JP2007311779A - Cmp abrasive, and method of polishing substrate - Google Patents
Cmp abrasive, and method of polishing substrate Download PDFInfo
- Publication number
- JP2007311779A JP2007311779A JP2007113044A JP2007113044A JP2007311779A JP 2007311779 A JP2007311779 A JP 2007311779A JP 2007113044 A JP2007113044 A JP 2007113044A JP 2007113044 A JP2007113044 A JP 2007113044A JP 2007311779 A JP2007311779 A JP 2007311779A
- Authority
- JP
- Japan
- Prior art keywords
- polishing
- metal hydroxide
- cmp
- abrasive
- cmp abrasive
- 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.)
- Granted
Links
- 239000000758 substrate Substances 0.000 title claims description 35
- 238000007517 polishing process Methods 0.000 title description 2
- 238000005498 polishing Methods 0.000 claims abstract description 117
- 239000002245 particle Substances 0.000 claims abstract description 43
- 238000000034 method Methods 0.000 claims abstract description 39
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910000000 metal hydroxide Inorganic materials 0.000 claims abstract description 32
- 150000004692 metal hydroxides Chemical class 0.000 claims abstract description 32
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 29
- -1 nitrogen-containing heterocyclic compound Chemical class 0.000 claims abstract description 27
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 23
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 7
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 7
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000004065 semiconductor Substances 0.000 claims description 27
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 claims description 12
- PCKPVGOLPKLUHR-UHFFFAOYSA-N OH-Indolxyl Natural products C1=CC=C2C(O)=CNC2=C1 PCKPVGOLPKLUHR-UHFFFAOYSA-N 0.000 claims description 12
- XSCHRSMBECNVNS-UHFFFAOYSA-N benzopyrazine Natural products N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 claims description 12
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 claims description 12
- 239000002002 slurry Substances 0.000 claims description 12
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 10
- QWENRTYMTSOGBR-UHFFFAOYSA-N 1H-1,2,3-Triazole Chemical compound C=1C=NNN=1 QWENRTYMTSOGBR-UHFFFAOYSA-N 0.000 claims description 9
- 239000012964 benzotriazole Substances 0.000 claims description 9
- BAXOFTOLAUCFNW-UHFFFAOYSA-N 1H-indazole Chemical compound C1=CC=C2C=NNC2=C1 BAXOFTOLAUCFNW-UHFFFAOYSA-N 0.000 claims description 8
- SGZFJWQQBHYNNF-UHFFFAOYSA-N 3-hydroxyindolin-2-one Chemical compound C1=CC=C2C(O)C(=O)NC2=C1 SGZFJWQQBHYNNF-UHFFFAOYSA-N 0.000 claims description 8
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 claims description 8
- KDCGOANMDULRCW-UHFFFAOYSA-N 7H-purine Chemical compound N1=CNC2=NC=NC2=C1 KDCGOANMDULRCW-UHFFFAOYSA-N 0.000 claims description 8
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 claims description 8
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 8
- JXDYKVIHCLTXOP-UHFFFAOYSA-N isatin Chemical compound C1=CC=C2C(=O)C(=O)NC2=C1 JXDYKVIHCLTXOP-UHFFFAOYSA-N 0.000 claims description 8
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- SNTWKPAKVQFCCF-UHFFFAOYSA-N 2,3-dihydro-1h-triazole Chemical compound N1NC=CN1 SNTWKPAKVQFCCF-UHFFFAOYSA-N 0.000 claims description 7
- 239000011163 secondary particle Substances 0.000 claims description 7
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- JHFAEUICJHBVHB-UHFFFAOYSA-N 1h-indol-2-ol Chemical compound C1=CC=C2NC(O)=CC2=C1 JHFAEUICJHBVHB-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 5
- ZVJHJDDKYZXRJI-UHFFFAOYSA-N pyrroline Natural products C1CC=NC1 ZVJHJDDKYZXRJI-UHFFFAOYSA-N 0.000 claims description 5
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims description 4
- RSEBUVRVKCANEP-UHFFFAOYSA-N 2-pyrroline Chemical compound C1CC=CN1 RSEBUVRVKCANEP-UHFFFAOYSA-N 0.000 claims description 4
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 4
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 claims description 4
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 claims description 4
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 claims description 4
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 claims description 4
- JYGFTBXVXVMTGB-UHFFFAOYSA-N indolin-2-one Chemical compound C1=CC=C2NC(=O)CC2=C1 JYGFTBXVXVMTGB-UHFFFAOYSA-N 0.000 claims description 4
- IJAPPYDYQCXOEF-UHFFFAOYSA-N phthalazin-1(2H)-one Chemical compound C1=CC=C2C(=O)NN=CC2=C1 IJAPPYDYQCXOEF-UHFFFAOYSA-N 0.000 claims description 4
- LFSXCDWNBUNEEM-UHFFFAOYSA-N phthalazine Chemical compound C1=NN=CC2=CC=CC=C21 LFSXCDWNBUNEEM-UHFFFAOYSA-N 0.000 claims description 4
- CPNGPNLZQNNVQM-UHFFFAOYSA-N pteridine Chemical compound N1=CN=CC2=NC=CN=C21 CPNGPNLZQNNVQM-UHFFFAOYSA-N 0.000 claims description 4
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical compound C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 claims description 4
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 claims description 4
- JWVCLYRUEFBMGU-UHFFFAOYSA-N quinazoline Chemical compound N1=CN=CC2=CC=CC=C21 JWVCLYRUEFBMGU-UHFFFAOYSA-N 0.000 claims description 4
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 claims description 3
- DPOPAJRDYZGTIR-UHFFFAOYSA-N Tetrazine Chemical compound C1=CN=NN=N1 DPOPAJRDYZGTIR-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 125000003172 aldehyde group Chemical group 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 150000003536 tetrazoles Chemical class 0.000 claims description 3
- 239000011229 interlayer Substances 0.000 abstract description 4
- 239000005380 borophosphosilicate glass Substances 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 238000009413 insulation Methods 0.000 abstract 2
- UNJPQTDTZAKTFK-UHFFFAOYSA-K cerium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Ce+3] UNJPQTDTZAKTFK-UHFFFAOYSA-K 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 15
- 239000010410 layer Substances 0.000 description 15
- 229910000420 cerium oxide Inorganic materials 0.000 description 14
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 14
- 238000002955 isolation Methods 0.000 description 13
- 238000004519 manufacturing process Methods 0.000 description 12
- 238000011156 evaluation Methods 0.000 description 11
- 239000007788 liquid Substances 0.000 description 11
- 239000002609 medium Substances 0.000 description 11
- 230000009471 action Effects 0.000 description 10
- 229910052581 Si3N4 Inorganic materials 0.000 description 9
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 8
- 230000007423 decrease Effects 0.000 description 7
- 239000004744 fabric Substances 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 6
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- ICSNLGPSRYBMBD-UHFFFAOYSA-N 2-aminopyridine Chemical compound NC1=CC=CC=N1 ICSNLGPSRYBMBD-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000004518 low pressure chemical vapour deposition Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 3
- 239000003082 abrasive agent Substances 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000011164 primary particle Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- VUIMBZIZZFSQEE-UHFFFAOYSA-N 1-(1h-indol-3-yl)ethanone Chemical compound C1=CC=C2C(C(=O)C)=CNC2=C1 VUIMBZIZZFSQEE-UHFFFAOYSA-N 0.000 description 2
- TXQAZWIBPGKHOX-UHFFFAOYSA-N 1H-indol-3-amine Chemical compound C1=CC=C2C(N)=CNC2=C1 TXQAZWIBPGKHOX-UHFFFAOYSA-N 0.000 description 2
- DNCYBUMDUBHIJZ-UHFFFAOYSA-N 1h-pyrimidin-6-one Chemical compound O=C1C=CN=CN1 DNCYBUMDUBHIJZ-UHFFFAOYSA-N 0.000 description 2
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 2
- CUYKNJBYIJFRCU-UHFFFAOYSA-N 3-aminopyridine Chemical compound NC1=CC=CN=C1 CUYKNJBYIJFRCU-UHFFFAOYSA-N 0.000 description 2
- ITQTTZVARXURQS-UHFFFAOYSA-N 3-methylpyridine Chemical compound CC1=CC=CN=C1 ITQTTZVARXURQS-UHFFFAOYSA-N 0.000 description 2
- 238000004438 BET method Methods 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 229910021485 fumed silica Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- CAWHJQAVHZEVTJ-UHFFFAOYSA-N methylpyrazine Chemical compound CC1=CN=CC=N1 CAWHJQAVHZEVTJ-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- SIOXPEMLGUPBBT-UHFFFAOYSA-N picolinic acid Chemical compound OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 229920003169 water-soluble polymer Polymers 0.000 description 2
- VLBGIFUKQYTZCN-UHFFFAOYSA-N (+)-2,3-Dihydro-3-methyl-1H-pyrrole Chemical compound CC1CNC=C1 VLBGIFUKQYTZCN-UHFFFAOYSA-N 0.000 description 1
- GDAXJBDYNVDMDF-UHFFFAOYSA-N 1,2,4-benzotriazine Chemical compound N1=NC=NC2=CC=CC=C21 GDAXJBDYNVDMDF-UHFFFAOYSA-N 0.000 description 1
- ABJFBJGGLJVMAQ-UHFFFAOYSA-N 1,4-dihydroquinoxaline-2,3-dione Chemical compound C1=CC=C2NC(=O)C(=O)NC2=C1 ABJFBJGGLJVMAQ-UHFFFAOYSA-N 0.000 description 1
- FYNQKUVKOPNJHH-UHFFFAOYSA-N 1-(2h-pyran-2-yl)ethanone Chemical compound CC(=O)C1OC=CC=C1 FYNQKUVKOPNJHH-UHFFFAOYSA-N 0.000 description 1
- ASOKPJOREAFHNY-UHFFFAOYSA-N 1-Hydroxybenzotriazole Chemical compound C1=CC=C2N(O)N=NC2=C1 ASOKPJOREAFHNY-UHFFFAOYSA-N 0.000 description 1
- PVOAHINGSUIXLS-UHFFFAOYSA-N 1-Methylpiperazine Chemical compound CN1CCNCC1 PVOAHINGSUIXLS-UHFFFAOYSA-N 0.000 description 1
- OXHNLMTVIGZXSG-UHFFFAOYSA-N 1-Methylpyrrole Chemical compound CN1C=CC=C1 OXHNLMTVIGZXSG-UHFFFAOYSA-N 0.000 description 1
- VPUAYOJTHRDUTK-UHFFFAOYSA-N 1-ethylpyrrole Chemical compound CCN1C=CC=C1 VPUAYOJTHRDUTK-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- CVBUKMMMRLOKQR-UHFFFAOYSA-N 1-phenylbutane-1,3-dione Chemical compound CC(=O)CC(=O)C1=CC=CC=C1 CVBUKMMMRLOKQR-UHFFFAOYSA-N 0.000 description 1
- IHWDSEPNZDYMNF-UHFFFAOYSA-N 1H-indol-2-amine Chemical compound C1=CC=C2NC(N)=CC2=C1 IHWDSEPNZDYMNF-UHFFFAOYSA-N 0.000 description 1
- DMSSTTLDFWKBSX-UHFFFAOYSA-N 1h-1,2,3-benzotriazin-4-one Chemical compound C1=CC=C2C(=O)N=NNC2=C1 DMSSTTLDFWKBSX-UHFFFAOYSA-N 0.000 description 1
- HUTNOYOBQPAKIA-UHFFFAOYSA-N 1h-pyrazin-2-one Chemical compound OC1=CN=CC=N1 HUTNOYOBQPAKIA-UHFFFAOYSA-N 0.000 description 1
- AAILEWXSEQLMNI-UHFFFAOYSA-N 1h-pyridazin-6-one Chemical compound OC1=CC=CN=N1 AAILEWXSEQLMNI-UHFFFAOYSA-N 0.000 description 1
- TVCXVUHHCUYLGX-UHFFFAOYSA-N 2-Methylpyrrole Chemical compound CC1=CC=CN1 TVCXVUHHCUYLGX-UHFFFAOYSA-N 0.000 description 1
- LNJMHEJAYSYZKK-UHFFFAOYSA-N 2-methylpyrimidine Chemical compound CC1=NC=CC=N1 LNJMHEJAYSYZKK-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- KEKCQXQAPNKMLX-UHFFFAOYSA-N 2h-1,2,4-benzotriazin-3-one Chemical compound C1=CC=CC2=NC(O)=NN=C21 KEKCQXQAPNKMLX-UHFFFAOYSA-N 0.000 description 1
- PRPNZPPJPIEXJI-UHFFFAOYSA-N 2h-triazin-1-amine Chemical compound NN1NN=CC=C1 PRPNZPPJPIEXJI-UHFFFAOYSA-N 0.000 description 1
- FEKWWZCCJDUWLY-UHFFFAOYSA-N 3-methyl-1h-pyrrole Chemical compound CC=1C=CNC=1 FEKWWZCCJDUWLY-UHFFFAOYSA-N 0.000 description 1
- MXDRPNGTQDRKQM-UHFFFAOYSA-N 3-methylpyridazine Chemical compound CC1=CC=CN=N1 MXDRPNGTQDRKQM-UHFFFAOYSA-N 0.000 description 1
- JVQIKJMSUIMUDI-UHFFFAOYSA-N 3-pyrroline Chemical compound C1NCC=C1 JVQIKJMSUIMUDI-UHFFFAOYSA-N 0.000 description 1
- ITMIGVTYYAEAJP-UHFFFAOYSA-N 4,5,6-trimethyltriazine Chemical compound CC1=NN=NC(C)=C1C ITMIGVTYYAEAJP-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
本発明は、半導体素子製造技術に好適に使用されるＣＭＰ研磨剤及び基板の研磨方法に関し、特に、半導体絶縁膜表面の平坦化工程用の研磨に適したＣＭＰ研磨剤及び基板の研磨法に関する。 The present invention relates to a CMP polishing agent and a substrate polishing method that are preferably used in a semiconductor element manufacturing technique, and more particularly to a CMP polishing agent and a substrate polishing method that are suitable for polishing for a planarization process of a semiconductor insulating film surface.
現在のＵＬＳＩ半導体素子製造工程では、高密度・微細化のための加工技術が研究開発されている。その一つであるＣＭＰ（ケミカルメカニカルポリッシング）技術は、半導体素子の製造工程において、層間絶縁膜の平坦化、シャロートレンチ素子分離形成、プラグ及び埋め込み金属配線形成などを行う際に必須の技術となってきている。 In the current ULSI semiconductor device manufacturing process, processing technology for high density and miniaturization has been researched and developed. CMP (Chemical Mechanical Polishing) technology, which is one of them, is an indispensable technology when performing planarization of interlayer insulating films, shallow trench element isolation formation, plug and embedded metal wiring formation, etc. in the manufacturing process of semiconductor elements. It is coming.
従来、半導体素子の製造工程において、プラズマ−ＣＶＤ、低圧−ＣＶＤ等の方法で形成される酸化珪素絶縁膜等無機絶縁膜層を平坦化するための化学機械研磨剤としてフュームドシリカ系の研磨剤が一般的に検討されている。フュームドシリカ系の研磨剤は、四塩化珪素を熱分解する等の方法で粒成長させ、ｐＨ調整を行って製造している。しかしながら、この様な研磨剤は、研磨速度が低いという技術課題がある。 Conventionally, a fumed silica-based polishing agent as a chemical mechanical polishing agent for planarizing an inorganic insulating film layer such as a silicon oxide insulating film formed by a method such as plasma-CVD or low-pressure CVD in a manufacturing process of a semiconductor element Is generally considered. A fumed silica-based abrasive is produced by growing grains by a method such as thermal decomposition of silicon tetrachloride and adjusting pH. However, such an abrasive has a technical problem that the polishing rate is low.
また、デザインルール０．２５μｍ以降の世代では、集積回路内の素子分離にシャロートレンチ分離が用いられている。シャロートレンチ分離では、基板上に成膜した余分の酸化珪素膜を除くためにＣＭＰが使用され、研磨を停止させるために、酸化珪素膜の下に研磨速度の遅いストッパ膜が形成される。 In the generations after the design rule 0.25 μm, shallow trench isolation is used for element isolation in the integrated circuit. In shallow trench isolation, CMP is used to remove an extra silicon oxide film formed on the substrate, and a stopper film having a low polishing rate is formed under the silicon oxide film in order to stop polishing.
ストッパ膜には窒化珪素などが使用され、酸化珪素膜とストッパ膜との研磨速度比が大きいことが望ましい。 Silicon nitride or the like is used for the stopper film, and it is desirable that the polishing rate ratio between the silicon oxide film and the stopper film is large.
従来のコロイダルシリカ系の研磨剤は、上記の酸化珪素膜とストッパ膜の研磨速度比が３程度と小さく、シャロートレンチ分離用としては実用に耐える特性を有していなかった。 Conventional colloidal silica-based abrasives have a polishing rate ratio of the above-described silicon oxide film and stopper film as small as about 3, and have no practical characteristics for shallow trench isolation.
一方、フォトマスク、レンズ等のガラス表面研磨剤として、酸化セリウム研磨剤が用いられている。酸化セリウム粒子はシリカ粒子やアルミナ粒子に比べ硬度が低く、したがって、研磨表面に傷が入りにくいことから、仕上げ鏡面研磨に有用である。また、シリカ研磨剤に比べ、研磨速度が早い利点がある。 On the other hand, a cerium oxide abrasive is used as a glass surface abrasive for photomasks, lenses and the like. Cerium oxide particles have a lower hardness than silica particles and alumina particles, and therefore are less likely to scratch the polished surface, and are useful for finish mirror polishing. In addition, there is an advantage that the polishing rate is higher than that of the silica abrasive.
近年、高純度酸化セリウム砥粒を用いた半導体用ＣＭＰ研磨剤が使用されている。例えば、その技術は特許文献１に開示されている。 In recent years, CMP abrasives for semiconductors using high-purity cerium oxide abrasive grains have been used. For example, this technique is disclosed in Patent Document 1.
また、酸化セリウム研磨液の研磨速度を制御し、グローバルな平坦性を向上させるために添加剤を加えることが知られている。例えば、この技術は特許文献２に開示されている。 It is also known to add an additive to control the polishing rate of the cerium oxide polishing liquid and improve global flatness. For example, this technique is disclosed in Patent Document 2.
また、酸化セリウムは強い酸化剤として知られるように、化学的活性な性質を有している。この利点を活かして、半導体絶縁膜用ＣＭＰ研磨剤への適用が有用である。
しかしながら、フォトマスクガラス表面研磨用酸化セリウム研磨剤をそのまま半導体絶縁膜研磨に適用すると、１次粒子径が大きく、そのため絶縁膜表面に目視で観察できる研磨傷が入ってしまう。１次粒子径を小さくすると、研磨傷は入りにくくなるが、研磨速度が低下してしまう。 However, if the cerium oxide abrasive for polishing the photomask glass surface is applied as it is to the semiconductor insulating film polishing, the primary particle size is large, and therefore, the insulating film surface has polishing scratches that can be visually observed. When the primary particle size is reduced, polishing scratches are difficult to enter, but the polishing rate decreases.
酸化セリウム研磨剤による研磨は、酸化セリウムの化学的作用と粒子による機械的除去作用で加工が進行するとされている。 Polishing with a cerium oxide abrasive is said to proceed by chemical action of cerium oxide and mechanical removal action by particles.
粒子による機械的除去作用があると研磨傷が入る。 If there is a mechanical removal action by the particles, polishing scratches will be introduced.
そこで、所望の研磨速度と研磨傷等の表面状態になる酸化セリウム１次粒子径を選択しているが、酸化セリウム粒子を用いる限り研磨傷フリーの表面を得るのは困難である。今後、半導体素子の多層化・高精細化が進むにつれ、半導体素子の歩留り向上には研磨傷フリーな研磨剤が必須となる。 Therefore, a desired polishing speed and a primary particle diameter of cerium oxide that results in a surface state such as polishing scratches are selected. However, it is difficult to obtain a polishing scratch-free surface as long as cerium oxide particles are used. In the future, as the number of semiconductor elements increases and the definition becomes higher, a polishing agent that is free from polishing scratches is essential for improving the yield of semiconductor elements.
本発明は、層間絶縁膜、ＢＰＳＧ膜、シャロートレンチ分離用絶縁膜を平坦化するＣＭＰ技術において、酸化珪素膜を研磨傷なく、高速に、かつウェハ面内を均一に研磨できるＣＭＰ研磨剤及び基板の研磨法を提供するものである。粒子による研磨傷を無くすには、粒子の化学的作用を活かし、機械的作用を極力小さくする手法が挙げられる。そこで、本発明では、粒子が被研磨膜と化学反応層を形成し、それを粒子の微小な機械的作用と研磨パッドの機械的除去とによって研磨する。 The present invention relates to a CMP polishing agent and substrate capable of polishing a silicon oxide film at high speed and uniformly in a wafer surface without polishing scratches in CMP technology for planarizing an interlayer insulating film, a BPSG film, and a shallow trench isolation insulating film. A polishing method is provided. In order to eliminate abrasive scratches caused by particles, there is a method of making the mechanical action as small as possible by utilizing the chemical action of the particles. Therefore, in the present invention, the particles form a chemical reaction layer with the film to be polished, and are polished by the fine mechanical action of the particles and the mechanical removal of the polishing pad.
本発明は、（１） ４価の金属水酸化物粒子、含窒素複素環化合物及び媒体を含むＣＭＰ研磨剤に関する。 The present invention relates to (1) a CMP abrasive comprising tetravalent metal hydroxide particles, a nitrogen-containing heterocyclic compound and a medium.
また、本発明は、（２） 前記含窒素複素環化合物がピロール、ピロリン、ピロリドン、インドール、インドレニン、インドリン、オキシインドール、ジオキシインドール、オキシルインドール、イサチン、インドキシル、ピラゾール、２Ｈ−１，２，３−トリアゾール、１，２，３−トリアゾール、４Ｈ−１，２，４−トリアゾール、１Ｈ−１，２，４−トリアゾール、１Ｈ−１，２，３，４−トリアゾール、２Ｈ−１，２，３，４−トリアゾール、ベンゾイミダゾール、１，２−ベンゾピラゾール、２，１−ベンゾピラゾール、１−ベンゾトリアゾール、２−ベンゾトリアゾール、ピリジン、２，２´−ビピリジニル、キノリン、イソキノリン、ピリダジン、シンシノリン、フタラジン、フタラジノン、ピリミジン、プリン、プテリジン、キナゾリン、ピラジン、キノキサリン、トリアジン、テトラジン、テトラゾール及びそれらの化合物中の水素原子が、アルキル基、水酸基、アミノ基、カルボニル基またはアルデヒド基で置換された誘導体からなる群から選ばれる１種以上である前記（１）のＣＭＰ研磨剤に関する。 In the present invention, (2) the nitrogen-containing heterocyclic compound is pyrrole, pyrroline, pyrrolidone, indole, indolenine, indoline, oxindole, dioxindole, oxylindole, isatin, indoxyl, pyrazole, 2H-1, 2,3-triazole, 1,2,3-triazole, 4H-1,2,4-triazole, 1H-1,2,4-triazole, 1H-1,2,3,4-triazole, 2H-1, 2,3,4-triazole, benzimidazole, 1,2-benzopyrazole, 2,1-benzopyrazole, 1-benzotriazole, 2-benzotriazole, pyridine, 2,2′-bipyridinyl, quinoline, isoquinoline, pyridazine, Cinchinoline, phthalazine, phthalazinone, pyrimidine, purine, pteridine, Quinazoline, pyrazine, quinoxaline, triazine, tetrazine, tetrazole and one or more selected from the group consisting of derivatives in which hydrogen atoms in these compounds are substituted with alkyl groups, hydroxyl groups, amino groups, carbonyl groups or aldehyde groups The present invention relates to the CMP polishing agent (1).
また、本発明は、（３） 前記含窒素複素環化合物酸添加量が、ＣＭＰ研磨剤１００質量部に対して０．０１質量部以上５質量部以下である前記（１）または（２）のＣＭＰ研磨剤に関する。 Moreover, this invention is (3) Said nitrogen-containing heterocyclic compound acid addition amount is 0.01 to 5 mass parts with respect to 100 mass parts of CMP abrasive | polishing agents, (1) or (2) The present invention relates to a CMP abrasive.
また、本発明は、（４） ４価の金属水酸化物粒子の比表面積が１００ｍ２／ｇ以上である前記（１）〜（３）のいずれかのＣＭＰ研磨剤に関する。 The present invention also relates to (4) the CMP polishing slurry according to any one of (1) to (3), wherein the specific surface area of the tetravalent metal hydroxide particles is 100 m 2 / g or more.
また、本発明は、（５） 媒体に分散させた４価の金属水酸化物粒子の２次粒子径の中央値が、３００ｎｍ以下である前記（１）〜（４）のいずれかのＣＭＰ研磨剤に関する。 The present invention also provides (5) CMP polishing according to any one of (1) to (4), wherein the median secondary particle diameter of the tetravalent metal hydroxide particles dispersed in the medium is 300 nm or less. It relates to the agent.
また、本発明は、（６） 研磨剤のｐＨが、３以上９以下である前記（１）〜（５）のいずれかのＣＭＰ研磨剤に関する。 The present invention also relates to (6) the CMP polishing slurry according to any one of (1) to (5), wherein the pH of the polishing slurry is 3 or more and 9 or less.
また、本発明は、（７） ４価の金属水酸化物が希土類金属水酸化物及び水酸化ジルコニウムの少なくとも一方である前記（１）〜（６）のいずれかのＣＭＰ研磨剤に関する。 The present invention also relates to (7) the CMP polishing slurry according to any one of (1) to (6), wherein the tetravalent metal hydroxide is at least one of a rare earth metal hydroxide and zirconium hydroxide.
また、本発明は、（８） 金属水酸化物が、４価の金属塩とアルカリ液を混合して得られたものである前記（１）〜（７）のいずれかのＣＭＰ研磨剤に関する。 The present invention also relates to the CMP polishing slurry according to any one of (1) to (7), wherein (8) the metal hydroxide is obtained by mixing a tetravalent metal salt and an alkali solution.
また、本発明は、（９） 前記（１）〜（８）のいずれかのＣＭＰ研磨剤で基板を研磨することを特徴とする基板の研磨方法に関する。 The present invention also relates to (9) a method for polishing a substrate, characterized in that the substrate is polished with the CMP abrasive of any one of (1) to (8).
さらに、本発明は、（１０） 基板が、酸化珪素絶縁膜が形成された半導体ウェハである前記（９）の基板の研磨方法に関する。 Furthermore, the present invention relates to (10) the method for polishing a substrate according to (9), wherein the substrate is a semiconductor wafer on which a silicon oxide insulating film is formed.
本発明によれば、層間絶縁膜、ＢＰＳＧ膜、シャロートレンチ分離用絶縁膜等を平坦化するＣＭＰ技術において、酸化珪素絶縁膜等の被研磨面を研磨傷なく、高速かつ均一に研磨することが可能である。 According to the present invention, in a CMP technique for flattening an interlayer insulating film, a BPSG film, a shallow trench isolation insulating film, etc., a surface to be polished such as a silicon oxide insulating film can be polished at high speed and uniformly without polishing scratches. Is possible.
本発明において、金属水酸化物を作製する方法として、４価の金属塩とアルカリ液とを混合する手法が使用できる。この方法は、例えば「希土類の科学」（足立吟也編、化学同人）３０４〜３０５頁に説明されている。 In the present invention, a method of mixing a tetravalent metal salt and an alkali solution can be used as a method for producing a metal hydroxide. This method is described in, for example, “Science of rare earths” (edited by Adiya Ginya, Kagaku Dojin) pages 304-305.
４価の金属塩としては、例えばＭ（ＳＯ４）２、Ｍ（ＮＨ４）２（ＮＯ３）６、Ｍ（ＮＨ４）４（ＳＯ４）４（ただしＭはＣｅ、Ｙ、Ｌａ等の希土類を示す。）、Ｚｒ（ＳＯ４）２・４Ｈ２Ｏが好ましい。特に化学的に活性なＣｅ塩がより好ましい。 Examples of the tetravalent metal salt include M (SO 4 ) 2 , M (NH 4 ) 2 (NO 3 ) 6 , M (NH 4 ) 4 (SO 4 ) 4 (where M is Ce, Y, La, etc.). Rare earths are preferred), Zr (SO 4 ) 2 .4H 2 O is preferred In particular, a chemically active Ce salt is more preferable.
アルカリ液としては、例えばアンモニア水、水酸化カリウム、水酸化ナトリウムが使用できる。好ましくはアンモニア水が用いられる。 As the alkaline solution, for example, aqueous ammonia, potassium hydroxide, or sodium hydroxide can be used. Preferably aqueous ammonia is used.
４価の金属水酸化物として、希土類金属水酸化物および水酸化ジルコニウムの少なくとも一方を使用するのが好ましい。希土類金属水酸化物および水酸化ジルコニウムから二種以上を選択して使用してもよい。希土類金属水酸化物としては、水酸化セリウムがより好ましい。 It is preferable to use at least one of rare earth metal hydroxide and zirconium hydroxide as the tetravalent metal hydroxide. Two or more rare earth metal hydroxides and zirconium hydroxide may be selected and used. As the rare earth metal hydroxide, cerium hydroxide is more preferable.
金属水酸化物の同定方法として、熱重量分析法が挙げられる（上記「希土類の科学」参照。）。例えば、米国特許第５３８９３５２号明細書で開示しているように３価のセリウム塩から酸化セリウムを合成したものと、本発明で得られた水酸化セリウムを４０℃で１５時間乾燥し、熱重量分析を行うと、１０００℃までの重量減少は、酸化セリウムの３重量％に対して、水酸化セリウムは１７〜２６重量％と大きい。 As a method for identifying metal hydroxide, there is a thermogravimetric analysis method (see “Science of rare earth” above). For example, as disclosed in US Pat. No. 5,389,352, cerium oxide synthesized from a trivalent cerium salt and cerium hydroxide obtained in the present invention were dried at 40 ° C. for 15 hours, When analyzed, the weight loss up to 1000 ° C. is as large as 17 to 26% by weight for cerium hydroxide with respect to 3% by weight for cerium oxide.
水酸化セリウムの化学式はＣｅ（ＯＨ）４又はＣｅＯ２・２Ｈ２Ｏと表され、酸化セリウムとの重量減少の差は結晶水である。 The chemical formula of cerium hydroxide is expressed as Ce (OH) 4 or CeO 2 .2H 2 O, and the difference in weight reduction from cerium oxide is crystal water.
上記方法で作製された粒子状の４価の金属水酸化物は、洗浄して金属不純物を除去できる。金属水酸化物の洗浄は、遠心分離等で固液分離を数回繰り返す方法等が使用できる。 The particulate tetravalent metal hydroxide produced by the above method can be washed to remove metal impurities. For washing the metal hydroxide, a method of repeating solid-liquid separation several times by centrifugation or the like can be used.
上記で洗浄して得られた４価の金属水酸化物粒子を、液状の媒体中に分散させることによって、スラリーを作製できる。媒体としては水が好ましく用いられる。 A slurry can be produced by dispersing the tetravalent metal hydroxide particles obtained by washing in the above in a liquid medium. Water is preferably used as the medium.
上記スラリーに、後述する含窒素複素環化合物を添加して本発明のＣＭＰ研磨剤を得ることができる。添加方法には特に制限は無く、分散前の媒体に予め加えても、分散処理と同時に混合しても、分散後に加えても良い。さらに必要に応じて適宜各種添加剤を加えてもよい。 The CMP abrasive | polishing agent of this invention can be obtained by adding the nitrogen-containing heterocyclic compound mentioned later to the said slurry. The addition method is not particularly limited, and may be added in advance to the medium before dispersion, mixed simultaneously with the dispersion treatment, or added after dispersion. Furthermore, you may add various additives suitably as needed.
これらの４価の金属水酸化物粒子を媒体に分散させる方法としては、通常の撹拌機による分散処理の他に、ホモジナイザー、超音波分散機、ボールミル等を用いることができる。分散処理後の研磨剤をＳＵＳ等で作製されたフィルタでろ過することができる。 As a method for dispersing these tetravalent metal hydroxide particles in a medium, a homogenizer, an ultrasonic disperser, a ball mill, or the like can be used in addition to a dispersion treatment using a normal stirrer. The abrasive after the dispersion treatment can be filtered with a filter made of SUS or the like.
分散された金属水酸化物粒子をさらに微粒子化する方法として、金属水酸化物粒子分散液を長時間静置させて大粒子を沈降させ、上澄みをポンプで汲み取ることによる沈降分級法が用いられる。他に、分散媒中の金属水酸化物粒子同士を高圧力で衝突させる高圧ホモジナイザを使用する方法も使用される。 As a method for further finely dispersing the dispersed metal hydroxide particles, a sedimentation classification method is used in which the metal hydroxide particle dispersion is allowed to stand for a long time to precipitate large particles, and the supernatant is pumped out by a pump. In addition, a method using a high-pressure homogenizer that causes metal hydroxide particles in the dispersion medium to collide with each other at a high pressure is also used.
また、媒体は４価の金属水酸化物粒子１００質量部に対して１０，０００〜１，０００，０００質量部使用することが好ましい。 The medium is preferably used in an amount of 10,000 to 1,000,000 parts by mass with respect to 100 parts by mass of the tetravalent metal hydroxide particles.
媒体として、水の他、アルコール、エーテル、ケトン等を含んでも良い。水、メタノール、エタノール、２-プロパノール、テトラヒドロフラン、エチレングリコール、アセトン、メチルエチルケトンがより好ましく、高研磨速度が得られる点で水が特に好ましい。 As a medium, in addition to water, alcohol, ether, ketone or the like may be included. Water, methanol, ethanol, 2-propanol, tetrahydrofuran, ethylene glycol, acetone, and methyl ethyl ketone are more preferable, and water is particularly preferable in that a high polishing rate can be obtained.
媒体に分散させる４価の金属水酸化物粒子の比表面積は１００ｍ２／ｇ以上であることが好ましい。媒体に分散させた４価の金属水酸化物粒子の２次粒子の中央値（平均粒径）は３００ｎｍ以下であることが好ましい。 The specific surface area of the tetravalent metal hydroxide particles dispersed in the medium is preferably 100 m 2 / g or more. The median value (average particle size) of secondary particles of tetravalent metal hydroxide particles dispersed in a medium is preferably 300 nm or less.
本発明で、研磨剤中粒子の粒径の測定は、光子相関法（例えばベックマン・コールター（株）製の、コールターＮ４ＳＤ、Ｍａｌｖｅｒｎ Ｉｎｓｔｒｕｍｅｎｔ製の Ｚｅｔａｓｉｚｅｒ ３０００ＨＳ）で測定する。また、粒子の比表面積はＢＥＴ法によって測定できる。 In the present invention, the particle size of the particles in the abrasive is measured by a photon correlation method (for example, Coulter N4SD manufactured by Beckman Coulter, Inc., Zetasizer 3000HS manufactured by Malvern Instrument). The specific surface area of the particles can be measured by the BET method.
粒子は、被研磨膜と化学的作用を及ぼす必要があり、比表面積が１００ｍ２／ｇより小さいと化学研磨作用を有する表面部位が減少し、被研磨膜との接触面積が小さくなり、研磨速度が低下する傾向がある。 The particles must have a chemical action with the film to be polished. If the specific surface area is less than 100 m 2 / g, the surface portion having the chemical polishing action decreases, the contact area with the film to be polished becomes small, and the polishing rate Tends to decrease.
また、媒体に分散させた４価の金属水酸化物粒子の２次粒子径の中央値が３００ｎｍより大きいと、同様に化学研磨作用を有する表面部位が減少し、研磨速度が低下する傾向がある。本発明において、２次粒子径の中央値とは、粒度分布計で測定したＤ５０の値（体積分布のメジアン径、累積中央値）をいう。 In addition, when the median value of the secondary particle diameter of the tetravalent metal hydroxide particles dispersed in the medium is larger than 300 nm, the surface portion having the chemical polishing action similarly decreases, and the polishing rate tends to decrease. . In the present invention, the median secondary particle size refers to the value of D50 (median diameter of volume distribution, cumulative median value) measured with a particle size distribution meter.
研磨剤のｐＨは３以上９以下が好ましい。ｐＨが３より小さいと化学的作用力が小さくなり、研磨速度が低下する傾向がある。ｐＨが９より大きいと２次粒子径が大きくなり、研磨速度が低下する傾向がある。 The pH of the abrasive is preferably 3 or more and 9 or less. If the pH is smaller than 3, the chemical action force tends to be small, and the polishing rate tends to decrease. If the pH is greater than 9, the secondary particle size increases and the polishing rate tends to decrease.
また、本発明の含窒素複素環化合物としては、特に制限はなく、下記の化合物からなる群から選ばれる１種以上が好ましい。ピロール、ピロリン、ピロリドン、インドール、インドレニン、インドリン、オキシインドール、ジオキシインドール、オキシルインドール、イサチン、インドキシル、ピラゾール、２Ｈ−１，２，３−トリアゾール、１，２，３−トリアゾール、４Ｈ−１，２，４−トリアゾール、１Ｈ−１，２，４−トリアゾール、１Ｈ−１，２，３，４−トリアゾール、２Ｈ−１，２，３，４−トリアゾール、ベンゾイミダゾール、１，２−ベンゾピラゾール、２，１−ベンゾピラゾール、１−ベンゾトリアゾール、２−ベンゾトリアゾール、ピリジン、２，２´−ビピリジニル、キノリン、イソキノリン、ピリダジン、シンシノリン、フタラジン、フタラジノン、ピリミジン、プリン、プテリジン、キナゾリン、ピラジン、キノキサリン、トリアジン、テトラジン、テトラゾール、及びそれらの中の水素原子が、アルキル基、水酸基、アミノ基、カルボニル基またはアルデヒド基で置換された誘導体。 Moreover, there is no restriction | limiting in particular as a nitrogen-containing heterocyclic compound of this invention, 1 or more types chosen from the group which consists of the following compound are preferable. Pyrrole, pyrroline, pyrrolidone, indole, indolenine, indoline, oxindole, dioxindole, oxylindole, isatin, indoxyl, pyrazole, 2H-1,2,3-triazole, 1,2,3-triazole, 4H- 1,2,4-triazole, 1H-1,2,4-triazole, 1H-1,2,3,4-triazole, 2H-1,2,3,4-triazole, benzimidazole, 1,2-benzo Pyrazole, 2,1-benzopyrazole, 1-benzotriazole, 2-benzotriazole, pyridine, 2,2′-bipyridinyl, quinoline, isoquinoline, pyridazine, cincinoline, phthalazine, phthalazinone, pyrimidine, purine, pteridine, quinazoline, pyrazine, Quinoxaline, triazine Tetrazine, tetrazole, and hydrogen atoms in their alkyl group, a hydroxyl group, derivatives substituted with an amino group, a carbonyl group or aldehyde group.
例えば１−メチルピロール、２−メチルピロール、３−メチルピロール、１−エチルピロール、ピロール−２−アルデヒド、ピロール−２−アルデヒドオキシム、メチル−２−ピリルケトン、ジピリルメタン、ジピリルメチン、１−ピロリン、２−ピロリン、３−ピロリン、２−メチル−２−ピロリン、４−メチル−２−ピロリン、２−ピロリドン、３−ピロリドン、Ｎ−メチル−２−ピロリドン、Ｎ−ビニル−２−ピロリドン、インドール、インドレニン、インドリン、オキシインドール、ジオキシインドール、オキシルインドール、イサチン、インドキシル、３，３´−ジインドイリル、３，２´−インドイリル、２−アミノインドール、３−アミノインドール、２−ヒドロキシインドール、３−インドリルカルビノール、３−インドールグリセリン、５，６−ジオキシインドール、６−オキシ−３−フェニルインドール、インドール−３−アルデヒド、３−アセチルインドール、ピラゾール、２Ｈ−１，２，３−トリアゾール、１，２，３−トリアゾール、４Ｈ−１，２，４−トリアゾール、１Ｈ−１，２，４−トリアゾール、１Ｈ−１，２，３，４−トリアゾール、２Ｈ−１，２，３，４−トリアゾール、ベンゾイミダゾール、１，２−ベンゾピラゾール、２，１−ベンゾピラゾール、１−ベンゾトリアゾール、２−ベンゾトリアゾール、ピリジン、ピリジン−Ｎ−オキシド、２−メチルピリジン、３−メチルピリジン、２−ビニルピリジン、４−ビニルピリジン、２，２´−ビピリジニル、２−ピリジノール、４−ピリジノール、キノリン、２−キノリノール、３−キノリロール、４−キノリノール、５，８−キノリンジオン、５，６−キノリンジオン、イソキノリン、ピリダジン、３−メチルピリダジン、４−メチルピリダジン、３−ピリダジノン、３−アミノピリダジン、シンシノリン、フタラジン、フタラジノン、ピリミジン、２−メチルピリミジン、４−メチルピリミジン、５−メチルピリミジン、４−ピリミジノール、６−ピリミジノール、２，６−ピリジミオール、２，４−ピリミジオール、２，４，６−ピリミジトリオール、２−アミノピリジン、プリン、プテリジン、キナゾリン、ピラジン、メチルピラジン、ピラジノール、アミノピラジン、キノキサリン、２−キノキサリオール、２，３−キノキサリンジオール、２−アミノキノキサリン、トリアジン、トリメチルトリアジン、６-アミノトリアジン−２，４−ジオール、ジメチルトリアジン−３−オール、トリアジン−３，５−ジオール、３−アミノトリアジン、１，２，４−ベンゾトリアジン、１，２，４−ベンゾトリアジン−３−オール、１，２，３−ベンゾトリアジン−４−オール、テトラジン等を例示することができる。これらは、１種単独又は２種以上組み合わせて用いることができる。 For example, 1-methylpyrrole, 2-methylpyrrole, 3-methylpyrrole, 1-ethylpyrrole, pyrrol-2-aldehyde, pyrrole-2-aldehyde oxime, methyl-2-pyryl ketone, dipyrylmethane, dipyrylmethine, 1-pyrroline, 2- Pyrroline, 3-pyrroline, 2-methyl-2-pyrroline, 4-methyl-2-pyrroline, 2-pyrrolidone, 3-pyrrolidone, N-methyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, indole, indolenine , Indoline, oxindole, dioxindole, oxylindole, isatin, indoxyl, 3,3′-diindoyryl, 3,2′-indoyryl, 2-aminoindole, 3-aminoindole, 2-hydroxyindole, 3-yne Drill carbinol, 3-indole Glycerin, 5,6-dioxyindole, 6-oxy-3-phenylindole, indole-3-aldehyde, 3-acetylindole, pyrazole, 2H-1,2,3-triazole, 1,2,3-triazole, 4H-1,2,4-triazole, 1H-1,2,4-triazole, 1H-1,2,3,4-triazole, 2H-1,2,3,4-triazole, benzimidazole, 1,2 -Benzopyrazole, 2,1-benzopyrazole, 1-benzotriazole, 2-benzotriazole, pyridine, pyridine-N-oxide, 2-methylpyridine, 3-methylpyridine, 2-vinylpyridine, 4-vinylpyridine, 2 , 2'-bipyridinyl, 2-pyridinol, 4-pyridinol, quinoline, 2-quinolinol, 3-quinolin 4-quinolinol, 5,8-quinolinedione, 5,6-quinolinedione, isoquinoline, pyridazine, 3-methylpyridazine, 4-methylpyridazine, 3-pyridazinone, 3-aminopyridazine, cincinoline, phthalazine, phthalazinone, Pyrimidine, 2-methylpyrimidine, 4-methylpyrimidine, 5-methylpyrimidine, 4-pyrimidinol, 6-pyrimidinol, 2,6-pyrimimiol, 2,4-pyrimididiol, 2,4,6-pyrimiditriol, 2-amino Pyridine, purine, pteridine, quinazoline, pyrazine, methylpyrazine, pyrazinol, aminopyrazine, quinoxaline, 2-quinoxalyol, 2,3-quinoxalinediol, 2-aminoquinoxaline, triazine, trimethyltriazine, 6-aminotri Gin-2,4-diol, dimethyltriazin-3-ol, triazine-3,5-diol, 3-aminotriazine, 1,2,4-benzotriazine, 1,2,4-benzotriazin-3-ol, Examples include 1,2,3-benzotriazin-4-ol, tetrazine and the like. These can be used alone or in combination of two or more.
上記含窒素複素環化合物の添加量は、研磨剤１００質量部に対して０．０１質量部以上５質量部以下の範囲が好ましい。０．０５質量部以上３質量部以下の範囲がより好ましい。０．１質量部以上２質量部以下の範囲がさらに好ましい。添加量が少なすぎると高選択比が得られず、多すぎると酸化珪素の研磨速度が大きく低下する場合がある。 The amount of the nitrogen-containing heterocyclic compound added is preferably in the range of 0.01 to 5 parts by mass with respect to 100 parts by mass of the abrasive. A range of 0.05 parts by mass or more and 3 parts by mass or less is more preferable. A range of 0.1 parts by mass or more and 2 parts by mass or less is more preferable. If the addition amount is too small, a high selection ratio cannot be obtained, and if it is too large, the polishing rate of silicon oxide may be greatly reduced.
浅素子間分離（ＳＴＩ）ＣＭＰにおいて、上記含窒素化合物を添加することにより、含窒素化合物が金属水酸化物表面に結合し、金属水酸化物粒子が研磨布（パッド）表面に吸着しやすくなり、被研磨膜（酸化珪素）を高速に研磨可能となる。また、高平坦化及びウェハ面内を均一に研磨可能となる。 In shallow element isolation (STI) CMP, by adding the nitrogen-containing compound, the nitrogen-containing compound is bonded to the surface of the metal hydroxide, and the metal hydroxide particles are easily adsorbed to the surface of the polishing cloth (pad). The film to be polished (silicon oxide) can be polished at high speed. Further, high planarization and uniform polishing of the wafer surface can be achieved.
本発明の研磨剤は、上記含窒素複素環化合物を含む４価の金属水酸化物粒子のスラリ−をそのまま使用してもよいが、ｐＨ安定剤、分散剤等を必要に応じて適宜添加してもよい。これらの添加方法も組成により適宜選択される。 The abrasive of the present invention may use a slurry of tetravalent metal hydroxide particles containing the above nitrogen-containing heterocyclic compound as it is, but a pH stabilizer, a dispersant and the like may be appropriately added as necessary. May be. These addition methods are also appropriately selected depending on the composition.
研磨剤のｐＨ安定剤としてカルボン酸塩、リン酸塩、ホウ酸塩、アミン塩を用いることができる。ｐＨ安定化剤少なくとも一方の構成成分のｐＫａ値が、研磨剤ｐＨの１．０単位以内にあるものが好ましく使用される。 Carboxylate, phosphate, borate, and amine salt can be used as the pH stabilizer of the abrasive. A pH stabilizer having a pKa value of at least one component within 1.0 unit of the abrasive pH is preferably used.
例えば、研磨剤ｐＨを５．０から６．０に調整する場合、リン酸、酢酸、プロピオン酸、マロン酸、コハク酸、グルタル酸、アジピン酸、マレイン酸、フマル酸、フタル酸、クエン酸等及びその塩、及びエチレンジアミン、ピリジン、２−アミノピリジン、３−アミノピリジン、キサントシン、トルイジン、ピコリン酸、ヒスチジン、ピペラジン、１−メチルピペラジン、２−ビス（２−ヒドロキシエチル）アミノ−２−（ヒドロキシメチル）−１，３−プロパンジオール、尿酸等及びその塩が好適に使用される。 For example, when adjusting the abrasive pH from 5.0 to 6.0, phosphoric acid, acetic acid, propionic acid, malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, phthalic acid, citric acid, etc. And salts thereof, and ethylenediamine, pyridine, 2-aminopyridine, 3-aminopyridine, xanthosine, toluidine, picolinic acid, histidine, piperazine, 1-methylpiperazine, 2-bis (2-hydroxyethyl) amino-2- (hydroxy Methyl) -1,3-propanediol, uric acid and the like and salts thereof are preferably used.
分散剤は、メタクリル酸メチル、メタクリル酸−２−ヒドロキシエチル等のアクリル酸エステル、アセチルアセトン、ベンゾイルアセトン等のβ−ジケトン及びそれらの誘導体が挙げられる。また水溶性ポリマーでもよい。これらの分散剤添加量は、粒子１００質量部に対して、０．０１質量部以上、１０質量部以下の範囲が好ましい。 Examples of the dispersant include acrylic acid esters such as methyl methacrylate and -2-hydroxyethyl methacrylate, β-diketones such as acetylacetone and benzoylacetone, and derivatives thereof. A water-soluble polymer may also be used. The amount of these dispersants added is preferably in the range of 0.01 to 10 parts by mass with respect to 100 parts by mass of the particles.
また、本発明の研磨剤は多糖類、ポリカルボン酸、ポリエチレンイミン、ビニル系ポリマー等、及びそれらの塩、エステル等の誘導体の水溶性高分子を含有してもよい。 Moreover, the abrasive | polishing agent of this invention may contain polysaccharide, polycarboxylic acid, polyethyleneimine, vinyl polymer, etc., and water-soluble polymers of derivatives, such as those salts and ester.
本発明のＣＭＰ研磨剤は、金属水酸化物粒子及び水を含むスラリー（Ａ液）と、含窒素複素環化合物、及び水を含む添加液（Ｂ液）とを分けた二液式ＣＭＰ研磨剤として保存しても、また予め金属水酸化物粒子、水、含窒素複素環化合物等を配合した一液式ＣＭＰ研磨剤として保存しても安定した特性が得られる。上記のＡ液とＢ液とに分けた二液式のＣＭＰ研磨剤で基板を研磨する際に、両液は別々の配管で送液し、これらの配管を合流させて供給配管出口の直前で混合して研磨定盤上に供給する方法か、研磨直前に混合する方法がとられる。 The CMP abrasive | polishing agent of this invention is a two-component CMP abrasive | polishing agent which divided | segmented the slurry (A liquid) containing a metal hydroxide particle and water, and the addition liquid (B liquid) containing a nitrogen-containing heterocyclic compound and water. Stable characteristics can be obtained even when stored as a one-component CMP abrasive containing metal hydroxide particles, water, a nitrogen-containing heterocyclic compound and the like. When the substrate is polished with the two-component CMP abrasive divided into the A liquid and the B liquid described above, both liquids are sent through separate pipes, and these pipes are merged and immediately before the supply pipe outlet. The method of mixing and supplying on a polishing surface plate, or the method of mixing just before grinding | polishing is taken.
本発明の研磨剤が使用される無機絶縁膜の作製方法として、低圧ＣＶＤ法、プラズマＣＶＤ法等が挙げられる。低圧ＣＶＤ法による酸化珪素絶縁膜形成は、Ｓｉ源としてモノシラン：ＳｉＨ４、酸素源として酸素：Ｏ２を用いる。このＳｉＨ４−Ｏ２系酸化反応を４００℃程度以下の低温で行わせることにより得られる。高温リフローによる表面平坦化を図るためにリン：Ｐをドープするときには、ＳｉＨ４−Ｏ２−ＰＨ３系反応ガスを用いることが好ましい。 Examples of a method for manufacturing an inorganic insulating film in which the abrasive of the present invention is used include a low pressure CVD method and a plasma CVD method. In the formation of the silicon oxide insulating film by the low pressure CVD method, monosilane: SiH 4 is used as the Si source, and oxygen: O 2 is used as the oxygen source. It can be obtained by performing this SiH 4 —O 2 -based oxidation reaction at a low temperature of about 400 ° C. or less. When doping phosphorus: P in order to achieve surface flattening by high-temperature reflow, it is preferable to use a SiH 4 —O 2 —PH 3 reaction gas.
プラズマＣＶＤ法は、通常の熱平衡下では高温を必要とする化学反応が低温でできる利点を有する。プラズマ発生法には、容量結合型と誘導結合型の２つが挙げられる。 The plasma CVD method has an advantage that a chemical reaction requiring a high temperature can be performed at a low temperature under normal thermal equilibrium. There are two plasma generation methods, capacitive coupling type and inductive coupling type.
反応ガスとしては、Ｓｉ源としてＳｉＨ４、酸素源としてＮ２Ｏを用いたＳｉＨ４−Ｎ２Ｏ系ガスと、テトラエトキシシラン（ＴＥＯＳ）をＳｉ源に用いたＴＥＯＳ−Ｏ２系ガス（ＴＥＯＳ−プラズマＣＶＤ法）が挙げられる。 As a reactive gas, SiH 4 -N 2 O-based gas using SiH 4 as an Si source, N 2 O as an oxygen source, and TEOS-O 2 -based gas (TEOS) using tetraethoxysilane (TEOS) as an Si source. -Plasma CVD method).
基板温度は２５０℃〜４００℃、反応圧力は６７〜４００Ｐａの範囲が好ましい。酸化珪素絶縁膜にはリン、ホウ素等の元素がドープされていても良い。同様に、低圧ＣＶＤ法による窒化珪素絶縁膜形成は、Ｓｉ源としてジクロルシラン：ＳｉＨ２Ｃｌ２、窒素源としてアンモニア：ＮＨ３を用いる。 The substrate temperature is preferably 250 to 400 ° C., and the reaction pressure is preferably 67 to 400 Pa. The silicon oxide insulating film may be doped with an element such as phosphorus or boron. Similarly, in forming the silicon nitride insulating film by the low pressure CVD method, dichlorosilane: SiH 2 Cl 2 is used as the Si source, and ammonia: NH 3 is used as the nitrogen source.
このＳｉＨ２Ｃｌ２−ＮＨ３系酸化反応を９００℃の高温で行わせることにより得られる。プラズマＣＶＤ法は、Ｓｉ源としてＳｉＨ４、窒素源としてＮＨ３を用いたＳｉＨ４−ＮＨ３系ガスが挙げられる。基板温度は３００〜４００℃が好ましい。 It can be obtained by performing this SiH 2 Cl 2 —NH 3 oxidation reaction at a high temperature of 900 ° C. Examples of the plasma CVD method include SiH 4 —NH 3 gas using SiH 4 as a Si source and NH 3 as a nitrogen source. The substrate temperature is preferably 300 to 400 ° C.
本発明の研磨方法は、上記本発明の研磨剤で基板を研磨することを特徴とする。 The polishing method of the present invention is characterized in that the substrate is polished with the above-described polishing agent of the present invention.
基板としては、半導体基板上に絶縁膜が形成された基板が使用できる。例えば、回路素子と配線パターンが形成された段階の半導体基板、回路素子が形成された段階の半導体基板等が挙げられる。絶縁膜は、酸化珪素膜或いは酸化珪素絶縁膜及び窒化珪素膜などの無機絶縁膜が挙げられる。基板は酸化珪素絶縁膜が形成された半導体ウェハであるのが好ましい。このような半導体基板上に形成された酸化珪素絶縁膜層を上記研磨剤で研磨することによって、酸化珪素絶縁膜層表面の凹凸を解消し、半導体基板全面に渡って平滑な面とする。 As the substrate, a substrate in which an insulating film is formed on a semiconductor substrate can be used. For example, a semiconductor substrate on which a circuit element and a wiring pattern are formed, a semiconductor substrate on which a circuit element is formed, and the like can be given. Examples of the insulating film include a silicon oxide film or an inorganic insulating film such as a silicon oxide insulating film and a silicon nitride film. The substrate is preferably a semiconductor wafer on which a silicon oxide insulating film is formed. By polishing the silicon oxide insulating film layer formed on such a semiconductor substrate with the above-described polishing agent, unevenness on the surface of the silicon oxide insulating film layer is eliminated, and the entire surface of the semiconductor substrate is made smooth.
シャロートレンチ分離の場合には、酸化珪素膜層の凹凸を解消しながら下層の窒化珪素層まで研磨することによって、素子分離部に埋め込んだ酸化珪素膜のみを残す。この際、ストッパとなる窒化珪素との研磨速度比が大きければ、研磨のプロセスマージンが大きくなる。また、シャロートレンチ分離に使用するためには、研磨時に傷発生が少ないことも好ましい。 In the case of shallow trench isolation, only the silicon oxide film embedded in the element isolation portion is left by polishing the underlying silicon nitride layer while eliminating the unevenness of the silicon oxide film layer. At this time, if the polishing rate ratio with the silicon nitride serving as a stopper is large, the polishing process margin becomes large. Further, for use in shallow trench isolation, it is also preferable that scratches are less likely to occur during polishing.
ここで、研磨する装置としては、半導体基板を保持するホルダーと、研磨布（パッド）を貼り付けることができ、回転数が変更可能なモータ等を取り付けてある定盤とを有する一般的な研磨装置が使用できる。 Here, as an apparatus for polishing, a general polishing having a holder for holding a semiconductor substrate and a surface plate to which a polishing cloth (pad) can be attached and a motor capable of changing the number of rotations is mounted. The device can be used.
研磨布としては、一般的な不織布、発泡ポリウレタン、多孔質フッ素樹脂などが使用でき、特に制限がない。また、研磨布には研磨剤が溜まる様な溝加工を施すことが好ましい。研磨条件には制限はないが、定盤の回転速度は半導体が飛び出さない様に１００ｍｉｎ−１以下の低回転が好ましい。 As an abrasive cloth, a general nonwoven fabric, a polyurethane foam, a porous fluororesin, etc. can be used, and there is no restriction | limiting in particular. Further, it is preferable that the polishing cloth is subjected to groove processing so that an abrasive is collected. The polishing conditions are not limited, but the rotation speed of the surface plate is preferably low rotation of 100 min −1 or less so that the semiconductor does not jump out.
被研磨膜を有する半導体基板の研磨布への押しつけ圧力が９．８×１０−３ＭＰａ〜９．８×１０−２ＭＰａ（１００〜１０００ｇｆ／ｃｍ２）であることが好ましく、研磨速度のウェハ面内均一性及びパターンの平坦性を満足するためには、１９．６×１０−３ＭＰａ〜４．９×１０−２ＭＰａ（２００〜５００ｇｆ／ｃｍ２）であることがより好ましい。研磨している間、研磨布には研磨剤をポンプ等で連続的に供給する。この供給量には制限はないが、研磨布の表面が常に研磨剤で覆われていることが好ましい。 The pressure applied to the polishing cloth of the semiconductor substrate having the film to be polished is preferably 9.8 × 10 −3 MPa to 9.8 × 10 −2 MPa (100 to 1000 gf / cm 2 ), and the wafer has a polishing rate. In order to satisfy the in-plane uniformity and the flatness of the pattern, it is more preferably 19.6 × 10 −3 MPa to 4.9 × 10 −2 MPa (200 to 500 gf / cm 2 ). During polishing, an abrasive is continuously supplied to the polishing cloth with a pump or the like. Although there is no restriction | limiting in this supply amount, It is preferable that the surface of polishing cloth is always covered with the abrasive | polishing agent.
研磨終了後の半導体基板は、流水中で良く洗浄後、スピンドライヤ等を用いて半導体基板上に付着した水滴を払い落としてから乾燥させることが好ましい。このようにして、Ｓｉ基板上にシャロートレンチ分離を形成したあと、酸化珪素絶縁膜層及びその上にアルミニウム配線を形成し、その上に形成した酸化珪素絶縁膜を平坦化する。 The semiconductor substrate after the polishing is preferably washed in running water, and then dried after removing water droplets adhering to the semiconductor substrate using a spin dryer or the like. Thus, after forming shallow trench isolation on the Si substrate, a silicon oxide insulating film layer and an aluminum wiring are formed thereon, and the silicon oxide insulating film formed thereon is planarized.
平坦化された酸化珪素絶縁膜層の上に、第２層目のアルミニウム配線を形成し、その配線間及び配線上に再度上記方法により酸化珪素絶縁膜を形成後、上記酸化セリウム研磨剤を用いて研磨することによって、酸化珪素絶縁膜表面の凹凸を解消し、半導体基板全面に渡って平滑な面とする。この工程を所定数繰り返すことにより、所望の層数の半導体を製造することができる。 A second-layer aluminum wiring is formed on the planarized silicon oxide insulating film layer, a silicon oxide insulating film is formed again between the wirings and on the wiring by the above method, and then the cerium oxide abrasive is used. By polishing, the unevenness on the surface of the silicon oxide insulating film is eliminated, and a smooth surface is obtained over the entire surface of the semiconductor substrate. By repeating this step a predetermined number of times, a semiconductor having a desired number of layers can be manufactured.
本発明の研磨剤は、半導体基板に形成された酸化珪素絶縁膜や窒化珪素膜だけでなく、所定の配線を有する配線板に形成された酸化珪素絶縁膜、ガラス、窒化珪素等の無機絶縁膜、フォトマスク・レンズ・プリズムなどの光学ガラス、ＩＴＯ等の無機導電膜、ガラス及び結晶質材料で構成される光集積回路・光スイッチング素子・光導波路、光ファイバーの端面、シンチレ−タ等の光学用単結晶、固体レーザ単結晶、青色レーザ用ＬＥＤサファイア基板、ＳｉＣ、ＧａＰ、ＧａＡｓ等の半導体単結晶、磁気ディスク用ガラス基板、磁気ヘッド等を研磨するために使用される。 The abrasive of the present invention includes not only a silicon oxide insulating film and a silicon nitride film formed on a semiconductor substrate, but also a silicon oxide insulating film formed on a wiring board having a predetermined wiring, an inorganic insulating film such as glass and silicon nitride. Optical glass such as optical masks such as photomasks, lenses, and prisms, inorganic conductive films such as ITO, glass and crystalline materials, optical integrated circuits, optical switching elements, optical waveguides, optical fiber end faces, scintillators, etc. It is used for polishing single crystals, solid laser single crystals, LED sapphire substrates for blue lasers, semiconductor single crystals such as SiC, GaP, and GaAs, glass substrates for magnetic disks, magnetic heads, and the like.
実施例１
（金属水酸化物粒子の調製）
４３０ｇのＣｅ(ＮＨ４)２(ＮＯ３)６を７３００ｇの純水に溶解し、次にこの溶液に２４０ｇのアンモニア水（２５％水溶液）を混合・攪拌することにより、１６０ｇの水酸化セリウム（黄白色）を得た。得られた水酸化セリウムを遠心分離（日立工機（株）製の遠心分離機 ＣＴ５ＤＬ、ローターＲＴ３Ｓ−２８１、３０００ｍｉｎ−１、１０分間）によって、固液分離を施して液体を除去し、新たに純水を加えて、再び上記条件で遠心分離を行った。
Example 1
(Preparation of metal hydroxide particles)
430 g of Ce (NH 4 ) 2 (NO 3 ) 6 is dissolved in 7300 g of pure water, and then 240 g of ammonia water (25% aqueous solution) is mixed and stirred in this solution, whereby 160 g of cerium hydroxide ( Yellowish white) was obtained. The obtained cerium hydroxide was subjected to solid-liquid separation by centrifugation (centrifuge CT5DL manufactured by Hitachi Koki Co., Ltd., rotor RT3S-281, 3000 min −1 , 10 minutes) to remove the liquid, and newly Pure water was added and centrifuged again under the above conditions.
このような操作を４回繰り返し、洗浄を行った。ＱＵＡＮＴＡＣＨＲＯＭＥ社製ガス吸着量測定装置ＡＵＴＯＳＯＲＢ−１ＭＰを用いたＢＥＴ法によって、得られた粒子の比表面積を測定した。測定に先立ち試料を１５０℃、３時間乾燥してから測定に供した。得られた水酸化セリウムの比表面積は、２００ｍ２／ｇであった。 Such an operation was repeated 4 times for washing. The specific surface area of the obtained particles was measured by the BET method using a gas adsorption amount measuring device AUTOSORB-1MP manufactured by QUANTACHROME. Prior to measurement, the sample was dried at 150 ° C. for 3 hours and then subjected to measurement. The specific surface area of the obtained cerium hydroxide was 200 m 2 / g.
（研磨剤の作製）
上記水酸化セリウム粒子１６０ｇと純水１５８４０ｇとを混合し、超音波分散を施し、さらに１μｍのＳＵＳフィルタでろ過を行い、固形分１質量％の水酸化セリウム懸濁液を得た。研磨剤粒子をＭａｌｖｅｒｎ社製のレーザ回折式粒度分布計商品名Ｚｅｔａｓｉｚｅｒ ＨＳ３０００を用い、光子相関法によって粒径を測定したところ、２次粒子径の中央値は９０ｎｍであった。また、研磨剤ｐＨは３．５であった。
(Production of abrasive)
160 g of the above cerium hydroxide particles and 15840 g of pure water were mixed, subjected to ultrasonic dispersion, and further filtered through a 1 μm SUS filter to obtain a cerium hydroxide suspension having a solid content of 1% by mass. When the particle size of the abrasive particles was measured by a photon correlation method using a laser diffraction particle size distribution meter trade name Zetasizer HS3000 manufactured by Malvern, the median value of the secondary particle size was 90 nm. The abrasive pH was 3.5.
上記水酸化セリウム懸濁液（１質量％）１０００ｇと純水３９６５ｇを混合し、さらに含窒素化合物として１−ベンゾトリアゾール３５ｇを加え、よく攪拌した。イミダゾール水溶液（５質量％）でｐＨを５．５に調整し、水酸化セリウム研磨剤を得た。 1000 g of the above cerium hydroxide suspension (1% by mass) and 3965 g of pure water were mixed, and 35 g of 1-benzotriazole was further added as a nitrogen-containing compound and stirred well. The pH was adjusted to 5.5 with an imidazole aqueous solution (5% by mass) to obtain a cerium hydroxide abrasive.
（絶縁膜層の研磨）
浅素子分離（ＳＴＩ）絶縁膜ＣＭＰ評価用試験パターンウェハとして、ＳＥＭＡＴＥＣＨ製８６４ウェハ（φ２００ｍｍ）を用いた。トレンチ深さ５００ｎｍ、アクティブ部上のＬＰ−ＣＶＤ法で形成された窒化珪素膜の膜厚は１５０ｎｍ、ＴＥＯＳ−プラズマＣＶＤ法でウェハ全体に形成された酸化珪素膜の膜厚は６００ｎｍであった。
(Polishing the insulating film layer)
As a test pattern wafer for shallow element isolation (STI) insulating film CMP evaluation, an 864 wafer (φ200 mm) made by SEMATECH was used. The trench depth was 500 nm, the thickness of the silicon nitride film formed by LP-CVD on the active portion was 150 nm, and the thickness of the silicon oxide film formed on the entire wafer by TEOS-plasma CVD was 600 nm.
研磨装置（荏原製作所製の型番ＥＰＯ−１１１）の、保持する基板取り付け用の吸着パッドを貼り付けたホルダーに上記パターンウェハをセットし、一方、φ６００ｍｍの研磨定盤にロデール社製多孔質ウレタン樹脂製の研磨パッド型番ＩＣ−１０００（パーフォレート溝）を貼り付けた。 The pattern wafer is set in a holder of a polishing apparatus (model number EPO-111 manufactured by Ebara Seisakusho Co., Ltd.) on which a suction pad for attaching a substrate to be held is attached. On the other hand, a porous urethane resin manufactured by Rodel Co., Ltd. is mounted on a polishing surface plate of φ600 mm. A manufactured polishing pad model number IC-1000 (perforated groove) was attached.
該パッド上に絶縁膜面を下にして前記ホルダーを載せ、さらに加工荷重として研磨圧力、バックサイドプレッシャーをそれぞれ３０ｋＰａ、１５ｋＰａに設定した。定盤上に上記で調製した水酸化セリウム研磨剤を１５０ｍＬ／分の速度で滴下しながら、定盤とウェハとをそれぞれ５０ｍｉｎ−１、５０ｍｉｎ−１で作動させてＳＴＩ絶縁膜ＣＭＰ評価用試験ウェハを研磨した。 The holder was placed on the pad with the insulating film face down, and the polishing pressure and backside pressure were set to 30 kPa and 15 kPa, respectively, as processing loads. Dropwise platen to cerium hydroxide slurry prepared above in 150 mL / min, the platen and the wafer and the respective 50min -1, operated at 50min -1 by STI insulating film CMP evaluation test wafer Polished.
研磨定盤トルク電流値をモニタすることで、研磨の終点検出を行った。研磨後のウェハを純水で良く洗浄後、乾燥した。その後、光干渉式膜厚装置（ナノメトリクス社製商品名、Ｎａｎｏｓｐｅｃ ＡＦＴ−５１００）を用いて、凹部の絶縁膜の残膜厚、凸部の絶縁膜の残膜厚、あるいは窒化珪素膜の残膜厚を測定した。 The polishing end point was detected by monitoring the polishing platen torque current value. The polished wafer was thoroughly washed with pure water and then dried. Then, using an optical interference film thickness apparatus (trade name, Nanospec AFT-5100, manufactured by Nanometrics), the remaining film thickness of the recessed insulating film, the remaining film thickness of the protruding insulating film, or the remaining silicon nitride film The film thickness was measured.
さらにVeeco社製段差計Ｄｅｋｔａｋ Ｖ２００−Ｓｉを用いて、研磨後の凸部と凹部の残段差を測定し、表１に示す結果を得た。 Furthermore, using a step meter Dektak V200-Si manufactured by Veeco, the remaining steps of the convex and concave portions after polishing were measured, and the results shown in Table 1 were obtained.
また、Ｎｉｋｏｎ社製光学顕微鏡ＯＰＴＩＰＨＯＴ（４００倍）を用いて研磨後のＳＴＩ絶縁膜ＣＭＰ評価用試験ウェハの絶縁膜表面を観察したところ、明確な研磨傷は観察されなかった。 Moreover, when the surface of the insulating film of the STI insulating film CMP evaluation test wafer after polishing was observed using a Nikon optical microscope OPTIPHOT (400 times), no clear polishing flaw was observed.
実施例２
（研磨剤の作製）
実施例１記載の水酸化セリウム懸濁液（１質量％）１０００ｇと純水３９２５ｇを混合し、さらに含窒素化合物として１−ヒドロキシベンゾトリアゾール２５ｇを加え、よく攪拌した。イミダゾール水溶液（５質量％）でｐＨを６．０に調整し、水酸化セリウム研磨剤を得た。
Example 2
(Production of abrasive)
1000 g of the cerium hydroxide suspension (1% by mass) described in Example 1 and 3925 g of pure water were mixed, and further 25 g of 1-hydroxybenzotriazole was added as a nitrogen-containing compound and stirred well. The pH was adjusted to 6.0 with an imidazole aqueous solution (5% by mass) to obtain a cerium hydroxide abrasive.
（絶縁膜層の研磨）
実施例１と同様の研磨条件にてＳＴＩ絶縁膜ＣＭＰ評価用試験ウェハの研磨を行った。その後、実施例１と同様の方法にて評価を行い、表１に示す結果を得た。
(Polishing the insulating film layer)
The test wafer for STI insulating film CMP evaluation was polished under the same polishing conditions as in Example 1. Thereafter, evaluation was performed in the same manner as in Example 1, and the results shown in Table 1 were obtained.
実施例３
（研磨剤の作製）
実施例１記載の水酸化セリウム懸濁液（１質量％）１０００ｇと純水３９２５ｇを混合し、さらに含窒素化合物として５−メチルベンゾトリアゾール７５ｇを加え、よく攪拌した。イミダゾール水溶液（５質量％）でｐＨを５．５に調整し、水酸化セリウム研磨剤を得た。
Example 3
(Production of abrasive)
1000 g of the cerium hydroxide suspension (1% by mass) described in Example 1 and 3925 g of pure water were mixed, and 75 g of 5-methylbenzotriazole was further added as a nitrogen-containing compound and stirred well. The pH was adjusted to 5.5 with an imidazole aqueous solution (5% by mass) to obtain a cerium hydroxide abrasive.
（絶縁膜層の研磨）
実施例１と同様の研磨条件にてＳＴＩ絶縁膜ＣＭＰ評価用試験ウェハの研磨を行った。その後実施例１と同様の方法にて評価を行い、表１に示す結果を得た。
(Polishing the insulating film layer)
The test wafer for STI insulating film CMP evaluation was polished under the same polishing conditions as in Example 1. Thereafter, evaluation was performed in the same manner as in Example 1, and the results shown in Table 1 were obtained.
比較例１
（研磨剤の作製）
実施例１記載の水酸化セリウム懸濁液（１質量％）１０００ｇと純水３９３０ｇを混合し、よく攪拌した。イミダゾール水溶液（５質量％）でｐＨを６．５に調整し、水酸化セリウム研磨剤を得た。
Comparative Example 1
(Production of abrasive)
1000 g of the cerium hydroxide suspension (1% by mass) described in Example 1 and 3930 g of pure water were mixed and stirred well. The pH was adjusted to 6.5 with an imidazole aqueous solution (5% by mass) to obtain a cerium hydroxide abrasive.
（絶縁膜層の研磨）
実施例１と同様の研磨条件にてＳＴＩ絶縁膜ＣＭＰ評価用試験ウェハの研磨を行った。その後実施例１と同様の方法にて評価を行い、表１に示す結果を得た。
(Polishing the insulating film layer)
The test wafer for STI insulating film CMP evaluation was polished under the same polishing conditions as in Example 1. Thereafter, evaluation was performed in the same manner as in Example 1, and the results shown in Table 1 were obtained.
比較例２
（研磨剤の作製）
実施例１記載の水酸化セリウム懸濁液（１質量％）１０００ｇと純水３９３０ｇを混合し、よく攪拌した。イミダゾール水溶液（５質量％）でｐＨを５．５に調整し、水酸化セリウム研磨剤を得た。
Comparative Example 2
(Production of abrasive)
1000 g of the cerium hydroxide suspension (1% by mass) described in Example 1 and 3930 g of pure water were mixed and stirred well. The pH was adjusted to 5.5 with an imidazole aqueous solution (5% by mass) to obtain a cerium hydroxide abrasive.
（絶縁膜層の研磨）
実施例１と同様の研磨条件にてＳＴＩ絶縁膜ＣＭＰ評価用試験ウェハの研磨を行った。その後実施例１と同様の方法にて評価を行い、表１に示す結果を得た。
The test wafer for STI insulating film CMP evaluation was polished under the same polishing conditions as in Example 1. Thereafter, evaluation was performed in the same manner as in Example 1, and the results shown in Table 1 were obtained.
表１に示されるように、実施例１〜３の研磨剤によって、試験ウェハは研磨され、その凸部窒化膜が露出するまでの研磨時間は、１６７〜２１０秒であった。凹部酸化膜の面内均一性は４６〜５５ｎｍと均一に研磨されていた。平坦性の指標となる１００／１００μｍラインアンドスペースの残段差は５６〜８３ｎｍであった。 As shown in Table 1, the test wafer was polished by the abrasives of Examples 1 to 3, and the polishing time until the convex nitride film was exposed was 167 to 210 seconds. The in-plane uniformity of the recessed oxide film was uniformly polished at 46 to 55 nm. The remaining step of the 100/100 μm line and space serving as an index of flatness was 56 to 83 nm.
一方、比較例１では研磨時間は２００秒と実施例１〜３と同等であったが、面内均一性は１５３ｎｍと不均一であった。 On the other hand, in Comparative Example 1, the polishing time was 200 seconds, which was the same as in Examples 1 to 3, but the in-plane uniformity was non-uniform at 153 nm.
また、ｐＨを５．５に低下させた比較例２では研磨がまったく進行しなかった。 In Comparative Example 2 where the pH was lowered to 5.5, polishing did not proceed at all.
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| WO2020066786A1 (en) * | 2018-09-28 | 2020-04-02 | 花王株式会社 | Polishing liquid composition for silicon oxide film |
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