JP2007144536A - Method for manufacturing substrate - Google Patents
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- JP2007144536A JP2007144536A JP2005340160A JP2005340160A JP2007144536A JP 2007144536 A JP2007144536 A JP 2007144536A JP 2005340160 A JP2005340160 A JP 2005340160A JP 2005340160 A JP2005340160 A JP 2005340160A JP 2007144536 A JP2007144536 A JP 2007144536A
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- 239000000758 substrate Substances 0.000 title claims abstract description 110
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 33
- 238000005498 polishing Methods 0.000 claims abstract description 166
- 239000000203 mixture Substances 0.000 claims abstract description 83
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000008119 colloidal silica Substances 0.000 claims abstract description 27
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 21
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000002253 acid Substances 0.000 claims abstract description 19
- 150000003839 salts Chemical class 0.000 claims abstract description 13
- 239000007788 liquid Substances 0.000 claims description 39
- 239000002699 waste material Substances 0.000 claims description 4
- 239000012530 fluid Substances 0.000 abstract 4
- 239000004065 semiconductor Substances 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 8
- 230000003287 optical effect Effects 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 239000002184 metal Substances 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- -1 iron ion Chemical class 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 5
- 238000009616 inductively coupled plasma Methods 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 230000010354 integration Effects 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 229910018104 Ni-P Inorganic materials 0.000 description 3
- 229910018536 Ni—P Inorganic materials 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
- 238000007517 polishing process Methods 0.000 description 3
- QQVDJLLNRSOCEL-UHFFFAOYSA-N (2-aminoethyl)phosphonic acid Chemical compound [NH3+]CCP(O)([O-])=O QQVDJLLNRSOCEL-UHFFFAOYSA-N 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010494 dissociation reaction Methods 0.000 description 2
- 230000005593 dissociations Effects 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- SIOXPEMLGUPBBT-UHFFFAOYSA-N picolinic acid Chemical compound OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 235000019353 potassium silicate Nutrition 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 description 1
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 description 1
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- 239000004111 Potassium silicate Substances 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 235000003704 aspartic acid Nutrition 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- HGAZMNJKRQFZKS-UHFFFAOYSA-N chloroethene;ethenyl acetate Chemical compound ClC=C.CC(=O)OC=C HGAZMNJKRQFZKS-UHFFFAOYSA-N 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000006063 cullet Substances 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 235000013922 glutamic acid Nutrition 0.000 description 1
- 239000004220 glutamic acid Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010191 image analysis Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 229910052752 metalloid Inorganic materials 0.000 description 1
- 150000002738 metalloids Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- KHIWWQKSHDUIBK-UHFFFAOYSA-N periodic acid Chemical compound OI(=O)(=O)=O KHIWWQKSHDUIBK-UHFFFAOYSA-N 0.000 description 1
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 229940081066 picolinic acid Drugs 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 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
- 239000002002 slurry Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
Landscapes
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
- Manufacturing Of Magnetic Record Carriers (AREA)
Abstract
Description
本発明は、基板の製造方法及びナノスクラッチの低減方法に関する。 The present invention relates to a method for manufacturing a substrate and a method for reducing nanoscratches.
近年のメモリーハードディスクドライブには、高容量・小径化が求められ、記録密度を上げるために磁気ヘッドの浮上量を低下させて、単位記録面積を小さくすることが求められている。それに伴い、磁気ディスク用基板の製造工程においても研磨後に要求される表面品質は年々厳しくなってきており、ヘッドの低浮上化に対応して、表面粗さ、微小うねり、ロールオフ及びピットや突起を低減する必要があり、また、単位記録面積の減少に対応して、許容される基板面当たりのスクラッチ数は少なく、その大きさと深さはますます小さくなってきている。 Recent memory hard disk drives are required to have a high capacity and a small diameter, and in order to increase the recording density, the flying height of the magnetic head is reduced to reduce the unit recording area. Along with this, the surface quality required after polishing in the manufacturing process of magnetic disk substrates has become stricter year by year, and the surface roughness, micro waviness, roll-off, pits and protrusions correspond to the low flying height of the head. In addition, the number of scratches per substrate surface that can be tolerated is small, and the size and depth thereof are becoming smaller and smaller corresponding to the decrease in the unit recording area.
また、半導体分野においても、高集積化と高速化が進んでおり、特に高集積化では配線の微細化が要求されている。その結果、半導体基板の製造プロセスにおいては、フォトレジストの露光の際の焦点深度が浅くなり、より一層欠陥の少ない表面品質が望まれている。 Also in the semiconductor field, high integration and high speed are advancing. In particular, miniaturization of wiring is required for high integration. As a result, in the manufacturing process of a semiconductor substrate, the depth of focus at the time of exposure of a photoresist becomes shallow, and surface quality with fewer defects is desired.
このような要求に対して、メモリーハードディスク基板のピットや突起を低減することにより表面平滑性を向上させる研磨液組成物が知られている（特許文献１）。
しかし、メモリーハードディスク基板や半導体基板等の精密部品基板の高密度化又は高集積化に必要な表面品質を達成するためには、ピットや突起の低減の他、ナノスクラッチの低減も重要な課題となっている。 However, in order to achieve the surface quality required for high density or high integration of precision component substrates such as memory hard disk substrates and semiconductor substrates, in addition to reducing pits and protrusions, reducing nanoscratches is also an important issue. It has become.
従って、本発明の目的は、研磨後の基板のナノスクラッチを顕著に低減できる基板の製造方法及びナノスクラッチの低減方法を提供することにある。 Accordingly, an object of the present invention is to provide a method for manufacturing a substrate and a method for reducing nanoscratches that can significantly reduce nanoscratches of a substrate after polishing.
即ち、本発明の要旨は、
［１］ コロイダルシリカと、酸又はその塩とを含有する研磨液組成物を基板又は研磨パッドに供給して該基板を研磨する工程を有する基板の製造方法であって、基板又は研磨パッドに供給される際の研磨液組成物中のアルミニウム濃度が５０ｐｐｍ以下である基板の製造方法、及び
［２］ コロイダルシリカと、酸又はその塩とを含有する研磨液組成物を基板又は研磨パッドに供給して該基板を研磨する工程を有するナノスクラッチの低減方法であって、基板又は研磨パッドに供給される際の研磨液組成物中のアルミニウム濃度が５０ｐｐｍ以下であるナノスクラッチの低減方法
に関する。
That is, the gist of the present invention is as follows.
[1] A substrate manufacturing method comprising a step of supplying a polishing composition containing colloidal silica and an acid or a salt thereof to a substrate or polishing pad and polishing the substrate, and supplying the substrate or polishing pad to the substrate or polishing pad A method for producing a substrate having an aluminum concentration of 50 ppm or less in the polishing liquid composition and [2] a polishing liquid composition containing colloidal silica and an acid or a salt thereof is supplied to the substrate or the polishing pad. The present invention relates to a method for reducing nanoscratches comprising a step of polishing the substrate, wherein the aluminum concentration in the polishing composition when supplied to the substrate or polishing pad is 50 ppm or less.
本発明の基板の製造方法及びナノスクラッチの低減方法により、ナノスクラッチが顕著に低減された基板を得ることができるという効果が奏される。 According to the substrate manufacturing method and the nano scratch reducing method of the present invention, it is possible to obtain a substrate in which nano scratches are remarkably reduced.
本発明の基板の製造方法は、コロイダルシリカと、酸又はその塩とを含有する研磨液組成物を基板又は研磨パッドに供給して該基板を研磨する工程を有する基板の製造方法であって、基板又は研磨パッドに供給される際の研磨液組成物中のアルミニウム（Ａｌ）濃度が５０ｐｐｍ以下であることを特徴とする。基板又は研磨パッドに供給される際の研磨液組成物中のＡｌ濃度を特定値以下に調節することは、従来全く考慮されていなかったが、驚くべきことに、上記のような特徴を有する本発明の基板の製造方法を用いることにより、ナノスクラッチが顕著に低減された基板を得ることができるという優れた効果が奏される。その作用機構については明らかではないが、Ａｌ濃度を特定値以下に調節することによりコロイダルシリカの凝集が抑えられ、それによりナノスクラッチが低減されると推定される。 The method for producing a substrate of the present invention is a method for producing a substrate comprising a step of supplying a polishing composition containing colloidal silica and an acid or a salt thereof to the substrate or a polishing pad and polishing the substrate, The aluminum (Al) concentration in the polishing composition when supplied to the substrate or polishing pad is 50 ppm or less. Adjusting the Al concentration in the polishing composition when supplied to the substrate or polishing pad to a specific value or less has not been considered at all in the past, but surprisingly, the book having the above-described features By using the substrate manufacturing method of the invention, an excellent effect is obtained that a substrate with significantly reduced nanoscratches can be obtained. Although the mechanism of action is not clear, it is presumed that the aggregation of colloidal silica is suppressed by adjusting the Al concentration below a specific value, thereby reducing nanoscratches.
本発明において、Ａｌの濃度は、被験試料をフッ化水素酸、硝酸等で溶解し、シリカ等のＡｌ定量に妨害となる元素を除去した後、４重極型誘導結合プラズマ質量分析装置（ＩＣＰ質量分析装置）にて定量を行うことで求めることができる。ＩＣＰ質量分析装置としては、商品名：ＳＰＱ−８０００（セイコーインスツルメンツ（株）製）等が挙げられる。 In the present invention, the concentration of Al is determined by dissolving a test sample with hydrofluoric acid, nitric acid, etc., and removing elements such as silica that interfere with Al determination, and then inductively coupled plasma mass spectrometer (ICP). It can be obtained by performing quantification with a mass spectrometer. Examples of the ICP mass spectrometer include trade name: SPQ-8000 (manufactured by Seiko Instruments Inc.).
また、本発明におけるナノスクラッチとは、深さが１０ｎｍ以上、１００ｎｍ未満、幅が５ｎｍ以上５００ｎｍ未満、長さが１００μｍ以上の基板表面の微細な傷である。ナノスクラッチは、例えば研磨液組成物や環境に由来する粗大粒子又は研磨中に生成する研磨粒子の凝集体により生じると推測される。ナノスクラッチは、原子間力顕微鏡（ＡＦＭ）で検出することができ、後述の実施例に記載の目視検査装置である「ＭｉｃｒｏＭａｘ」による測定でナノスクラッチ本数として定量評価できる。 The nano scratch in the present invention is a fine scratch on the substrate surface having a depth of 10 nm or more and less than 100 nm, a width of 5 nm or more and less than 500 nm, and a length of 100 μm or more. Nano scratches are presumed to be caused by, for example, coarse particles derived from the polishing composition or the environment, or aggregates of abrasive particles generated during polishing. Nanoscratches can be detected with an atomic force microscope (AFM), and can be quantitatively evaluated as the number of nanoscratches by measurement with “MicroMax” which is a visual inspection apparatus described in Examples described later.
本発明で使用される研磨液組成物に含有されるコロイダルシリカは、珪酸ナトリウムや珪酸カリウム等の珪酸塩を原料とする、所謂珪酸塩法により製造されたコロイダルシリカである。かかるコロイダルシリカの態様としては、特に限定されないが、例えば、ゾル又はゲル状態である。
珪酸塩法としては、珪酸塩を原料とし、縮合反応させシリカ粒子を生成させる方法（水ガラス法）等が挙げられる。
本発明においては、かかる珪酸塩法により製造されたコロイダルシリカを用いることで、従来のアルコキシシラン法で得られるコロイダルシリカや乾式法で得られるヒュームドシリカを使用する場合に比べて、ナノスクラッチを顕著に低減することができるという利点がある。
The colloidal silica contained in the polishing composition used in the present invention is colloidal silica produced by a so-called silicate method using a silicate such as sodium silicate or potassium silicate as a raw material. Although it does not specifically limit as an aspect of this colloidal silica, For example, it is a sol or gel state.
Examples of the silicate method include a method (water glass method) in which silicate is used as a raw material and a condensation reaction is performed to produce silica particles.
In the present invention, by using colloidal silica produced by such a silicate method, compared to the case of using colloidal silica obtained by a conventional alkoxysilane method or fumed silica obtained by a dry method, nanoscratches can be used. There is an advantage that it can be remarkably reduced.
コロイダルシリカの一次粒子の平均粒径は、研磨速度を向上させる観点から、好ましくは１ｎｍ以上、より好ましくは２ｎｍ以上、さらに好ましくは５ｎｍ以上であり、ナノスクラッチを低減する観点から、好ましくは２００ｎｍ以下、より好ましくは１５０ｎｍ以下、さらに好ましくは１２０ｎｍ以下、さらにより好ましくは１００ｎｍ以下である。該一次粒子の平均粒径は、好ましくは１〜２００ｎｍ、より好ましくは１〜１５０ｎｍ、さらに好ましくは２〜１２０ｎｍ、さらにより好ましくは５〜１００ｎｍである。なお、該シリカ粒子の粒径は透過型電子顕微鏡で観察して（好適には3000倍〜500000倍）画像解析を行い、２軸平均径を測定することにより求めることができる。また、平均粒径は、小粒径側からの積算粒径分布（個数基準）が５０％となる粒径（Ｄ５０）とする。 The average particle size of the primary particles of colloidal silica is preferably 1 nm or more, more preferably 2 nm or more, further preferably 5 nm or more from the viewpoint of improving the polishing rate, and from the viewpoint of reducing nanoscratches, preferably 200 nm or less. More preferably, it is 150 nm or less, More preferably, it is 120 nm or less, More preferably, it is 100 nm or less. The average particle size of the primary particles is preferably 1 to 200 nm, more preferably 1 to 150 nm, still more preferably 2 to 120 nm, and even more preferably 5 to 100 nm. The particle size of the silica particles can be determined by observing with a transmission electron microscope (preferably 3000 times to 500000 times) and performing image analysis to measure the biaxial average diameter. Further, the average particle diameter is a particle diameter (D50) at which the cumulative particle diameter distribution (number basis) from the small particle diameter side is 50%.
研磨液組成物中におけるコロイダルシリカの含有量は、研磨速度を向上させる観点から、好ましくは０．５重量％以上、より好ましくは１重量％以上、さらに好ましくは３重量％以上、さらにより好ましくは５重量％以上であり、また、表面品質を向上させる観点、及び経済性の観点から、好ましくは２０重量％以下、より好ましくは１５重量％以下、さらに好ましくは１３重量％以下、さらにより好ましくは１０重量％以下である。すなわち、該含有量は、好ましくは０．５〜２０重量％、より好ましくは１〜１５重量％、さらに好ましくは３〜１３重量％、さらにより好ましくは５〜１０重量％である。 The content of colloidal silica in the polishing composition is preferably 0.5% by weight or more, more preferably 1% by weight or more, still more preferably 3% by weight or more, and still more preferably from the viewpoint of improving the polishing rate. From the viewpoint of improving surface quality and economy, it is preferably 20% by weight or less, more preferably 15% by weight or less, still more preferably 13% by weight or less, and even more preferably. 10% by weight or less. That is, the content is preferably 0.5 to 20% by weight, more preferably 1 to 15% by weight, still more preferably 3 to 13% by weight, and even more preferably 5 to 10% by weight.
本発明で使用される研磨液組成物に含有される酸としては、ｐＫ１が７以下の化合物が好ましく、ナノスクラッチを低減する観点から、より好ましくはｐＫ１が３以下、さらに好ましくは２．５以下、さらにより好ましくは２以下、さらにより好ましくは１．５以下、さらにより好ましくはｐＫ１で表せない程の強い酸性を示す化合物が望ましい。その例としては、硝酸、硫酸、亜硫酸、過硫酸、塩酸、過塩素酸、リン酸、ホスホン酸、ホスフィン酸、ピロリン酸、シュウ酸、アミド硫酸、アスパラギン酸、２−アミノエチルホスホン酸、グルタミン酸、ピコリン酸等が挙げられる。中でも、ナノスクラッチを低減する観点から、硝酸、硫酸、塩酸及び過塩素酸が好ましい。これらの酸は単独で又は２種以上を混合して用いてもよい。ここで、ｐＫ１とは有機化合物または無機化合物の酸解離定数（２５℃）の逆数の対数値を通常ｐＫａと表し、そのうちの第一酸解離定数の逆数の対数値をｐＫ１としている。各化合物のｐＫ１は例えば改訂４版化学便覧（基礎編）II、ｐｐ３１６−３２５（日本化学会編）等に記載されている。なお、本発明においては、ナノスクラッチの低減と研磨速度の向上の両立の観点から、ｐＫ１が２以下の酸を用いることが特に好ましい。 The acid contained in the polishing composition used in the present invention is preferably a compound having a pK1 of 7 or less, and more preferably has a pK1 of 3 or less, more preferably 2.5 or less, from the viewpoint of reducing nanoscratches. Even more preferably, it is 2 or less, still more preferably 1.5 or less, and still more preferably a compound exhibiting strong acidity that cannot be expressed by pK1. Examples include nitric acid, sulfuric acid, sulfurous acid, persulfuric acid, hydrochloric acid, perchloric acid, phosphoric acid, phosphonic acid, phosphinic acid, pyrophosphoric acid, oxalic acid, amidosulfuric acid, aspartic acid, 2-aminoethylphosphonic acid, glutamic acid, Examples include picolinic acid. Among these, nitric acid, sulfuric acid, hydrochloric acid, and perchloric acid are preferable from the viewpoint of reducing nanoscratches. These acids may be used alone or in admixture of two or more. Here, pK1 represents the logarithm of the reciprocal of the acid dissociation constant (25 ° C.) of an organic compound or inorganic compound, usually pKa, and the logarithm of the reciprocal of the first acid dissociation constant is pK1. The pK1 of each compound is described in, for example, the revised 4th edition, Chemical Handbook (Basic Edition) II, pp316-325 (Edited by Chemical Society of Japan). In the present invention, it is particularly preferable to use an acid having a pK1 of 2 or less from the viewpoint of achieving both reduction of nanoscratches and improvement of the polishing rate.
また、本発明においては、前記酸の塩を酸のかわりに使用することができる。塩の対イオンとしては、イオン化傾向がＮｉより大きい金属元素の陽イオン、アンモニウムイオン等が挙げられ、中でも、ナトリウムイオン、ニッケルイオン、カリウムイオン、鉄イオン、アンモニウムイオン等が好ましい。 In the present invention, the acid salt may be used in place of the acid. Examples of the counter ion of the salt include a cation of a metal element having an ionization tendency larger than that of Ni, an ammonium ion, and the like. Among them, sodium ion, nickel ion, potassium ion, iron ion, ammonium ion, and the like are preferable.
酸又はその塩の研磨液組成物中における含有量は、充分な研磨速度を発揮する観点および表面品質を向上させる観点から、０．０００１〜５重量％が好ましく、より好ましくは０．０００３〜３重量％であり、さらに好ましくは０．００１〜２重量％、さらにより好ましくは０．００２５〜１重量％である。 The content of the acid or its salt in the polishing composition is preferably 0.0001 to 5% by weight, more preferably 0.0003 to 3% from the viewpoint of exhibiting a sufficient polishing rate and improving the surface quality. % By weight, more preferably 0.001 to 2% by weight, still more preferably 0.0025 to 1% by weight.
本発明で使用される研磨液組成物は、媒体として水を含有する。研磨液組成物中における水の含有量は、被研磨物を効率よく研磨する観点から、好ましくは７５重量％以上であり、より好ましくは８２重量％以上であり、さらに好ましくは８５重量％以上であり、さらにより好ましくは８９重量％以上であり、また、好ましくは９９．４重量％以下であり、より好ましくは９８．９重量％以下であり、さらに好ましくは９６．９重量％以下であり、さらにより好ましくは９４．９重量％以下である。すなわち、該含有量は、好ましくは７５〜９９．４重量％であり、より好ましくは８２〜９８．９重量％であり、さらに好ましくは８５〜９６．９重量％であり、さらにより好ましくは８９〜９４．９重量％である。 The polishing composition used in the present invention contains water as a medium. The content of water in the polishing composition is preferably 75% by weight or more, more preferably 82% by weight or more, and still more preferably 85% by weight or more from the viewpoint of efficiently polishing the object to be polished. More preferably 89% by weight or more, preferably 99.4% by weight or less, more preferably 98.9% by weight or less, still more preferably 96.9% by weight or less, Even more preferably, it is 94.9% by weight or less. That is, the content is preferably 75 to 99.4% by weight, more preferably 82 to 98.9% by weight, still more preferably 85 to 96.9% by weight, and even more preferably 89. ~ 94.9% by weight.
本発明で使用される研磨液組成物は、必要に応じて、さらに過酸化水素、過ヨウ素酸塩、過マンガン酸塩等の酸化剤、ラジカル捕捉剤、包摂化合物、防錆剤、消泡剤、抗菌剤等を添加剤として含有することができる。これらの添加剤の含有量としては、ナノスクラッチ低減の観点から、研磨液組成物中、０．００１〜５重量％が好ましく、０．０１〜１重量％がより好ましい。 The polishing liquid composition used in the present invention may further include, if necessary, oxidizing agents such as hydrogen peroxide, periodate, and permanganate, radical scavengers, inclusion compounds, rust inhibitors, and antifoaming agents. Further, an antibacterial agent or the like can be contained as an additive. The content of these additives is preferably 0.001 to 5% by weight, more preferably 0.01 to 1% by weight in the polishing composition from the viewpoint of reducing nanoscratches.
本発明で使用される研磨液組成物は、コロイダルシリカ、酸又はその塩、水、及び必要であれば前記の添加剤等の他の成分を公知の方法で混合することにより調製することができる。尚、前記の研磨液組成物中の各成分の濃度は、該組成物製造時の濃度及び使用時の濃度のいずれであってもよい。通常、濃縮液として研磨液組成物は製造され、これを使用時に希釈して用いる場合が多い。 The polishing composition used in the present invention can be prepared by mixing colloidal silica, an acid or a salt thereof, water, and, if necessary, other components such as the aforementioned additives by a known method. . The concentration of each component in the polishing composition may be either the concentration at the time of manufacturing the composition or the concentration at the time of use. Usually, a polishing composition is produced as a concentrated liquid, and it is often used after being diluted at the time of use.
前記の研磨液組成物を用いた基板の研磨方法としては、例えば、研磨液組成物を希釈し、次いで不織布状の有機高分子系研磨パッド等を貼り付けた研磨盤で基板を挟み込み、基板又は研磨パッドに前記希釈された研磨液組成物をポンプ等で汲み上げ配管を通して供給し、一定圧力を加えながら研磨盤や基板を動かすことにより研磨する方法等が挙げられる。 As a method for polishing a substrate using the above polishing liquid composition, for example, the polishing liquid composition is diluted, and then the substrate is sandwiched between polishing boards on which a nonwoven organic polymer polishing pad or the like is attached. Examples include a method in which the diluted polishing liquid composition is pumped up to a polishing pad by a pump or the like and supplied through a piping, and polishing is performed by moving a polishing plate or a substrate while applying a constant pressure.
前記の研磨方法において、基板又は研磨パッドに供給される際の研磨液組成物中のＡｌ濃度は、ナノスクラッチを低減する観点から、５０ｐｐｍ以下であり、好ましくは４０ｐｐｍ以下、より好ましくは３０ｐｐｍ以下、さらに好ましくは２５ｐｐｍ以下、さらにより好ましくは２０ｐｐｍ以下、さらにより好ましくは１５ｐｐｍ以下である。 In the polishing method, the Al concentration in the polishing composition when supplied to the substrate or polishing pad is 50 ppm or less, preferably 40 ppm or less, more preferably 30 ppm or less, from the viewpoint of reducing nanoscratches. More preferably, it is 25 ppm or less, still more preferably 20 ppm or less, and still more preferably 15 ppm or less.
したがって、前記の研磨方法は、前記の研磨液組成物を基板又は研磨パッドに供給して該基板を研磨する方法であって、基板又は研磨パッドに供給される際の研磨液組成物中のアルミニウムの濃度が５０ｐｐｍ以下である研磨方法である。かかる方法を用いることにより、ナノスクラッチの発生をより効果的に抑制し、かつ研磨速度を向上させることができる。即ち、前記の研磨方法はまた、基板のナノスクラッチを低減する方法であり、具体的には、前記の研磨液組成物を基板又は研磨パッドに供給して該基板を研磨する工程を有するナノスクラッチの低減方法であって、基板又は研磨パッドに供給される際の研磨液組成物中のアルミニウム濃度が５０ｐｐｍ以下であるナノスクラッチの低減方法である。 Therefore, the polishing method is a method of polishing the substrate by supplying the polishing composition to the substrate or the polishing pad, and the aluminum in the polishing composition when supplied to the substrate or the polishing pad. Is a polishing method having a concentration of 50 ppm or less. By using such a method, it is possible to more effectively suppress the generation of nano scratches and improve the polishing rate. That is, the polishing method is also a method for reducing nano scratches on a substrate, and specifically, a nano scratch having a step of polishing the substrate by supplying the polishing composition to the substrate or polishing pad. This is a method for reducing nanoscratches in which the aluminum concentration in the polishing composition when supplied to the substrate or polishing pad is 50 ppm or less.
ナノスクラッチを低減する観点から、基板又は研磨パッドに供給される際の研磨液組成物中のコロイダルシリカに対するアルミニウムの含有量比（アルミニウム重量／コロイダルシリカ重量）は、５／１００００以下であることが好ましく、より好ましくは４／１００００以下、さらに好ましくは３／１００００以下、さらにより好ましくは２．５／１００００以下、さらにより好ましくは２／１００００以下、さらにより好ましくは１．５／１００００以下である。 From the viewpoint of reducing nanoscratches, the aluminum content ratio (aluminum weight / colloidal silica weight) to colloidal silica in the polishing composition when supplied to the substrate or polishing pad is 5/10000 or less. Preferably, it is 4/10000 or less, more preferably 3/10000 or less, even more preferably 2.5 / 10000 or less, even more preferably 2/10000 or less, and even more preferably 1.5 / 10000 or less. .
基板又は研磨パッドに供給される際の研磨液組成物中のＡｌ濃度を特定値以下に低減するための手段としては、前記のＡｌ濃度及び含有量比を満たすように予め調製された研磨液組成物を用いる手段や、 研磨液組成物をイオン交換樹脂で処理する手段等が挙げられる。なかでも、操作性の観点から、後述のように研磨液組成物の製造設備及び供給配管等からのＡｌの汚染を防止した上で、前記のＡｌ濃度及び含有量比を満たすように予め調製された研磨液組成物を用いることが好ましい。 As a means for reducing the Al concentration in the polishing composition when supplied to the substrate or polishing pad to a specific value or less, a polishing composition prepared in advance so as to satisfy the Al concentration and the content ratio. And means for treating the polishing composition with an ion exchange resin. Among them, from the viewpoint of operability, it is prepared in advance so as to satisfy the above Al concentration and content ratio after preventing contamination of Al from the manufacturing equipment and supply piping of the polishing composition as described later. It is preferable to use a polishing composition.
Ａｌ濃度が特定値以下に低減された研磨液組成物を調製するためには、研磨液組成物を調製するそれぞれの原料のＡｌ含有量を低減することが好ましい。例えば、Ａｌ含有量が低濃度に管理された原料を選定することが好ましく、また研磨液組成物の製造においては、各原料中のＡｌの除去、製造後の精製そして製造設備からの汚染防止対策等が講じられることが好ましい。例えば、研磨材として使用されるコロイダルシリカの原料となるシリカカレット等の製造においても、原石の選定、精製が十分なものであることが好ましく、製造装置、設備に至るまでＡｌの汚染を防止する種々の対策が講じられたものであることが好ましい。 In order to prepare a polishing liquid composition in which the Al concentration is reduced to a specific value or less, it is preferable to reduce the Al content of each raw material for preparing the polishing liquid composition. For example, it is preferable to select a raw material whose Al content is controlled at a low concentration, and in the production of polishing composition, removal of Al in each raw material, purification after production, and measures for preventing contamination from production equipment Etc. are preferably taken. For example, in the production of silica cullet as a raw material for colloidal silica used as an abrasive, it is preferable that the selection and purification of the raw stone is sufficient, and it prevents Al contamination up to the production equipment and facilities. It is preferable that various measures are taken.
Ａｌは、研磨液組成物を構成する後述のコロイダルシリカや酸又はその塩等の添加剤、水の各成分から持ち込まれたり、研磨液組成物を製造する装置等から持ち込まれる。そのために、本発明で使用される研磨液組成物においては、Ａｌの含有量の少ない成分を用いたり、研磨液組成物を製造する装置は、Ａｌを含む部材を使用しないようにして、研磨液組成物中のＡｌの含有量が前記範囲を越えないようにすることが好ましい。たとえば、研磨液組成物の調製、保管、又は輸送のための容器からの金属元素、特にＡｌの持ち込みに注意を払う必要があり、樹脂容器、又はポリプロピレン、ポリエチレン等の樹脂でコーティング若しくは内袋された金属製容器を使用することが好ましい。 Al is brought in from an additive such as colloidal silica or acid or salt thereof described later constituting the polishing liquid composition, water, or from an apparatus for producing the polishing liquid composition. Therefore, in the polishing composition used in the present invention, a component containing a small amount of Al or an apparatus for producing a polishing composition is used so that a member containing Al is not used. It is preferable that the Al content in the composition does not exceed the above range. For example, it is necessary to pay attention to bringing metal elements, particularly Al, from containers for the preparation, storage, or transportation of polishing liquid compositions, and they are coated or encased in resin containers or resins such as polypropylene and polyethylene. It is preferable to use a metal container.
Ａｌは、研磨液組成物を供給する配管等からも持ち込まれ得るため、基板又は研磨パッドに供給される際の研磨液組成物中のＡｌ濃度を特定値以下に低減するためには、研磨液組成物を供給する配管等についても上記と同様の対策を講じることが好ましい。具体的には、研磨液組成物を希釈するための容器やタンク、配管、ポンプ等の研磨液組成物と接触する部材は、金属元素、特にＡｌの混入を避けるために、テフロン（登録商標：ポリテトラフルオロエチレン）等の樹脂でコートされた金属、あるいはポリシリコン等の樹脂製の部材を使用することが好ましい。 Since Al can also be brought in from a pipe or the like that supplies the polishing liquid composition, in order to reduce the Al concentration in the polishing liquid composition when supplied to the substrate or polishing pad to a specific value or less, the polishing liquid It is preferable to take the same measures as described above for the piping for supplying the composition. Specifically, the member in contact with the polishing liquid composition such as a container, tank, pipe, or pump for diluting the polishing liquid composition is made of Teflon (registered trademark: It is preferable to use a metal coated with a resin such as polytetrafluoroethylene) or a resin member such as polysilicon.
本発明の基板の製造方法は、前記研磨液組成物を用いた研磨工程を有する。研磨工程としては、前記研磨方法を用いるものであればよく、具体的には、コロイダルシリカと、酸又はその塩とを含有する前記の研磨液組成物を基板又は研磨パッドに供給して該基板を研磨する工程であって、基板又は研磨パッドに供給される際の研磨液組成物中のアルミニウム濃度が５０ｐｐｍ以下である工程が挙げられる。 The manufacturing method of the board | substrate of this invention has a grinding | polishing process using the said polishing liquid composition. Any polishing process may be used as long as the polishing method is used. Specifically, the polishing composition containing colloidal silica and an acid or a salt thereof is supplied to a substrate or a polishing pad, and then the substrate is polished. And a step in which the aluminum concentration in the polishing liquid composition when supplied to the substrate or polishing pad is 50 ppm or less.
本発明の基板の製造方法では、前記研磨工程は、複数の研磨工程の中でも第２工程以降に行われるのが好ましく、最終研磨工程に行われるのが特に好ましい。中でも、基板の腐食量が少なく、表面欠陥が発生しにくい観点から、本発明の基板の製造方法においては、研磨工程の中でも前記研磨液組成物を表面研磨の仕上げ工程に用いることが好ましい。 In the substrate manufacturing method of the present invention, the polishing step is preferably performed after the second step among the plurality of polishing steps, and particularly preferably performed in the final polishing step. Among these, from the viewpoint that the amount of corrosion of the substrate is small and surface defects are less likely to occur, it is preferable to use the polishing composition in the polishing step in the polishing step in the substrate manufacturing method of the present invention.
前記の研磨液組成物を用いた研磨工程における研磨廃液、即ち、研磨機より排出された直後の研磨液組成物のpＨは、研磨速度向上及びナノスクラッチの低減の観点から、好ましくは４以下、より好ましくは３以下、さらに好ましくは２．５以下、さらにより好ましくは２以下である。また、研磨機腐食防止の観点から、該ｐＨは、好ましくは１以上、より好ましくは１．２以上、さらに好ましくは１．４以上である。即ち、該ｐＨは、好ましくは１〜４、より好ましくは１．２〜３、さらに好ましくは１．４〜２．５、さらにより好ましくは１．４〜２である。研磨廃液のｐＨは、例えば、研磨液組成物の供給流量を増減させたり、研磨液組成物中の酸の量や種類を調整することにより、上記の範囲内に調整され得る。 The polishing waste liquid in the polishing step using the polishing liquid composition, that is, the pH of the polishing liquid composition immediately after being discharged from the polishing machine, is preferably 4 or less from the viewpoint of improving the polishing rate and reducing nanoscratches. More preferably, it is 3 or less, More preferably, it is 2.5 or less, More preferably, it is 2 or less. Further, from the viewpoint of preventing corrosion of the polishing machine, the pH is preferably 1 or more, more preferably 1.2 or more, and still more preferably 1.4 or more. That is, the pH is preferably 1 to 4, more preferably 1.2 to 3, still more preferably 1.4 to 2.5, and still more preferably 1.4 to 2. The pH of the polishing waste liquid can be adjusted within the above range by, for example, increasing or decreasing the supply flow rate of the polishing liquid composition, or adjusting the amount and type of acid in the polishing liquid composition.
本発明の基板の製造方法が対象とする被研磨物（基板）の材質としては、例えば、シリコン、アルミニウム、ニッケル、タングステン、銅、タンタル、チタン等の金属又は半金属およびこれらの合金、及びガラス、ガラス状カーボン、アモルファスカーボン等のガラス状物質、アルミナ、二酸化珪素、窒化珪素、窒化タンタル、炭化チタン等のセラミック材料、ポリイミド樹脂等の樹脂等が挙げられる。これらの中では、アルミニウム、ニッケル、タングステン、銅等の金属及びこれらの金属を主成分とする合金が被研磨物であるか、又は半導体素子等の半導体基板のような、それらが金属を含んだ被研磨物であるのが好ましく、Ｎｉ−Ｐメッキされたアルミニウム合金基板がより好ましい。 Examples of the material of the object to be polished (substrate) targeted by the substrate manufacturing method of the present invention include metals, metalloids such as silicon, aluminum, nickel, tungsten, copper, tantalum, and titanium, alloys thereof, and glass. And glassy substances such as glassy carbon and amorphous carbon, ceramic materials such as alumina, silicon dioxide, silicon nitride, tantalum nitride, and titanium carbide, and resins such as polyimide resin. Among these, metals such as aluminum, nickel, tungsten, and copper and alloys based on these metals are objects to be polished, or they include metals such as semiconductor substrates such as semiconductor elements. An object to be polished is preferable, and an Ni-P plated aluminum alloy substrate is more preferable.
被研磨物の形状には特に制限がなく、例えば、ディスク状、プレート状、スラブ状、プリズム状等の平面部を有する形状や、レンズ等の曲面部を有する形状が前記の研磨液組成物を用いた研磨の対象となる。その中でも、前記の研磨液組成物は、ディスク状の被研磨物の研磨に特に優れている。 The shape of the object to be polished is not particularly limited. For example, the shape having a flat portion such as a disk shape, a plate shape, a slab shape, or a prism shape, or a shape having a curved surface portion such as a lens can be used for the polishing liquid composition. It becomes the object of polishing used. Among these, the polishing liquid composition is particularly excellent for polishing a disk-shaped workpiece.
本発明で使用される研磨パッドとしては、特に制限はなく、スエードタイプ、不織布タイプ、ポリウレタン独立発泡タイプ、及びこれらを積層した二層タイプ等の研磨パッドを使用することができる。 There is no restriction | limiting in particular as a polishing pad used by this invention, Polishing pads, such as a suede type, a nonwoven fabric type, a polyurethane independent foam type, and the two-layer type which laminated | stacked these, can be used.
本発明の基板の製造方法は、精密部品基板の製造に好適に用いられる。たとえば、メモリーハードディスク基板等の磁気ディスク、光ディスク、光磁気ディスク等の磁気記録媒体の基板、フォトマスク基板、光学レンズ、光学ミラー、光学プリズム、半導体基板等の精密部品基板の研磨に適している。中でも、本発明の基板の製造方法は、高密度化、高集積化において重要なナノスクラッチを顕著に低減し得るものであるため、メモリーハードディスク基板等の磁気ディスク基板や半導体基板の研磨により好適である。 The substrate manufacturing method of the present invention is suitably used for manufacturing precision component substrates. For example, it is suitable for polishing a magnetic disk medium such as a memory hard disk substrate, a magnetic recording medium substrate such as an optical disk and a magneto-optical disk, a precision component substrate such as a photomask substrate, an optical lens, an optical mirror, an optical prism, and a semiconductor substrate. Among them, the substrate manufacturing method of the present invention can remarkably reduce nano scratches that are important for higher density and higher integration, and is therefore more suitable for polishing magnetic disk substrates such as memory hard disk substrates and semiconductor substrates. is there.
本発明の製造方法により製造された基板はナノスクラッチが極めて少ないものである。従って、該基板が、たとえば、メモリーハードディスク基板である場合には、記録密度９０Ｇ／ｉｎｃｈ2 、さらには１２０Ｇ／ｉｎｃｈ2 のものにも対応することができ、半導体基板である場合には、配線幅６５ｎｍ、さらには４５ｎｍのものにも対応することができる。 The substrate manufactured by the manufacturing method of the present invention has very few nano scratches. Accordingly, when the substrate is, for example, a memory hard disk substrate, it can also cope with a recording density of 90 G / inch 2 and further 120 G / inch 2 , and when it is a semiconductor substrate, the wiring width 65 nm and even 45 nm can be supported.
実施例１〜５、比較例１〜４
以下に記載するように、Ａｌ濃度の異なる研磨液組成物を調製し、該研磨液組成物を用いて被研磨物を研磨することにより、ナノスクラッチを評価した。
Examples 1-5, Comparative Examples 1-4
As described below, nano scratches were evaluated by preparing polishing liquid compositions having different Al concentrations and polishing the object to be polished using the polishing liquid composition.
《研磨液組成物の調製》
表１に示すコロイダルシリカスラリーＡ〜Ｄ、硫酸（和光純薬工業社製 特級）、硫酸アルミニウム（和光純薬工業社製 特級）及びイオン交換水を表２に示す組成となるように、１０Ｌ容のポリエチレン製容器に添加・混合し、Ａｌ濃度の異なる研磨液組成物を得た。また、研磨液組成物を供給する際の配管には、タイゴン(登録商標)製のものを用いた。
<< Preparation of polishing liquid composition >>
Colloidal silica slurries A to D shown in Table 1, sulfuric acid (special grade manufactured by Wako Pure Chemical Industries, Ltd.), aluminum sulfate (special grade manufactured by Wako Pure Chemical Industries, Ltd.) and ion-exchanged water are prepared in a volume of 10 L so as to have the composition shown in Table 2. Were added to and mixed with a polyethylene container to obtain polishing liquid compositions having different Al concentrations. In addition, a pipe made by Tygon (registered trademark) was used as a pipe for supplying the polishing composition.
《被研磨物》
被研磨物として、Ｎｉ−Ｐメッキされたアルミニウム基板を、アルミナ研磨材を含有する研磨液組成物であらかじめ粗研磨し、Ｒａを１ｎｍとした、厚さ１．２７ｍｍのアルミニウム合金基板（外周９５ｍｍφ、内周２５ｍｍ）（以下、Ｎｉ−Ｐメッキした被研磨基板）を用いた。
《Polished object》
As an object to be polished, a Ni-P plated aluminum substrate was coarsely polished in advance with a polishing liquid composition containing an alumina abrasive, and Ra was 1 nm, and an aluminum alloy substrate (outer diameter 95 mmφ, Inner circumference 25 mm) (hereinafter, Ni-P plated substrate to be polished) was used.
《研磨条件》
・研磨試験機：スピードファム社製、両面９Ｂ研磨機
・研磨布：フジボウ社製、仕上げ研磨用パッド（厚さ０．９ｍｍ、開孔径３０μｍ、ショアＡ硬度６０°）
・定盤回転数：３２．５ｒ／ｍｉｎ
・研磨液組成物供給量：１００ｍＬ／ｍｉｎ
・研磨時間：４分
・研磨荷重：７．８ｋＰａ
・投入した基板の枚数：１０枚
<Polishing conditions>
・ Polishing tester: Speed Fam Co., double-sided 9B polishing machine ・ Polishing cloth: Fujibow Co., Ltd. polishing pad (thickness 0.9 mm, aperture diameter 30 μm, Shore A hardness 60 °)
・ Surface plate speed: 32.5r / min
Polishing liquid composition supply amount: 100 mL / min
Polishing time: 4 minutes Polishing load: 7.8 kPa
・ Number of loaded substrates: 10
《ナノスクラッチの測定条件》
・測定機器：ＶＩＳＩＯＮ ＰＳＹＴＥＣ製、「ＭｉｃｒｏＭａｘ ＶＭＸ−２１００ＣＳＰ」
・光源：２Ｓλ（２５０Ｗ）及び３Ｐλ（２５０Ｗ）共に１００％
・チルト角：−６°
・倍率：最大（視野範囲：全面積の１２０分の１）
・観察領域：全面積（外周９５ｍｍφで内周２５ｍｍの基板）
・アイリス：ｎｏｔｃｈ
・評価：研磨試験機に投入した基板の中から、無作為に４枚を選択し、その４枚の基板の各々両面にあるナノスクラッチ数（本）の合計を８で除して、基板面当たりのナノスクラッチ数を算出した。
《Nano scratch measurement conditions》
・ Measuring equipment: “MicroMax VMX-2100CSP” manufactured by VISION PSYTEC
-Light source: 100% for both 2Sλ (250W) and 3Pλ (250W)
-Tilt angle: -6 °
・ Magnification: Maximum (Field range: 1/120 of the total area)
・ Observation area: total area (substrate with outer circumference 95mmφ and inner circumference 25mm)
・ Iris: notch
・ Evaluation: 4 substrates were selected at random from the substrates put into the polishing tester, and the total number of nano scratches (both) on both surfaces of each of the 4 substrates was divided by 8. The number of nano scratches per unit was calculated.
《Ａｌの定量方法》
研磨液組成物及び基板又は研磨パッドへの供給直前で採取された研磨液組成物中のＡｌ濃度は、研磨液組成物をフッ化水素酸、硝酸で溶解し、シリカ等のＡｌ定量の妨害となる元素を除去した後、４重極型誘導結合プラズマ質量分析装置（ＩＣＰ質量分析装置：セイコーインスツルメンツ（株）製、商品名：ＳＰＱ−８０００）にて定量して求めた。
《Quantitative method of Al》
The Al concentration in the polishing liquid composition and the polishing liquid composition collected immediately before supply to the substrate or the polishing pad is obtained by dissolving the polishing liquid composition with hydrofluoric acid and nitric acid, and hindering the determination of Al such as silica. After the element was removed, it was quantitatively determined using a quadrupole type inductively coupled plasma mass spectrometer (ICP mass spectrometer: Seiko Instruments Inc., trade name: SPQ-8000).
表２に示される通り、実施例１〜５で得られた基板は、Ａｌ濃度が高い研磨液組成物を用いた比較例１〜４で得られた基板に比べ、ナノスクラッチが少ないものであることがわかる。
また、研磨液組成物中のコロイダルシリカに対するアルミニウムの含有量比が小さいと、ナノスクラッチが少なくなる傾向にあることがわかる。
また、研磨廃液のｐＨが低いと、ナノスクラッチが少なくなる傾向にあることがわかる。
As shown in Table 2, the substrates obtained in Examples 1 to 5 have less nano scratches than the substrates obtained in Comparative Examples 1 to 4 using a polishing composition having a high Al concentration. I understand that.
It can also be seen that when the content ratio of aluminum to colloidal silica in the polishing composition is small, nanoscratches tend to decrease.
It can also be seen that when the polishing waste liquid has a low pH, nanoscratches tend to decrease.
本発明の基板の製造方法は、精密部品基板の製造に好適に用いられる。たとえば、メモリーハードディスク基板等の磁気ディスク、光ディスク、光磁気ディスク等の磁気記録媒体の基板、フォトマスク基板、光学レンズ、光学ミラー、光学プリズム、半導体基板等の精密部品基板の研磨に適している。
The substrate manufacturing method of the present invention is suitably used for manufacturing precision component substrates. For example, it is suitable for polishing a magnetic disk medium such as a memory hard disk substrate, a magnetic recording medium substrate such as an optical disk and a magneto-optical disk, a precision component substrate such as a photomask substrate, an optical lens, an optical mirror, an optical prism, and a semiconductor substrate.
Claims (5)
A method for reducing nanoscratches, which comprises a step of supplying a polishing composition containing colloidal silica and an acid or a salt thereof to a substrate or a polishing pad and polishing the substrate, and the method is supplied to the substrate or the polishing pad. The method for reducing nanoscratches, wherein the aluminum concentration in the polishing composition is 50 ppm or less.
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| WO2023243611A1 (en) * | 2022-06-15 | 2023-12-21 | 株式会社レゾナック | Cmp polishing liquid and polishing method |
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