JP5993323B2 - Polishing material - Google Patents
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- JP5993323B2 JP5993323B2 JP2013040110A JP2013040110A JP5993323B2 JP 5993323 B2 JP5993323 B2 JP 5993323B2 JP 2013040110 A JP2013040110 A JP 2013040110A JP 2013040110 A JP2013040110 A JP 2013040110A JP 5993323 B2 JP5993323 B2 JP 5993323B2
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- 238000005498 polishing Methods 0.000 title claims description 135
- 239000000463 material Substances 0.000 title claims description 52
- 239000002245 particle Substances 0.000 claims description 121
- 239000002994 raw material Substances 0.000 claims description 36
- 239000003082 abrasive agent Substances 0.000 claims description 34
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 30
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 30
- 239000000203 mixture Substances 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 28
- 239000011163 secondary particle Substances 0.000 claims description 21
- 238000004519 manufacturing process Methods 0.000 claims description 19
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 18
- 239000010436 fluorite Substances 0.000 claims description 18
- 238000005118 spray pyrolysis Methods 0.000 claims description 14
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- 238000012216 screening Methods 0.000 claims description 8
- 238000003786 synthesis reaction Methods 0.000 claims description 8
- 229910052726 zirconium Inorganic materials 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- 229910052712 strontium Inorganic materials 0.000 claims description 7
- 230000002194 synthesizing effect Effects 0.000 claims description 6
- 238000013329 compounding Methods 0.000 claims description 3
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 claims description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 239000011164 primary particle Substances 0.000 description 19
- 239000000523 sample Substances 0.000 description 14
- 239000011521 glass Substances 0.000 description 13
- 239000000919 ceramic Substances 0.000 description 12
- 239000000843 powder Substances 0.000 description 12
- 239000002002 slurry Substances 0.000 description 12
- 239000000126 substance Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 239000006061 abrasive grain Substances 0.000 description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 230000009471 action Effects 0.000 description 5
- 239000002609 medium Substances 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 229910000420 cerium oxide Inorganic materials 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000002270 dispersing agent Substances 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 4
- 230000003746 surface roughness Effects 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- 239000012736 aqueous medium Substances 0.000 description 3
- 238000009499 grossing Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000011246 composite particle Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 229910004261 CaF 2 Inorganic materials 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 241000414697 Tegra Species 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 229920003086 cellulose ether Polymers 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000013068 control sample Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000009837 dry grinding Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- -1 hexametaphosphate Chemical compound 0.000 description 1
- 229940005740 hexametaphosphate Drugs 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 229910052713 technetium Inorganic materials 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 238000001238 wet grinding Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 239000002888 zwitterionic surfactant Substances 0.000 description 1
Landscapes
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
Description
本明細書は、研磨材料、研磨用組成物、研磨方法及び研磨材料の製造方法に関する。 The present specification relates to a polishing material, a polishing composition, a polishing method, and a manufacturing method of the polishing material.
現在、電子デバイスや半導体デバイスにおけるガラス、セラミックス、金属など各種材料の研磨、特に精密研磨に用いる砥粒（研磨材料）としては、セリアを含む研磨材料が用いられている。セリアは、研磨において、化学作用性及び機械作用性を併せ持つ。こうした研磨材料として、セリア以外に、ペロブスカイト型酸化物からなる研磨材料（特許文献１）、セリウム及びジルコニウムを含む研磨材料（特許文献２）、酸化セリウム、酸化ジルコニウム及び酸化ケイ素からなる研磨材料（特許文献３）、酸化セリウム、ランタン、アルカリ土類金属、及びジルコニウムを含む研磨材料（特許文献４）が知られている。 At present, polishing materials containing ceria are used as abrasive grains (polishing materials) used for polishing various materials such as glass, ceramics, and metals in electronic devices and semiconductor devices, particularly for precision polishing. Ceria has both chemical action and mechanical action in polishing. As such an abrasive material, in addition to ceria, an abrasive material composed of a perovskite oxide (Patent Document 1), an abrasive material containing cerium and zirconium (Patent Document 2), an abrasive material composed of cerium oxide, zirconium oxide and silicon oxide (patent Literature 3), an abrasive material (Patent Literature 4) containing cerium oxide, lanthanum, alkaline earth metal, and zirconium is known.
さらに、特定の鉄系ペロブスカイト型酸化物がセリアに替わる新たな研磨材料として開示されている（特許文献５）。 Furthermore, a specific iron-based perovskite oxide has been disclosed as a new polishing material replacing ceria (Patent Document 5).
しかしながら、特許文献１の研磨材料は、研磨速度が低いという問題がある。また、特許文献２〜４に係る製造方法によっては、ジルコニウム又は酸化ジルコニウムがセリア中に固溶、もしくはセリウム又は酸化セリウムが酸化ジルコニウム中に固溶するために、材料設計が複雑になり、研磨材料の化学作用性及び機械作用性を制御することは困難である。また、特許文献５に開示される研磨材料も更なる研磨速度の向上が求められていた。 However, the polishing material of Patent Document 1 has a problem that the polishing rate is low. Further, depending on the manufacturing method according to Patent Documents 2 to 4, since zirconium or zirconium oxide is dissolved in ceria, or cerium or cerium oxide is dissolved in zirconium oxide, the material design becomes complicated, and the polishing material It is difficult to control the chemical and mechanical properties of Further, the polishing material disclosed in Patent Document 5 has been required to further improve the polishing rate.
本明細書は、化学作用性及び機械作用性のバランスに優れた研磨材料を提供することを１つの目的とし、表面平滑性能や研磨速度に優れた研磨材料を提供することを他の１つの目的とする。 One object of the present specification is to provide an abrasive material excellent in balance between chemical action and mechanical action, and another object is to provide an abrasive material excellent in surface smoothing performance and polishing rate. And
本発明者らは、上記した課題を解決するため、ペロブスカイト型酸化物を含む相と蛍石型酸化物を含む相とを含む粒子を含む研磨材料を作製し、当該研磨材料が高い研磨速度及び表面平滑性を有することを見出し、化学作用性及び機械作用性のバランスに優れることを見出した。即ち、本明細書によれば以下の手段が提供される。 In order to solve the above-described problems, the present inventors have produced a polishing material containing particles containing a phase containing a perovskite oxide and a phase containing a fluorite oxide, and the polishing material has a high polishing rate and It has been found that it has surface smoothness and has an excellent balance between chemical activity and mechanical activity. That is, according to the present specification, the following means are provided.
（１）少なくともストロンチウム（Ｓｒ）及びジルコニウム（Ｚｒ）を含むペロブスカイト型酸化物を含む第１の相と、少なくともセリア（ＣｅＯ２）を含む蛍石型酸化物を含む第２の相とを含む、粒子を含む研磨材料。
（２）前記ペロブスカイト型酸化物は、ＳｒＺｒＯ３であり、前記蛍石型酸化物は、ＣｅＯ２である、（１）に記載の研磨材料。
（３）ＳｒＺｒＯ３とＣｅＯ２とのモル比がｘ：（１０−ｘ）（ただし、１≦ｘ≦９）である、（１）又は（２）に記載の研磨材料。
（４）前記粒子は、前記第１の相における前記ペロブスカイト型酸化物を含む第１の粒子と、前記第２の相における前記蛍石型酸化物を含む第２の粒子と、が複合化した二次粒子である、（１）〜（３）のいずれかに記載の研磨材料。
（５）前記二次粒子の平均粒子径が０．５μｍ以上３μｍ以下であり、前記二次粒子の平均粒子径は、走査型電子顕微鏡で前記研磨材料を５０００倍に拡大した画像によって測定される、２００個の前記二次粒子それぞれの粒子径の相加平均である、（４）に記載の研磨材料。
（６）前記第１の粒子及び第２の粒子のそれぞれの平均粒子径が１０ｎｍ以上２００ｎｍ以下であり、前記第１の粒子及び第２の粒子の平均粒子径は、走査型電子顕微鏡で前記研磨材料を１０万倍に拡大した画像によって測定される、２００個の第１の粒子及び前記第２の粒子のそれぞれの粒子径の相加平均である、（４）又は（５）に記載の研磨材料。
（７）研磨用組成物であって、（１）〜（６）のいずれかに記載の研磨材料を含有する、組成物。
（８）研磨材料の製造方法であって、少なくともＳｒ及びＺｒを含むペロブスカイト型酸化物の第１の原料と、少なくともＣｅＯ２を含む蛍石型酸化物の第２の原料と、を準備する工程と、前記第１の原料と前記第２の原料とを用いて、前記ペロブスカイト型酸化物を含む第１の粒子と、前記蛍石型酸化物を含む第２の粒子と、が複合化した二次粒子を合成する工程と、を備える製造方法。
（９）前記合成工程は、噴霧熱分解法で実施する、（８）に記載の方法。
（１０）被研磨体の生産方法であって、（７）に記載の研磨用組成物を用いてワークを研磨する工程、を備える、方法。
（１１）研磨材料のスクリーニング方法であって、１種又は２種以上のペロブスカイト型酸化物の原料と、セリア（ＣｅＯ２）の原料とを含む原料液を準備する工程と、前記原料液から前記ペロブスカイト型酸化物と前記セリアを合成する条件下で、前記ペロブスカイト型酸化物相とセリア相とをそれぞれ含む粒子の合成を評価する工程と、
を備え、セリアとの複合化に適したペロブスカイト型酸化物をスクリーニングする、方法。
(1) including a first phase including a perovskite oxide including at least strontium (Sr) and zirconium (Zr), and a second phase including a fluorite oxide including at least ceria (CeO 2 ). Abrasive material containing particles.
(2) The polishing material according to (1), wherein the perovskite oxide is SrZrO 3 and the fluorite oxide is CeO 2 .
(3) The polishing material according to (1) or (2), wherein the molar ratio of SrZrO 3 and CeO 2 is x: (10−x) (where 1 ≦ x ≦ 9).
(4) The particle is a composite of the first particle containing the perovskite oxide in the first phase and the second particle containing the fluorite oxide in the second phase. The polishing material according to any one of (1) to (3), which is a secondary particle.
(5) The average particle diameter of the secondary particles is 0.5 μm or more and 3 μm or less, and the average particle diameter of the secondary particles is measured by an image obtained by enlarging the polishing material 5000 times with a scanning electron microscope. The polishing material according to (4), which is an arithmetic average of the particle diameters of the 200 secondary particles.
(6) The average particle diameter of each of the first particles and the second particles is 10 nm or more and 200 nm or less, and the average particle diameter of the first particles and the second particles is determined by the polishing using a scanning electron microscope. The polishing according to (4) or (5), which is an arithmetic average of the particle diameters of 200 first particles and the second particles measured by an image obtained by magnifying the material at a magnification of 100,000 times material.
(7) A polishing composition comprising the polishing material according to any one of (1) to (6).
(8) A method for producing a polishing material, comprising preparing a first raw material of a perovskite oxide containing at least Sr and Zr and a second raw material of a fluorite oxide containing at least CeO 2 And a first particle containing the perovskite oxide and a second particle containing the fluorite oxide are combined using the first raw material and the second raw material. A step of synthesizing the secondary particles.
(9) The method according to (8), wherein the synthesis step is performed by a spray pyrolysis method.
(10) A method for producing an object to be polished, comprising the step of polishing a workpiece using the polishing composition according to (7).
(11) A method for screening an abrasive material, the step of preparing a raw material liquid containing a raw material of one or more perovskite oxides and a raw material of ceria (CeO 2 ); A step of evaluating synthesis of particles each containing the perovskite type oxide phase and the ceria phase under conditions for synthesizing the perovskite type oxide and the ceria;
And a method for screening a perovskite oxide suitable for compounding with ceria.
本明細書の開示は、研磨材料、研磨用組成物、研磨材料の製造方法、及び研磨方法に関する。本明細書に開示される研磨材料は、ペロブスカイト型酸化物を含む第１の相と蛍石型酸化物を含む第２の相とを含む粒子であり、研磨速度及び表面平滑性に優れている。これは、化学作用性と機械作用性とのバランスがよいことに基づいている。本明細書の開示を拘束するものではないが、ペロブスカイト型酸化物が蛍石型酸化物に固溶するのではなく、これらがそれぞれ個別の結晶として複合化されており、セリアの持つ化学機械研磨性にペロブスカイト酸化物の持つ化学研磨性がさらに付与されることによって、研磨特性が向上したものと考えられる。さらに、セリアの使用量を低減することができる。 The present disclosure relates to an abrasive material, an abrasive composition, a method for producing an abrasive material, and an abrasive method. The polishing material disclosed in the present specification is a particle containing a first phase containing a perovskite oxide and a second phase containing a fluorite oxide, and is excellent in polishing rate and surface smoothness. . This is based on the good balance between chemical activity and mechanical activity. Although it does not constrain the disclosure of this specification, the perovskite oxide is not dissolved in the fluorite oxide, but these are compounded as individual crystals, and the chemical mechanical polishing possessed by ceria It is considered that the polishing characteristics are improved by further imparting the chemical polishing property of the perovskite oxide to the properties. Furthermore, the amount of ceria used can be reduced.
なお、研磨材料は、通常２種の成分を併存させると、それぞれ単独の成分による研磨性能と同等、もしくはより低い研磨性能しか発揮しないのが通例である。本明細書の開示によれば、特定の酸化物を有する第１の相と第２の相とを含む粒子とすることで、２種の酸化物のそれぞれの効果を相乗的に発揮させることができる。 In general, when two kinds of components are present together, the polishing material usually exhibits polishing performance equivalent to or lower than that of each single component. According to the disclosure of the present specification, the effects of the two kinds of oxides can be exhibited synergistically by forming particles including the first phase and the second phase having a specific oxide. it can.
また、本明細書に開示される研磨材料を用いることで、研磨特性に優れた研磨用組成物が提供される。こうした研磨用組成物を用いることで、安定的にかつ効率的に研磨工程を実施できる研磨方法や研磨製品の生産方法も提供される。さらに、本明細書の開示によれば、当該研磨材料の製造方法も提供される。 Further, by using the polishing material disclosed in this specification, a polishing composition having excellent polishing characteristics is provided. By using such a polishing composition, a polishing method capable of stably and efficiently performing a polishing step and a method for producing a polished product are also provided. Further, according to the disclosure of the present specification, a method for manufacturing the abrasive material is also provided.
以下、本明細書の開示の実施形態について詳細に説明する。 Hereinafter, embodiments of the present disclosure will be described in detail.
（研磨材料）
本明細書に開示される研磨材料（以下、単に本研磨材料という。）は、ペロブスカイト型酸化物を含む第１の相と蛍石型酸化物を含む第２の相とが複合化された粒子（以下、単に本粒子ともいう。）を含んでいる。こうした粒子は、研磨速度及び／又は表面平滑性能に優れており、結果として、化学研磨性能と機械研磨性能とに優れた研磨材料を提供できる。本研磨材料は、こうした本粒子を主体とするが、複合化されていない、第１の相からなる粒子（第１の粒子）や第２の相からなる粒子（第２の粒子）を含んでいてもよい。
(Abrasive material)
The abrasive material disclosed herein (hereinafter simply referred to as the abrasive material) is a particle in which a first phase containing a perovskite oxide and a second phase containing a fluorite oxide are combined. (Hereinafter also simply referred to as the present particles). Such particles are excellent in polishing rate and / or surface smoothing performance, and as a result, an abrasive material excellent in chemical polishing performance and mechanical polishing performance can be provided. The present abrasive material mainly comprises such main particles but is not complexed and includes particles composed of the first phase (first particles) and particles composed of the second phase (second particles). May be.
本粒子の典型形態は、第１の相からなる第１の粒子と第２の相からなる第２の粒子を一次粒子とする二次粒子の形態である。 A typical form of the present particles is a form of secondary particles in which the first particles composed of the first phase and the second particles composed of the second phase are primary particles.
（本粒子）
本粒子は、ペロブスカイト型酸化物を含む第１の相と蛍石型酸化物を含む第２の相を含み、粒子を構成している。
(This particle)
The present particle includes a first phase containing a perovskite oxide and a second phase containing a fluorite oxide to form a particle.
（第１の相）
第１の相は、ペロブスカイト型酸化物を含んでいる。ペロブスカイト型酸化物は、少なくともＳｒ及びＺｒを含んでいる。このようなペロブスカイト型酸化物として、ＳｒＺｒＯ３が好ましく用いられる。
(First phase)
The first phase contains a perovskite oxide. The perovskite oxide contains at least Sr and Zr. As such a perovskite oxide, SrZrO 3 is preferably used.
ペロブスカイト型酸化物は、Ｓｒ及びＺｒ以外の元素として、例えば、Ｙ、Ｎｂ、Ｍｏ、Ｔｃ、Ｒｕ、Ｒｈ、Ｐｄ、Ａｇ、Ｃｄ等を含んでいてもよい。これらの元素は、Ｚｒと同様に、４ｄ遷移元素である。また、ＳｒＺｒＯ３以外のペロブスカイト型酸化物（例えばＣａＴｉＯ３等）を含んでいてもよい。ペロブスカイト型酸化物は、ＳｒＺｒＯ３を主体とすることが好ましく、より好ましくは、ＳｒＺｒＯ３からなる（９９．９質量％以上）ことが好ましい。 The perovskite oxide may contain, for example, Y, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, etc. as elements other than Sr and Zr. These elements are 4d transition elements like Zr. Moreover, perovskite type oxides (for example, CaTiO 3 etc.) other than SrZrO 3 may be included. The perovskite oxide is preferably mainly composed of SrZrO 3 , more preferably composed of SrZrO 3 (99.9% by mass or more).
蛍石型酸化物は、ＣｅＯ２以外の蛍石型酸化物として、例えば、ＺｒＯ２、（ＺｒＯ２）１−ｙ（Ｙ２Ｏ３）ｙ、（ＺｒＯ２）１−ｙ（ＣａＯ）ｙ、ＣａＦ２を含んでいてもよい（ただし、０＜ｙ＜１）。蛍光型酸化物は、ＣｅＯ２を主体とすることが好ましく、より好ましくは、ＣｅＯ２からなる（９９．９質量％以上）ことが好ましい。 The fluorite-type oxide is, for example, ZrO 2 , (ZrO 2 ) 1-y (Y 2 O 3 ) y , (ZrO 2 ) 1-y (CaO) y , as fluorite-type oxides other than CeO 2 . CaF 2 may be included (however, 0 <y <1). The fluorescent oxide is preferably mainly composed of CeO 2 , more preferably CeO 2 (99.9% by mass or more).
粒子の外形形態は特に限定しないで、各種形態を採ることができるが、好ましくは球状である。球状であると、研磨傷の発生を抑制できるからである。粒子は、外皮形状であってもよいが、好ましくは中実状である。中実状であることにより、研磨材料として要求される砥粒の硬度を確保しやすくなり、研磨によって構成する一次粒子の脱落が生じても継続的に研磨作用を発揮しやすくなる。 The external form of the particles is not particularly limited and can take various forms, but is preferably spherical. This is because the occurrence of polishing scratches can be suppressed when the shape is spherical. The particles may be in the form of a skin, but are preferably solid. By being solid, it becomes easy to ensure the hardness of the abrasive grains required as a polishing material, and even if the primary particles constituted by polishing fall off, it becomes easy to exert the polishing action continuously.
（粒子の平均粒子径）
粒子の平均粒子径は、０．５μｍ以上３μｍ以下であることが好ましく、さらに好ましくは０．５μｍ以上１．５μｍ以下である。粒子の平均粒子径が０．５μｍ未満であると、研磨速度が低くなる可能性があり、３μｍを超えると、研磨傷の原因となり、表面平滑性が低下するおそれがある。粒子の平均粒子径は、個数換算であり、具体的には以下の手順で算出される。
(Average particle diameter of particles)
The average particle diameter of the particles is preferably 0.5 μm or more and 3 μm or less, and more preferably 0.5 μm or more and 1.5 μm or less. If the average particle size of the particles is less than 0.5 μm, the polishing rate may be lowered, and if it exceeds 3 μm, it may cause polishing scratches and the surface smoothness may be reduced. The average particle diameter of the particles is converted into the number, and specifically, is calculated by the following procedure.
走査型電子顕微鏡によって、粒子の表面を５０００倍に拡大し、例えば写真などの画像を取得する。該画像上で目視可能な２００個の粒子の粒子径を測定する。これらの粒子径の相加平均が粒子の平均粒子径である。本粒子の粒子径は、本粒子の画像上の形態が円形又は球形）であるときには、画像で確認できる最大直径とし、円形等以外の場合には、画像で確認できる最大差し渡し径とする。なお、粒子の平均粒子径は、走査型顕微鏡による方法と同等の正確性と精度を確保できるのであれば、レーザ回折方式の粒度分布測定装置、沈降式粒度分布計を使用して求めることもできる。 The surface of the particles is magnified 5000 times by a scanning electron microscope, and an image such as a photograph is acquired. The particle size of 200 particles visible on the image is measured. The arithmetic average of these particle sizes is the average particle size of the particles. The particle diameter of the present particles is the maximum diameter that can be confirmed by the image when the shape of the image of the present particle on the image is circular or spherical, and is the maximum diameter that can be confirmed by the image otherwise. The average particle size of the particles can also be determined using a laser diffraction type particle size distribution measuring device and a sedimentation type particle size distribution meter, as long as the accuracy and accuracy equivalent to the method using a scanning microscope can be ensured. .
（一次粒子の平均粒子径）
本粒子が、第１の粒子と第２の粒子とを含む二次粒子であるとき、第１の粒子及び第２の粒子の平均粒子径は、１０ｎｍ以上２００ｎｍ以下であることが好ましい。平均一次粒子径が１０ｎｍ未満であると、研磨速度が低くなる可能性があり、２００ｎｍを超えると、第１の粒子と第２の粒子が独立に研磨に作用し、複合効果が得られなくなるおそれがある。さらに好ましくは３０ｎｍ以上１００ｎｍ以下である。なお、ここでいう一次粒子の平均粒子径は、個数換算であり、具体的には以下の手順で算出される。また、一次粒子径の算出の場合には、第１の粒子であるか第２の粒子であるかを区別しないで算出するものとする。
(Average particle size of primary particles)
When the present particles are secondary particles including the first particles and the second particles, the average particle diameter of the first particles and the second particles is preferably 10 nm or more and 200 nm or less. If the average primary particle size is less than 10 nm, the polishing rate may be low. If the average primary particle size is more than 200 nm, the first particles and the second particles may independently act on the polishing and the composite effect may not be obtained. There is. More preferably, it is 30 nm or more and 100 nm or less. In addition, the average particle diameter of a primary particle here is conversion in number, and is specifically calculated in the following procedures. In the case of calculating the primary particle diameter, it is calculated without distinguishing whether the particle is the first particle or the second particle.
走査型電子顕微鏡によって、一次粒子の表面を１０万倍に拡大し、例えば写真などの画像を取得する。該画像上で目視可能な２００個の一次粒子の粒子径を測定する。これらの一次粒子の粒子径の相加平均が一次粒子の平均粒子径である。一次粒子の粒子径は、一次粒子の画像上の形態が円形又は球形であるときには、画像で確認できる最大直径とし、円形等以外の場合には、画像で確認できる最大差し渡し径とする。 The surface of the primary particles is magnified 100,000 times by a scanning electron microscope, and an image such as a photograph is acquired. The particle size of 200 primary particles visible on the image is measured. The arithmetic average of the particle diameters of these primary particles is the average particle diameter of the primary particles. The particle diameter of the primary particles is the maximum diameter that can be confirmed by the image when the form of the primary particles on the image is a circle or a sphere, and the particle diameter that can be confirmed by the image is other than the circle or the like.
本粒子における第１の相と第２の相とのモル比は、ｘ：（１０−ｘ）（０＜ｘ＜１０）は特に限定されないが、好ましくは、ｘは１以上９以下である。この範囲であると、セリアに比較して同等以上の高い表面平滑性能及び／又は研磨速度を得ることができる。より好ましくは、ｘは２以上であり、さらに好ましくはｘは３以上である。また、好ましくは４以上である。また、ｘは好ましくは８以下であり、より好ましくは７以下である。さらに好ましくは６以下であり、一層好ましくは５以下である。 The molar ratio between the first phase and the second phase in the particles is not particularly limited to x: (10−x) (0 <x <10), but preferably x is 1 or more and 9 or less. Within this range, high surface smoothness performance and / or polishing rate equivalent to or higher than that of ceria can be obtained. More preferably, x is 2 or more, and more preferably x is 3 or more. Further, it is preferably 4 or more. Further, x is preferably 8 or less, more preferably 7 or less. More preferably, it is 6 or less, More preferably, it is 5 or less.
本粒子は、公知のセラミックス合成方法で取得することができる。第１の相と第２の相とは、本発明者らによれば、互いに固溶せずに、独立した結晶相を形成できることがわかっている。例えば、第１の相の原料と第２の相の原料とを含む原料液から、共沈法等を用いて合成してもよいし、噴霧熱分解法を用いて合成してもよい。好ましくは、粒子径分布が良好である点、及び球状の二次粒子を得ることができる点において、噴霧熱分解法を用いる。噴霧熱分解法は、原料を含む溶液あるいは分散液を、焼成ガス流が流れる加熱炉に液滴状態で導入し、乾燥、熱分解を経て、合成セラミックス粒子を得ることができる。各種方法で得られた合成セラミックス粉末は、必要に応じて仮焼あるいは解砕されてもよい。 The present particles can be obtained by a known ceramic synthesis method. According to the present inventors, it has been found that the first phase and the second phase can form independent crystal phases without being dissolved in each other. For example, a raw material liquid containing a first phase raw material and a second phase raw material may be synthesized using a coprecipitation method or the like, or may be synthesized using a spray pyrolysis method. Preferably, the spray pyrolysis method is used in that the particle size distribution is good and spherical secondary particles can be obtained. In the spray pyrolysis method, a solution or dispersion containing a raw material is introduced in a droplet state into a heating furnace in which a firing gas flow flows, and dried and pyrolyzed to obtain synthetic ceramic particles. The synthetic ceramic powder obtained by various methods may be calcined or crushed as necessary.
また、本粒子は、公知のセラミックス合成法で独立して合成した第１の粒子と第２の粒子とを、混合、必要に応じて粉砕することで、複合化して二次粒子化することもできる。例えば、メカノケミカル結合法などを用いることができる。 Further, the present particles may be combined into secondary particles by mixing the first particles and the second particles independently synthesized by a known ceramic synthesis method, and pulverizing as necessary. it can. For example, a mechanochemical bonding method or the like can be used.
本研磨材料は、通常、砥粒という形態で用いられ、粉末形態となっている。本研磨材料は、ガラスに好ましく適用でき、光学レンズ用ガラス基板、光ディスクや磁気ディスク用ガラス基板、プラズマディスプレー用ガラス基板、薄膜トランジスタ（ＴＦＴ）型ＬＣＤやねじれネマチック（ＴＮ）型ＬＣＤなどの液晶用ガラス基板、液晶テレビ用カラーフィルター、ＬＳＩフォトマスク用等のガラス基板などの、各種光学、エレクトロニクス関連ガラス材料や一般のガラス製品等の仕上げ研磨に用いられる。 This abrasive material is usually used in the form of abrasive grains and is in powder form. This polishing material can be preferably applied to glass. Glass substrates for optical lenses, glass substrates for optical disks and magnetic disks, glass substrates for plasma displays, thin film transistor (TFT) type LCDs, twisted nematic (TN) type LCDs, etc. It is used for finish polishing of various optical and electronics related glass materials and general glass products such as substrates, color filters for liquid crystal televisions, and glass substrates for LSI photomasks.
本研磨材料は、各種の研磨方法及び研磨対象に適用できる。例えば、従来、セリアが研磨材料として用いられていた研磨方法及び研磨対象に適用できる。例えば、本研磨材料を適用する研磨方法としては、通常の研磨のほか、化学機械研磨が挙げられる。また、本研磨材料を適用する研磨対象（ワーク）は特に限定されないで、ガラス、金属、セラミックス等が挙げられる。 This polishing material can be applied to various polishing methods and polishing objects. For example, the present invention can be applied to a polishing method and a polishing object in which ceria is conventionally used as a polishing material. For example, the polishing method to which the present polishing material is applied includes chemical mechanical polishing in addition to normal polishing. Moreover, the grinding | polishing object (workpiece | work) to which this grinding | polishing material is applied is not specifically limited, Glass, a metal, ceramics, etc. are mentioned.
（研磨材料の製造方法）
上記のとおり、本明細書によれば、研磨材料の製造方法も提供される。本製造方法は、少なくともＳｒ及びＺｒを含むペロブスカイト型酸化物の第１の原料と、少なくともＣｅＯ２を含む蛍石型酸化物の第２の原料と、を準備する工程と、前記第１の原料と前記第２の原料とを用いて、前記ペロブスカイト型酸化物を含む第１の相と、前記蛍石型酸化物を含む第２の相と、が複合化した二次粒子を合成する工程と、を備える。合成工程では、好ましくは噴霧熱分解法を用いる。噴霧熱分解法によると、比較的均一な粒子形状及び粒子径分布をもった複合粒子を得ることができ、研磨材料として好適である。
(Manufacturing method of polishing material)
As described above, according to the present specification, a method for producing an abrasive material is also provided. The present manufacturing method includes a step of preparing a first raw material of a perovskite oxide containing at least Sr and Zr and a second raw material of a fluorite oxide containing at least CeO 2 , and the first raw material And synthesizing secondary particles in which the first phase containing the perovskite oxide and the second phase containing the fluorite oxide are combined using the second raw material and the second raw material; . In the synthesis step, spray pyrolysis is preferably used. According to the spray pyrolysis method, composite particles having a relatively uniform particle shape and particle size distribution can be obtained, which is suitable as an abrasive material.
噴霧熱分解法における原料の調製方法は、当業者において公知であり、当業者であれば、特定のペロブスカイト型酸化物と蛍石型酸化物に対応する原料（溶液又は分散液）を準備、合成条件を設定することができる。 The raw material preparation method in the spray pyrolysis method is known to those skilled in the art, and those skilled in the art prepare and synthesize raw materials (solutions or dispersions) corresponding to specific perovskite oxides and fluorite oxides. Conditions can be set.
（研磨用組成物）
本明細書に開示される研磨用組成物（以下、単に、本組成物という。）は、本研磨材料を含有する組成物である。本組成物の形態は特に限定されない。本組成物は、粉末等の固形であっても、スラリー形態であってもよい。また、本組成物は、そのままワークの研磨に用いられるあるいは適当な媒体に適宜分散しあるいは当該媒体で適宜希釈してワークの研磨に用いられるように構成されていてもよい。研磨材料は、通常、研磨時にスラリーとして使用される。本組成物は、本研磨材料と同様の研磨方法及び研磨対象に適用することができる。
(Polishing composition)
The polishing composition disclosed herein (hereinafter simply referred to as the present composition) is a composition containing the present polishing material. The form of the composition is not particularly limited. The present composition may be a solid such as a powder or may be in a slurry form. Further, the present composition may be used as it is for polishing a workpiece, or may be appropriately dispersed in an appropriate medium, or may be appropriately diluted with the medium and used for polishing a workpiece. The polishing material is usually used as a slurry during polishing. This composition can be applied to the same polishing method and polishing object as the present polishing material.
本組成物は、研磨材料としては、本研磨材料のほか、本研磨材料以外の他の研磨材料を含むことができる。こうした研磨材料としては、例えば、酸化セリウム、酸化ケイ素、酸化鉄、酸化アルミニウム、酸化チタン、酸化マンガン、酸化クロム、炭化ケイ素、ダイヤモンドが挙げられる。なお、これらの他の研磨材料の本組成物における含有比率は特に限定されない。 The present composition may contain an abrasive material other than the abrasive material as well as the abrasive material. Examples of such polishing materials include cerium oxide, silicon oxide, iron oxide, aluminum oxide, titanium oxide, manganese oxide, chromium oxide, silicon carbide, and diamond. In addition, the content ratio in the present composition of these other polishing materials is not particularly limited.
本組成物がスラリー形態を採るとき、本研磨材料を本組成物の全質量に対して１質量％以上含むことが好ましく、より好ましくは３質量％以上である。また、好ましくは２０質量％以下であり、より好ましくは１０質量％以下である。 When this composition takes a slurry form, it is preferable to contain this polishing material 1 mass% or more with respect to the total mass of this composition, More preferably, it is 3 mass% or more. Moreover, Preferably it is 20 mass% or less, More preferably, it is 10 mass% or less.
本組成物がスラリー形態を採るとき、研磨材料を分散する媒体は、特に限定されないで、公知の研磨スラリーに用いられる媒体を用いることができる。例えば、水、水溶性有機溶媒及びこれらの混液から選択される水性媒体を用いることができる。 When this composition takes a slurry form, the medium which disperse | distributes polishing material is not specifically limited, The medium used for a well-known polishing slurry can be used. For example, an aqueous medium selected from water, a water-soluble organic solvent, and a mixture thereof can be used.
水溶性有機溶媒としては、メタノール、エタノール、プロパノール、イソプロパノール、ブタノール等の炭素数が１以上１０以下程度の１価アルコール類、エチレングリコール、グリセリン等の炭素数３以上１０以下程度の多価アルコール、アセトン、ジメチルスルホキシド（ＤＭＳＯ）、ジメチルホムアミド（ＤＭＦ）、テトラヒドロフラン、ジオキサン等が挙げられる。なかでも、水、アルコール及びグリコールが好ましく用いられる。 Examples of the water-soluble organic solvent include monohydric alcohols having 1 to 10 carbon atoms such as methanol, ethanol, propanol, isopropanol and butanol, polyhydric alcohols having 3 to 10 carbon atoms such as ethylene glycol and glycerin, Acetone, dimethyl sulfoxide (DMSO), dimethylformamide (DMF), tetrahydrofuran, dioxane and the like can be mentioned. Of these, water, alcohol and glycol are preferably used.
本組成物は、本研磨材料及び他の研磨材料を含む場合には、これらを媒体に良好に分散させるために分散剤を含むことができる。かかる分散剤としては、トリポリリン酸塩のような高分子分散剤、ヘキサメタリン酸塩等のリン酸塩、メチルセルロース、カルボキシメチルセルロース等のセルロースエーテル類、ポリビニルアルコール等の水溶性高分子などの添加剤を添加することもできる。これらの添加剤の添加量は、研磨材に対して、０．０５質量％以上２０質量％以下の範囲内であることが一般的に好ましく、特に好ましくは０．１質量％以上１０質量％以下の範囲である。なお、分散剤としては、このほか、アルカリ、無機塩類が挙げられる。 When the present composition contains the present abrasive material and other abrasive materials, it can contain a dispersing agent in order to disperse them well in the medium. Additives such as polymer dispersants such as tripolyphosphate, phosphates such as hexametaphosphate, cellulose ethers such as methylcellulose and carboxymethylcellulose, and water-soluble polymers such as polyvinyl alcohol are added as such dispersants. You can also The addition amount of these additives is generally preferably in the range of 0.05% by mass or more and 20% by mass or less, particularly preferably 0.1% by mass or more and 10% by mass or less, with respect to the abrasive. Range. In addition, examples of the dispersant include alkalis and inorganic salts.
また、本組成物は、界面活性剤を含んでいてもよい。界面活性剤としては、アニオン系界面活性剤、カチオン系界面活性剤、ノニオン系界面活性剤等や両性イオン界面活性剤が挙げられ、これらは単独で用いても２種以上を混合して用いてもよい。 Further, the present composition may contain a surfactant. Examples of the surfactant include an anionic surfactant, a cationic surfactant, a nonionic surfactant, and a zwitterionic surfactant. These may be used alone or in combination of two or more. Also good.
さらに、本組成物は、研磨対象や研磨方法に応じた各種の成分を含んでいてもよい。例えば、化学機械研磨の場合には、ワーク表面を改質するための酸やアルカリを含んでいてもよい。また、金属研磨の場合には、キレート剤を含んでいてもよい。 Furthermore, the present composition may contain various components according to the object to be polished and the polishing method. For example, in the case of chemical mechanical polishing, an acid or an alkali for modifying the work surface may be included. In the case of metal polishing, a chelating agent may be included.
本組成物は、本研磨材料ほか、上記した成分等公知の研磨用組成物に用いられる材料を用いて、公知の方法で製造することができる。たとえば、スラリー形態の本組成物は、本研磨材料等の研磨材料を水性媒体に分散させて得ることができる。必要に応じて、湿式粉砕を組み合わせてもよい。あるいは、本研磨材料を乾式粉砕後に、水性媒体に分散させてもよい。 The present composition can be produced by a known method using the present polishing material and materials used for known polishing compositions such as the above-described components. For example, the present composition in a slurry form can be obtained by dispersing an abrasive material such as the present abrasive material in an aqueous medium. If necessary, wet grinding may be combined. Alternatively, the abrasive material may be dispersed in an aqueous medium after dry grinding.
（被研磨体の生産方法）
本明細書によれば、本研磨用組成物を用いてワークを研磨する工程、を備える、被研磨体の生産方法も提供される。本生産方法によれば、効率的に表面平滑性の良好な被研磨体を得ることができる。本生産方法は、従来、セリアが研磨材料として用いられていた被研磨体の生産方法並びに研磨対象に適用できる。例えば、本生産方法は、通常の研磨のほか、化学機械研磨が挙げられる。また、本研磨材料を適用するワークは特に限定されないで、ガラス、金属、セラミックス等が挙げられる。
(Production method of the object to be polished)
According to this specification, the manufacturing method of a to-be-polished body provided with the process of grind | polishing a workpiece | work using this polishing composition is also provided. According to this production method, it is possible to efficiently obtain an object to be polished having good surface smoothness. This production method can be applied to a production method of an object to be polished and the object to be polished, for which ceria has been conventionally used as an abrasive material. For example, this production method includes chemical mechanical polishing in addition to normal polishing. Moreover, the workpiece | work which applies this abrasive material is not specifically limited, Glass, a metal, ceramics, etc. are mentioned.
（研磨材料のスクリーニング方法）
本明細書に開示されるスクリーニング方法は、
１種又は２種以上のペロブスカイト型酸化物の原料と、セリア（ＣｅＯ２）の原料とを含む原料液を準備する工程と、前記原料液から前記ペロブスカイト型酸化物と前記セリアを合成する条件下で、前記ペロブスカイト型酸化物相とセリア相とをそれぞれ含む粒子の合成を評価する工程と、を備えることができる。本方法によれば、セリアとの複合化に適したペロブスカイト型酸化物をスクリーニングすることができる。
(Polishing material screening method)
The screening methods disclosed herein include:
A step of preparing a raw material liquid containing a raw material of one or more perovskite oxides and a ceria (CeO 2 ) raw material, and conditions for synthesizing the perovskite oxide and the ceria from the raw material liquid And the step of evaluating the synthesis of the particles each containing the perovskite oxide phase and the ceria phase. According to this method, a perovskite oxide suitable for compounding with ceria can be screened.
本スクリーニング方法は、２種以上の成分を同時に合成して複合化するとき、セリア相と独立した結晶相を形成できるペロブスカイト型酸化物をスクリーニングできる。本発明者らによれば、こうしたスクリーニング方法で抽出されたペロブスカイト型酸化物の相とセリア相との複合化により、新たな研磨材料を提供できる可能性がある。なお、合成評価工程は、噴霧熱分解法を含む公知のセラミックス合成法で行うことができる。 This screening method can screen a perovskite oxide that can form a crystalline phase independent of a ceria phase when two or more components are synthesized and combined simultaneously. According to the present inventors, there is a possibility that a new polishing material can be provided by combining the phase of the perovskite oxide extracted by such a screening method and the ceria phase. The synthesis evaluation step can be performed by a known ceramic synthesis method including a spray pyrolysis method.
以上、本明細書の開示の実施形態について説明したが、本発明はこれに限定されるものではなく、本発明の趣旨を逸脱しない限りにおいて、種々の変更が可能である。 As mentioned above, although embodiment of the indication of this specification was described, this invention is not limited to this, A various change is possible unless it deviates from the meaning of this invention.
以下、本明細書の開示を、実施例を挙げて具体的に説明するが、本明細書の開示は、以下の実施例に限定されるものではない。 Hereinafter, the disclosure of the present specification will be specifically described with reference to examples. However, the disclosure of the present specification is not limited to the following examples.
Ｓｒ源として硝酸ストロンチウム、Ｚｒ源として硝酸ジルコニルを用いて、ＳｒＺｒＯ３の酸化物換算で０．４ｍｏｌ／Ｌの原料溶液を調製した。また、Ｃｅ源として硝酸セリウムを用いて、ＣｅＯ２の酸化物換算で０．４ｍｏｌ／Ｌの原料溶液を調製した。次いで、これらの各原料溶液から算出されるＳｒＺｒＯ３とＣｅＯ２とのモル比が表１に示す各種比率となるように、各原料液を混合して噴霧熱分解用の原料溶液（試料１〜５、比較試料１、２）を調製した。これらの各種噴霧熱分解用の原料溶液を噴霧熱分解法に適用して、ＳｒＺｒＯ３とＣｅＯ２との複合粒子を得た。合成にあたって、加熱温度は、加熱炉の入り口付近を２００℃とし、さらに４００℃、８００℃とし、出口温度を１０００℃と段階的に上げ、キャリアガスとして空気を３Ｌ／分で流した。 A raw material solution of 0.4 mol / L in terms of oxide of SrZrO 3 was prepared using strontium nitrate as the Sr source and zirconyl nitrate as the Zr source. A cerium nitrate was used as a Ce source to prepare a 0.4 mol / L raw material solution in terms of CeO 2 oxide. Subsequently, each raw material liquid is mixed so that the molar ratio of SrZrO 3 and CeO 2 calculated from each of these raw material solutions becomes various ratios shown in Table 1, and the raw material solution for spray pyrolysis (sample 1 to sample 1). 5. Comparative samples 1, 2) were prepared. These raw material solutions for spray pyrolysis were applied to the spray pyrolysis method to obtain composite particles of SrZrO 3 and CeO 2 . In the synthesis, the heating temperature was 200 ° C. near the entrance of the heating furnace, further 400 ° C. and 800 ° C., the outlet temperature was increased stepwise to 1000 ° C., and air was flowed at 3 L / min as the carrier gas.
得られた粒子の硬度を向上させる目的で、１０００℃、４時間の仮焼を行った。 In order to improve the hardness of the obtained particles, calcination was performed at 1000 ° C. for 4 hours.
また、仮焼後の各合成粉末につき、以下の項目について試験を行った。結果を併せて表１に示す。また、これらの項目のうち、研磨速度及び平均面粗さＲａの結果を図３に表した。なお、研磨速度及び表面平滑性については、対照試料として市販のセリア系砥粒を用いて試験を行った。 Moreover, about the following items, each synthetic powder after calcination was tested. The results are also shown in Table 1. Of these items, the results of the polishing rate and the average surface roughness Ra are shown in FIG. In addition, about the grinding | polishing speed | rate and surface smoothness, it tested using the commercially available ceria-type abrasive grain as a control sample.
（１）二次粒子及び一次粒子の平均粒子径
（二次粒子の平均粒子径の測定方法）
走査型電子顕微鏡によって、粒子を５０００倍に拡大し、画像を取得した。該画像上で目視可能な２００個の二次粒子の粒子径（直径）を測定し、これらの粒子径の相加平均を二次粒子の平均粒子径とした。
（一次粒子の平均粒子径の測定方法）
粒子を１０万倍に拡大し、画像を取得した。該画像上で目視可能な２００個の一次粒子の粒子径を測定し、これらの一次粒子の粒子径の相加平均を一次粒子の平均粒子径とした。
(1) Average particle diameter of secondary particles and primary particles (measurement method of average particle diameter of secondary particles)
With a scanning electron microscope, the particles were magnified 5000 times to obtain an image. The particle diameter (diameter) of 200 secondary particles visible on the image was measured, and the arithmetic average of these particle diameters was taken as the average particle diameter of the secondary particles.
(Measurement method of average particle size of primary particles)
The particles were magnified 100,000 times and images were acquired. The particle diameters of 200 primary particles visible on the image were measured, and the arithmetic average of the particle diameters of these primary particles was defined as the average particle diameter of the primary particles.
なお、図１に、合成した試料１の合成セラミックス粉末の走査型電子顕微鏡像を示す。 In addition, in FIG. 1, the scanning electron microscope image of the synthetic | combination ceramic powder of the synthetic | combination sample 1 is shown.
（２）（Ｘ線粉末回折スペクトル）
各粉末につき、Ｘ線回折パターンを取得した。結果を図２に示す。
(2) (X-ray powder diffraction spectrum)
An X-ray diffraction pattern was obtained for each powder. The results are shown in FIG.
（３）研磨速度
各種合成セラミックス粉末１５ｇと蒸留水３００ｇを混ぜ、濃度５質量％のスラリーとした。研磨試験には片面研磨機（テグラシステム、丸本ストルアス製）を用いた。研磨スラリーはダイヤフラムポンプを用いて循環した。その他、研磨試験は以下の条件で行った。
研磨対象：37.5 mm×30 mm LCD用ガラス
研磨パッド：発泡ポリウレタンパッド（MH-C15A、ニッタ・ハース製）
定盤径：300 mm
定盤回転数：150 rpm
スラリー供給量：100 mL / min
研磨圧力：102 g / cm2
研磨時間：30分
(3) Polishing speed 15 g of various synthetic ceramic powders and 300 g of distilled water were mixed to form a slurry having a concentration of 5% by mass. A single-side polishing machine (Tegra System, manufactured by Marumoto Struers) was used for the polishing test. The polishing slurry was circulated using a diaphragm pump. In addition, the polishing test was performed under the following conditions.
Polishing object: 37.5 mm x 30 mm LCD glass polishing pad: Foam polyurethane pad (MH-C15A, manufactured by Nitta Haas)
Surface plate diameter: 300 mm
Plate rotation speed: 150 rpm
Slurry supply amount: 100 mL / min
Polishing pressure: 102 g / cm2
Polishing time: 30 minutes
研磨速度試験に供する研磨前のＬＣＤガラスにつき、その厚さ（各５点）及び研磨前後の重量を測定し、重量減少分を厚み換算し、研磨速度を計算した。 With respect to the LCD glass before polishing used for the polishing rate test, the thickness (5 points each) and the weight before and after polishing were measured, and the weight reduction was converted into thickness, and the polishing rate was calculated.
（４）表面平滑性
研磨後のガラス表面性状は原子間力顕微鏡（ＳＰＭ−９６００、島津製作所）を用いて評価した。原子間力顕微鏡により研磨面の３０μｍ四方の領域の平均面粗さＲａを測定した。
(4) Surface smoothness The glass surface properties after polishing were evaluated using an atomic force microscope (SPM-9600, Shimadzu Corporation). The average surface roughness Ra of the 30 μm square area of the polished surface was measured with an atomic force microscope.
表１において（ ）内の数字は、比較試料３の研磨速度に対するそれぞれの試料の研磨速度の割合を百分率及び比較試料２の研磨速度に対するそれぞれの試料の研磨速度の割合を百分率で示す。 In Table 1, the numbers in parentheses indicate the percentage of the polishing rate of each sample with respect to the polishing speed of Comparative Sample 3 and the percentage of the polishing rate of each sample with respect to the polishing speed of Comparative Sample 2.
図１に示すように、合成したセラミックス粉末を構成する粒子は、一次粒子が凝集して複合化した二次粒子であった。また、図２に示すように、二次粒子には、双方の粒子がそれぞれ個別の結晶を構成して粒子として含まれていることがわかった。 As shown in FIG. 1, the particles constituting the synthesized ceramic powder were secondary particles in which primary particles were aggregated and combined. In addition, as shown in FIG. 2, it was found that the secondary particles contained both particles as individual crystals constituting individual crystals.
また、表１及び図３からも明らかなように、比較試料１のＳｒＺｒＯ３は、研磨速度に劣るが表面平滑性能に優れ、比較試料２及び３のＣｅＯ2は、ＳｒＺｒＯ３に比較して研磨速度に優れ表面平滑性能に関し、ＳｒＺｒＯ３にやや劣る。しかしながら、実施例１〜５によれば、表面平滑性能が向上し、特に、実施例１〜４においては、表面平滑性能と研磨速度との双方が向上している。このように、これらの成分が互いの特性を維持又は向上された状態で複合化できたことは、当業者といえども予測できないことであった。 Further, as is clear from Table 1 and FIG. 3, SrZrO 3 of Comparative Sample 1 is inferior in polishing rate but excellent in surface smoothness performance, and CeO 2 of Comparative Samples 2 and 3 is polished compared to SrZrO 3. It is excellent in speed and slightly inferior to SrZrO 3 in terms of surface smoothness performance. However, according to Examples 1 to 5, the surface smoothness performance is improved. In particular, in Examples 1 to 4, both the surface smoothness performance and the polishing rate are improved. As described above, it was impossible for those skilled in the art to predict that these components could be combined while maintaining or improving the properties of each other.
さらに、表１及び図３に示すように、試料１〜５の合成粉末を用いたスラリーは、平均面粗さＲａが比較試料３（市販セリア系砥粒）の場合よりも最も小さくて半分程度（試料１）であり、最大でも、９０％未満（試料２）であった。また、これらの試料は、市販セリア系砥粒（比較試料３）よりも表面平滑性能に優れる単独合成粉末（比較試料１、２）と同等あるいはより小さかった。即ち、試料１〜５のスラリーは、表面平滑性能に優れた研磨材料となっている。 Furthermore, as shown in Table 1 and FIG. 3, the slurry using the synthetic powders of Samples 1 to 5 has an average surface roughness Ra that is the smallest and about half that of Comparative Sample 3 (commercially available ceria-based abrasive grains). (Sample 1), which was less than 90% (Sample 2) at the maximum. Moreover, these samples were equivalent to or smaller than single synthetic powders (Comparative Samples 1 and 2), which were superior in surface smoothing performance to commercially available ceria-based abrasive grains (Comparative Sample 3). That is, the slurries of Samples 1 to 5 are polishing materials excellent in surface smoothness performance.
さらにまた、試料１〜４はいずれも市販セリア系砥粒（比較試料３）由来のスラリーの研磨速度の約９０％以上、単独合成セリア粉末（比較試料２）の研磨速度の１１０％以上１２０％程度が確保されていた。このことから、試料１〜４は、化学機械研磨特性及びそのバランスに優れた研磨材料となっていることがわかった。 Furthermore, samples 1 to 4 are all about 90% or more of the polishing rate of slurry derived from commercially available ceria-based abrasive grains (comparative sample 3), and 110% or more and 120% of the polishing rate of single synthetic ceria powder (comparative sample 2). The degree was secured. From this, it was found that Samples 1 to 4 were polishing materials excellent in chemical mechanical polishing characteristics and their balance.
Claims (11)
を備える製造方法。 A method for producing an abrasive material, comprising: preparing a first raw material of a perovskite oxide containing at least Sr and Zr; and a second raw material of a fluorite oxide containing at least CeO 2 ; Using the first raw material and the second raw material, secondary particles in which the first particles containing the perovskite oxide and the second particles containing the fluorite oxide are combined are combined. A step of synthesizing;
A manufacturing method comprising:
を備え、セリアとの複合化に適したペロブスカイト型酸化物をスクリーニングする、方法。
A method for screening an abrasive material, comprising: preparing a raw material liquid containing a raw material of one or more perovskite oxides and a ceria (CeO 2 ) raw material; and the perovskite oxidation from the raw material liquid Evaluating the synthesis of particles each containing the perovskite oxide phase and the ceria phase under conditions for synthesizing the product and the ceria;
And a method for screening a perovskite oxide suitable for compounding with ceria.
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| JPH10237425A (en) * | 1997-02-24 | 1998-09-08 | Toray Ind Inc | Polishing agent |
| JP2007061989A (en) * | 2005-09-02 | 2007-03-15 | Hitachi Maxell Ltd | Composite oxide particles for polishing and slurry-like abrasives |
| JP5726501B2 (en) * | 2010-12-10 | 2015-06-03 | 一般財団法人ファインセラミックスセンター | Polishing material, polishing composition and polishing method |
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2013
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