TWI838445B - 化學機械拋光液及其應用 - Google Patents
化學機械拋光液及其應用 Download PDFInfo
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- 238000005498 polishing Methods 0.000 title claims abstract description 117
- 239000002002 slurry Substances 0.000 title abstract 4
- 238000000034 method Methods 0.000 title description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 85
- 229910021420 polycrystalline silicon Inorganic materials 0.000 claims abstract description 41
- 229910052581 Si3N4 Inorganic materials 0.000 claims abstract description 38
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 38
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims abstract description 38
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 36
- -1 nitrogenous heterocyclic compound Chemical class 0.000 claims abstract description 22
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 15
- 125000005233 alkylalcohol group Chemical group 0.000 claims abstract description 13
- 239000002245 particle Substances 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims description 38
- 239000000126 substance Substances 0.000 claims description 36
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 claims description 14
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 14
- SIOXPEMLGUPBBT-UHFFFAOYSA-N picolinic acid Chemical compound OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 claims description 12
- ONIBWKKTOPOVIA-UHFFFAOYSA-N Proline Chemical compound OC(=O)C1CCCN1 ONIBWKKTOPOVIA-UHFFFAOYSA-N 0.000 claims description 4
- RWRDLPDLKQPQOW-UHFFFAOYSA-N tetrahydropyrrole Natural products C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- WJJMNDUMQPNECX-UHFFFAOYSA-N dipicolinic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=N1 WJJMNDUMQPNECX-UHFFFAOYSA-N 0.000 claims description 3
- XJLSEXAGTJCILF-UHFFFAOYSA-N nipecotic acid Chemical compound OC(=O)C1CCCNC1 XJLSEXAGTJCILF-UHFFFAOYSA-N 0.000 claims description 3
- WXUOEIRUBILDKO-UHFFFAOYSA-N piperidine-2,4-dicarboxylic acid Chemical compound OC(=O)C1CCNC(C(O)=O)C1 WXUOEIRUBILDKO-UHFFFAOYSA-N 0.000 claims description 3
- JLUIOEOHOOLSJC-UHFFFAOYSA-N pyrrole-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)N1 JLUIOEOHOOLSJC-UHFFFAOYSA-N 0.000 claims description 3
- WRHZVMBBRYBTKZ-UHFFFAOYSA-N pyrrole-2-carboxylic acid Chemical compound OC(=O)C1=CC=CN1 WRHZVMBBRYBTKZ-UHFFFAOYSA-N 0.000 claims description 3
- ZKXSPYPKBXRBNP-UHFFFAOYSA-N pyrrolidine-2,5-dicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)N1 ZKXSPYPKBXRBNP-UHFFFAOYSA-N 0.000 claims description 3
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 2
- SOOPBZRXJMNXTF-UHFFFAOYSA-N 2,6-Piperidinedicarboxylic acid Chemical compound OC(=O)C1CCCC(C(O)=O)N1 SOOPBZRXJMNXTF-UHFFFAOYSA-N 0.000 claims description 2
- NRSBQSJHFYZIPH-UHFFFAOYSA-N 4-carboxypyrrolidin-1-ium-2-carboxylate Chemical compound OC(=O)C1CNC(C(O)=O)C1 NRSBQSJHFYZIPH-UHFFFAOYSA-N 0.000 claims description 2
- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- MUYSADWCWFFZKR-UHFFFAOYSA-N cinchomeronic acid Chemical compound OC(=O)C1=CC=NC=C1C(O)=O MUYSADWCWFFZKR-UHFFFAOYSA-N 0.000 claims description 2
- MPFLRYZEEAQMLQ-UHFFFAOYSA-N dinicotinic acid Chemical compound OC(=O)C1=CN=CC(C(O)=O)=C1 MPFLRYZEEAQMLQ-UHFFFAOYSA-N 0.000 claims description 2
- TWBYWOBDOCUKOW-UHFFFAOYSA-N isonicotinic acid Chemical compound OC(=O)C1=CC=NC=C1 TWBYWOBDOCUKOW-UHFFFAOYSA-N 0.000 claims description 2
- SRJOCJYGOFTFLH-UHFFFAOYSA-N isonipecotic acid Chemical compound OC(=O)C1CCNCC1 SRJOCJYGOFTFLH-UHFFFAOYSA-N 0.000 claims description 2
- MJIVRKPEXXHNJT-UHFFFAOYSA-N lutidinic acid Chemical compound OC(=O)C1=CC=NC(C(O)=O)=C1 MJIVRKPEXXHNJT-UHFFFAOYSA-N 0.000 claims description 2
- 235000001968 nicotinic acid Nutrition 0.000 claims description 2
- 239000011664 nicotinic acid Substances 0.000 claims description 2
- HXEACLLIILLPRG-UHFFFAOYSA-N pipecolic acid Chemical compound OC(=O)C1CCCCN1 HXEACLLIILLPRG-UHFFFAOYSA-N 0.000 claims description 2
- PTLWNCBCBZZBJI-UHFFFAOYSA-N piperidine-2,3-dicarboxylic acid Chemical compound OC(=O)C1CCCNC1C(O)=O PTLWNCBCBZZBJI-UHFFFAOYSA-N 0.000 claims description 2
- YWWGOKNLNRUDAC-UHFFFAOYSA-N piperidine-3,5-dicarboxylic acid Chemical compound OC(=O)C1CNCC(C(O)=O)C1 YWWGOKNLNRUDAC-UHFFFAOYSA-N 0.000 claims description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- DOYOPBSXEIZLRE-UHFFFAOYSA-N pyrrole-3-carboxylic acid Chemical compound OC(=O)C=1C=CNC=1 DOYOPBSXEIZLRE-UHFFFAOYSA-N 0.000 claims description 2
- JAEIBKXSIXOLOL-UHFFFAOYSA-N pyrrolidin-1-ium-3-carboxylate Chemical compound OC(=O)C1CCNC1 JAEIBKXSIXOLOL-UHFFFAOYSA-N 0.000 claims description 2
- GJAWHXHKYYXBSV-UHFFFAOYSA-N quinolinic acid Chemical compound OC(=O)C1=CC=CN=C1C(O)=O GJAWHXHKYYXBSV-UHFFFAOYSA-N 0.000 claims description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N tetrahydropyridine hydrochloride Natural products C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 2
- 229920005591 polysilicon Polymers 0.000 abstract description 9
- 238000007517 polishing process Methods 0.000 abstract description 6
- 235000012431 wafers Nutrition 0.000 abstract description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052710 silicon Inorganic materials 0.000 abstract description 2
- 239000010703 silicon Substances 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 28
- 229910004298 SiO 2 Inorganic materials 0.000 description 15
- 229910052814 silicon oxide Inorganic materials 0.000 description 8
- 239000004065 semiconductor Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000005530 etching Methods 0.000 description 3
- 239000003002 pH adjusting agent Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- VMAQYKGITHDWKL-UHFFFAOYSA-N 5-methylimidazolidine-2,4-dione Chemical compound CC1NC(=O)NC1=O VMAQYKGITHDWKL-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 239000003899 bactericide agent Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003989 dielectric material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 description 2
- XTIOPFFOPUPVFH-UHFFFAOYSA-N 2-phenyl-1,2-thiazolidin-4-one Chemical compound C1C(=O)CSN1C1=CC=CC=C1 XTIOPFFOPUPVFH-UHFFFAOYSA-N 0.000 description 1
- HPGGRRWTQXPMHJ-UHFFFAOYSA-N 3-iodoprop-1-ynyl carbamate Chemical compound NC(=O)OC#CCI HPGGRRWTQXPMHJ-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- NLLUNOTYWKPNRW-UHFFFAOYSA-N [N]C(O)=O Chemical compound [N]C(O)=O NLLUNOTYWKPNRW-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- DHNRXBZYEKSXIM-UHFFFAOYSA-N chloromethylisothiazolinone Chemical compound CN1SC(Cl)=CC1=O DHNRXBZYEKSXIM-UHFFFAOYSA-N 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229940093915 gynecological organic acid Drugs 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- BEGLCMHJXHIJLR-UHFFFAOYSA-N methylisothiazolinone Chemical compound CN1SC=CC1=O BEGLCMHJXHIJLR-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- KJIOQYGWTQBHNH-UHFFFAOYSA-N undecanol Chemical compound CCCCCCCCCCCO KJIOQYGWTQBHNH-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000001039 wet etching Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09G—POLISHING COMPOSITIONS; SKI WAXES
- C09G1/00—Polishing compositions
- C09G1/02—Polishing compositions containing abrasives or grinding agents
-
- 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
- C23F3/00—Brightening metals by chemical means
- C23F3/04—Heavy metals
- C23F3/06—Heavy metals with acidic solutions
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
- H01L21/30625—With simultaneous mechanical treatment, e.g. mechanico-chemical polishing
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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
- H01L21/31051—Planarisation of the insulating layers
- H01L21/31053—Planarisation of the insulating layers involving a dielectric removal step
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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
- H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
- H01L21/321—After treatment
- H01L21/32115—Planarisation
- H01L21/3212—Planarisation by chemical mechanical polishing [CMP]
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- General Chemical & Material Sciences (AREA)
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Abstract
本發明公開了一種化學機械拋光液,包含二氧化矽研磨顆粒、含一個或多個羧基的含氮雜環化合物,及乙氧基化丁氧基化的烷基醇。本發明還提供了一種上述的化學機械拋光液在二氧化矽、多晶矽、氮化矽的拋光中的應用。本發明的拋光液對氮化矽的拋光速率遠遠大於對二氧化矽、多晶矽的拋光速率,從而能夠很好地應用於二氧化矽/多晶矽為停止層的化學機械拋光之中,可以較好地控制拋光過程中基板表面上的氧化物及多晶矽的去除量。
Description
本發明是關於一種化學機械拋光領域,尤其是關於一種化學機械拋光液及其應用。
在半導體晶片的生產過程中,各個階段都要進行去除氮化矽層的步驟,例如,在形成元素分離結構的步驟中,要去除作為阻擋層的氮化矽層。但是,這種去除步驟通常是在約150℃的高溫下,通過使用例如磷酸/硝酸混合溶液的濕法刻蝕處理進行,很少採用化學機械拋光的方法。
目前,關於隔離半導體器件中各元件的方法,主要為淺溝槽隔離(STI)工藝,即首先在矽基板上形成氮化矽層,經蝕刻或光刻法形成淺溝槽,之後沉積介電層以填充這些溝槽。由於蝕刻過程中形成的溝槽或線路的深度經常發生變化,所以需要在沉積過程中將過量的介電材料沉積在基板頂部以確保所有溝槽完全填滿。在此之後,通過化學機械平坦化工藝來移除過量的介電材料(例如氧化物)以暴露出氮化矽層。最後,通過拋光除去氮化矽層,以獲得高度平坦且均勻的表面。
通常,對於化學機械拋光液來說,一直強調氧化物的拋光優先於氮化矽拋光。在拋光過程中,氮化矽層暴露後整體拋光速率會降低。因此,氮化矽層化學機械拋光中常作為終止層。隨著蝕刻技術的進步,氧化物線寬變得更小。此時,拋光過程中使用的化學機械拋光液對氮化矽的拋光能力應當高於對氧化物的拋光能力,以盡可能地降低基板表面的氧化物的去除量。
另外,對於一些半導體器件,需要在拋光中除去氮化矽層,而將氧化矽和多晶矽層作為化學機械拋光的停止層。故需要化學機械拋光液具有特定的氮化矽/氧化矽/多晶矽三種物質的拋光速率選擇性,即需要相對較高的氮化矽的去除速率和較低的氧化矽和多晶矽的去除速率。而現有的化學機械拋光液並不具備如上所述的氮化矽/氧化矽/多晶矽三種物質的拋光速率選擇性。
為了解決上述問題,本發明提供了一種化學機械拋光液,通過將含一個或多個羧基的含氮雜環化合物及乙氧基化丁氧基化的烷基醇複配使用,獲得較高的氮化矽的拋光速率,和較低的二氧化矽和多晶矽的拋光速率,從而具有適當的氮化矽/氧化矽/多晶矽的拋光速率選擇性。
具體地,本發明提供了一種化學機械拋光液,包括二氧化矽研磨顆粒、含一個或多個羧基的含氮雜環化合物、乙氧基化丁氧基化的烷基醇。
較佳地,所述二氧化矽研磨顆粒的質量百分比含量為0.5%-8%。
較佳地,所述二氧化矽研磨顆粒的質量百分比含量為1%-5%。
較佳地,所述含一個或多個羧基的含氮雜環化合物包括含一個或多個羧基的吡啶化合物、哌啶化合物、吡咯烷化合物或吡咯化合物中的一種或多種。
較佳地,所述含一個或多個羧基的含氮雜環化合物包括2-羧基吡啶、3-羧基吡啶、4-羧基吡啶、2,3-二羧基吡啶、2,4-二羧基吡啶、3,4-二羧基吡啶、2,6-二羧基吡啶、3,5-二羧基吡啶、2-羧基哌啶、3-羧基哌啶、4-羧基哌啶、2,3-二羧基哌啶、2,4-二羧基哌啶、2,6-二羧基哌啶、3,5-二羧基哌啶、2-羧基吡咯烷、3-羧基吡咯烷、2,4-二羧基吡咯烷、2,5-二羧基吡咯烷、2-羧基吡咯、3-羧基吡咯、2,5-二羧基吡咯中的一種或多種。
較佳地,所述含一個或多個羧基的含氮雜環化合物的質量百分比含量為0.01%-0.5%。
較佳地,所述乙氧基丁氧基化的烷基醇中,乙氧基數x為5-20,丁氧基數y為5-20,烷基為碳原子數11-15的直鏈或支鏈。
較佳地,所述乙氧基化丁氧基化的烷基醇的質量百分比含量為0.01%-1%。
較佳地,所述化學機械拋光液的pH為2-6。
本發明的化學機械拋光液中,還可以包括殺菌劑和pH調節劑。其中,殺菌劑可以選擇5-氯-2-甲基-4-異噻唑啉-3-酮、2-甲基-4-異噻唑啉酮、1, 2-苯丙異噻唑啉酮、碘代丙炔基胺基甲酸酯,及1,3-二羥甲基-5,5-甲基海因等,pH調節劑可以選擇HNO3
、KOH、K2
HPO4
或KH2
PO4
等。
本發明的另一方面,提供了一種上述的化學機械拋光液在二氧化矽、多晶矽、氮化矽的拋光中的應用。
與現有技術相比,本發明的優點在於:在含二氧化矽研磨顆粒的拋光液中將含一個或多個羧基的含氮雜環化合物和乙氧基化丁氧基化的烷基醇複配使用,使拋光液對氮化矽的拋光速率遠遠大於對二氧化矽、多晶矽的拋光速率,從而能夠很好地應用於二氧化矽/多晶矽為停止層時的化學機械拋光之中,能較好地控制拋光過程中基板表面上的氧化物及多晶矽的去除量。
下面通過具體實施例進一步闡述本發明的優點,但本發明的保護範圍不僅僅侷限於下述實施例。
表1為本發明實施例1-10以及對比例1-5的拋光液的成分及含量。按照該表配製實施例和對比例拋光液,將各組分混合均勻,用水補足質量百分比至100%,用pH調節劑調節pH至相應值,得到本發明各實施例及對比例的拋光液。
表1 本發明實施例1-10和對比例1-5的拋光液成分
研磨顆粒 | 羧基吡啶化合物/有機酸 | (乙氧基)x 化(丁氧基)y 化烷基醇 | pH | ||||
名稱 | 含量(%) | 名稱 | 含量(%) | 種類 | 含量 | ||
對比例1 | SiO2 | 3 | - | - | - | - | 2 |
對比例2 | SiO2 | 3 | 羥基亞乙基-1,1-二磷酸 | 0.05 | - | - | 2 |
對比例3 | SiO2 | 3 | 抗壞血酸 | 0.05 | - | - | 2 |
對比例4 | SiO2 | 3 | 2-羧基吡啶 | 0.05 | - | - | 2 |
對比例5 | SiO2 | 3 | - | - | (乙氧基)5 (丁氧基)10 C12醇 | 0.01 | 2 |
實施例1 | SiO2 | 3 | 2-羧基吡啶 | 0.2 | (乙氧基)8 (丁氧基)5 C11醇 | 0.01 | 2 |
實施例2 | SiO2 | 0.5 | 2,6-二羧基吡啶 | 0.01 | (乙氧基)12 (丁氧基)8 C12醇 | 0.05 | 3 |
實施例3 | SiO2 | 1 | 3-羧基哌啶 | 0.06 | (乙氧基)20 (丁氧基)12 C13醇 | 0.1 | 4.5 |
實施例4 | SiO2 | 5 | 2,4-二羧基哌啶 | 0.04 | (乙氧基)16 (丁氧基)20 C14醇 | 0.2 | 5.6 |
實施例5 | SiO2 | 6 | 2-羧基吡咯烷 | 0.3 | (乙氧基)8 (丁氧基)5 C15醇 | 0.5 | 6 |
實施例6 | SiO2 | 8 | 2,5-二羧基吡咯烷 | 0.03 | (乙氧基)10 (丁氧基)14 C12醇 | 0.1 | 4.8 |
實施例7 | SiO2 | 2 | 2-羧基吡咯 | 0.1 | (乙氧基)13 (丁氧基)8 C14醇 | 0.03 | 5 |
實施例8 | SiO2 | 2 | 2,5-二羧基吡咯 | 0.05 | (乙氧基)10 (丁氧基)7 C12醇 | 1 | 5.3 |
實施例9 | SiO2 | 2 | 2-羧基吡啶 | 0.5 | (乙氧基)9 (丁氧基)7 C13醇 | 0.6 | 4.3 |
實施例10 | SiO2 | 2 | 2-羧基吡啶 | 0.05 | (乙氧基)16 (丁氧基)6 C13醇 | 0.3 | 5.8 |
分別用上述實施例1-10和對比例1-5的化學機械拋光液對含有氮化矽、二氧化矽和多晶矽的12吋晶片進行拋光,拋光條件為:採用LK拋光機進行拋光,使用IC1010拋光墊,轉速為拋光盤/拋光頭=93/87rpm,拋光壓力為1.5psi,拋光液流量為150ml/min,得到每個實施例的拋光液對氮化矽、二氧化矽和多晶矽的拋光速率,記於表2。
表2 本發明實施例1-10和對比例1-4的拋光結果
氮化矽速率 (Å/min) | 二氧化矽速率 (Å /min) | 多晶矽速率 (Å /min) | |
對比例1 | 23 | 623 | 547 |
對比例2 | 405 | 426 | 641 |
對比例3 | 325 | 401 | 594 |
對比例4 | 656 | 611 | 543 |
對比例5 | 23 | 321 | 258 |
實施例1 | 648 | 45 | 58 |
實施例2 | 445 | 10 | 24 |
實施例3 | 514 | 8 | 17 |
實施例4 | 784 | 13 | 22 |
實施例5 | 902 | 14 | 23 |
實施例6 | 1084 | 19 | 34 |
實施例7 | 605 | 9 | 16 |
實施例8 | 567 | 7 | 14 |
實施例9 | 658 | 8 | 7 |
實施例10 | 457 | 4 | 12 |
由表2可見,與對比例相比,本發明實施例1-10的拋光液對氮化矽的拋光速率較高,而對二氧化矽和多晶矽的拋光速率較低,從而很好地滿足了二氧化矽/多晶矽為停止層時的拋光需求。對比例1的拋光液只包括二氧化矽研磨顆粒,對氮化矽的拋光速率低,而對二氧化矽和多晶矽的拋光速率較高,即該拋光液對三種物質的拋光速率選擇性與上述拋光需求恰好相反;對比例2和3的拋光液在對比例1的基礎上分別添加了羥基亞乙基-1,1-二磷酸或者抗壞血酸,其應用於拋光時,相對於對比例1提高了氮化矽的拋光速率,但是,其對二氧化矽和多晶矽的拋光速率與對氮化矽的拋光速率非常接近,因此不能體現對這三種物質的拋光速率選擇性,不適用於將氧化矽和多晶矽層作為化學機械拋光的停止層的半導體器件製造工藝中。對比例4中利用2-羧基吡啶替換了對比例2或對比例3中的有機酸類,其對氮化矽和二氧化矽的拋光速率進一步提高了,但是仍接近與對多晶矽的拋光速率,無法體現對這三種物質的拋光速率選擇性,也無法適用於將氧化矽和多晶矽層作為化學機械拋光的停止層的半導體器件製造工藝中。對比例5與對比例1相比,添加了乙氧基化丁氧基化烷基醇,其表現出了對二氧化矽和多晶矽的拋光速率的抑制作用,但對二者拋光速度仍在200 Å/min以上,而且,對氮化矽的拋光速度仍然很低,即對比例5並沒有改變對比例1中氮化矽的拋光速率低,二氧化矽和多晶矽的拋光速率較高的狀況,從而,無法實現提高氮化矽與二氧化矽或者氮化矽與多晶矽之間的拋光速率選擇比的效果,也無法適用於將氧化矽和多晶矽層作為化學機械拋光的停止層的半導體器件製造工藝中。
本發明實施例1-10的拋光液,將含一個或多個羧基的含氮雜環化合物和乙氧基化丁氧基化的烷基醇複配使用,獲得的拋光液對氮化矽的拋光速率達到了500 Å/min以上,而對二氧化矽和多晶矽的拋光速率均處於60 Å/min以下,即拋光液對氮化矽的拋光速率遠遠大於對二氧化矽、多晶矽的拋光速率,從而能夠很好地應用於二氧化矽/多晶矽為停止層時的化學機械拋光之中。由於本發明實施例的拋光液對二氧化矽和多晶矽的拋光速率低,所以可以較好地控制拋光過程中基板表面上的氧化物及多晶矽的去除量。
另外,本發明拋光液可以通過選擇適當的研磨顆粒的含量、不同種類的含羧基的含氮雜環化合物和不同烷基鏈長的乙氧基化丁氧基化烷基醇,在保持拋光液對氮化矽的拋光速率遠遠大於對二氧化矽、多晶矽的拋光速率的情況下,獲得更高的氮化矽拋光速率或者更低的二氧化矽和多晶矽的拋光速率。例如,實施例6的拋光液中,研磨顆粒的含量高,對氮化矽的拋光速率超過了1000 Å/min;而實施例10的拋光液中,各種物質的含量均比較低,對二氧化矽和多晶矽的拋光速率均只有4 Å/min和12 Å/min。從而,本發明實施例的拋光液具有較廣的拋光速率選擇範圍,可以適用於多種情形下的化學機械拋光。
綜上所述,本發明的拋光液中利用一個或多個羧基的含氮雜環化合物來提高氮化矽的拋光速率,利用乙氧基化丁基化烷基醇來抑制二氧化矽及多晶矽的拋光速率,從而拋光液對氮化矽的拋光速率遠遠大於對二氧化矽、多晶矽的拋光速率,從而能夠很好地應用於二氧化矽/多晶矽為停止層時的化學機械拋光之中,可以較好地控制拋光過程中基板表面上的氧化物及多晶矽的去除量。
應當注意的是,本發明中的含量,如果沒有特別說明,均為質量百分比含量。
應當理解的是,本發明的實施例有較佳的實施性,且並非對本發明作任何形式的限制,任何熟悉該領域的技術人員可能利用上述揭示的技術內容變更或修飾為等同的有效實施例,但凡未脫離本發明技術方案的內容,依據本發明的技術實質對以上實施例所作的任何修改或等同變化及修飾,均仍屬於本發明技術方案的範圍內。
Claims (6)
- 一種化學機械拋光液,包含二氧化矽研磨顆粒、含一個或多個羧基的含氮雜環化合物,及乙氧基化丁氧基化的烷基醇;所述含一個或多個羧基的含氮雜環化合物包括含一個或多個羧基的吡啶化合物、哌啶化合物、吡咯烷化合物或吡咯化合物中的一種或多種;所述乙氧基化丁氧基化的烷基醇中,乙氧基數x為5-20,丁氧基數y為5-20,烷基為碳原子數11-15的直鏈或支鏈,所述乙氧基化丁氧基化的烷基醇的質量百分比含量為0.01%-1%;所述化學機械拋光液的pH為2-6。
- 如請求項1所述之化學機械拋光液,其中,所述二氧化矽研磨顆粒的質量百分比含量為0.5%-8%。
- 如請求項2所述之化學機械拋光液,其中,所述二氧化矽研磨顆粒的質量百分比含量為1%-5%。
- 如請求項1所述之化學機械拋光液,其中,所述含一個或多個羧基的含氮雜環化合物包括2-羧基吡啶、3-羧基吡啶、4-羧基吡啶、2,3-二羧基吡啶、2,4-二羧基吡啶、3,4-二羧基吡啶、2,6-二羧基吡啶、3,5-二羧基吡啶、2-羧基哌啶、3-羧基哌啶、4-羧基哌啶、2,3-二羧基哌啶、2,4-二羧基哌啶、2,6-二羧基哌啶、3,5-二羧基哌啶、2-羧基吡咯烷、3-羧基吡咯烷、2,4-二羧基吡咯烷、2,5-二羧基吡咯烷、2-羧基吡咯、3-羧基吡咯、 2,5-二羧基吡咯中的一種或多種。
- 如請求項1所述之化學機械拋光液,其中,所述含一個或多個羧基的含氮雜環化合物的質量百分比含量為0.01%-0.5%。
- 一種如請求項1至5中任一項所述之化學機械拋光液在二氧化矽、多晶矽、氮化矽的拋光中的應用。
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