CN111527589A - Polishing composition - Google Patents
Polishing composition Download PDFInfo
- Publication number
- CN111527589A CN111527589A CN201880084023.1A CN201880084023A CN111527589A CN 111527589 A CN111527589 A CN 111527589A CN 201880084023 A CN201880084023 A CN 201880084023A CN 111527589 A CN111527589 A CN 111527589A
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- CN
- China
- Prior art keywords
- polishing composition
- polishing
- structural unit
- unit represented
- abrasive grains
- Prior art date
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- 238000005498 polishing Methods 0.000 title claims abstract description 63
- 239000000203 mixture Substances 0.000 title claims abstract description 42
- 239000006061 abrasive grain Substances 0.000 claims abstract description 25
- 150000007514 bases Chemical class 0.000 claims abstract description 16
- 229920005989 resin Polymers 0.000 claims abstract description 13
- 239000011347 resin Substances 0.000 claims abstract description 13
- 150000000180 1,2-diols Chemical class 0.000 claims abstract description 12
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 claims abstract description 12
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 12
- 125000000962 organic group Chemical group 0.000 claims abstract description 10
- -1 alkali metal salts Chemical class 0.000 claims description 22
- 239000002736 nonionic surfactant Substances 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 7
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 2
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims 1
- 239000004065 semiconductor Substances 0.000 abstract description 18
- 125000000914 phenoxymethylpenicillanyl group Chemical group CC1(S[C@H]2N([C@H]1C(=O)*)C([C@H]2NC(COC2=CC=CC=C2)=O)=O)C 0.000 description 28
- 230000007547 defect Effects 0.000 description 23
- 235000012431 wafers Nutrition 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 8
- 229920002451 polyvinyl alcohol Polymers 0.000 description 8
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 7
- HOVAGTYPODGVJG-UVSYOFPXSA-N (3s,5r)-2-(hydroxymethyl)-6-methoxyoxane-3,4,5-triol Chemical compound COC1OC(CO)[C@@H](O)C(O)[C@H]1O HOVAGTYPODGVJG-UVSYOFPXSA-N 0.000 description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 description 6
- HOVAGTYPODGVJG-UHFFFAOYSA-N methyl beta-galactoside Natural products COC1OC(CO)C(O)C(O)C1O HOVAGTYPODGVJG-UHFFFAOYSA-N 0.000 description 6
- 229920003169 water-soluble polymer Polymers 0.000 description 6
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 5
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000007127 saponification reaction Methods 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229920001451 polypropylene glycol Polymers 0.000 description 4
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 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
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000008119 colloidal silica Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 150000004679 hydroxides Chemical group 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 150000003973 alkyl amines Chemical class 0.000 description 2
- 150000005215 alkyl ethers Chemical class 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 229910021485 fumed silica Inorganic materials 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000007689 inspection Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229920001987 poloxamine Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 2
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 1
- PVOAHINGSUIXLS-UHFFFAOYSA-N 1-Methylpiperazine Chemical compound CN1CCNCC1 PVOAHINGSUIXLS-UHFFFAOYSA-N 0.000 description 1
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- RVGRUAULSDPKGF-UHFFFAOYSA-N Poloxamer Chemical compound C1CO1.CC1CO1 RVGRUAULSDPKGF-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 description 1
- IMUDHTPIFIBORV-UHFFFAOYSA-N aminoethylpiperazine Chemical compound NCCN1CCNCC1 IMUDHTPIFIBORV-UHFFFAOYSA-N 0.000 description 1
- STIAPHVBRDNOAJ-UHFFFAOYSA-N carbamimidoylazanium;carbonate Chemical compound NC(N)=N.NC(N)=N.OC(O)=O STIAPHVBRDNOAJ-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- MSQACBWWAIBWIC-UHFFFAOYSA-N hydron;piperazine;chloride Chemical compound Cl.C1CNCCN1 MSQACBWWAIBWIC-UHFFFAOYSA-N 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- LSHROXHEILXKHM-UHFFFAOYSA-N n'-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCN LSHROXHEILXKHM-UHFFFAOYSA-N 0.000 description 1
- 239000005445 natural material Substances 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 229960005141 piperazine Drugs 0.000 description 1
- 229960003506 piperazine hexahydrate Drugs 0.000 description 1
- AVRVZRUEXIEGMP-UHFFFAOYSA-N piperazine;hexahydrate Chemical compound O.O.O.O.O.O.C1CNCCN1 AVRVZRUEXIEGMP-UHFFFAOYSA-N 0.000 description 1
- 229920001983 poloxamer Polymers 0.000 description 1
- 229960000502 poloxamer Drugs 0.000 description 1
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
Classifications
-
- 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
- H01L21/02002—Preparing wafers
- H01L21/02005—Preparing bulk and homogeneous wafers
- H01L21/02008—Multistep processes
- H01L21/0201—Specific process step
- H01L21/02024—Mirror polishing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
- B24B37/00—Lapping machines or devices; Accessories
- B24B37/04—Lapping machines or devices; Accessories designed for working plane surfaces
- B24B37/042—Lapping machines or devices; Accessories designed for working plane surfaces operating processes therefor
- B24B37/044—Lapping machines or devices; Accessories designed for working plane surfaces operating processes therefor characterised by the composition of the lapping agent
-
- 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
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
- C09K3/1409—Abrasive particles per se
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
- C09K3/1454—Abrasive powders, suspensions and pastes for polishing
- C09K3/1463—Aqueous liquid suspensions
-
- 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
- H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Mechanical Engineering (AREA)
- Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
- Polishing Bodies And Polishing Tools (AREA)
Abstract
The invention provides a polishing composition which can further reduce the micro-defects and haze of a polished semiconductor wafer. The polishing composition comprises abrasive grains, a basic compound, and a vinyl alcohol resin having a 1, 2-diol structural unit represented by the following general formula (1), wherein the molar concentration of the structural unit represented by the following general formula (2) in the vinyl alcohol resin is 2 mol% or more of the total structural units. Wherein R is1、R2And R3Each independently represents a hydrogen atom or an organic group, X represents a single bond or a bonding chain, R4、R5And R6Are respectively independentAnd represents a hydrogen atom or an organic group.
Description
Technical Field
The present invention relates to a polishing composition.
Background
Polishing of a semiconductor wafer by CMP is performed in 3-stage or 4-stage multi-stage polishing, whereby highly accurate smoothing and planarization are achieved. The main purpose of the finish polishing step performed at the final stage is to reduce minute defects or haze (surface clouding).
Polishing compositions used in the finish polishing step of semiconductor wafers generally contain a water-soluble polymer such as Hydroxyethylcellulose (HEC). The water-soluble polymer has an effect of hydrophilizing the surface of the semiconductor wafer, and suppresses damage to the semiconductor wafer caused by adhesion of abrasive grains to the surface, excessive chemical etching, aggregation of abrasive grains, and the like. It is known that micro-defects or haze can be reduced thereby.
HEC is a natural material, i.e., cellulose, and therefore may contain water-insoluble impurities derived from cellulose. Therefore, in the polishing composition containing HEC, there is a case where a small number of defects are generated due to the influence of the impurities. Further, HEC often has a molecular weight of about several hundred thousand to million, and as the molecular weight is higher, clogging of a filter is more likely to occur, and it is difficult to pass a liquid through a filter having a small pore size. Therefore, when a water-soluble polymer having a relatively large molecular weight is used, it is difficult to remove coarse particles. Further, aggregation of abrasive grains is also likely to occur, and therefore, there is also a concern about long-term stability of the polishing composition.
Jp 2012-216723 a discloses a polishing composition containing at least 1 or more water-soluble polymers selected from vinyl alcohol resins having a 1, 2-diol structural unit. By containing a vinyl alcohol resin having a 1, 2-diol structural unit in the polishing composition, minute defects and surface roughness of the semiconductor wafer after polishing can be reduced. This is considered to be because crystallization of polyvinyl alcohol is suppressed by introducing a modifying group (1, 2-diol structure) having steric hindrance.
Disclosure of Invention
In recent years, with the progress of miniaturization of design rules of semiconductor devices, more strict management is required for minute defects and haze on the surface of a semiconductor wafer.
The present invention aims to provide a polishing composition which can further reduce the micro defects and haze of a polished semiconductor wafer.
A polishing composition according to one embodiment of the present invention comprises abrasive grains, a basic compound, and a vinyl alcohol resin having a 1, 2-diol structural unit represented by the following general formula (1), wherein the molar concentration of the structural unit represented by the following general formula (2) in the vinyl alcohol resin is 2 mol% or more of the total structural units.
Wherein R is1、R2And R3Each independently represents a hydrogen atom or an organic group, X represents a single bond or a bonding chain (JI-lock), R4、R5And R6Each independently represents a hydrogen atom or an organic group.
According to the present invention, the minute defects and haze of the polished semiconductor wafer can be further reduced.
Detailed Description
The present inventors have made various studies to solve the above problems. As a result, the following findings were obtained.
As described above, the water-soluble polymer is added to hydrophilize the surface of the semiconductor wafer. It is considered that, for this purpose, the more the number of hydroxyl groups as hydrophilic groups is, the more preferable, and therefore, a completely saponified product (having a saponification degree of 98 mol% or more) is generally used as the vinyl alcohol resin to be added to the polishing composition.
However, as a result of investigation by the present inventors, it has been found that in the case of a vinyl alcohol resin having a 1, 2-diol structural unit, the use of a partially saponified product can reduce the fine defects and haze more than in the case of a completely saponified product.
The mechanism is not clear, but as one factor, it is considered that the use of a partially saponified product reduces hydrogen bonds between hydroxyl groups and weakens bonding between molecules, whereby a polymer is easily dissolved in water, and generation of undissolved substances or gel-like foreign matter is suppressed. As another factor, it is considered that the hydrophobic interaction with the semiconductor wafer is enhanced and the protection of the semiconductor wafer is increased by increasing the content of vinyl acetate as a hydrophobic group.
The present invention has been completed based on these findings. The polishing composition according to one embodiment of the present invention is described in detail below.
A polishing composition according to one embodiment of the present invention includes abrasive grains, a basic compound, and a polyvinyl alcohol resin having a 1, 2-diol structural unit (hereinafter referred to as "modified PVA").
As the abrasive particles, those commonly used in the art can be used, and examples thereof include: colloidal silica, fumed silica, colloidal alumina, fumed alumina, ceria, and the like, and colloidal silica or fumed silica is particularly preferable. The particle size of the abrasive grains is not particularly limited, and for example, a secondary average particle size of 30 to 100nm can be used.
The content of the abrasive grains is not particularly limited, and is, for example, 0.10 to 20% by mass of the entire polishing composition. The polishing composition is diluted 10 to 40 times during polishing. The polishing composition of the present embodiment is preferably diluted and used so that the concentration of abrasive grains is 100 to 5000ppm (mass ppm, the same applies hereinafter). The higher the concentration of the abrasive grains, the more the fine defects and the haze tend to decrease. The lower limit of the concentration of the abrasive grains after dilution is preferably 1000ppm, and more preferably 2000 ppm. The upper limit of the concentration of the abrasive grains after dilution is preferably 4000ppm, and more preferably 3000 ppm.
The alkaline compound etches the surface of the semiconductor wafer to perform chemical polishing. The basic compound is, for example, an amine compound, an inorganic basic compound, or the like.
Examples of the amine compound include primary amines, secondary amines, tertiary amines, quaternary amines and hydroxides thereof, heterocyclic amines, and the like. Specifically, there may be mentioned: ammonia, tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH), tetrabutylammonium hydroxide (TBAH), methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, hexylamine, cyclohexylamine, ethylenediamine, hexamethylenediamine, Diethylenetriamine (DETA), triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, monoethanolamine, diethanolamine, triethanolamine, N- (β -aminoethyl) ethanolamine, anhydrous piperazine, piperazine hexahydrate, 1- (2-aminoethyl) piperazine, N-methylpiperazine, piperazine hydrochloride, guanidine carbonate, and the like.
Examples of the inorganic basic compound include: hydroxides of alkali metals, salts of alkali metals, hydroxides of alkaline earth metals, salts of alkaline earth metals, and the like. Specific examples of the inorganic alkali compound include potassium hydroxide, sodium hydroxide, potassium hydrogencarbonate, potassium carbonate, sodium hydrogencarbonate, sodium carbonate and the like.
The above-mentioned basic compounds may be used singly or in combination of two or more. Among the above-mentioned basic compounds, alkali metal hydroxides, alkali metal salts, ammonia, amines, ammonium salts, and quaternary ammonium hydroxides are particularly preferable.
The content of the basic compound (when two or more are contained, the total amount thereof) is not particularly limited, and for example, the content is, in terms of a mass ratio to the abrasive grains, abrasive grains: the ratio of the basic compound is 1: 0.001-1: 0.10. The polishing composition of the present embodiment is preferably used in a form diluted to a concentration of 5 to 200ppm of the basic compound.
The modified PVA is a vinyl alcohol resin having a 1, 2-diol structural unit represented by the following general formula (1).
Wherein R is1、R2And R3Each independently represents a hydrogen atom or an organic group, X represents a single bond or a bonding chain, R4、R5And R6Each independently represents a hydrogen atom or an organic group.
The "vinyl alcohol resin" refers to a water-soluble polymer containing structural units represented by the following formulae (2) and (3).
The modified PVA has a 1, 2-diol structural unit represented by the formula (1) in addition to the structural units represented by the formulae (2) and (3). This suppresses crystallization of the polyvinyl alcohol, and can further reduce fine defects and haze of the polished semiconductor wafer. The modification amount of the 1, 2-diol structural unit in the polymer is not particularly limited, and is, for example, 1 to 20 mol%.
Most preferred is R in the 1, 2-diol structural unit represented by the general formula (1)1～R3And R4～R6All are hydrogen atoms, and X is a single bond.
The average degree of polymerization of the modified PVA is not particularly limited, and is, for example, 200 to 3000. The average polymerization degree of the modified PVA can be measured in accordance with JIS K6726.
The content of the modified PVA (when two or more kinds are contained, the total amount thereof) is not particularly limited, and is, for example, abrasive grains in terms of a mass ratio to the abrasive grains: the modified PVA is 1: 0.001-1: 0.40. The lower limit of the mass ratio of the modified PVA to the abrasive grains is preferably 0.0050, and more preferably 0.0070.
The polishing composition of the present embodiment is preferably used after diluted to a concentration of 10 to 200ppm of the modified PVA. The higher the concentration of the diluted modified PVA, the more the fine defects and the haze tend to decrease. The lower limit of the concentration of the diluted modified PVA is preferably 20ppm, and more preferably 50 ppm.
The modified PVA is produced, for example, by saponifying a copolymer of a vinyl ester monomer and a compound represented by the following general formula (4).
Wherein R is1、R2And R3Each independently represents a hydrogen atom or an organic group, X represents a single bond or a bonding chain, R4、R5And R6Each independently represents a hydrogen atom or an organic group, R7And R8Each independently represents a hydrogen atom or R9-CO-(R9An alkyl group having 1 to 4 carbon atoms).
In the polishing composition of the present embodiment, the molar concentration of the structural unit represented by the following general formula (2) in the modified PVA is 2 mol% or more of the total structural units.
The higher the molar concentration of the structural unit represented by formula (2) in the modified PVA, the more the fine defects and haze of the semiconductor wafer after polishing can be reduced. The lower limit of the molar concentration of the structural unit represented by formula (2) in the modified PVA is preferably 5 mol%, and more preferably 10 mol%. On the other hand, the higher the molar concentration of the structural unit represented by formula (2) in the modified PVA, the lower the hydrophilization force of the semiconductor wafer. The upper limit of the molar concentration of the structural unit represented by formula (2) in the modified PVA is preferably 30 mol%, and more preferably 20 mol%.
The molar concentration (mol%) of the structural unit represented by formula (2) in the modified PVA may be regarded as a value equal to the degree of saponification (mol%) of the modified PVA subtracted from 100 mol%. The saponification degree of the modified PVA was measured in accordance with JIS K6726 in the same manner as the PVA.
The polishing composition of the present embodiment may further contain a nonionic surfactant. By including the nonionic surfactant, minute defects or haze can be further reduced.
Examples of the nonionic surfactant suitable for the polishing composition of the present embodiment include ethylenediamine tetrapolyoxyethylene polyoxypropylene (poloxamine (ポ, port キサミン)), poloxamer, polyoxyalkylene alkyl ether, polyoxyalkylene fatty acid ester, polyoxyalkylene alkylamine, and polyoxyalkylene methyl glucoside.
Examples of polyoxyalkylene alkyl ethers include: polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, and the like. Examples of the polyoxyalkylene fatty acid ester include: polyoxyethylene monolaurate, polyoxyethylene monostearate, and the like. Examples of polyoxyalkylene alkylamines include: polyoxyethylene lauryl amine, polyoxyethylene oleylamine, and the like. Examples of polyoxyalkylene methyl glucoside include: polyoxyethylene methyl glucoside, polyoxypropylene methyl glucoside, and the like.
The content of the nonionic surfactant (when two or more are contained, the total amount thereof) is not particularly limited, and for example, the content is calculated as abrasive grains in a mass ratio to the abrasive grains: the nonionic surfactant is 1: 0.0001-1: 0.015. The polishing composition of the present embodiment is preferably used by diluting the nonionic surfactant to a concentration of 0.5 to 30 ppm.
The polishing composition of the present embodiment may further contain a pH adjuster. The polishing composition of the present embodiment preferably has a pH of 8.0 to 12.0.
The polishing composition of the present embodiment may optionally contain a blending agent generally known in the field of polishing compositions, in addition to the above.
The polishing composition of the present embodiment is produced by appropriately mixing abrasive grains, a basic compound, a modified PVA, and other compounding materials and adding water. Alternatively, the polishing composition of the present embodiment is produced by mixing abrasive grains, a basic compound, a modified PVA, and other blending materials in water in this order. As a method for mixing these components, a method commonly used in the technical field of polishing compositions, such as a homogenizer and ultrasonic waves, is used.
The polishing composition described above is diluted with water to an appropriate concentration and used for polishing a semiconductor wafer.
The polishing composition of the present embodiment can be suitably used for finish polishing of a silicon wafer in particular.
Examples
The present invention will be described in more detail below with reference to examples. The present invention is not limited to these examples.
[ polishing example 1]
Polishing compositions of examples 1 to 10 and comparative examples 1 to 4 shown in Table 1 were prepared.
[ Table 1]
Molar concentration of structural unit represented by the corresponding formula (2)
The contents in table 1 are all the contents after dilution. The abrasive grains are colloidal silica. The "particle diameter" in table 1 represents the average secondary particle diameter of the abrasive grains. "NH4OH "represents an aqueous ammonia solution. The modified PVAs a to D each represent a butylene glycol vinyl alcohol polymer having a different degree of polymerization and saponification. PVA A and B represent polyvinyl alcohols having different degrees of saponification.
The polishing compositions of examples and comparative examples were used to polish a 12-inch silicon wafer. A silicon wafer having a P-type conductivity and a resistivity of 0.1 omega cm or more and less than 100 omega cm is used. The abrasive surface is<100>And (5) kneading. The polishing apparatus was a single-side polishing apparatus using SPP800S manufactured by kyo machine tools. The polishing pad uses a suede pad. The polishing composition was diluted 31 times and supplied at a supply rate of 1L/min. The rotation speed of the surface plate was 40rpm, the rotation speed of the carrier was 39rpm, and the polishing load was 100gf/cm2Then, the polishing was carried out for 2 minutes. Before polishing with the polishing compositions of examples and comparative examples, preliminary polishing was performed for 3 minutes using polishing slurry NP7050S (manufactured by Nitta Haas corporation).
The polished silicon wafer was measured for minute defects and haze. The minute defects were measured by using a wafer surface inspection apparatus MAGICS M5640 (manufactured by Lasertec). The haze was measured using a wafer surface inspection apparatus LS6600 (manufactured by hitachi engineering co.). The results are shown in the columns of "defect" and "haze" in table 1.
As is clear from the comparison between example 1 and comparative example 1 and the comparison between example 3 and comparative example 2, when other conditions are constant, the higher the molar concentration of the structural unit represented by formula (2), the more the fine defects and the haze tend to decrease.
From the comparison between example 2 and example 4 and the comparison between examples 7, 9 and 10, it is found that the higher the concentration of the modified PVA is, the more the fine defects tend to be reduced if the other conditions are constant.
As is clear from comparison between example 2 and example 3 and comparison between example 7 and example 8, if other conditions are constant, the higher the concentration of the abrasive grains, the more the fine defects tend to decrease.
From comparison of examples 4 to 6, it is found that the lower the concentration of the basic compound is, the lower the fine defects and the haze tend to be if the other conditions are constant.
From comparison between comparative examples 3 and 4, it is understood that in the case of the ordinary PVA, the molar concentration of the structural unit represented by the formula (2) is increased, and thus the fine defects and the haze are increased, unlike the case of the modified PVA.
[ polishing example 2]
Polishing compositions of examples 11 to 26 and comparative examples 5 to 8 shown in tables 2 and 3 were prepared.
[ Table 2]
[ Table 3]
The contents in tables 2 and 3 are all the diluted contents. "poloxamine" represents ethylenediaminepolyoxyethylene polyoxypropylene having a weight average molecular weight of 7240, "polyol a" represents polyoxypropylene methyl glucoside having a weight average molecular weight of 775, and "polyol B" represents polyoxyethylene methyl glucoside having a weight average molecular weight of 1075. The rest is the same as in table 1.
Silicon wafers were polished in the same manner as in polishing example 1 using the polishing compositions of examples 11 to 26 and comparative examples 5 to 8, and the minute defects and haze were measured.
As is clear from comparison among examples 11, 12 and 5, when other conditions are constant, the higher the molar concentration of the structural unit represented by formula (2), the more the fine defects and the haze tend to decrease.
As is clear from comparison of examples 1 to 10 and examples 11 to 26, the inclusion of the nonionic surfactant significantly reduces the fine defects and haze.
The embodiments of the present invention have been described above. The above embodiments are merely illustrative for implementing the present invention. Therefore, the present invention is not limited to the above embodiments, and the above embodiments may be appropriately modified and implemented within a scope not departing from the gist thereof.
Claims (3)
1. A polishing composition comprising abrasive grains, a basic compound, and a vinyl alcohol resin having a 1, 2-diol structural unit represented by the following general formula (1),
in the vinyl alcohol resin, the molar concentration of the structural unit represented by the following general formula (2) is 2 mol% or more of the total structural units,
wherein R is1、R2And R3Each independently represents a hydrogen atom or an organic group, X represents a single bond or a bonding chain, R4、R5And R6Each independently represents a hydrogen atom or an organic group.
2. The polishing composition according to claim 1, further comprising a nonionic surfactant.
3. The polishing composition according to claim 1 or 2, wherein the basic compound is at least 1 selected from the group consisting of alkali metal oxides, alkali metal salts, ammonia, amines, ammonium salts, and quaternary ammonium hydroxides.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017252270A JP6978933B2 (en) | 2017-12-27 | 2017-12-27 | Polishing composition |
| JP2017-252270 | 2017-12-27 | ||
| PCT/JP2018/047025 WO2019131448A1 (en) | 2017-12-27 | 2018-12-20 | Polishing composition |
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| CN111527589A true CN111527589A (en) | 2020-08-11 |
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| JP (1) | JP6978933B2 (en) |
| KR (1) | KR20200098547A (en) |
| CN (1) | CN111527589A (en) |
| DE (1) | DE112018006626T5 (en) |
| SG (1) | SG11202004727UA (en) |
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| JP7349309B2 (en) * | 2019-09-30 | 2023-09-22 | 株式会社フジミインコーポレーテッド | Polishing composition for silicon wafers |
| JP7433042B2 (en) * | 2019-12-24 | 2024-02-19 | ニッタ・デュポン株式会社 | polishing composition |
| JP2021105145A (en) * | 2019-12-27 | 2021-07-26 | ニッタ・デュポン株式会社 | Composition for polishing, and method of polishing silicon wafer |
| CN114945649B (en) * | 2020-02-13 | 2024-05-07 | 富士胶片电子材料美国有限公司 | Polishing composition and method of use thereof |
| JP2023514586A (en) * | 2020-02-13 | 2023-04-06 | フジフイルム エレクトロニック マテリアルズ ユー．エス．エー．， インコーポレイテッド | Polishing composition and method of use thereof |
| JP7450439B2 (en) | 2020-03-31 | 2024-03-15 | 株式会社フジミインコーポレーテッド | Polishing composition and method for producing magnetic disk substrate |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012216723A (en) * | 2011-04-01 | 2012-11-08 | Nitta Haas Inc | Polishing composition |
| CN103563130A (en) * | 2011-06-02 | 2014-02-05 | 协立化学产业株式会社 | Coating agent composition for battery electrodes or separators |
| WO2014084091A1 (en) * | 2012-11-30 | 2014-06-05 | ニッタ・ハース株式会社 | Polishing composition |
| CN104245829A (en) * | 2012-04-27 | 2014-12-24 | 日本合成化学工业株式会社 | Resin composition and use therefor |
| WO2017069253A1 (en) * | 2015-10-23 | 2017-04-27 | ニッタ・ハース株式会社 | Polishing composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2016124943A (en) * | 2014-12-26 | 2016-07-11 | ニッタ・ハース株式会社 | Polishing composition |
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2018
- 2018-12-20 CN CN201880084023.1A patent/CN111527589A/en active Pending
- 2018-12-20 KR KR1020207018293A patent/KR20200098547A/en not_active Application Discontinuation
- 2018-12-20 SG SG11202004727UA patent/SG11202004727UA/en unknown
- 2018-12-20 DE DE112018006626.6T patent/DE112018006626T5/en active Pending
- 2018-12-20 WO PCT/JP2018/047025 patent/WO2019131448A1/en active Application Filing
- 2018-12-26 TW TW107147152A patent/TWI798325B/en active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012216723A (en) * | 2011-04-01 | 2012-11-08 | Nitta Haas Inc | Polishing composition |
| CN103563130A (en) * | 2011-06-02 | 2014-02-05 | 协立化学产业株式会社 | Coating agent composition for battery electrodes or separators |
| CN104245829A (en) * | 2012-04-27 | 2014-12-24 | 日本合成化学工业株式会社 | Resin composition and use therefor |
| WO2014084091A1 (en) * | 2012-11-30 | 2014-06-05 | ニッタ・ハース株式会社 | Polishing composition |
| WO2017069253A1 (en) * | 2015-10-23 | 2017-04-27 | ニッタ・ハース株式会社 | Polishing composition |
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| SG11202004727UA (en) | 2020-06-29 |
| WO2019131448A1 (en) | 2019-07-04 |
| JP6978933B2 (en) | 2021-12-08 |
| DE112018006626T5 (en) | 2020-09-10 |
| TW201930540A (en) | 2019-08-01 |
| KR20200098547A (en) | 2020-08-20 |
| JP2019117904A (en) | 2019-07-18 |
| TWI798325B (en) | 2023-04-11 |
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