CN101255286A - Abrasive particles, slurry for polishing and method of manufacturing the same - Google Patents
Abrasive particles, slurry for polishing and method of manufacturing the same Download PDFInfo
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- CN101255286A CN101255286A CNA2007103016209A CN200710301620A CN101255286A CN 101255286 A CN101255286 A CN 101255286A CN A2007103016209 A CNA2007103016209 A CN A2007103016209A CN 200710301620 A CN200710301620 A CN 200710301620A CN 101255286 A CN101255286 A CN 101255286A
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- Prior art keywords
- persursor material
- slurry
- abrasive grain
- polishing
- particle size
- Prior art date
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- Granted
Links
- 239000002002 slurry Substances 0.000 title claims abstract description 116
- 238000005498 polishing Methods 0.000 title claims abstract description 84
- 239000002245 particle Substances 0.000 title claims description 178
- 238000004519 manufacturing process Methods 0.000 title claims description 35
- 238000000034 method Methods 0.000 claims abstract description 95
- 239000000463 material Substances 0.000 claims description 101
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 75
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 75
- 238000001354 calcination Methods 0.000 claims description 65
- GHLITDDQOMIBFS-UHFFFAOYSA-H cerium(3+);tricarbonate Chemical compound [Ce+3].[Ce+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GHLITDDQOMIBFS-UHFFFAOYSA-H 0.000 claims description 58
- 239000003795 chemical substances by application Substances 0.000 claims description 58
- 239000006061 abrasive grain Substances 0.000 claims description 48
- 239000006185 dispersion Substances 0.000 claims description 25
- 238000002360 preparation method Methods 0.000 claims description 19
- 238000000227 grinding Methods 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 13
- 239000000654 additive Substances 0.000 claims description 12
- 230000000996 additive effect Effects 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 238000010304 firing Methods 0.000 claims description 2
- 239000004065 semiconductor Substances 0.000 abstract description 13
- 150000004767 nitrides Chemical class 0.000 abstract description 11
- 230000008569 process Effects 0.000 abstract description 4
- 235000012431 wafers Nutrition 0.000 abstract 1
- 238000012545 processing Methods 0.000 description 58
- 238000004513 sizing Methods 0.000 description 51
- 239000000843 powder Substances 0.000 description 33
- 229910000420 cerium oxide Inorganic materials 0.000 description 29
- 238000009826 distribution Methods 0.000 description 29
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 29
- 238000005516 engineering process Methods 0.000 description 12
- 230000008859 change Effects 0.000 description 11
- 230000006641 stabilisation Effects 0.000 description 11
- 238000011105 stabilization Methods 0.000 description 11
- 238000012360 testing method Methods 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000008187 granular material Substances 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 238000010298 pulverizing process Methods 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 238000001556 precipitation Methods 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 5
- 125000000129 anionic group Chemical group 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000002270 dispersing agent Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 235000011089 carbon dioxide Nutrition 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000002955 isolation Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000001238 wet grinding Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 229920006318 anionic polymer Polymers 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- -1 carboxyl-propenyl Chemical group 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229920000193 polymethacrylate Polymers 0.000 description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 229960001866 silicon dioxide Drugs 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000012010 growth Effects 0.000 description 2
- 230000002045 lasting effect Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 244000287680 Garcinia dulcis Species 0.000 description 1
- 206010021703 Indifference Diseases 0.000 description 1
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000003082 abrasive agent Substances 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000005586 carbonic acid group Chemical group 0.000 description 1
- HDXXSUQVQKJEBI-UHFFFAOYSA-N carbonic acid;cerium Chemical compound [Ce].OC(O)=O HDXXSUQVQKJEBI-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000005354 coacervation Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000000994 depressogenic effect Effects 0.000 description 1
- 238000009837 dry grinding Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
Images
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
- B82B3/00—Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
-
- 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
-
- 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
-
- 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
-
- 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]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Nanotechnology (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
Disclosed herein is a polishing slurry for use in an STI CMP process, necessary for fabricating ultra highly integrated semiconductors of 256 mega D-RAM or more (Design rule of 0.13 mum or less), which can polish wafers at a high removal rate, having an excellent the removal selectivity of oxide compared to nitride. The polishing slurry can be applied to various patterns required in the course of producing ultra highly integrated semiconductors, and thus excellent removal rate, removal selectivity, and within-wafer-nonuniformity (WIWNU), which indicates removal uniformity, as well as minimal occurrence of micro scratches, can be assured.
Description
The application is to be on December 16th, 2005 applying date, and application number is 200510134775.9, and denomination of invention is divided an application for " abrasive grain, polishing slurries and manufacture method thereof " patent application.
Technical field
The present invention relates to a kind of slurry that is used for chemically machinery polished (being designated hereinafter simply as " CMP ") processing procedure.Particularly relate to a kind of shallow-trench isolation (STI that is used for, shallow trench isolatein) polishing slurries of CMP processing procedure, this polishing slurries is essential by making 256M (mega) or higher D-RAM superelevation integrated semiconductor (standard is less than or equal to 0.13 μ m), it can polish wafer with the very high speed that removes, with nitride comparatively speaking, this polishing slurries has excellent oxide removal selectivity.In addition, the invention still further relates to abrasive grain, and the manufacture method of this abrasive grain and polishing slurries.
Background technology
Chemically machinery polished (CMP) is a kind of semiconductor processing technology, promptly uses abrasive grain to carry out also using slurry to carry out chemical milling in the mechanical workout between wafer and polishing pad.This method is succeeded in developing so far by American I BM company from the eighties of eighties of last century, has become the core process of the integral surface technology in the manufacturing of worldwide production submicron order semiconductor wafer.
The kind of polishing slurries wants process object to be broadly divided into three kinds of oxide cmp slurry, medal polish slurry and multi-silicon wafer polishing slurries etc. by it.The oxide cmp slurry is applicable to the surface and the silicon-dioxide (SiO of insulating film of intermediate layer in polishing shallow-trench isolation (STI, the shallow trench isolation) technology
2) layer, it roughly comprises compositions such as polishing particle, deionized water, pH stablizer and tensio-active agent.The role in the polishing processing procedure of polishing particle wherein is exactly mechanical polishing to be carried out on the machined object surface handled by the pressure of polishing machine generation.The composition of polishing particle can be silicon-dioxide (SiO
2), cerium dioxide (CeO
2) or aluminium sesquioxide (Al
2O
3).
Specifically, in STI technology, usually ceria sizing agent is used for the polishing silicon dioxide layer, at this moment, can mainly adopts silicon nitride layer as the polishing stop layer.Usually, additive can be added this ceria sizing agent reducing the removing speed of nitride layer, thereby improve the polishing velocity selectivity of oxide skin nitride layer.But it is disadvantageous using additive, and reason is that it can reduce the removing speed of oxide skin and the removing speed of nitride layer.In addition, the rumbling compound particle of ceria sizing agent is usually greater than the rumbling compound particle of silica slurry, and allows crystal column surface have cut.
But if oxide skin is lower to the polishing velocity selectivity of nitride layer, then because the excess oxide layer is removed, contiguous nitride layer pattern is destroyed, causes at surface to be machined generation depressed phenomenon.Therefore, can not realize uniform profile pattern.
Therefore, employed polishing slurries will possess highly selective, high polishing velocity, high degree of dispersion, the distribution of high stability microcosmic cut and high concentration and uniform particle size distribution range in the CMP of STI processing procedure.In addition, the quantity of the particle of granularity 〉=1 μ m must be controlled within the pre-determined range.
The U.S. Patent number of HIT is 6,221,118 and 6,343, two patented technologies of 976 provide the routine techniques that is adopted among the STI CMP, promptly prepare the method for cerium dioxide, adopt cerium dioxide to be the preparation method that the polishing particles period of the day from 11 p.m. to 1 a.m has the polishing slurries of highly selective.These two patents have described the prerequisite characteristic of polishing slurries in the STI CMP technology, contain the type of additive polymer and in various Special Circumstances with use their method generally speaking.Especially what deserves to be mentioned is, also proposed the scope of polishing particle, elementary polishing particle and secondary particle granularity average and the change of calcining temperature in these two patents and can cause polishing the situation that particle size changes and the glazed surface cut changes.Another routine techniques, U.S. Patent number are 6,420,269 to belong to the technology of Hitachi, Ltd, for we provide the method for preparing multiple ceria particles and have adopted cerium dioxide to be the preparation method that the polishing particles period of the day from 11 p.m. to 1 a.m has the polishing slurries of highly selective.Simultaneously, United States Patent (USP) numbering 6,615,499, the patented technology that belongs to Hitachi, Ltd also provides the velocity of variation of the polishing particle peak density that relies on the calcination heat-up rate in predetermined x-ray radiation scope and the changing conditions of polishing removal speed for us.In addition, the U.S. Patent number that belongs to Japanese Showa Denko company limited earlier period is 6,436,835,6,299,659,6,478,836,6,410,444 and 6,387, in 139 the technology that patent provided, also pointed out to prepare the method for cerium dioxide and adopted cerium dioxide to be the preparation method that the polishing particles period of the day from 11 p.m. to 1 a.m has the polishing slurries of highly selective for us.Be additive, its influence and coupling additive of describing polishing slurries mostly in these patents to polishing effect.
But, above-mentioned prior art only discloses the average particle size particle size and the scope thereof of the abrasive grain that constitutes polishing slurries, and lacks raw-material kind and feature about abrasive grain, relates to the calcining processing procedure of these features and the details such as characteristic of the cerium oxide particles that obtained in this way.
In fact, the characteristic of ceria sizing agent finished product, comprise specific surface area (specific surfacearea), porousness, degree of crystallinity and particle size distribution homogeneity, can change, thereby cause distinct STI CMP result according to material behavior and calcination condition.Specifically, along with standard reduces, can cause the big abrasive grain of little cut and the quantity of caking thereof to change.Therefore, extremely important is to specify and limit raw-material feature and according to the calcining processing procedure of these starting material features.
Summary of the invention
Therefore, the problems referred to above that The present invention be directed in the prior art to be taken place and producing.
Purpose of the present invention is calcined the method that processing procedure comes the one-tenth piece persursor material that manufacturing dimension is evenly distributed for providing a kind of suddenly by multistep.
The invention provides a kind of method of making the slurry abrasive grain, it comprises: the preparation persursor material; And so that two or more stages are calcined this persursor material at least.
Make in the method for slurry abrasive grain at this, calcining step comprises: at first calcine this persursor material; Pulverize or pulverize at first the incinerating persursor material to produce less secondary persursor material; And next this secondary persursor material of calcining.
Method according to the described manufacturing slurry of preferred embodiment of the present invention abrasive grain also comprises: pulverize or pulverize this next incinerating persursor material to form third stage persursor material; And this third stage persursor material of third firing.
Make in the method for slurry abrasive grain at this, can under from 500 to 1,000 ℃ temperature, carry out calcining step.
The present invention provides a kind of method of making polishing slurries in addition, and this method comprises: the abrasive grain for preparing above-mentioned manufacturing; In the grinding mixture that comprises deionized water, dispersion agent and additive, grind this abrasive grain; And filter this grinding mixture to remove larger particles wherein.
The present invention provides a kind of abrasive grain and polishing slurries by the aforesaid method manufacturing again.
The preferable cerium dioxide that comprises of abrasive grain, and the preferable cerous carbonate that comprises of persursor material.
Above-mentioned explanation only is the general introduction of technical solution of the present invention, for can clearer understanding technique means of the present invention, and can be implemented according to the content of specification sheets, below with preferred embodiment of the present invention and conjunction with figs. describe in detail as after.
Description of drawings
Fig. 1 is a schema, the processing procedure of the polishing slurries of its explanation one embodiment of the invention.
Fig. 2 is a schema, the processing procedure of the persursor material of its explanation one embodiment of the invention.
D1, the D50 of particle size and the definition of D99 are depended in Fig. 3 displaying.
Fig. 4 shows the distribution plan of the size of cerous carbonate secondary granule.
Fig. 5 is a graph of a relation, has drawn the size with respect to the cerous carbonate secondary granule of calcining temperature.
Fig. 6 a is a synoptic diagram, and the particulate of its explanation when calcining disperses persursor material forms.
Fig. 6 b is a synoptic diagram, and the particulate of its explanation when being sintered into the piece persursor material forms.
Fig. 7 a to 7c is for having the TEM photo of the abrasive grain of different secondary granule sizes at 800 ℃ of following incinerating.
Fig. 8 is a synoptic diagram, and its explanation is according to the calcining processing procedure of persursor material of the present invention.
Fig. 9 a is for disperseing the SEM photo of persursor material.
Fig. 9 b is into the SEM photo of piece persursor material.
Figure 10 is dispersion and the density that becomes the piece persursor material to be drawn and the graph of a relation of specific surface area for when calcining dispersion and becoming the piece persursor material with respect to particle size.
Figure 11 a is from disperseing the TEM figure of the prepared slurry of persursor material.
Figure 11 b is from becoming the TEM figure of the prepared slurry of piece persursor material.
Figure 12 is a figure, and it is illustrated in the slurry 1 of grinding processing procedure front and back and 2 particle size.
Figure 13 a is a figure, and it shows the variation of the particle size distribution of forcing dispersed paste 1 front and back.
Figure 13 b is a figure, and it shows the variation of the particle size distribution of forcing dispersed paste 2 front and back.
Figure 14 is a figure, and it shows CMP result.
Embodiment
Hereinafter the preparation method of polishing slurries among the present invention and the analysis that the performance of this polishing slurries is carried out will be elaborated respectively.Specifically, when the dimensional change of starting material cakings and when the introducing multistep is calcined processing procedure suddenly, will analyze the variation of polishing slurries characteristic respectively.In addition, the present invention also will set forth the method that the employing cerium dioxide is made the preparation method of the polishing slurries of polishing particle, made dispersion agent with deionized water and anionic polymer.And, will provide the CMP result of depending on the procedure for producing condition, for example oxide film polishing velocity and selectivity.Any those skilled in the art can utilize the structure of following announcement and technology contents to make a little change or be modified to the equivalent embodiment of equivalent variations, and category of the present invention is not limited to following description.
[manufacture method of ceria sizing agent]
Ceria sizing agent of the present invention comprises cerium oxide powder, deionized water, anionic polymeric dispersing agent and a kind of additive, as weak acid or weak base.The preparation method of polishing slurries may further comprise the steps (see figure 1).At first, presoma such as cerous carbonate are carried out pre-treatment, with composite solid state cerium oxide powder (S1).Perhaps, can before solid-state synthesizing, carry out multistep and calcine processing procedure suddenly, comprise drying, calcining, pulverizing (pulverizing) and/or pulverize (crushing) step.Afterwards, cerium oxide powder is mixed (S2) with deionized water in container, the mixture that obtains is in grinding machine for grinding, so that reduce particle diameter and meet the requirements of size distribution (S3).In the slurry that aforesaid method obtains, add anionic polymeric dispersing agent to increase the dispersion stabilization (S4) of polishing particle.Add additive in high-speed mixer, as weak acid, weak base, with the control pH value of slurry, by grinding stable dispersion (S5), to determine solid weight percent (wt%) in the slurry, promptly solid content (S6) reaches needed value again.Remove by filter macroparticle to stop the generation (S7) of precipitation and polishing processing procedure cut.Afterwards, by wearing out stable slurry (S8).The preparation method of cerium dioxide polishing slurries among the present invention is described in detail in detail below.
1. the manufacturing of cerium oxide powder
In the present invention, the first step of preparation ceria sizing agent is: adopt solid generation method to prepare cerium oxide powder by presoma.Presoma such as cerous carbonate produce cerium oxide powder by calcining, but before calcining, should adopt at first separately drying process remove wherein moisture so that its thermal conduction and manufacturability be guaranteed.Depend on for example characteristic of persursor material such as cerous carbonate, ceria sizing agent may change according to particular characteristics, and these particular characteristics comprise specific surface area, porousness, degree of crystallinity, particle size distribution etc., hereinafter will carry out sets forth in detail to it.
The performance of cerium oxide powder depends on the calcining effect of cerous carbonate and the performance of calciner.Cerous carbonate has water-absorbent, and is crystallizable with water, and the valency of its crystal water can be 4,5 or 6.Therefore the calcining effect of cerous carbonate is relevant with its water regain with the valency of the crystal water in its crystal.After the calcining, the moisture in the cerous carbonate is removed.But along with the rising of temperature and gathering of heat, the decarbonate reaction takes place, and carbonate has become carbonic acid gas.Cerium oxide powder also begins to generate.Secondly, carry out extra thermal treatment, produce the cerium oxide powder that particle constituted thus by various size to cause recrystallize.It is preferable 500-1000 ℃ of execution down wherein to calcine processing procedure.Herein, calcining temperature can be determined degree of crystallinity and particle size.The size of each particle or xln increases along with the rising of calcining temperature.
In addition, can a plurality of stages but not the single stage carry out calcining, introduce therebetween and pulverize or pulverize step.This multistep is calcined the characteristic that processing procedure can be determined ceria sizing agent suddenly, and for example specific surface area, porousness, crystal structure degree, particle size etc., and oxide removal rate and selectivity hereinafter also are described in greater detail.
2. mix and grinding
The cerium oxide powder that calcining process is generated above adopting in the mixing tank of high speed rotating with deionized water mixing humidification after, the mixture of gained is admitted to the superpower grinding machine for grinding to reduce its particle size and to make the particle good dispersion, so that generate nano level cerium dioxide polishing slurries.After water mixes, can adopt superpower shredder control polishing size of particles and disperse its caked particle.Shredder adopts wet type, dry type all can.But have the metallics corrosive possibility that is produced by itself wearing and tearing back in the processing procedure because of the dry grinding machine grinds, pottery system wet grinding machine is adopted in suggestion.But the wet grinding machine settling that particle coacervation forms may occur in grinding processing procedure, thereby generates large-scale macrobead particle, and the phenomenon that mill efficiency descends finally takes place.Therefore, be necessary concentration, pH value of slurry and the conductivity of polishing particle are controlled, and adopt dispersion agent to improve polishing particle dispersive stability.
3. the interpolation of dispersion stabilization and additive
Need in the polishing slurries to add a kind of anionic polymeric dispersing agent and other additive, as weak acid or weak base, thus the effect of playing control polishing slurries pH value, stablizing polishing slurries.After this, can use high-energy mills to grind the mixture that comprises dispersion agent and additive, to reduce size of particles and dispersed particle.Secondly, use during pump is conveyed into powdery and dispersive slurry independently jar, use suitable diverting device that it is disperseed once more subsequently, lump once more and precipitate to guarantee its dispersion stabilization and to prevent.
Can be any material that is selected from the group that following each thing forms as the anionic polymer batch mixing of dispersion agent: polymethyl acrylic acid (polymethacrylic acid), polyacrylic acid (polyacrylicacid), ammonium polymethacrylate (ammonium polyethacrylate), poly carboxylic acid ammonium (ammoniumpolycarboxylate), carboxyl-propenyl polymer (carboxyl-acryl polymer) and combination thereof.Its former because slurry of the present invention is based on water, and above-mentioned polymer composition water soluble at normal temperatures.In addition, calculate with the amount of polishing particles, the content of the anionic polymer batch mixing that is added is suitably for 0.0001-10.0wt%.The viscosity performance of the ceria sizing agent after stable is preferably newton's performance.
4. the control of solid load (wt%) and larger particles removes
As mentioned above, behind the stably dispersing processing procedure, the solid content of ceria sizing agent is controlled in certain scope, adopts filtration method to remove and deenergize to cause precipitation and the macroparticle that lumps and can cause cut in the CMP processing procedure.When the particle of large volume existed, the gravity of particle was greater than by the caused repulsive force of repulsive interaction between particle, and the surface-area of macroparticle is less than the surface-area of small-particle, so the dispersiveness of macroparticle is less than the dispersiveness of small-particle.When the macroparticle number of unit volume increases with the increase of solid content, the situation aggravation that can cause precipitating and condensing caking.Based on two above-mentioned reasons, make to precipitate and condense to lump to be easy to take place, cause the slurry instability, therefore be necessary to remove macroparticle, wherein the degree of macroparticle removal increases with filtering number of times.
5. slurry is aging
In container, can further increase stability of slurry by 24 hours stirrings are aging.This step also can prepare fully at slurry to be implemented after finishing, and can also omit as required.
[depending on the variation of the ceria sizing agent characteristic of persursor material characteristic]
As mentioned below, making under the situation of ceria sizing agent by above-mentioned manufacturing processed, analyze of the influence of the characteristic of persursor material cerous carbonate to the ceria sizing agent characteristic.Specific, the size that will become the piece secondary granule according to cerous carbonate is described in detail the variation of ceria sizing agent characteristic.
As indicated above, prepare abrasive grain by persursor material being carried out predrying and calcining, and before grinding, mix subsequently with DI water.After calcining, assembling widely of presoma cerous carbonate causes wider particle size distribution.That is, when calcining, can make meticulous cerium oxide particles and larger particles.
But if contain the larger particles of size greater than 1 μ m, polishing slurries can cause producing little cut, yet in the manufacturing processed of 0.13 μ m or littler superelevation integrated semiconductor, this will produce fatal influence to semiconductor device.Therefore, it is very important for the manufacturing of ceria sizing agent to get rid of larger particles as much as possible.For this reason, must control the particle size and the gathering of persursor material cerous carbonate.
Can prepare cerous carbonate according to program shown in Figure 2, with persursor material as ceria sizing agent.At first, with the raw ore mixing (S10) of rare earth metal, and be dissolved in the hydrochloric acid to obtain rare-earth chloride solution (S20).Carry out a plurality of extractions with isolation cycle so that Cerium II Chloride separates (S30) with other rare earth metal.Cerium II Chloride is mixed with volatile salt to form cerous carbonate throw out (S40), subsequently it is washed and drying (S50) so that desired high purity persursor material (S60) to be provided.
When using this coprecipitation method to prepare the persursor material cerous carbonate, the precipitin reaction condition for example all can be determined sedimentary characteristic for pH value, temperature, time etc.Specifically, presoma has crucial influence for the particle size of sedimentary trend and gained presoma to the characteristic of finished product ceria sizing agent.
Referring to Fig. 3, it is a synoptic diagram, and the definition of D1, D50 and D99 is described, that is, according to size particle is classified.
As shown in Figure 3, D50 is corresponding to a particle size, wherein this particle size is less than 50% population distribution particulate size, and D1 is corresponding to a particle size, wherein this particle size is bigger 1% population distribution particulate size, and D99 is corresponding to a particle size, and wherein this particle size is less 1% population distribution particulate size.Therefore, the shared secondary granule size of D1 greater than other both, and assemble widely and worse dispersion stabilization will produce higher D1 value.
For the characteristic that more can understand ceria sizing agent is to depend on the persursor material characteristic, hereinafter enumerated the example of many particle size distribution.
Table 1
| D1 (size is bigger) | D50 (size is medium) | D99 (size is less) | |
| |
365.3μm | 120.5μm | 2.4 |
| Persursor material | |||
| 2 | 107.7μm | 34.9μm | 2.5 |
| Persursor material | |||
| 3 | 51.9μm | 6.483μm | 1.5μm |
Fig. 4 has drawn the particle size distribution figure of persursor material cerous carbonate given in the table 1.As shown in Figure 4, compare with persursor material 2 or persursor material 3, because higher aggregation extent, persursor material 1 contains larger sized particle.At high temperature after the calcining, find that the cerous carbonate particle of persursor material 1 to 3 has particle size shown in Figure 5, it is as using X-ray diffractometer (XRD) measured.In order to reproduce data among Fig. 5, from various persursor materials, select two particles at random, and measure its size.As shown in Figure 5, along with the carrying out of calcining processing procedure and the increase of persursor material particle size, these particulate sizes will increase.
In the calcining processing procedure, can produce cerium carbonate powder, remove carbonic acid functional group (carbonate functional group) with form of carbon dioxide thereby decarburizating takes place simultaneously.Under higher calcining temperature, cerium carbonate powder meeting recrystallize is to generate larger sized particle.In addition, because the increase of the particle size that the high trend of cerous carbonate accumulative is caused will be made bigger particle size, its reason is as follows.
In highly dense caked nano-sized powders, many primary granules contact with each other.Necking point place between contiguous primary granule is easy to take place the motion of mass diffusion and lattice, thereby even also can forms larger particles by thermal destruction (thermal degradation) at low temperatures.That is, shown in Fig. 6 a, when particle scatter each other, itself in addition the calcining after also keep separated from one another.On the contrary, shown in Fig. 6 b, when particle contacted with each other, it was that the center forms larger particles with the necking point that calcining can make it.Thereby, even under uniform temp, calcine the identical time, also can generate particles of different sizes.
As shown in Figure 5, form in gathering under the situation of persursor material 1, can form larger particle, and cause the abnormal grain of cerium dioxide abrasive grain with relatively large particle size owing to cerous carbonate.
Referring to Fig. 7 a to 7c, it is respectively shows persursor material 1 to 3 photo 800 ℃ of following results for calcination.Shown in photo, the particle size of the quantity of larger particles and persursor material cerous carbonate increases pro rata in the abrasive grain.
Simultaneously, when particle became piece, persursor material was rendered as larger particles, and this moment is owing to not exclusively calcine so can form nano sized particles in big grumeleuse.Become the piece persursor material that mass transfer is had more on the whole drag, thereby make the mass transfer of reactant gases oxygen and by product carbonic acid gas and diffusion postpone, cause incomplete calcining.To be described in detail this phenomenon with lower section " depend on multistep calcine the variation of the ceria sizing agent characteristic of processing procedure suddenly ".Owing to this reason, along with the persursor material particle is assembled more widely, and be rendered as larger particle, wherein persursor material has fine granular, thereby broad particle size distribution is provided.
In order to control the particle size of cerous carbonate, as described above, the powders in the precipitation processing procedure of persursor material manufacture method is minimized.Gathering is to depend on the reaction conditions of powdered preparation and take place.Along with the generation of more precipitation from homogeneous solutions, the more difficult gathering of cerous carbonate precipitation.Can be by regulating CeCl
3The concentration of solution, mixing rate, temperature of reaction and/or obtain uniform precipitation by suitable dispersion agent.
[depend on multistep calcine the variation of the ceria sizing agent characteristic of processing procedure suddenly]
Herein, stating processing procedure in the use and make under the situation of ceria sizing agent, calcine the influence of processing procedure to the ceria sizing agent characteristic suddenly with describing multistep in detail, specifically, also is to be described with regard to CMP speed and little cut quantity.
As shown in Figure 8, the calcining processing procedure comprises five steps.At first, airborne oxygen and cerous carbonate produce reaction.Subsequently, oxygen diffuses into cerous carbonate and is adsorbed on reactive site by hole (pores).Secondly, oxygen reacts so that cerous carbonate is calcined.After this, discharge products such as carbonic acid gas from reactive site, and carbonic acid gas diffuses out cerous carbonate and enters air by the hole.Can represent this calcining processing procedure from following reaction equation 1.
[reaction equation 1]
Can understand, in the calcining processing procedure, oxygen and carbon dioxide depends on the form of cerous carbonate by the rate of diffusion in hole, thereby determines overall reaction rate.Therefore, even carry out calcining at uniform temp with the identical time limit, the gained particle also can be showed different particle growths or degree of crystallinity.
Specifically, the outside and the degree of crystallinity between the inside of luming at the cerous carbonate that is of a size of hundreds of μ m have very big difference, make particle show broad particle size distribution.
With reference to Fig. 9 a and 9b, it is respectively and disperses and the SEM photo that becomes the piece persursor material.In Figure 10, when calcining disperses persursor material and becomes the piece persursor material, to disperseing persursor material and the relation curve that becomes the drafting of piece persursor material with respect to the density and the specific surface area of particle size, wherein become piece persursor material acquisition sample A and B among the dispersion persursor material from Fig. 9 a and Fig. 9 b respectively.Can be easy to draw from graphic representation,, compare, become the piece cerous carbonate to have bigger specific surface area and lower density with disperseing cerous carbonate although have identical particle size.Its former because: under the situation of the one-tenth piece cerous carbonate shown in Fig. 9 b, its outside well-crystallized is rendered as larger particles thus, and its inner because not exclusively calcining and do not allow crystal growth, thereby shows low-crystallinity.
Referring to Figure 11 a and 11b, disperse cerous carbonate and the slurry that becomes the piece cerous carbonate to prepare with the TEM photo display by calcining respectively.As shown in the figure, show uneven particle size distribution, wherein have many fine granulars from becoming the prepared slurry of piece cerous carbonate.This is owing to the imperfect crystal in the persursor material.That is, become the particle size distribution of piece persursor material to increase, because have bigger size difference between inside and external particle, for example, external particle is big and internal particle is less.
In addition, larger particles inner generate than small-particle because it is easy to condense than bigger serface, and cause outside larger particles to have little cut.In addition, owing to its low internal crystallization degree has bad oxide cmp speed, strengthened the polishing velocity selectivity of oxide skin than small-particle thus to nitride layer.
Because in the manufacturing processed of 0.13 μ m or littler superelevation integrated semiconductor, little cut has fatal influence to semiconductor device, therefore must avoid little cut.Consider the aggregation extent of persursor material cerous carbonate, must regulate particle size.
For this reason, using the multistep of one embodiment of the invention to calcine processing procedure suddenly evenly calcines becoming the piece cerous carbonate.Can overcome into degree of crystallinity difference between piece cerous carbonate outside and the inside by the rapid calcining of multistep of the present invention, thereby make the uniform abrasive grain of particle size with controllable manner.
At first, the elementary persursor material to cerous carbonate carries out drying and carries out elementary calcining.Secondly, obtain less secondary persursor material, expose inside with low-crystallinity by pulverizing or pulverizing.Powdery or broken secondary persursor material are carried out secondary calcining step so that abrasive grain to be provided.
Can identical or different temperature carry out the primary and secondary calcining step.For pulverizing or pulverizing processing procedure, can utilize various dry types to pulverize or crushing device, for example sizer (classifier), crusher, airbrasive machine etc.
Use three steps calcining processing procedure can obtain further improvement.In this, before calcining step subsequently, carry out the step of pulverizing or pulverizing persursor material just.Specifically, after initial dry and calcining, persursor material is pulverized or pulverized, expose the inside that it has low-crystallinity to obtain less secondary persursor material.After secondary drying of experience and calcining, secondary persursor material is further pulverized or pulverized littler third stage persursor material, expose the inside that it has low-crystallinity.At last, third stage persursor material is carried out the dry and calcining step of the third stage so that abrasive grain to be provided.
Compare with known single stage calcining processing procedure, this multistep is calcined outside and the inside that processing procedure can make into the piece persursor material suddenly and is had similar degree of crystallinity, thereby makes particle size keep even in narrower particle size distribution.Therefore, the larger particles that causes little cut that forms in one-tenth piece persursor material outside can be pulverized suddenly or pulverize step and split into littler particle by multistep.In addition, because the degree of crystallinity of whole persursor material becomes evenly, has abrasive grain than narrow size distribution thereby calcine with manufacturing.
Table 2 has hereinafter provided calcine processing procedure and the degree of crystallinity measuring result that become piece cerous carbonate prepared abrasive grain of single stage calcining processing procedure from Fig. 9 b suddenly by multistep.In table 2, slurry 1 is by carrying out as multistep is calcined elementary calcining in the processing procedure suddenly, pulverizes or pulverizes and secondary calcining obtains, and slurry 2 is to calcine processing procedure by single stage to obtain.Use the particle size after the XRD measurement has just been calcined and measure then incinerating wet grinding processing procedure particle size afterwards.
Table 2
From table 2 and Figure 12 as can be known, calcine the prepared slurry of processing procedure 1 no change almost after calcining just and after grinding suddenly, after grinding, showed sharply reducing of particle size and calcine the prepared slurry 2 of processing procedure by single stage by multistep.
In X-ray diffraction, the degree of depth that X ray infiltrates sample only is 10 μ m or littler.But, shown in Fig. 9 b,, become the piece cerous carbonate to reach the diameter of hundreds of μ m, even and after the single stage calcining, still keep this form as in slurry 2.Therefore, when XRD is applied to the grumeleuse cerous carbonate, can measure that it is outside and can not analyze its inside.That is, XRD can be applicable to have the external particle of high-crystallinity, but can not be applied to have the internal particle of low-crystallinity.After carrying out the wet grinding processing procedure, XRD can analyze less internal particle, therefore makes average particle size particle size reduce 7nm.
On the contrary, as in slurry 1 since multistep calcine processing procedure suddenly can fully calcined inside, so the particulate size is even, even and after grinding, its mean sizes only reduces 1nm.
In addition, particle size distribution has influence to the dispersion stabilization of gained slurry.As measuring the effective standard of slurry accumulative, can use dD15 or dD50.In other words, the LA910 that uses Japanese Horiba company to produce measures particle size, and the result is used for it is calculated.It is defined as follows.
That dD1=D1 sound splits (sonication) is preceding-after D1 sound splits
Before dD15=D15 sound splits-after D15 sound splits
Before dD50=D50 sound splits-after D50 sound splits
Wherein, be defined as follows separately:
Before D1 sound splits: be exposed to the preceding measured D1 particle size of ultrasonic wave;
D1 sound splits the back: be exposed to measured D1 particle size after the ultrasonic wave;
Before D15 sound splits: be exposed to the preceding measured D15 particle size of ultrasonic wave;
D15 sound splits the back: be exposed to measured D15 particle size after the ultrasonic wave;
Before D50 sound splits: be exposed to the preceding measured D50 particle size of ultrasonic wave;
D50 sound splits the back: be exposed to measured D50 particle size after the ultrasonic wave.
Measure in the LA910 model of using Horiba company to produce under the situation of particle size,, then become the piece slurry to be reallocated, thereby can measure the particle size under the dispersion state if carry out measurement by ultrasonic wave.On the other hand, if do not carry out measurement, then become the piece slurry not reallocated, thereby measure into the particle size of piece slurry by ultrasonic wave.Therefore, particle size deviation dD1, dD15 or dD50 increase and increase along with the persursor material accumulative, or increase along with reducing of slurry dispersion stabilization.
Showed among the table 9b hereinafter that multistep is calcined processing procedure and single stage calcining processing procedure suddenly to be applied to become the comparison between the dispersion stabilization of gained respectively of piece cerous carbonate among Fig. 9 b.
Table 3
| dD1(nm) | dD15(nm) | dD50(nm) | |
| |
4 | 3 | 3 |
| |
234 | 110 | 43 |
Based on these data, can measure the degree of scatter of slurry 1 and 2, the result is showed in respectively among Figure 13 a and the 13b.In Figure 13 a,, calcine the prepared slurry of processing procedure 1 no change in secondary slurries particulate particle size distribution suddenly by multistep no matter whether force to disperse by ultrasonic wave.On the contrary, shown in Figure 13 b, forcing to disperse front and back, in secondary slurries particulate particle size distribution, having than big-difference by the prepared slurry 2 of single stage calcining processing procedure.In slurry 2 because the degree of crystallinity difference between persursor material outside and the inside, have than bigger serface than small-particle and larger particles coexistence with less specific surface area, make slurry have bad dispersion stabilization and extensive caking.Therefore, existing pressure to disperse and not existing between the pressure dispersive slurry, have than big-difference in the particle size distribution.
[variation of CMP characteristic]
Hereinafter, make cerium dioxide abrasive grain and slurry with separately predetermined condition from cerium oxide powder by aforesaid method, and analyzed pulp property such as the particle size of each ceria sizing agent for example and dispersion stabilization and for example removed CMP characteristics such as speed, little cut.
At first, the analytical instrument of characteristic is as follows:
1) particle size: the RINT/DMAX-2500 that uses Japanese Rigaku company to make is measured;
2) particle size distribution: the LA-910 that uses Japanese Horiba company to make is measured;
3) TEM: the JEM-2010 that uses Japanese JEOL company limited to make is measured.
Use ceria sizing agent that object is polished as above-mentioned manufacturing, and to assessing about removing speed, little cut quantity and removing selectivity.The 6EC that uses U.S. Strasbaugh company to make carries out the test of CMP polishing performance.Will be on it apply PE-TEOS (plasma fortified chemical vapour deposition TEOS oxide compound) on its whole surface, to form 8 of oxide film " wafer with and go up and apply Si
3N
4With on its whole surface, form nitride film another 8 " wafer is used for the test of CMP polishing performance.Employed test condition and material are as follows:
1) liner: IC1000/SUBAIV (available from U.S. Rodel company);
2) film thickness measuring apparatus: Nano-Spec 180 (available from U.S. Nano-metrics company);
3) table speed: 70rpm
4) speed of mainshaft: 70rpm
5) overdraft: 4psi
6) back pressure: 0psi
7) slurry supply: 100ml/min
8) measurement of residual particles and cut: the SurfscanSP1 that uses U.S. KLA-Tencor company to make measures.
Use ceria sizing agent to being formed with oxide film (PE-TEOS) or nitride film (Si on the whole surface
3N
4) polishing wafer 1 minute, determine to remove speed according to the variation in thickness of polishing rear film subsequently, and use Surfscan SP1 to measure little cut.Test the polishing performance of each slurry in this way, thereby measure the polishing feature in the back more than three times or three times double product wafer polishing.
[ceria sizing agent 1 to 3: depend on the comparison of the characteristic of persursor material particle size]
(1) preparation of cerium dioxide abrasive grain 1 to 3
In high purity cerium oxide powder 1 to 3 (corresponding respectively to persursor material 1 to 3) each container of packing into, the amount of cerium oxide powder is 800g separately, and calcines 4 hours down in 800 ℃ in continuous tunnel furnace (tunnel kiln).Cerium oxide powder 1 to 3 has the characteristic identical with the given persursor material of table 11 to 3 respectively.All cerium oxide powder 1 is made by cerous carbonate to 3, and presents more and more littler particle size distribution.Carry out calcining with 5 ℃/minute temperature increase rates.Reach after the top temperature, make the cerium oxide powder cooling.Make gas with 20m
3/ hour speed on the direction opposite, flow with saggar (saggar) direction of motion, thereby remove CO effectively
2By product.When analyzing, find that through incinerating cerium oxide powder 1 to 3 like this be high purity cerium dioxide (cerium oxide) abrasive grain 1 to 3 by X-ray diffractometer.
(2) preparation of ceria sizing agent 1 to 3
In super mixer (mixer), to mix 1 hour from cerium oxide powder 1 to 3 synthesis of high purity cerium dioxide abrasive grain, 1 to 3 each 10kg and with the deionized water of 90kg respectively subject to the foregoing or the longer time, thereby realize fully moistening, after this use channel-type to grind processing procedure and each slurry of 10% of acquisition like this ground, its be intended to particle size be controlled at want in the scope and the one-tenth piece particle of dispersed paste.Subsequently, in the weight of cerium oxide powder, add the ammonium polymethacrylate of 1wt%, it serves as anionic dispersing agents.Owing to consider absorption,, then filter to prepare ceria sizing agent 1 to 3 so make lasting 2 hours of mixing or longer time to disperse this slurry.
(3) comparison of ceria sizing agent 1 to 3
To analyzing from high purity cerium dioxide abrasive grain 1 to 3 prepared ceria sizing agent 1 to 3 respectively, the result shows the persursor material cerous carbonate, it is cerium oxide powder, extensively caking, and bigger particle size causes forming in the cerium dioxide abrasive grain particle of more unusual expansion.
(4) CMP test result
The CMP polishing performance of the ceria sizing agent 1 to 3 of test as above-mentioned preparation.
Table 4
Use carry out the CMP test under identical CMP condition, and the result provides in table 4 above from the prepared ceria sizing agent 1 to 3 of cerium oxide powder 1 to 3 (the persursor material cerous carbonate that promptly has varying particle size).
From the data of table 4 as can be known, show greater than the ceria sizing agent 1 of the persursor material preparation of 350 μ m from D1 to remove speed more greatly, but produce significantly more residual oxide membrane granule, therefore compare and produce more cut with ceria sizing agent 2 or 3.Its former because: along with the increase of cerous carbonate particle size, particle size also increases, and this causes being formed on the larger particles that causes little cut in the polishing processing procedure.On the other hand, the less D1 of persursor material can reduce the quantity of oxide film residual particles and little cut, removes speed, the polishing performance of having degenerated but reduced.
The D50 that surpasses 100 μ m has the higher speed that removes, but produces a large amount of oxide film residual particles and by cut that these particles caused.Mean the particle that has more than 50% greater than 100 μ m because surpass the D50 of 100 μ m, therefore form a large amount of larger particles, cause proportional little cut with it.On the other hand, if the D50 of persursor material is less, then removing speed can reduce, and causes bad polishing performance.
As described above, the quantity that removes speed and oxide film residual particles and cut is very important factor in the superelevation integrated semiconductor manufacturing processed, and it depends on the particle size of persursor material.
Compare with Comparative Example, show the excellent speed that removes from the prepared ceria sizing agent 2 or 3 of persursor material cerous carbonate that particle size is suitably controlled, simultaneous oxidation thing film residual particles and little cut remain in remarkable lower level.
Therefore, by providing D1 between 10 and 350 μ m and the persursor material of D50 between 4 and 100 μ m, can obtain the excellent rate that removes, polishing selectivity or remove speed and the least possible cut.The D1 of persursor material is better between 20 and 200 μ m, and D50 is better between 5 and 40 μ m.
[ceria sizing agent 4 and 5: depend on the comparison of the characteristic of calcination condition]
(1) cerium dioxide abrasive grain 4 and 5 preparation
With high purity carbonic acid cerium powder 4 and 5 (all corresponding to Fig. 9 b become the piece persursor material) each container of packing into, wherein the amount of cerium oxide powder is 800g separately.At first, cerium carbonate powder 4 is calcined twice in continuous tunnel furnace, calcined 4 hours down at 750 ℃ at first, secondly under 650 ℃, calcined again 4 hours, carry out therebetween and pulverize.On the other hand, cerium carbonate powder 5 is calcined 4 hours once at 780 ℃.Under these two kinds of situations, advance the speed with 5 ℃/minute temperature and to carry out calcining.After reaching top temperature, make the cerium carbonate powder cooling.Make gas with 20m
3/ hour speed on the direction opposite, flow with saggar direction of motion, thereby remove CO effectively
2By product.Find that through incinerating cerium oxide powder like this be high purity cerium dioxide (cerium oxide) abrasive grain 4 and 5 that average particle size particle size is respectively 29.8nm and 29.6nm, as analyzing by X-ray diffractometer.
(2) ceria sizing agent 4 and 5 preparation
Use super mixer, will be subject to the foregoing respectively will from cerium oxide powder 4 and 5 synthetic high purity cerium dioxide abrasive grains 4 and 5 each 10kg mix 1 hour with deionized water with 90kg or the longer time, thereby realize fully moistening, after this use channel-type to grind processing procedure each slurry of 10% of acquisition like this is ground, and be controlled at particle size in the desired scope and the one-tenth piece particle of dispersed paste.Subsequently, in the weight of cerium oxide powder, add the ammonium polymethacrylate of 1wt%, it can be used as anionic dispersing agents.Consider its absorption, make lasting 2 hours of mixing or longer time, then filter with preparation ceria sizing agent 4 and 5 to disperse this slurry.
(3) ceria sizing agent 4 and 5 comparison
As being easy to understand from table 2 and Figure 12, to respectively from prepared ceria sizing agent 4 of high purity cerium dioxide abrasive grain 4 and 5 and 5 analysis revealed, ceria sizing agent 4 no change almost in the particle size before and after grinding, and ceria sizing agent 5 particle size after grinding sharply reduces.Its reason is: because the presoma cerous carbonate extensively lumps, so the presoma cerous carbonate inside of ceria sizing agent 5 and the particle size distribution between the outside have than big-difference, thereby form outside larger particles, and inside incinerating situation fully.
In addition, use light scattering method to analyze the dispersion stabilization of ceria sizing agent 4 and 5 by grain size analysis instrument (LA-910 that Horiba makes).Shown in Figure 13 a, no matter whether carry out to force to disperse, the experience multistep is calcined ceria sizing agent 4 no change in secondary slurries particulate particle size distribution of processing procedure suddenly.On the contrary, shown in Figure 13 b, forcing to disperse front and back in secondary slurries particulate particle size distribution, to have than big-difference by the ceria sizing agent 5 of single stage calcining processing procedure preparation.In ceria sizing agent 4, less internal particle and big external particle coexistence make slurry have bad dispersion stabilization and extensive caking.
(4) CMP test result
Test as above-mentioned prepared ceria sizing agent 4 and 5 CMP polishing performance.
Table 5
The data of table 5 and Figure 14 show: calcine the prepared slurry of processing procedure 4 suddenly by multistep and have full and uniform degree of crystallinity, thereby can two-forty remove oxide film, and owing to becoming the incomplete calcining in the piece cerous carbonate to make slurry 5 have bad degree of crystallinity and bad oxide removal rate.In addition, for the electrical nitride film of the tensio-active agent of absorption q.s on it, it removes speed between slurry 4 and slurry 5 and indifference, thereby use slurry 4 can obtain the preferable selectivity that removes.
The degree of agglomeration of slurry 4 is obviously less, and in other words, the dispersive degree is bigger, thereby compares with slurry 5, and slurry 4 can be realized better Flatness when polishing wafer; And since the caking of slurry 5 and larger particles all more than slurry 4, so slurry 5 obviously can produce more oxide compound residual particles and little cut.
Therefore, using multistep calcines processing procedure suddenly and can realize the excellent rate that removes, polishing selectivity effectively or remove speed and minimum little cut quantity.In other words, by calcine the persursor material of cerium dioxide abrasive grain in the rapid mode of multistep, can be easy to obtain desired pulp property.
Therefore, the present invention is controlled in the pre-determined range by the particle size with the ceria sizing agent persursor material, makes ceria sizing agent can have good speed and the selectivity of removing, and has and do not cause little cut or make the minimized ability of little cut quantity.Thereby, can be easy to obtain desired pulp property by control the calcining processing procedure in the rapid mode of multistep.
As indicated above, can make polishing slurries according to the present invention with various good characteristics, these characteristics are to be used for the necessary characteristic of STI CMP abrasive material that semi-conductor is made.Specifically, when using polishing slurries of the present invention, what can keep behind CMP that quantity significantly reduces has the cut and the residual particles of fatal influence for semiconductor device.
In addition, the present invention can make a kind of slurry that can keep higher rate of removal to reduce the quantity of the cut that can cause defective simultaneously by carrying out a calcining processing procedure of considering the persursor material characteristic.
And the present invention can make the slurry of the necessary excellent physical characteristic of a kind of STI of having CMP rumbling compound.Thereby, polishing slurries of the present invention can be applicable to various patterns required in the manufacturing processed of superelevation integrated semiconductor, thereby can guarantee excellent to remove speed, remove heterogeneity (WIWNU) in selectivity and the wafer, its expression removes homogeneity and can minimizing little cut.
The above, it only is preferred embodiment of the present invention, be not that the present invention is done any pro forma restriction, though the present invention discloses as above with preferred embodiment, yet be not in order to limit the present invention, any those skilled in the art, in not breaking away from the technical solution of the present invention scope, when the structure that can utilize above-mentioned announcement and technology contents are made a little change or be modified to the equivalent embodiment of equivalent variations, but every content that does not break away from technical solution of the present invention, according to technical spirit of the present invention to any simple modification that above embodiment did, equivalent variations and modification all still belong in the scope of technical solution of the present invention.
Claims (9)
1. method of making the slurry abrasive grain is characterized in that comprising:
The preparation persursor material; And
So that two or more stages are calcined described persursor material at least.
2. according to the method for the described manufacturing slurry of claim 1 abrasive grain, it is characterized in that described incinerating step comprises:
At first calcine described persursor material;
Pulverize or pulverize described through incinerating persursor material at first to produce less secondary persursor material; And
Next calcines described secondary persursor material.
3. according to the method for the described manufacturing slurry of claim 2 abrasive grain, it is characterized in that further comprising:
Pulverize or pulverize described secondly incinerating persursor material to form third stage persursor material; And
The described third stage persursor material of third firing.
4. according to the method for the described manufacturing slurry of claim 1 abrasive grain, it is characterized in that described calcining step is to carry out under 500 to 1000 ℃ temperature.
5. according to the method for the described manufacturing slurry of claim 1 abrasive grain, it is characterized in that described abrasive grain comprises cerium dioxide.
6. according to the method for the described manufacturing slurry of claim 5 abrasive grain, it is characterized in that described persursor material comprises cerous carbonate.
7. method of making polishing slurries is characterized in that comprising:
Method according to each described manufacturing slurry abrasive grain in the claim 1 to 6 prepares described abrasive grain;
In the grinding mixture that comprises deionized water, dispersion agent and additive, grind described abrasive grain; And
Filter described grinding mixture with from wherein removing larger particles.
8. abrasive grain according to the method manufacturing of each described manufacturing slurry abrasive grain in the claim 1 to 6.
9. the polishing slurries of the method manufacturing of a manufacturing polishing slurries according to claim 7.
Applications Claiming Priority (6)
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| KR1020040107276 | 2004-12-16 | ||
| KR10-2004-0107276 | 2004-12-16 | ||
| KR1020040107276A KR101082620B1 (en) | 2004-12-16 | 2004-12-16 | Slurry for polishing |
| KR1020050063665A KR100637403B1 (en) | 2005-07-14 | 2005-07-14 | Abrasive particles, slurry for polishing and method of manufacturing the same |
| KR10-2005-0063665 | 2005-07-14 | ||
| KR1020050063665 | 2005-07-14 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103468149A (en) * | 2013-09-18 | 2013-12-25 | 苏州市博飞光学有限公司 | Chlorinated rare earth polishing powder and production method thereof |
| CN104673098A (en) * | 2013-11-28 | 2015-06-03 | 安阳工学院 | Preparation technique of cerium-oxide-base rare-earth polishing powder |
| CN112680115A (en) * | 2021-01-04 | 2021-04-20 | 上海晖研材料科技有限公司 | Application of cerium oxide particles in polishing process |
| CN112723405A (en) * | 2021-01-04 | 2021-04-30 | 上海晖研材料科技有限公司 | Cerium oxide particle and polishing slurry containing same |
| CN112724836A (en) * | 2020-12-24 | 2021-04-30 | 德米特（苏州）电子环保材料有限公司 | Cerium-zirconium-doped polishing solution and preparation method and application thereof |
| CN112758974A (en) * | 2021-01-04 | 2021-05-07 | 上海晖研材料科技有限公司 | Preparation method of cerium oxide particles |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101909816B (en) * | 2008-10-01 | 2013-01-23 | 旭硝子株式会社 | Polishing slurry, process for producing same, method of polishing, and process for producing glass substrate for magnetic disk |
| CN103011240A (en) * | 2012-12-24 | 2013-04-03 | 赣州虔东稀土集团股份有限公司 | Bulky-grain rare earth carbonate and preparation method and application of carbonate |
| KR102632104B1 (en) * | 2017-11-30 | 2024-02-02 | 솔브레인 주식회사 | Slurry composition for polishing, method for producing the same and method for polishing semiconductor thin film by using the same |
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| KR100622519B1 (en) * | 1996-09-30 | 2006-09-11 | 히다치 가세고교 가부시끼가이샤 | A Cerium Oxide Particle |
| EP1610367B1 (en) * | 1996-09-30 | 2010-03-17 | Hitachi Chemical Co., Ltd. | Cerium oxide abrasive and method of polishing substrates |
| JPH11181407A (en) * | 1997-12-18 | 1999-07-06 | Hitachi Chem Co Ltd | Cerium oxide abrasive and grinding of substrate |
| JPH11181403A (en) * | 1997-12-18 | 1999-07-06 | Hitachi Chem Co Ltd | Cerium oxide abrasive and grinding of substrate |
| US6143662A (en) * | 1998-02-18 | 2000-11-07 | Rodel Holdings, Inc. | Chemical mechanical polishing composition and method of polishing a substrate |
| KR100417529B1 (en) * | 2001-04-09 | 2004-02-05 | (주)케이.씨.텍 | Synthesis of nano size Cerium Oxide by Glycothermal Processing |
| JP2004289170A (en) * | 2004-05-10 | 2004-10-14 | Hitachi Chem Co Ltd | Cerium oxide polishing agent and method of polishing substrate |
| JP2004250714A (en) * | 2004-05-17 | 2004-09-09 | Hitachi Chem Co Ltd | Cerium oxide abrasive and method for grinding substrate |
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| CN103468149A (en) * | 2013-09-18 | 2013-12-25 | 苏州市博飞光学有限公司 | Chlorinated rare earth polishing powder and production method thereof |
| CN104673098A (en) * | 2013-11-28 | 2015-06-03 | 安阳工学院 | Preparation technique of cerium-oxide-base rare-earth polishing powder |
| CN104673098B (en) * | 2013-11-28 | 2017-01-18 | 安阳工学院 | Preparation technique of cerium-oxide-base rare-earth polishing powder |
| CN112724836A (en) * | 2020-12-24 | 2021-04-30 | 德米特（苏州）电子环保材料有限公司 | Cerium-zirconium-doped polishing solution and preparation method and application thereof |
| CN112724836B (en) * | 2020-12-24 | 2022-03-29 | 德米特（苏州）电子环保材料有限公司 | Cerium-zirconium-doped polishing solution and preparation method and application thereof |
| CN112680115A (en) * | 2021-01-04 | 2021-04-20 | 上海晖研材料科技有限公司 | Application of cerium oxide particles in polishing process |
| CN112723405A (en) * | 2021-01-04 | 2021-04-30 | 上海晖研材料科技有限公司 | Cerium oxide particle and polishing slurry containing same |
| CN112758974A (en) * | 2021-01-04 | 2021-05-07 | 上海晖研材料科技有限公司 | Preparation method of cerium oxide particles |
Also Published As
| Publication number | Publication date |
|---|---|
| KR101082620B1 (en) | 2011-11-15 |
| KR20060068556A (en) | 2006-06-21 |
| CN1818002A (en) | 2006-08-16 |
| CN101255286B (en) | 2011-09-14 |
| CN1818002B (en) | 2013-04-10 |
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