TWI434914B - 特洛卡酸(Troika acid)半導體清潔組成物及使用方法 - Google Patents
特洛卡酸(Troika acid)半導體清潔組成物及使用方法 Download PDFInfo
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- TWI434914B TWI434914B TW099132615A TW99132615A TWI434914B TW I434914 B TWI434914 B TW I434914B TW 099132615 A TW099132615 A TW 099132615A TW 99132615 A TW99132615 A TW 99132615A TW I434914 B TWI434914 B TW I434914B
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- Prior art keywords
- acid
- group
- entire entire
- alkyl
- composition
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- 239000002253 acid Substances 0.000 title claims description 120
- 239000000203 mixture Substances 0.000 title claims description 61
- 238000000034 method Methods 0.000 title claims description 48
- 238000004140 cleaning Methods 0.000 title claims description 33
- 239000004065 semiconductor Substances 0.000 title claims description 26
- -1 aryl ammonium Chemical compound 0.000 claims description 58
- 150000001875 compounds Chemical class 0.000 claims description 52
- 125000003118 aryl group Chemical group 0.000 claims description 31
- 239000000758 substrate Substances 0.000 claims description 26
- 125000000217 alkyl group Chemical group 0.000 claims description 25
- 150000003839 salts Chemical class 0.000 claims description 20
- 239000000126 substance Substances 0.000 claims description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims description 19
- 239000001257 hydrogen Substances 0.000 claims description 19
- 150000007513 acids Chemical class 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 14
- 239000002738 chelating agent Substances 0.000 claims description 13
- 125000001072 heteroaryl group Chemical group 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 229920005989 resin Polymers 0.000 claims description 11
- 239000011347 resin Substances 0.000 claims description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 9
- 125000004404 heteroalkyl group Chemical group 0.000 claims description 8
- 125000005210 alkyl ammonium group Chemical group 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 239000010949 copper Substances 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 6
- 239000004020 conductor Substances 0.000 claims description 6
- 239000000412 dendrimer Substances 0.000 claims description 6
- 229920000736 dendritic polymer Polymers 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 239000004094 surface-active agent Substances 0.000 claims description 6
- 239000012190 activator Substances 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 239000000356 contaminant Substances 0.000 claims description 5
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 5
- 230000001590 oxidative effect Effects 0.000 claims description 5
- 229920000768 polyamine Polymers 0.000 claims description 5
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 5
- 239000003082 abrasive agent Substances 0.000 claims description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 claims description 4
- 125000000636 p-nitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)[N+]([O-])=O 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 238000005498 polishing Methods 0.000 claims description 4
- 229920003053 polystyrene-divinylbenzene Polymers 0.000 claims description 4
- 229920000178 Acrylic resin Polymers 0.000 claims description 3
- 239000004925 Acrylic resin Substances 0.000 claims description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- 241001388844 Lorica Species 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- XBPCUCUWBYBCDP-UHFFFAOYSA-O dicyclohexylazanium Chemical compound C1CCCCC1[NH2+]C1CCCCC1 XBPCUCUWBYBCDP-UHFFFAOYSA-O 0.000 claims description 3
- 238000005530 etching Methods 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 claims description 3
- XYUGFPLAOGMREF-UHFFFAOYSA-N trimethyl(2-phenylethyl)azanium Chemical compound C[N+](C)(C)CCC1=CC=CC=C1 XYUGFPLAOGMREF-UHFFFAOYSA-N 0.000 claims description 3
- 239000002585 base Substances 0.000 claims description 2
- 239000003989 dielectric material Substances 0.000 claims description 2
- 239000003085 diluting agent Substances 0.000 claims description 2
- 239000007800 oxidant agent Substances 0.000 claims description 2
- FVJLCPJDDAGIJE-UHFFFAOYSA-N tris(2-hydroxyethyl)-methylazanium Chemical compound OCC[N+](C)(CCO)CCO FVJLCPJDDAGIJE-UHFFFAOYSA-N 0.000 claims description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims 3
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 claims 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims 1
- 150000004673 fluoride salts Chemical class 0.000 claims 1
- 150000002989 phenols Chemical class 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 description 21
- 239000002184 metal Substances 0.000 description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 239000002245 particle Substances 0.000 description 16
- 235000012431 wafers Nutrition 0.000 description 14
- 150000004706 metal oxides Chemical class 0.000 description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- 229910021645 metal ion Inorganic materials 0.000 description 9
- 229910044991 metal oxide Inorganic materials 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 9
- 150000001412 amines Chemical group 0.000 description 8
- 150000002431 hydrogen Chemical class 0.000 description 8
- 239000003960 organic solvent Substances 0.000 description 7
- 125000003107 substituted aryl group Chemical group 0.000 description 7
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 7
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 6
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 6
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 6
- 125000000547 substituted alkyl group Chemical group 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 5
- 125000004429 atom Chemical group 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 239000008139 complexing agent Substances 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 229940093915 gynecological organic acid Drugs 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 239000004615 ingredient Substances 0.000 description 5
- 150000007524 organic acids Chemical class 0.000 description 5
- 235000005985 organic acids Nutrition 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 229920006395 saturated elastomer Polymers 0.000 description 5
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
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- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 4
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- 239000004696 Poly ether ether ketone Substances 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
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- 150000001768 cations Chemical class 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
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- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 150000002500 ions Chemical group 0.000 description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
- 239000003446 ligand Substances 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
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- 238000002360 preparation method Methods 0.000 description 4
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 4
- SZHOJFHSIKHZHA-UHFFFAOYSA-N tridecanoic acid Chemical compound CCCCCCCCCCCCC(O)=O SZHOJFHSIKHZHA-UHFFFAOYSA-N 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
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 3
- 239000004471 Glycine Substances 0.000 description 3
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- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
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- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
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- 230000009920 chelation Effects 0.000 description 3
- 150000004696 coordination complex Chemical class 0.000 description 3
- 125000004093 cyano group Chemical group *C#N 0.000 description 3
- 150000004985 diamines Chemical class 0.000 description 3
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- 150000002739 metals Chemical class 0.000 description 3
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- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 3
- DIIIISSCIXVANO-UHFFFAOYSA-N 1,2-Dimethylhydrazine Chemical compound CNNC DIIIISSCIXVANO-UHFFFAOYSA-N 0.000 description 2
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- RJLKIAGOYBARJG-UHFFFAOYSA-N 1,3-dimethylpiperidin-2-one Chemical compound CC1CCCN(C)C1=O RJLKIAGOYBARJG-UHFFFAOYSA-N 0.000 description 2
- WDQFELCEOPFLCZ-UHFFFAOYSA-N 1-(2-hydroxyethyl)pyrrolidin-2-one Chemical compound OCCN1CCCC1=O WDQFELCEOPFLCZ-UHFFFAOYSA-N 0.000 description 2
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- RAEOEMDZDMCHJA-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-[2-[2-[bis(carboxymethyl)amino]ethyl-(carboxymethyl)amino]ethyl]amino]acetic acid Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CCN(CC(O)=O)CC(O)=O)CC(O)=O RAEOEMDZDMCHJA-UHFFFAOYSA-N 0.000 description 2
- OVBFMEVBMNZIBR-UHFFFAOYSA-N 2-methylvaleric acid Chemical compound CCCC(C)C(O)=O OVBFMEVBMNZIBR-UHFFFAOYSA-N 0.000 description 2
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- 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 description 2
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- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
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- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
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- WDJHALXBUFZDSR-UHFFFAOYSA-N acetoacetic acid Chemical compound CC(=O)CC(O)=O WDJHALXBUFZDSR-UHFFFAOYSA-N 0.000 description 2
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- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000005024 alkenyl aryl group Chemical group 0.000 description 2
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 235000001014 amino acid Nutrition 0.000 description 2
- 229940024606 amino acid Drugs 0.000 description 2
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- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3105—After-treatment
- H01L21/311—Etching the insulating layers by chemical or physical means
- H01L21/31127—Etching organic layers
- H01L21/31133—Etching organic layers by chemical means
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/04—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors
- C23G1/06—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors organic inhibitors
- C23G1/066—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors organic inhibitors phosphorus-containing compounds
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02041—Cleaning
- H01L21/02057—Cleaning during device manufacture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02041—Cleaning
- H01L21/02057—Cleaning during device manufacture
- H01L21/02068—Cleaning during device manufacture during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers
- H01L21/02074—Cleaning during device manufacture during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers the processing being a planarization of conductive layers
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- Materials Engineering (AREA)
- Detergent Compositions (AREA)
- Cleaning Or Drying Semiconductors (AREA)
Description
本申請案是一非臨時申請案,其要求U.S. Provisional Appl. No. 61/254,688(在2009年10月24日提出)之優先權,且整體倂入本文作為參考。
本發明是一種用於半導體處理中之組成物及方法,其中該組成物包含含水之特洛卡酸類、其衍生物及其鹽類,其有用積體裝置的製造過程中,例如但不限於後蝕刻殘留物移除、化學機械平面化及後化學機械平面化粒子移除。
大量之金屬離子用之錯合劑被用在多種不同應用中,例如:半導體清潔、除垢劑及清潔劑、電鍍、水處理及聚合作用、照相工業、紡織工業、製紙工業、醫藥、化妝品、食品及植物性飼料。
半導體處理應用逐漸依賴含有錯合劑之化學。在包含晶圓清潔或表面製備之標準IC製造過程中有多於一百個步驟,包括後阻劑汽提/灰份殘留物移除、原有的氧化物移除、及甚至是選擇性的蝕刻。雖然乾式過程持續逐步進行且對一些應用提供獨特優點,大部分之清潔/表面預備過程是“濕式的”,且已發現在得利於錯合劑在此種濕式組成物中的使用。
再者,此種濕式製程偶而包含可能會危害環境的化學品(例如氫氟酸、氫氯酸、硫酸、磷酸或過氧化氫)的使用。部分由於環境議題,更為稀釋之化學品的使用已增加且已受某種形式之機械能(例如百萬音波(megasonics)或噴射-噴霚處理)之使用的輔助。因此,需要可有效地以稀釋形式使用的化學品。
大部分之用在半導體應用中之調和物含有錯合劑或螯合劑。金屬螯合官能性是已知的,其中在相同分子中一個中心金屬離子藉由配位鍵連結至二或更多之非金屬原子(配位基)。簡單之酸性有機亞磷螯合劑,基本上藉由膦酸OH基之可置換部分與該共價金屬陽離子間之陽離子交換反應,清潔水溶液中之金屬。形成雜環性的環以作為該配位錯合物之部分,而該中心(金屬)原子作為每一環的一員。當該錯合物在含彼之溶液中變得更為可溶時,彼在清潔過程中作用。若該金屬錯合物不溶於含彼之溶液時,彼藉由形成不可溶膜於該金屬表面上方而成為鈍化劑。
錯合劑之實例是例如氮基三乙酸(NTA)、伸乙基二胺四乙酸(EDTA)、N,N’-雙(2-羥基苯基)伸乙基二胺基二乙酸(HPED)、三伸乙基四氮基六乙酸(TTHA)、代斯非瑞非瑞噁明B(desferriferrioxamin B)、N,N’,N”-三[2-(N-羥基羰基)乙基]-1,3,5-苯三羧醯胺(BAMTPH)、伸乙基二胺二鄰羥基苯基乙酸(EDDHA)、伸乙基二胺四伸甲基膦酸(EDTMP)、α-(羥基亞胺基)膦酸、伸丙基二胺四乙酸(PDTA)、羥基伸丙基二胺四乙酸(HPDTA)、異絲胺酸二乙酸(ISDA)、β-丙胺酸二乙酸(β-ADA)、羥基乙烷二膦酸、二伸乙基三胺四乙酸、二伸乙基三胺四伸甲基膦酸、羥基伸乙基胺基二乙酸、羥基乙基伸乙基二胺三乙酸、二伸乙基三胺五乙酸、二乙醇甘胺酸、乙醇甘胺酸、檸檬酸、乙醇酸、乙醛酸、乙酸、乳酸、膦酸、葡庚糖酸或酒石酸、聚丙烯酸鹽類、碳酸鹽類、膦酸鹽類、及葡萄糖酸鹽類。
現今在商業上使用之錯合劑(例如乙醇酸、乙醛酸、乳酸及膦酸)本質上是酸性的且具有侵蝕殘留物且移除金屬及金屬氧化物二者(例如銅及氧化銅)的傾向。此種非所欲之結果在尋求僅對金屬氧化物殘留物而非對金屬本身有選擇性螯合功能的情況中,例如在包含金屬(例如銅)的情況中,對於調配者帶來問題。因此,有需要使錯合物對金屬基材不具侵蝕性,但仍有效地螯合在製造過程中所生成之非所要的金屬離子殘留物。
美國專利申請案6,143,705、6,310,019、6,395,693、6,410,494、6,440,856、6,514,352、6,514,921、6,534,458、6,541,434、6,716,803、7,250,391、7,312,186、及7,541,322討論多種含有肟類、膦酸類及有機酸類之清潔半導體基材之組成物及方法。該等組成物及使用方法整體倂入本文作為參考。
萬國專利申請案WO 2009085072、WO2009058288、WO2009058278、WO2009058277、WO2009058275、WO2009058274、及WO2009058272討論一系列具有醯胺肟官能基之螯合劑。該清潔組成物及使用方法整體倂入本文作為參考。
然而,所有這些組成物需要具有羧官能性、醯胺肟官能性及膦官能性個別化合物之結合使用以達成所要之清潔效能,如美國專利6,395,693及6,541,434中所描述的。
美國專利7,427,361描述聚合結合之螯合劑化合物在黏附至粒子前之用途,且擁有至少三個選自下列之官能基團:羥基類、羧酸類、胺類、醯胺類、亞胺類、醯亞胺類、硫醇類、磺酸類、氧肪酸、羰基類、酯類、醚類、脲類、氰基類、硝基類、碳酸酯類、其無機鹽類、及其組合於拋光漿液系統中。聚合系統包括聚(苯乙烯磺酸)、聚(乙烯磺酸)、聚(丙烯酸)、聚(甲基丙烯酸)、聚(丙烯酸鹽)、聚(甲基丙烯酸鹽)、聚(烷基丙烯酸鹽)、聚(順丁烯二酸)、聚(乙酸乙烯酯)、聚(乙烯醇)、聚(丙烯醯胺)、聚(氰基丙烯酸鹽)、纖維素材料、及其組合物或共聚物。然而,不同的部分各自分別地黏附至該等聚合物而非是本身包含於相同分子中。另外,該‘361專利不包括膦及肟部分,此二部分分別與該羧部分提供獨特的協乘效果。再者,該‘361專利沒有指明官能基之排列或以特別方式黏附至該聚合物之該等部分的排列重要性。
美國專利7,527,733、6,218,563、5,948,931、5,945,082、5,935,542、5,905,163、5,861,525、5,859,290、5,859,278及5,858,317描述α-(羥基亞胺基)膦醯基乙酸之製備及其螯合性。美國專利公告申請案20060065604描述黏附α-(羥基亞胺基)膦醯基乙酸部分至巨孔性聚合系統之製備。
特洛卡酸是α-(羥基亞胺基)膦醯基乙酸或α,α-二取代之三官能肟,其在單一分子中具有固定至共同碳原子的膦酸根、肟及羧酸根部分。因該肟羥基之獨特的異構位置,此基團,視其定向,可以經由氫鍵結與其二相鄰基團的任一者交互作用。
特洛卡酸具有在其他於此技藝中所用之螯合劑中所未發現的特點。例如,供特洛卡酸用之螯合模式異於普通之螯合劑例如伸乙基二胺四乙酸(EDTA)。特別地,配位基諸如EDTA直接經由胺氮原子配位金屬離子,但特洛卡酸經由肟氮原子配位。
另外,由於其在特洛卡酸結構中之獨特中心位置,肟OH基團可與彼之二個相鄰基團的任一者氫鍵結,獲得二種異構物形態。二異構物是基於空間中N-OH之定向。二異構物分別具有不同性質。因此,肟羥基視其位置,若不導引則明顯影響彼之二個相鄰基團之任一者的化學反應性。
特洛卡酸類及其衍生物藉由在一對特洛卡酸雜原子與金屬陽離子之間形成配位鍵結,以作為螯合物。此表示:特洛卡酸可以,視其異構位置,經由磷酸根(酸或酯)基團上的氧原子或羧酸氧原子及肟氮原子螯合至金屬陽離子。在此二模式中,包含該金屬陽離子、該二螯合的原子及在彼之間的該特洛卡酸主幹的形態是5員環,其為一種特別安定之排列。關於該二螯合模式何者是有利的可以藉由pH及該特洛卡酸之合適衍化而改變。
然而通常特洛卡酸經由膦酸根及肟基團優先螯合金屬離子,亦即E-異構物形態。
在並置時,清潔需要及目標已變得更為迫切。逐漸地,晶圓要用單一晶圓方式處理,如與分批浸漬或分批噴霧系統比較地。該單一晶圓方式需要快速且有效的化學清潔。另外,在晶圓清潔應用中,粒子移除可能不是主要目的。其他目標諸如移除原有的氧化物或移除在條/灰份後之光阻殘留物變為焦點。因此,需要可用在單一晶圓及分批處理中且同時應付在該移除過程中的多種目標的化學。
在本文中所包含且例示的組成物及方法應付這些問題。
在本文中本發明之背景的討論被包括以說明本發明之內容,其各部分意欲支持本文中之申請專利範圍。在該背景中之陳述並非承認:所指稱之任何材料在本申請專利範圍之優先權日之時是公開的、已知的、或是普通一般的知識。
此外,在說明書之整個描述及申請專利範圍中,“包含”一辭及其變化形式之使用並未意圖包括其他添加劑、成分或步驟。
半導體處理組成物包含至少一種特洛卡酸、其衍生物或其鹽類的水溶液。
特洛卡酸、其衍生物、或其鹽類包含以下通式:
或其互變異構物,其中R1
是氫、烷基、雜烷基、芳基、雜芳基;R2
及R3
是獨立選自由氫、烷基、雜烷基、芳基、雜芳基、鈉、及烷基或芳基銨組成之群中。該特洛卡酸含量可以是約0.001至約35重量%。
烷基或芳基可以選自由甲基、乙基、丙基、丁基、苄基、苯基、對-硝基苯基、及鄰-硝基苄基組成之較佳群中,雖然該烷基或芳基可以是任何適合之烷基或芳基。
該烷基銨可以選自由苯銨、二環己基銨、四甲基銨、苄基四甲基銨、2-羥基乙基三甲基銨、及三(2-羥基乙基)甲基銨組成之較佳群中,雖然該烷基銨可以是任何適合之烷基銨。
該特洛卡酸、其衍生物或其鹽類可以是一種包含二或多種特洛卡酸類、衍生物或鹽類之樹枝狀聚合物。
基於應用及所要之結果,組成物也可以包括溶劑類、酸類、鹼類、表面活性劑、具有氧化及還原潛能之化合物、活化劑及氟化物。
使用在本文中所涵蓋之該組成物之方法是要清潔半導體基材。此種用途之實例可以包括以下步驟:提供一基材,其具有一包含含銅導體及低k介電材料之表面及一或多種阻劑、蝕刻殘留物、平面化殘留物、及氧化銅之一或多者配置在其表面上;使該基材之該表面與有效量之包含以下物質之溶液接觸:與本文所揭示之組成一致的至少一特洛卡酸、其衍生物、鹽類或其互變異構物的水溶液;其中該晶圓在足夠時間及溫度下曝於該溶液以有效地移除在半導體製造期間生成之表面殘留物及污染物。暴露時間可以是例如約10秒至約30分鐘且溫度可以是例如室溫至達50℃。
另一用途會是要在汽提過程及後蝕刻殘留物清潔過程期間施加本文中之特洛卡酸含水組成物至半導體基材。進一步用途會是要在清潔過程期間施加本文中之特洛卡酸含水組成物至基材,接著是在半導體製造期間之化學機械平面化步驟。或者,特洛卡酸含水組成物能用在該清潔過程及在該化學機械平面化步驟期間二者或僅用在利用或不利用適合之研磨材料的該化學機械平面化步驟期間。
該研磨粒子可以是任何適合的材料。例如,該研磨粒子可以包含金屬氧化物(諸如選自由氧化鋁、氧化矽、氧化鈦、氧化鈰、氧化鋯、氧化鍺、氧化鎂、其共形成之產物、及其組合物組成之群中的金屬氧化物)或碳化矽、氮化硼、鑽石、石榴石及陶瓷研磨材料。該研磨粒子可以是金屬氧化物及陶瓷之混合物或無機及有機材料之混合物。該等粒子也可以是聚合物粒子,其多被描述於美國專利5,314,512中,諸如聚苯乙烯粒子、聚甲基丙烯酸甲酯粒子、液晶聚合物(LCP,例如含萘單元之芳族共聚酯)、聚醚醚酮(PEEK’s)、粒狀熱塑性聚合物(例如粒狀熱塑性聚胺基甲酸酯)、粒狀交聯聚合物(例如粒狀交聯聚胺基甲酸酯或聚環氧化物)、或其組合物。該複合粒子可以是任何含核心及外塗層之粒子。例如,該複合粒子可以含有固體核心(例如金屬氧化物、金屬、陶瓷、或聚合物)及聚合物的外殼(例如聚胺基甲酸酯、尼龍、或聚乙烯)。澄清的粒子可以是頁矽酸鹽類(例如雲母類諸如氟化雲母,及黏土諸如滑石、高嶺土、蒙脫土、水輝石),玻璃纖維、玻璃珠、鑽石粒子、碳纖維、及類似者。
如在化學機械拋光或平面化中使用之基材係指待利用化學機械處理拋光之物體。基材也可以被稱為晶圓。基材可以是半傳導材料、非半傳導材料、或半傳導材料及非半傳導材料的組合。矽晶圓上可以形成多種材料薄膜。這些薄膜可以利用CMP方法拋光。其他基材諸如GaAs、在藍寶石上之矽、或在絕緣體上之矽(SOI)可以利用CMP方法拋光。
在一具體實例中,化學機械拋光漿液可以包含氧化劑、稀釋劑、選擇性地研磨材料、及黏結至聚合樹脂的特洛卡酸部分。該聚合樹脂是微孔性的、或中孔性、或巨孔性材料或其組合。孔性材料按照尺寸分成數類。依照IUPAC標記法,微孔性材料具有小於2奈米之孔直徑,中孔性材料具有在約2奈米及約50奈米之間的孔直徑,巨孔性材料具有大於50奈米的孔直徑。該樹脂較佳選自由以下組成之群中:例如PS-DVB、Chelex、聚胺、經胺改質之苯乙烯-二乙烯基苯、胺化之酚-甲醛樹脂、及經胺改質之丙烯酸系樹脂。其他適合之樹脂(諸如上列之較佳樹脂的衍生物)可用於聚合系統中。
在一些應用中,在本文中之組成物可以另外包括一或多種含量高至約99重量%之有機溶劑,一或多種含量約0.001至約45重量%之酸類,一或多種含量約0.001至約45重量%之鹼類,一或多種含量約0.001至約25重量%之活化劑,一或多種含量約0.001至約25重量%之具有氧化及還原潛能之化合物,一或多種含量高至約15重量%之另外的螯合或錯合劑。
在使用一或多種表面活性劑之情況中,該組成物可以另外包含含量約10 ppm至約5重量%之表面活性劑。
在一些用途中,較佳可以在使用前用水稀釋該特洛卡酸組成物。
在以上本發明之內容中,及在本發明之詳細說明、實例及以下申請專利範圍中,參考本發明之特別特徵。要了解:在本說明書中本發明之揭示包括此種特別特徵之所有合適的組合。例如,在特定特徵被揭示於特別具體實例或特別申請專利範圍之上下文中的情況下,該特徵也可以在合適的程度上被用在其他特別具體實例及申請專利範圍中,及一般性地用在本發明中。
本文中之說明描述例示的組成物及包含一或多種特洛卡酸化合物、其衍生物、或其鹽類(含有一或多個特洛卡酸官能基)之含水組成物在半導體應用中的用途,其中該特洛卡酸化合物與表面上、殘留物中、或二者的金屬(金屬氧化物)錯合以達成該表面之清潔及防護。
在一具體實例中,特洛卡酸是α-(羥基亞胺基)膦醯基乙酸類或α,α-二取代之三官能肟具有以下結構:
或其互變異構物。
在一具體實例中,該特洛卡酸化合物包含以下通式:
或其互變異構物。
其中R1
及R2
係獨立選自由氫、烷基、雜烷基、芳基、雜芳基、及烷基或芳基銨組成之群中;及R3
是獨立選自由氫、烷基、雜烷基、芳基、雜芳基、經取代之芳族及烷基或芳基銨組成之群中。
烷基或芳基係選自由甲基、乙基、丙基、丁基、苄基、苯基及類似者組成之群中。
經取代之芳族係選自由對硝基苯基、鄰硝基苄基及類似者組成之群中。
烷基及芳基銨係選自由四級銨氫氧化物組成之群中、諸如氫氧化二環己基銨、氫氧化四甲基銨、氫氧化苄基四甲基銨、氫氧化2-羥基乙基三甲基銨、及氫氧化三(2-羥基乙基)甲基銨及類似者。
本發明之一具體實例係關於該特洛卡酸、或其衍生物或其鹽之樹枝狀聚合物或聚合物,其包含二或多個藉由羧酸部分之酯位置或膦酸根部分之單酯位置或肟部分之羥基位置或其組合連接的特洛卡酸。
本發明之具體實例係關於黏結至聚合物的特洛卡酸部分,諸如美國專利5,314,512、7,427,361中所述之聚合漿液粒子,諸如聚苯乙烯粒子、聚甲基丙烯酸甲酯粒子、液晶聚合物(LCP,例如含有萘單元之芳族共聚酯類)、聚醚醚酮類(PEEK’s)、粒狀熱塑性聚合物(例如粒狀熱塑性聚胺基甲酸酯)、粒狀交聯聚合物(例如粒狀交聯的聚胺基甲酸酯或聚環氧化物)、或其組合。該組成物及使用方法整體倂入本文作為參考。
特洛卡酸之樹枝狀聚合物之實例具有以下通式:
其中N~OH表示在氮與OH之氧之間的鍵結,其代表Z或E異構型;其中R1
、R2
、R3
、R4
、R5
及R6
係選自由氫、烷基、芳基、經取代之烷基及經取代之芳基組成之群中;R1
及R2
之至少一者並非氫;R5
及R6
之至少一者並非氫;X1
及X2
個別獨立選自由O、NR7
、及S組成之群中,其中R7
是氫、烷基、芳基、經取代之烷基、或經取代之芳基;且Y是選自由以下組成之群中的連接基團:伸烷基、經取代之伸烷基、次烷基、經取代之次烷基、伸芳基、或經取代之伸芳基。Y另外包含結合至該樹脂之取代基。該樹脂可以選自由以下組成之群中:PS-DVB、Chelex、聚胺、經胺改質之苯乙烯-二乙烯基苯、胺化之酚-甲醛樹脂、經胺改質之丙烯酸系樹脂、及類似者。
在本文中之另一具體實例包括一或多種以下結構之化合物作為一或多種特洛卡酸化合物:
其中N~OH表示在氮與OH之氧之間的鍵結,其代表Z或E異構型;其中X1
、X2
及X3
個別獨立選自由O、NR3
、及S組成之群中;R1
、R2
、Y1
、Y2
、Y3
、Y4
、及Y5
係選自由氫、烷基、芳基、經取代之烷基及經取代之芳基組成之群中;Y1
、Y2
、及Y3
之至少一者係選自由伸烷基、氧基伸烷基、胺基伸烷基、硫基伸烷基、--(CH2
)nC(=O)NH--、--(CH2
)nC(=O)O--、伸芳基、經取代之伸芳基、雜伸芳基、及經取代之雜伸芳基組成之群中;R1
及Y1
之至少一者並非氫;且R1
、R2
、Y1
、Y2
、Y4
、及Y5
之至少一者是氫;且R1
及Y1
之至少一者並非氫。其中該樹脂經由Y1
、Y2
、Y4
或Y5
中之一者連接至該化合物。該樹脂可以選自由PS-DVB、Chelex、聚胺、經胺改質之苯乙烯-二乙烯基苯、胺化之酚-甲醛樹脂、經胺改質之丙烯酸系樹脂、及類似者組成之群中。
在本文中之另一具體實例包括一或多種以下結構之化合物作為一或多種特洛卡酸化合物:
其中加星號之原子表示連接點;N~O表示代表Z或E異構型之鍵結;X1
、X2
、X3
或X4
獨立地選自由O、NR4
、及S組成之群中;X1
直接連接至該樹脂;Y2
及Y3
獨立選自由伸烷基、胺基伸烷基、硫基伸烷基、伸芳基、經取代之伸芳基、雜伸芳基、及經取代之雜伸芳基;R1
、R2
、R3
或R4
獨立選自由氫、烷基、芳基、經取代之烷基、及經取代之芳基組成之群中;且n是1至5。伸甲基可以另外衍生以形成羥基-亞胺基,當n=1以提供伸甲基時。
其中當n=1以提供伸甲基,且該伸甲基被衍生以形成羥基-亞胺基。其中n=1以提供伸甲基,且該伸甲基被衍生以形成羥基-亞胺基。
本文中所述之特洛酸類是不具有已知毒性之安定化合物。因此,此種化合物適合於環境議題存在且提供綠色技術優點而不犧牲效率的應用。
本發明之一具體實例包含使用一種包含特洛卡酸、其衍生物、或鹽類之含水組成物於半導體應用中,其中特洛卡酸類化合物與在表面上、雜質中或在表面上及雜質中的金屬(金屬氧化物)錯合。
本發明之一具體實例包含使用一種包含特洛卡酸樹枝狀聚合物(亦即含有一或多個特洛卡酸類官能基之化合物)之含水組成物於半導體應用中,其中特洛卡酸樹枝狀聚合物化合物與在表面上、雜質中或在表面上及雜質中的金屬(金屬氧化物)錯合。
本發明之組成物可以含有足量之一或多種特洛卡酸類化合物而使該組成物能有效地移除在半導體製造過程期間產生之表面殘留物及污染物。
在本發明之範圍內,水可以基本上僅為化學或物理結合型式或作為原料或化合物之一成分的型式被導入該組成物中。
該組成物另外包含由以下所選之一或多群的化學品:約1至約99重量%之溶劑。
本發明之組成物也包括0重量%至約99重量%且更典型地約1重量%至約80重量%之與水互溶的有機溶劑,其中該溶劑較佳是選自與水互溶之有機溶劑。與水互溶之有機溶劑的實例包括但不限於二甲基乙醯胺(DMAC)、N-甲基吡咯烷酮(NMP)、N-乙基吡咯烷酮(NEP)、N-羥基乙基吡咯烷酮(HEP)、N-環己基吡咯烷酮(CHP)、二甲基亞碸(DMSO)、環丁碸、二甲基碸醯胺(dimethylfonnamide,DMF)、N-甲基碸醯胺(DMF)、碸醯胺、單乙醇胺(MEA)、二甘醇胺、二甲基-2-哌啶酮(DMPD)、嗎啉、N-嗎啉-N-氧化物(NMNO);咪唑啶酮類(諸如1,3-二甲基-2-咪唑啶酮、1,2-二乙基-2-咪唑啶酮、或1,3-二異丙基-2-咪唑啶酮);內酯類(諸如γ-丁內酯或δ-戊內酯);四氫糠醇、環己醇、環己酮、聚乙二醇類及聚丙二醇類、甘油、甘油碳酸酯、甘油三已酸酯、乙二醇、丙二醇、碳酸丙二酯、己二醇、乙醇及正丙醇及/或異丙醇、二甘醇、丙基或丁基二甘醇、己二醇、乙二醇甲基醚、乙二醇乙基醚、乙二醇丙基醚、乙二醇單正丁基醚、二乙二醇甲基醚、二乙二醇乙基醚、丙二醇甲基、乙基或丙基醚、二丙二醇甲基或乙基醚、甲氧基、乙氧基或丁氧基三甘醇、異丁氧基乙氧基-2-丙醇、3-甲基-3-甲氧基丁醇、丙二醇第三丁基醚、及其他醯胺類、醇類或吡咯烷酮類、酮類、亞碸類、或多功能化合物(諸如羥基醯胺類或胺基醇類)、及這些溶劑之混合物。當利用時,較佳之溶劑是二甲基乙醯胺及二甲基-2-哌啶酮、二甲基亞碸及N-甲基吡咯烷酮、二甘醇胺、及單乙醇胺。
約0.001重量%至45重量%之酸類。
可能之酸類包括無機酸類或有機酸類,只要這些與其他成分相容。
無機酸類包括氫氯酸、氫氟酸、硫酸、磷酸、亞磷酸、次磷酸、膦酸、硝酸、及類似者。
有機酸類包括單體的及/或聚合的有機酸類,其選自由非支鏈型之飽和或不飽和單羧酸類,支鏈型之飽和或不飽和單羧酸類,飽和及不飽和之二羧酸類、芳族單、二及三羧酸類、糖酸類、羥基酸類、氧代酸類、胺基酸類及/或聚合之羧酸類是較佳的。
選自非支鏈型飽和或不飽和之單羧酸類之群中:甲酸(蟻酸)、乙酸(醋酸)、丙酸(甲基乙酸)、戊酸(擷草酸)、己酸(羊油酸)、庚酸、辛酸(羊羶酸)、壬酸(天竺葵酸)、癸酸(羊脂酸)、十一酸、十二酸(月桂酸)、十三酸、十四酸(肉豆蔻酸)、十五酸、十六酸(棕櫚酸)、十七酸(真珠酸)、十八酸(硬脂酸)、二十酸(花生酸)、二十二酸(山萮酸)、二十四酸(巴西棕櫚酸)、二十六酸(蠟酸)、三十酸(蜜蠟酸)、棕櫚油酸、派挫賽酸(petroselic acid)、派挫賽拉酸(petroselaidic acid)、油酸、石油酸、亞麻油酸、力諾拉酸(linolaidic acid)及次亞麻酸。
選自支鏈型飽和或不飽和單羧酸類之群中:2-甲基戊酸、2-乙基己酸、2-丙基庚酸、2-丁基辛酸、2-戊基壬酸、2-己基癸酸、2-庚基十一酸、2-辛基十二酸、2-壬基十三酸、2-癸基十四酸、2-十一基十五酸、2-十二基十六酸、2-十三基十七酸、2-十四基十八酸、2-十五基十九酸、2-十六基二十酸、2-十七基二十一酸。選自非支鏈型飽和或不飽和之二或三羧酸類之群中:丙二酸、丁二酸、戊二酸、己二酸(肥酸)、庚二酸(蒲桃酸)、辛二酸(栓酸)、壬二酸(杜鵑花酸)、癸二酸(皮脂酸)、2c-丁烯二酸(馬來酸)、2t-丁烯二酸(富馬酸)、2-丁炔二羧酸(乙炔二羧酸)。選自芳族單、二及三羧酸類之群中:苯甲酸、2-羧基苯甲酸(苯二甲酸)、3-羧基苯甲酸(異苯二甲酸)、4-羧基苯甲酸(對苯二甲酸)、3,4-二羧基苯甲酸(偏苯三酸)、3,5-二羧基苯甲酸(苯均三酸)。
選自糖酸類之群中:半乳糖酸、甘露糖酸、果糖酸、***糖酸、木糖酸、核糖酸、2-去氧核糖酸、藻酸。選自羥基酸類之群中:羥基苯基乙酸(苦杏仁酸)、2-羥基丙酸(乳酸)、羥基丁二酸(蘋果酸)、2,3-二羥基丁二酸(酒石酸)、2-羥基-1,2,3-丙三羧酸(檸檬酸)、抗壞血酸、2-羥基苯甲酸(水楊酸)及3,4,5-三羥基苯甲酸(沒食子酸)。
選自氧代酸類:2-氧代丙酸(丙酮酸)及4-氧代戊酸(左旋糖酸)。
選自胺基酸類之群中:丙胺酸、纈胺酸、白胺酸、異白胺酸、脯胺酸、色胺酸、苯基丙胺酸、甲硫胺酸、甘胺酸、絲胺酸、酪胺酸、蘇胺酸、半胱胺酸、天冬醯胺酸、麩醯胺酸、天冬胺酸、麩胺酸、離胺酸、精胺酸、及組胺酸。
選自由甲烷磺酸、二甲苯磺酸、甲苯磺酸、十二烷基苯磺酸、三氟乙酸、及其混合物組成之群中。
約0.001重量%至45重量%之鹼。
可能的鹼是無機鹼或有機鹼,只要這些鹼與其他成分相容。無機鹼包括氫氧化鈉、氫氧化鋰、氫氧化鉀、氫氧化銨及類似者。有機鹼包括有機胺類及四級烷基銨氫氧化物。有機胺很多是包括但不限於烷醇胺類,適用於本發明者是與水互溶的。
在一具體實例中,烷醇胺類是一級、二級或三級胺類。在一例示之具體實例中,該烷醇胺類是單胺類、二胺類或三胺類。該胺類之烷醇基較佳具有1至5個碳原子。適合之烷醇胺類之實例包括但不限於單乙醇胺(MEA)、二乙醇胺、三乙醇胺、第三丁基二乙醇胺異丙醇胺、2-胺基-1-丙醇、3-胺基-1-丙醇、異丁醇胺、2-胺基-2-乙氧基乙醇、及2-胺基-2-乙氧基丙醇。四級烷基銨氫氧化物可以包括但不限於氫氧化四甲基銨(TMAH)、TMAH五水合物、氫氧化苄基四甲基銨(BTMAH)、氫氧化四丁基銨(TBAH)、氫氧化2-羥基乙基三甲基銨(膽鹼)、及氫氧化三(2-羥基乙基)甲基銨(THEMAH)。
約0.001重量%至25重量%之活化劑。
依本發明,清潔組成物包含一或多種選自活化劑之群中的物質,特別是選自聚醯基化伸烷基二胺類(特別是四乙醯基伸烷基二胺(TAED)),N-醯基醯亞胺類(特別是N-壬醯基丁二醯亞胺(NaSI)),醯基化之酚磺酸酯類(特別是正壬醯-或異壬醯氧基苯磺酸酯(正-或異-NaBS))及正甲基嗎啉鎓乙腈,硫酸甲酯(MMA),及“四級腈”化合物,其量是0.1至20重量%,較佳是0.5至15重量%且特別是1至10重量%,在各情況中是以總組成物為基準計,以加強清潔組成物之氧化/還原效能。”四級腈”(陽離子性腈類)具有下式:
其中R1是-H,-CH3
,C2-24-烷基或-烯基,具有至少一個選自-Cl、-Br、-OH、-NH2
、-CN之經取代之C2-24-烷基或烯基,具有C1-24-烷基之烷基-或烯基芳基,或是具有C1-24-烷基及在該芳族環上之至少另一取代基之經取代的烷基-或烯基芳基,R2及R3互相獨立是選自CH2
-CN、-CH3
、-CH2
-CH3
、-CH2
-CH2
-CH3
、CH(CH3
)-CH3
、-CH2
-OH、-CH2
-CH2
-OH、-CH(OH)-CH3
、-CH2
-CH2
-CH2
-OH、-CH2
-CH(OH)-CH3
、-CH(OH)-CH2
-CH3
、-CH2
CH2
-O)n
H,其中n=1、2、3、4、5或6,且X是陰離子。
約0.001重量%至25重量%之具有氧化及還原潛能的化合物。
這些化合物包括羥基胺及其鹽類(諸如羥基胺氯化物、羥基胺硝酸鹽、羥基胺硫酸鹽、羥基胺磷酸鹽)或其衍生物(諸如N,N-二乙基羥基胺、N-苯基羥基胺肼及其衍生物);過氧化氫;銨、鉀及鈉之過硫酸鹽,鉀、鈉之過錳酸鹽;及其他過氧化物來源係選自由以下組成之群中:過硼酸鹽單水合物、過硼酸鹽四水合物、過碳酸鹽、其鹽類及其組合。由於環境之故,羥基胺磷酸鹽並非較佳。
可用來作為本發明之成份的其他化合物是二醯基過氧化物,諸如過氧化二苯甲醯。
具有氧化/還原潛能之另外典型的有機化合物是過氧酸類,特別實例是烷基過氧酸類及芳基過氧酸類。較佳之代表是(a)過氧苯酸及其環經取代的衍生物(諸如烷基過氧苯酸類),但也可以使用過氧基-a-萘酸及單過氧苯二甲酸鎂,(b)脂族或經取代之脂族過氧酸類(諸如過氧基月桂酸、過氧基硬脂酸、c-苯二甲醯胺基過氧基己酸[苯二甲醯亞胺基過氧基己酸(PAP)],鄰-羧基苯醯胺基過氧基己酸,N-壬烯基醯胺基過氧己二酸及N-壬烯基醯胺基過氧基丁二酸,及(c)脂族及芳脂族過氧基二羧酸類(諸如1;2-二過氧基羧酸、1,9-二過氧基壬二酸、二過氧基癸二酸、二過氧基十三烷三酸、二過氧基苯二甲酸類、2-癸基二過氧基丁烷-1,4-二酸、N,N-對苯二甲醯基二(6-胺基過氧己酸)。
其他螯合劑及腐蝕抑制劑。
較佳地,清潔組成物包含(按組成物之重量計)0.0%至15%之另外的一或多種螯合劑。另外可能之成分類別是螯合物錯合劑。螯合物錯合劑是與金屬離子形成環狀化合物的物質,其中單一配位基在中心原子上佔據多於一個配位位址,亦即是至少“二配位基”。在此情況中,經拉伸之化合物因此一般藉由離子之錯合物形成而封閉以獲得環。經鍵結之配位基數目視中心離子之配位數目而定。普通錯合物形成用之聚合物的錯合基團(配位基)是亞胺基二乙酸、羥基喹啉、硫脲、胍、二硫基胺基甲酸鹽、羥胺酸、α-(羥基亞胺基)膦醯基乙酸、胺基磷酸、(環)聚胺基、硫醇、1,3-二羰基及冠醚基團,其中一些對於不同金屬之離子具有極專特之活性。為本發明之目的,可能使用先前技藝之錯合劑。這些可以分屬不同的化學族群。較佳之螯合/錯合劑,獨立地或與另一者之混合地,包括以下。其中之羧基及選擇性地羥基之合是至少5的多元羧酸(諸如葡糖酸),含氮之單或多元羧酸類(諸如伸乙基二胺四乙酸(EDTA)、N-羥基乙基伸乙基二胺三乙酸、二伸乙基三胺五乙酸、羥基-乙基亞胺基二乙酸、硝基二乙酸3-丙酸、異絲胺酸二乙酸、N,N-二(.~.羥基乙基)甘胺酸、N-(1,2-二羧基-2-羥基乙基)甘胺酸、N-(1,2-二羧基-2-羥乙基)天冬胺酸或氮基三乙酸(NTA)),成對的二膦酸類(諸如1-羥基乙烷-1,1-二膦酸(HEDP),其之具有高至8個碳原子的較高同系物,其含羥基或胺基之衍生物,及1-胺基乙烷-1,1-二膦酸,其之具有高至8個碳原子之較高同系物,及其含羥基或胺基之衍生物),胺基膦酸(諸如伸乙基二胺四(伸甲基膦酸)、二伸乙基三胺五(伸甲基膦酸)或氮基三(伸甲基膦酸)),膦醯基多元羧酸(諸如2-膦醯基丁烷-1,2,4-三羧酸)及環糊精類。
約10ppm至5%之表面活性劑。
依本發明之組成物因此也可以包含非離子性、陰離子性、陽離子性、及/或兩性表面活性劑作為表面活性劑成分。
含量約0.001%至10%之氟離子源。
氟離子源包括但不限於二氟化銨、氟化銨、氫氟酸、六氟矽酸鈉、氟矽酸及四氟硼酸。
本發明之組成物預計有以上選擇性成分之多種組合。
例如,該組成物可以包含或基本上由至少一種特洛卡酸化合物及水組成。在另一例示方面中,該組成物可以包含至少一種特洛卡酸化合物、水及一或多種與水互溶之有機溶劑。在另一例示方面中,該組成物可以包含至少一種特洛卡酸化合物、水及一或多種酸化合物。在另一例示方面,該組成物可以包含至少一種特洛卡酸化合物、水及一或多種鹼化合物。在另一實例中,該組成物可以包含至少一種特洛卡酸化合物、水、一或多種與水互溶之有機溶劑、及一或多種酸化合物。在另一實例中,該組成物可以包含至少一種特洛卡酸化合物、水、及一或多種基本上不含金屬離子之含氟化合物。在另一實例中,該組成物可以包含至少一種特洛卡酸化合物、水、一或多種螯合劑及/或腐蝕抑制劑。在另一實例中,該組成物可以包含至少一種特洛卡酸化合物、水、一或多種與水互溶之有機溶劑及一或多種基本上不含金屬離子之含氟化合物。
該特洛卡酸化合物可以用在半導體製造過程中;包括但不限於作為錯合劑以將殘留物從半導體基材上及CMP漿液中移除。
本發明之一例示的具體實例是一種施加含至少水及特洛卡酸化合物之組成物至半導體基材上的方法,其包含令該基材與該組成物接觸。
該組成物可以在清潔過程期間及汽提過程期間被施加至該半導體基材上以成為CMP過程的部分。選擇性地,維持pH使鈍化層形成在半導體基材表面上。
本發明之另一例示的具體實例是一種處理晶圓的方法,其包含:將晶圓置於單一晶圓清潔裝置或分批清潔裝置中且將該晶圓曝於包含至少一種特洛卡酸化合物之清潔水溶液中,其中該晶圓在合適時間內曝於該溶液,諸如在30秒至90秒之大略範圍內。
包含至少一種特洛卡酸化合物之清潔溶液可以另外在使用前被稀釋(例如約10至約500倍稀釋)。
不希望侷限於任何特定理論,據了解:上述之多配位基錯合劑與基材表面錯合以移除在此種表面上之污染物。特洛卡酸化合物可以被設計以在金屬表面上作為鈍化劑(此係藉由使由該特洛卡酸化合物所形成之金屬錯合物不可溶),或者藉由增加含殘留物之金屬錯合物的溶解度而作為清潔劑。
已顯示特洛卡酸銅錯合物在鹼性條件下容易溶於水中,但在酸性條件下較不溶。因此,該特洛卡酸化合物之鈍化/清潔效果可以藉由改變pH或其分子而控制。
因為本文中所揭示之螯合劑含有多重配位基位址,本發明另外提供對在半導體製造過程中所發現之金屬離子(諸如在電漿蝕刻後之殘留物)更有效率且更有效之結合效益,特別是在利用導引邊緣(leading edge)技術的情況中,其中使用銅作為傳導金屬。
本文中所揭示之螯合劑之另一優點是此種螯合劑可以稀釋形式被使用以作為後銅CMP清潔劑,因為這些類別之化合物與有機酸類相比更不具酸性且比氨、氫氧化膽鹼及THEMAH更不具鹼性。在一例示的具體實例中,包含特洛卡酸化合物之組成物在由基材移除殘留物之前(諸如在積體電路製造期間)另外用水稀釋。在一特別具體實例中,稀釋倍數是約10至約500。
本發明之一具體實例係關於一種在積體電路製造期間由基材移除殘留物的方法,該方法包括以下步驟:提供一基材,其包含金屬及/或金屬合金部分及/或層,以及其上具有有機、有機金屬、及/或金屬氧化物蝕刻殘留物的表面;及使該基材與包含至少一種特洛卡酸化合物及水之組成物在由該基材充分移除該殘留物之時間及溫度下接觸。
令人驚訝地,已發現:此種化合物添加至殘留物移除、預先清潔、及阻劑汽提應用中會有效地移除污染物,同時對該基材表面無負面影響。
要領會所揭示之本發明之特定具體實例僅是說明本發明,且精於此技藝之人士將領會取代各特徵及消除所揭示之特徵的能力。以此情況,本申請人之清潔溶液及清潔方法的範圍是要藉由以下所附之申請專利範圍來估計。因此,已描述一種新穎之用於清潔過程中的清潔方法及溶液。
雖然本發明已在本文中參考多種特定材料、程序及實例描述及說明,據了解本發明不限於供該目的所選之材料及程序的特定結合。此種細節之多種變化可被暗示,正如經於此技藝之人士所領會的。本說明書及實例意圖被認定僅是例示性的,而本發明之真實範圍及精神由以下申請專利範圍所表示。在本申請案中所指出之所有參考資料、專利及專利申請案整體被倂入本文作為參考。
Claims (19)
- 一種半導體處理用組成物,其包含:a.含量約0.001至約35重量%之一或多種特洛卡酸類、其衍生物或其鹽類;及b.水。
- 如申請專利範圍第1項之組成物,其中該特洛卡酸類、衍生物或鹽類包含以下通式;
- 如申請專利範圍第2項之組成物,其中該烷基或芳基是選自由甲基、乙基、丙基、丁基、苄基、苯基、對-硝基苯基、及鄰-硝基苄基組成之群中。
- 如申請專利範圍第2項之組成物,其中該烷基銨是選自由苯銨、二環己基銨、四甲基銨、苄基四甲基銨、2-羥基乙基三甲基銨、及三(2-羥基乙基)甲基銨組成之群中。
- 如申請專利範圍第2項之組成物,其中該一或多種特洛卡酸類、其衍生物或其鹽類包括至少一種包含二或 多種特洛卡酸類、或其衍生物或其鹽之樹枝狀聚合物(dendrimer)。
- 如申請專利範圍第1項之組成物,其另外包含一或多種溶劑、酸類、鹼類、表面活性劑、具有氧化或還原潛能之化合物、活化劑、及氟化物。
- 一種化學機械拋光用漿液,其包含:氧化劑;稀釋劑;選擇性地研磨材料;及黏附至微孔性或巨孔性聚合系統之特洛卡酸部分。
- 如申請專利範圍第7項之漿液,其中該聚合系統使用一種選自由PS-DVB、切利克斯(Chelex)、聚胺、經胺改質之苯乙烯-二乙烯基苯、胺化之酚-甲醛樹脂、及經胺改質之丙烯酸系樹脂組成之群中的樹脂。
- 一種清潔半導體基材之方法,其包含以下步驟:a.提供一基材,其具有一包含含銅導體及低k介電材料之表面及阻劑、蝕刻殘留物、平面化殘留物、及氧化銅之一或多者配置在其表面上;b.使該基材之該表面與有效量之包含以下物質之清潔溶液接觸:包含以下通式或其互變異構物之一或多種特洛卡酸類、其衍生物或其鹽類的水溶液:
- 如申請專利範圍第9項之方法,其中該烷基或芳基是選自由甲基、乙基、丙基、丁基、苄基、苯基、對-硝基苯基、及鄰-硝基苄基組成之群中。
- 如申請專利範圍第9項之方法,其中該烷基銨是選自由苯銨、二環己基銨、四甲基銨、苄基四甲基銨、2-羥基乙基三甲基銨、及三(2-羥基乙基)甲基銨組成之群中。
- 如申請專利範圍第9項之方法,其中該特洛卡酸類、衍生物或鹽類中至少一者是包括二或多種特洛卡酸類、衍生物或其鹽類之樹枝狀聚合物。
- 如申請專利範圍第9項之方法,其中該清潔溶液在汽提過程及後蝕刻殘留物接觸過程期間被施加至該半導體基材。
- 如申請專利範圍第9項之方法,其中該接觸過程是在該半導體製造方法期間之化學機械平面化步驟之後。
- 如申請專利範圍第9項之方法,其中該清潔溶液另外包含含量約0.001至約25重量%之具有氧化及還原潛能之化合物。
- 如申請專利範圍第9項之方法,其中該清潔溶液另外包含含量高至約15重量%之另外的螯合劑或錯合 劑。
- 如申請專利範圍第9項之方法,其中該包含至少一種特洛卡酸類化合物之清潔溶液另外在使用前被稀釋。
- 如申請專利範圍第14項之方法,其中在該化學機械平面化步驟中使用一種包含至少一種特洛卡酸、其衍生物或其鹽類之組成物。
- 如申請專利範圍第18項之方法,其中在該化學機械平面化步驟中使用之組成物另外包含研磨材料。
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