UHFFFAOYSA-N 0.000 claims description 4
- 229960004230 oxidronic acid Drugs 0.000 claims description 4
- 229920000141 poly(maleic anhydride) Polymers 0.000 claims description 4
- 235000019260 propionic acid Nutrition 0.000 claims description 4
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 4
- 239000011975 tartaric acid Substances 0.000 claims description 4
- 235000002906 tartaric acid Nutrition 0.000 claims description 4
- QHQZEEGNGSZBOL-UHFFFAOYSA-N 2-(aminomethyl)-2-(hydroxymethyl)propane-1,3-diol Chemical compound NCC(CO)(CO)CO QHQZEEGNGSZBOL-UHFFFAOYSA-N 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
- ACSIXWWBWUQEHA-UHFFFAOYSA-N clodronic acid Chemical compound OP(O)(=O)C(Cl)(Cl)P(O)(O)=O ACSIXWWBWUQEHA-UHFFFAOYSA-N 0.000 claims description 3
- 229960002286 clodronic acid Drugs 0.000 claims description 3
- 239000001630 malic acid Substances 0.000 claims description 3
- 235000011090 malic acid Nutrition 0.000 claims description 3
- 229960003080 taurine Drugs 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 2
- 239000004020 conductor Substances 0.000 claims description 2
- 239000003989 dielectric material Substances 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims 2
- BAVYZALUXZFZLV-UHFFFAOYSA-O Methylammonium ion Chemical compound [NH3+]C BAVYZALUXZFZLV-UHFFFAOYSA-O 0.000 claims 2
- IVFGIXMLURJXBZ-UHFFFAOYSA-N 1-phosphonopropylphosphonic acid Chemical compound CCC(P(O)(O)=O)P(O)(O)=O IVFGIXMLURJXBZ-UHFFFAOYSA-N 0.000 claims 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 claims 1
- 239000007983 Tris buffer Substances 0.000 claims 1
- 125000003277 amino group Chemical group 0.000 claims 1
- 239000008367 deionised water Substances 0.000 claims 1
- 229910021641 deionized water Inorganic materials 0.000 claims 1
- 238000005530 etching Methods 0.000 claims 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 1
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 4
- IJGSGCGKAAXRSC-UHFFFAOYSA-M tris(2-hydroxyethyl)-methylazanium;hydroxide Chemical compound [OH-].OCC[N+](C)(CCO)CCO IJGSGCGKAAXRSC-UHFFFAOYSA-M 0.000 description 4
- 235000012431 wafers Nutrition 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000000356 contaminant Substances 0.000 description 3
- 238000005498 polishing Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 3
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 229910000420 cerium oxide Inorganic materials 0.000 description 2
- 239000002738 chelating agent Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 description 1
- CNPURSDMOWDNOQ-UHFFFAOYSA-N 4-methoxy-7h-pyrrolo[2,3-d]pyrimidin-2-amine Chemical compound COC1=NC(N)=NC2=C1C=CN2 CNPURSDMOWDNOQ-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229920001174 Diethylhydroxylamine Polymers 0.000 description 1
- 239000013543 active substance 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
- 150000003868 ammonium compounds Chemical class 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- BRXCDHOLJPJLLT-UHFFFAOYSA-N butane-2-sulfonic acid Chemical compound CCC(C)S(O)(=O)=O BRXCDHOLJPJLLT-UHFFFAOYSA-N 0.000 description 1
- 229960004106 citric acid Drugs 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- FVCOIAYSJZGECG-UHFFFAOYSA-N diethylhydroxylamine Chemical compound CCN(O)CC FVCOIAYSJZGECG-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- YECKUPRAIDRPKU-UHFFFAOYSA-N ethane-1,2-diamine hydrazine Chemical compound NN.NCCN YECKUPRAIDRPKU-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical group 0.000 description 1
- 229960000448 lactic acid Drugs 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 229940116315 oxalic acid Drugs 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic 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
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/042—Acids
-
- 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
-
- 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
- C11D3/24—Organic compounds containing halogen
- C11D3/245—Organic compounds containing halogen containing fluorine
-
- 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
- C11D3/34—Organic compounds containing sulfur
- C11D3/3418—Toluene -, xylene -, cumene -, benzene - or naphthalene sulfonates or sulfates
-
- 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
- C11D3/34—Organic compounds containing sulfur
- C11D3/349—Organic compounds containing sulfur additionally containing nitrogen atoms, e.g. nitro, nitroso, amino, imino, nitrilo, nitrile groups containing compounds or their derivatives or thio urea
-
- 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
- C11D3/36—Organic compounds containing phosphorus
- C11D3/361—Phosphonates, phosphinates or phosphonites
-
- 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
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Description
本申請案主張2009年10月24日申請之美國臨時性專利申請案61/254669號的優先權。
本發明關於用於自金屬或介電表面或化學機械拋光銅或鋁表面後除去化學殘留物的組成物及方法，其包含一含有烷基二膦酸化合物之水溶液，並施加經歷足以除去化學殘留物的時間。
美國專利6,143,705號、6,310,019號、6,440,856號、6,514,352號、6,514,921號、6,534,458號、6,541,434號、6,716,803號、7,250,391號、7,312,186號及7,541,322號揭示各種用於清潔半導體基材之組成物及方法，該等組成物含有膦酸。
美國專利6,395,693號及6,541,434號揭示一種在半導體晶圓經化學機械拋光後清潔該半導體晶圓表面之污染物的組成物及方法，該方法包含將帶有研磨料微粒及金屬離子污染物之該半導體晶圓表面與一包含數量在約2重量%或更少之羧酸、約0.1重量%或更少之含胺化合物及約2重量%或更少之該膦酸的組成物接觸。該清潔組成物較合宜地具有約4-6之pH。較佳地該清潔組成物具有約4.5-5.5的pH。膦酸對羧酸之重量比為1：1。
美國專利申請案200110051597號揭示一種檸檬酸濃度大於1體積%之水溶液，且將螯合劑以10 ppm或更多加到該含有檸檬酸之水溶液中。膦酸對羧酸之重量比為1：1000(亦即10 ppm膦酸對1%檸檬酸)。
膦酸，特別是1-羥乙烷-1,1-二膦酸(一般稱為HEDPA)，其作為腐蝕抑制劑及錯合劑而用於商業用途已多年。已充分了解當HEDPA係以數量小於30份對百萬份水來使用時，可作用為腐蝕抑制劑。超過150份對百萬份水時則充當為螯合劑。在30-150份HEDPA對百萬份水的範圍內會有死區；HEDPA無法執行運作。
本發明關於用於清潔半導體基材之組成物及方法。本發明在半導體製造過程及其類似者中可特別應用作為殘留物及微粒之去除劑。
所含括的一個具體實施例係為清潔溶液，其包含基本結構如下之烷基二膦酸：
其中R1
及R2
係相同或不同並選自由下列所組成之群組：氫(H)、氫氧化物(OH)、氯(Cl)、具有1至約8個碳原子之烷基或芳基及烷基胺或芳基胺。某些組成物含有第二酸性化合物、緩衝數量之一或多種金屬離子游離鹼性化合物以調節pH大於6至約10、隨意地從0重量%及最多至5重量%之表面活性劑、及剩餘量為水。
所含括之組成物可具有烷基二膦酸對第二酸性化合物之莫耳比為約1：1至約10：1。
較佳之烷基二膦酸係為1-羥乙烷-1,1-二膦酸、亞甲基二膦酸、羥亞甲基二膦酸、二氯亞甲基二膦酸、羥環己基亞甲基二膦酸、1-羥基-3-胺丙烷-1,1-二膦酸、1-羥基-4-胺丁烷-1,1-二膦酸、及彼等之混合物。
在組成物含有第二酸之情況下，舉例之，此第二酸可為十二烷基苯磺酸、二甲苯磺酸、甲苯磺酸、磷醯基甲酸、胺基磺酸、2-胺基乙磺酸、氟硼酸或有機羧酸。該組成物也可包含有機羧酸。
在組成物含有有機羧酸之情況下，該酸可為草酸、乳酸、檸檬酸、甲酸、酒石酸、丙酸、苯甲酸、抗壞血酸、葡糖酸、蘋果酸、丙二酸、琥珀酸、五倍子酸、丁酸、三氟乙酸及彼等之混合物。
同時可預期的是，該等組成物也可包含緩衝鹼性化合物，例如氫氧化鉀、氫氧化鈉及金屬離子游離鹼。該等組成物可包含此一化合物或化合物混合物。
金屬離子游離鹼性化合物或混合物可為由下所組成之鹼性化合物中之至少一者：羥基胺游離鹼或羥基胺衍生物、氫氧化四烷基銨(TMAH)、氫氧化四烷基銨五水合物(TMAH五水合物)、氫氧化苄四甲銨(BTMAH)、氫氧化四丁銨(TBAH)、膽鹼氫氧化物、或氫氧化三(2-羥乙基)甲銨(THEMAH)、一乙醇胺、2-(2-羥乙胺基)乙醇、2-(2-胺乙氧基)乙醇、N,N,N-三(2-羥乙基)氨、異丙醇胺、3-胺基-1-丙醇、2-胺基-1-丙醇、2-(N-甲胺基)乙醇、2-(2-胺乙胺基)乙醇、三(羥甲基)胺基乙烷、或彼等之混合物。
較佳之pH範圍係從大於6至約10。
表面活性劑也可用於本文所含括之組成物中。較佳之表面活性劑包括非離子性、陰離子性、陽離子性、及/或兩性、聚丙烯酸或其水溶性鹽類、或水解之聚馬來酸酐或其水溶性鹽類及其類似者。
在某些應用中，舉例之，該等組成物可在稀釋比最多至1：10、最多至1：50、最多至1：100、最多至1：150、最多至1：250、及最多至1：500或本文中之任何比例下以DI水稀釋。HEDPA與表面活性劑組合可產生協同效果。表面活性劑不僅作用為分散劑，當HEDPA以超過150份對百萬份水的濃度使用時也可增進HEDPA之殘留物溶解性能。
一種利用本文所述之組成物的方法，其包含提供一基材，該基材具有的表面包含含銅導體及低-k介電物質及一或多種位於該表面上之阻劑、蝕刻殘留物、平面化殘留物、及氧化銅，該基材係自嵌入式或雙嵌入式製造過程中產生；將該基材表面與有效量之含有基本結構如下之烷基二膦酸的溶液接觸：
其中R1
及R2
係相同或不同並選自由下列所組成之群組：氫(H)、氫氧化物(OH)、氯(Cl)、具有1至約8個碳原子之烷基或芳基及烷基胺或芳基胺，該溶液可加入第二酸性化合物及緩衝數量之鹼性化合物以調節pH大於6至約10，隨意地還可包含0重量%及最多至5重量%之表面活性劑，及剩餘量的水。此組成物係在足以除去阻劑、殘留物及/或氧化銅之時間與溫度下與基材接觸。用於此方法之較佳溫度係從約常溫至約70℃，更佳地為約50℃，且較佳的接觸時間係在約10秒與約30分鐘之間。本文所述之組成物可在半導體製造過程期間用於跟隨著化學機械拋光之平面化步驟後面的清潔過程，以及用於熟諳此藝者已知之其他適當的清潔過程。
本發明關於一種改良之清潔溶液，該溶液係為烷基二膦酸與第二酸性化合物在莫耳比約1：1至約10：1下溶於水的摻合物。
烷基二膦酸之基本結構如下：
其中R1
及R2
係相同或不同並選自由下列所組成之群組：氫(H)、氫氧化物(OH)、氯(Cl)、具有1至約8個碳原子之烷基或芳基及烷基胺或芳基胺。
烷基二膦酸之實例如下列：
根據本發明，係將1至10莫耳的烷基二膦酸與1莫耳的下列酸性物質中之一者混合。
適當之烷基二膦酸包括，但不限於1-羥乙烷-1,1-二膦酸、亞甲基二膦酸、羥亞甲基二膦酸、二氯亞甲基二膦酸、羥環己基亞甲基二膦酸、1-羥基-3-胺丙烷-1,1-二膦酸、1-羥基-4-胺丁烷-1,1-二膦酸及其類似者。
適當之酸包括甲磺酸、草酸、乳酸、檸檬酸、十二烷基苯磺酸、二甲苯磺酸、甲苯磺酸、甲酸、酒石酸、丙酸、苯甲酸、抗壞血酸、葡糖酸、蘋果酸、丙二酸、琥珀酸、五倍子酸、丁酸、三氟乙酸、磷醯基甲酸、胺基磺酸、草酸、羥基乙酸、2-胺基乙磺酸、或氟硼酸及彼等之混合物。
該混合物或摻合物係經緩衝數量之鹼性化合物調節至pH大於6至約10，而這些鹼性化合物為氫氧化鉀、氫氧化鈉及由下列之銨化合物所組成之金屬離子游離鹼化合物：氫氧化銨、氫氧化四烷基銨(TMAH)、氫氧化四烷基銨五水合物(TMAH五水合物)、氫氧化苄四甲銨(BTMAH)、TBAH、膽鹼氫氧化物、或氫氧化三(2-羥乙基)甲銨(THEMAH)、羥基胺游離鹼、羥基胺衍生物如N,N-二乙羥基胺、烷醇胺組份，該烷醇胺包括但不限於肼、乙二胺、一乙醇胺、N,N-二乙胺基乙醇、2-(2-羥乙胺基)乙醇、2-(2-胺乙氧基)乙醇、N,N,N-三(2-羥乙基)氨、異丙醇胺、3-胺基-1-丙醇、、2-胺基-1-丙醇、2-(N-甲胺基)乙醇、2-(2-胺基乙胺基)乙醇、三(羥甲基)胺基乙烷、或彼等之混合物。
鹼性緩衝劑之數量可為最多至約25重量%。
較佳之pH係從大於6至約10。
下列係作為解說性實施例的各摻合物之明細表。
pH之調節表示為中間值，舉例之，調節至pH 7表示約6.5＜pH＜約7.5；調節至pH 8表示約75＜pH＜約8.5；等。
此實施例說明在本發明之清潔組成物中烷基二膦酸對第二酸性組份之莫耳比，對減少基材表面上之漿料微粒殘留物及金屬離子殘留物的重要性。
將氧化矽晶圓浸入銅污染之漿料30秒。然後以上文所列之各別組成物清洗該等氧化矽晶圓，接著以DI水沖洗。其會完全且相當快速地溶解殘留物。每一種摻合物無需攻擊暴露的金屬表面即可除去基材表面的漿料微粒殘留物及金屬離子。
以5份組成物9溶於100份DI水(1：20水稀釋)並重複該步驟。此溶液有效地包含1.343%1-羥基-3-胺丙烷-1,1-二膦酸及0.122%羥基乙酸。其仍然維持6：1莫耳比的烷基二膦酸對第二酸性化合物。藉由使用此混合物可獲得相同的結果。
以1份組成物5溶於100份DI水(1：100水稀釋)並重複該步驟。此溶液有效地包含0.141% 1-羥乙烷二膦酸及0.009%羥基乙酸。其仍然維持6：1莫耳比的烷基二膦酸對第二酸性化合物。藉由使用此混合物可獲得相同的結果。
以1份組成物15溶於100份DI水(1：100水稀釋)並重複該步驟。此溶液有效地包含0.0711% 1-羥乙烷二膦酸及0.009%羥基乙酸。其仍然維持3：1莫耳比的烷基二膦酸對第二酸性化合物。藉由使用此混合物可獲得相同的結果。
以5份組成物14溶於100份DI水(1：20水稀釋)並重複該步驟。此溶液有效地包含1.185% 1-羥乙烷二膦酸及0.056%胺基磺酸。其仍然維持10：1莫耳比的烷基二膦酸對第二酸性化合物。藉由使用此混合物可獲得相同的結果。
上述溶液之pH為7.24-7.26。此溶液可依原樣使用或若需要時可進一步以水稀釋。
該溶液具有7.7之pH。此溶液可依原樣使用或若需要時可進一步以水稀釋。
熟諳此藝者可顯見的是，去除微粒及金屬離子污染物的效力係視問題的嚴重性而定。較高濃度之摻合組成物將可導致更快速的效果。
本文中具體實施例的組成物不用檢索(request)且沒有任何清潔的死區或不執行區。
該烷基二膦酸在遍及很大範圍內(從數份對百萬份水開始)可作用為清潔劑。
在另一具體實施例中，該組成物含有可協同地提高組成物之清潔性能的表面活性劑而優於單獨有烷基二膦酸之組成物。
較佳地，係將表面活性劑與摻合物混合以維持該摻合物不會再沉澱且提高組成物之清潔能力。有數種形式之表面活性劑可使用。可輕易使用且相對便宜之表面活性劑包括陰離子性、陽離子性、非離子性、兩性、或聚丙烯酸、聚丙烯酸之水溶性鹽類、水解之聚馬來酸酐、或聚丙烯酸之水溶性鹽類。
雖然這些具體實施例已參考各種特定物質、步驟及實施例敘述說明，但應明瞭的是本發明並不受限於這些基於此目的所選擇之物質與步驟的特定組合。如熟諳此藝者所明瞭般，這些詳細資料的眾多變異都可涵蓋在內。本專利說明書及實施例僅意圖視為範例性，且本發明之正確範圍及精神係由下文之申請專利範圍所明定。與此申請案相關之所有參考文獻、專利、專利申請案其全部內容將併入本文中供參考。
Claims (20)
- 一種清潔溶液，其包含a.基本結構如下之烷基二膦酸：
- 如申請專利範圍第1項之清潔溶液，其中烷基二膦酸對第二酸性化合物之莫耳比係從約1：1至約10：1。
- 如申請專利範圍第1項之清潔溶液，其中該烷基二膦酸係為1-羥乙烷-1,1-二膦酸、亞甲基二膦酸、羥亞甲基二膦酸、二氯亞甲基二膦酸、羥環己基亞甲基二膦酸、1-羥基-3-胺丙烷-1,1-二膦酸、1-羥基-4-胺丁烷-1,1-二膦酸或彼等之混合物。
- 如申請專利範圍第1項之清潔溶液，其中該第二酸性化合物係選自由下列所組成之群組：十二烷基苯磺酸、二甲苯磺酸、甲苯磺酸、磷醯基甲酸、胺基磺酸、2-胺基乙磺酸、氟硼酸及有機羧酸。
- 如申請專利範圍第4項之清潔溶液，其中該有機羧酸係選自由下列所組成之群組：草酸、乳酸、檸檬酸、甲酸、酒石酸、丙酸、苯甲酸、抗壞血酸、葡糖酸、蘋果酸、丙二酸、琥珀酸、五倍子酸、丁酸、三氟乙酸及彼等之混合物。
- 如申請專利範圍第1項之清潔溶液，其中該鹼性化合物係選自由下列所組成之群組：氫氧化鉀、氫氧化鈉、金屬離子游離鹼及彼等之混合物。
- 如申請專利範圍第6項之清潔溶液，其中該鹼性化合物係選自由下列所組成之鹼性化合物中之至少一者：羥基胺游離鹼、羥基胺衍生物、氫氧化四烷基銨(TMAH)、氫氧化四烷基銨五水合物(TMAH五水合物)、氫氧化苄四甲銨(BTMAH)、氫氧化四丁銨(TBAH)、膽鹼氫氧化物、或氫氧化三(2-羥乙基)甲銨(THEMAH)、一乙醇胺、2-(2-羥乙胺基)乙醇、2-(2-胺乙氧基)乙醇、N,N,N-三(2-羥乙基)氨、異丙醇胺、3-胺基-1-丙醇、2-胺基-1-丙醇、2-(N-甲胺基)乙醇、2-(2-胺乙胺基)乙醇、三(羥甲基)胺基乙烷、及彼等之混合物。
- 如申請專利範圍第1項之清潔溶液，其具有pH大於6至約10。
- 如申請專利範圍第1項之清潔溶液，其中該表面活性劑包括陰離子性、陽離子性、非離子性、兩性或聚丙烯酸、聚丙烯酸之水溶性鹽類、水解之聚馬來酸酐、或聚丙 烯酸之水溶性鹽類。
- 如申請專利範圍第1項之清潔溶液，其中該組成物係在稀釋比為1：500以去離子水稀釋。
- 一種清潔半導體基材之方法，其包括下列步驟：a.提供一基材，該基材具有的表面包含含銅導體及低-k介電材料及一或多種位於在該表面上之阻劑、蝕刻殘留物、平面化殘留物、及氧化銅，該基材係自嵌入式或雙嵌入式製造過程中產生；b.以足以除去阻劑、殘留物及/或氧化銅之時間與溫度將該基材表面與有效量之包含下列的溶液接觸：i.基本結構如下之烷基二膦酸：
- 如申請專利範圍第11項之方法，其中烷基二膦酸對第二酸性化合物之莫耳比係從約1：1至約10：1。
- 如申請專利範圍第11項之方法，其中該烷基二膦酸係為1-羥乙烷-1,1-二膦酸、亞甲基二膦酸、羥亞甲基二膦酸、二氯亞甲基二膦酸、羥環己基亞甲基二膦酸、1-羥基-3-胺丙烷-1,1-二膦酸、1-羥基-4-胺丁烷-1,1-二膦酸或彼等之混合物。
- 如申請專利範圍第11項之方法，其中該第二酸性化合物係選自由下列所組成之群組：十二烷基苯磺酸、二甲苯磺酸、甲苯磺酸、磷醯基甲酸、胺基磺酸、2-胺基乙磺酸、氟硼酸及有機羧酸。
- 如申請專利範圍第14項之方法，其中該有機羧酸係選自由下列所組成之群組：草酸、乳酸、檸檬酸、甲酸、酒石酸、丙酸、苯甲酸、抗壞血酸、葡糖酸、蘋果酸、丙二酸、琥珀酸、五倍子酸、丁酸、三氟乙酸及彼等之混合物。
- 如申請專利範圍第11項之方法，其中該鹼性化合物係選自由下列所組成之群組：氫氧化鉀、氫氧化鈉、金屬離子游離鹼及彼等之混合物。
- 如申請專利範圍第16項之方法，其中該鹼性化合物係選自由下列所組成之鹼性化合物中之至少一者：羥基胺游離鹼、羥基胺衍生物、氫氧化四烷基銨(TMAH)、氫氧化四烷基銨五水合物(TMAH五水合物)、氫氧化苄四甲銨(BTMAH)、氫氧化四丁銨(TBAH)、膽鹼氫氧化物、或氫氧化三(2-羥乙基)甲銨(THEMAH)、一乙醇胺、2-(2-羥乙胺基)乙醇、2-(2-胺乙氧基)乙醇、 N,N,N-三(2-羥乙基)氨、異丙醇胺、3-胺基-1-丙醇、2-胺基-1-丙醇、2-(N-甲胺基)乙醇、2-(2-胺乙胺基)乙醇、三(羥甲基)胺基乙烷、及彼等之混合物。
- 如申請專利範圍第11項之方法，其具有pH大於6至約10。
- 如申請專利範圍第11項之方法，其中該表面活性劑包括陰離子性、陽離子性、非離子性、兩性或聚丙烯酸、聚丙烯酸之水溶性鹽類、水解之聚馬來酸酐、或聚丙烯酸之水溶性鹽類。
- 如申請專利範圍第11項之方法，其中該方法在半導體製造過程期間係跟隨於化學機械平面化步驟之後。
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| WO2015089023A1 (en) * | 2013-12-11 | 2015-06-18 | Fujifilm Electronic Materials U.S.A., Inc. | Cleaning formulation for removing residues on surfaces |
| US9957469B2 (en) | 2014-07-14 | 2018-05-01 | Versum Materials Us, Llc | Copper corrosion inhibition system |
| CN106158618A (zh) * | 2015-04-23 | 2016-11-23 | 中芯国际集成电路制造(上海)有限公司 | 化学机械研磨后残留物的去除方法 |
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| FI127667B (en) * | 2017-03-09 | 2018-11-30 | Palonot Oy | Composition and process for its preparation |
| EP3824059A4 (en) | 2018-07-20 | 2022-04-27 | Entegris, Inc. | CORROSION INHIBITOR CLEANING COMPOSITION |
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