WO2011158522A1 - Polishing slurry and polishing method using same - Google Patents

Polishing slurry and polishing method using same Download PDF

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Publication number
WO2011158522A1
WO2011158522A1 PCT/JP2011/050632 JP2011050632W WO2011158522A1 WO 2011158522 A1 WO2011158522 A1 WO 2011158522A1 JP 2011050632 W JP2011050632 W JP 2011050632W WO 2011158522 A1 WO2011158522 A1 WO 2011158522A1
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Prior art keywords
polishing
slurry
polishing slurry
substrate
cerium oxide
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PCT/JP2011/050632
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French (fr)
Japanese (ja)
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靖英 山口
幹正 堀内
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三井金属鉱業株式会社
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Publication of WO2011158522A1 publication Critical patent/WO2011158522A1/en

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B24—GRINDING; POLISHING
    • B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
    • B24B37/00—Lapping machines or devices; Accessories
    • B24B37/04—Lapping machines or devices; Accessories designed for working plane surfaces
    • B24B37/042—Lapping machines or devices; Accessories designed for working plane surfaces operating processes therefor
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/14—Anti-slip materials; Abrasives
    • C09K3/1409—Abrasive particles per se
    • C09K3/1418—Abrasive particles per se obtained by division of a mass agglomerated by sintering
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/14—Anti-slip materials; Abrasives
    • C09K3/1454—Abrasive powders, suspensions and pastes for polishing
    • C09K3/1463—Aqueous liquid suspensions

Definitions

  • the present invention relates to a polishing slurry containing dimanganese trioxide as a main component and a polishing method using the slurry, and particularly to a polishing slurry suitable for polishing glass.
  • cerium oxide capable of polishing the glass at a high polishing speed is widely used. Although cerium oxide is produced only in China and other countries, demand is expected to increase with the expansion of production of hard disks and flat-screen TVs. Yes. Therefore, development of abrasive particles equivalent to cerium oxide has been demanded, and manganese oxide is known as one of the abrasive particles (cited documents 1 to 3).
  • a method of polishing the surface of the substrate to be polished with a polishing slurry in which polishing particles are dispersed in an aqueous liquid can be employed.
  • the concentration of the abrasive particles it is considered that the higher the concentration of the abrasive particles, the greater the contact frequency between the substrate and the abrasive particles, so that the polishing rate of the substrate can be improved.
  • the manganese oxide concentration in the polishing slurry tends to be set high in order to improve the polishing rate.
  • the manganese oxide concentration is 10 wt%.
  • an object of the present invention is to provide a polishing treatment technique that can maintain both the polishing speed and the high accuracy of the polishing surface even when the polishing particles are made of manganese oxide.
  • the present inventors have conducted intensive research on an abrasive slurry in which manganese oxide is used as abrasive particles and dispersed in an aqueous liquid. Even when the concentration of the abrasive particles is low, the chemistry of the abrasive particles has been reduced. The inventors have found that the polishing speed can be increased due to the specific characteristics, and have come up with the present invention.
  • the present invention relates to a polishing slurry for polishing a substrate.
  • the polishing particles are mainly composed of dimanganese trioxide, and the content of the polishing particles is less than 10% by weight with respect to the polishing slurry. Relates to a polishing slurry having a pH of 4 or more.
  • manganese oxide is an excellent abrasive material
  • manganese manganese oxide (Mn 2 O 3 ) is dispersed in the slurry at a low concentration of less than 10% by weight.
  • polishing performance comparable to that of conventional abrasives can be realized.
  • the polishing slurry of the present invention it is possible to maintain a polishing rate comparable to that of cerium oxide even when the content of abrasive particles is as low as less than 10% by weight (wt%), and the polished surface of the substrate is also smooth.
  • the substrate to be polished is a substrate containing Si as a component such as soda (lime) glass, quartz glass, or liquid crystal glass, or a substrate having a surface oxide film such as a SiO 2 film.
  • a polishing material comparable to the polishing rate of cerium oxide has not been provided.
  • a polishing rate higher than that of cerium oxide can also be realized by adjusting the pH of the polishing slurry.
  • the polishing slurry of the present invention contains dimanganese trioxide as a main component as polishing particles. According to the present invention, while maintaining a polishing speed equivalent to or higher than that when cerium oxide is used, the polished surface accuracy is also good because dimanganese trioxide has a chemical action with the glass substrate. This is considered to be because the surface portion of the glass can be removed at the atomic level.
  • the abrasive particles are mainly composed of dimanganese trioxide.
  • the oxide has an X-ray peak of 10% or less.
  • the abrasive particle content in the polishing slurry is less than 10% by weight. Even if it is 10% by weight or more, the polishing speed is hardly increased, but the surface accuracy of the polished surface tends to be lowered.
  • the content of the abrasive particles is preferably 5% by weight or less, and more preferably 3% by weight or less. This is because the polishing slurry has a good balance between the polishing speed and the polishing surface accuracy.
  • the content is preferably 1% by weight or more, and if it is less than 1% by weight, the polishing rate tends to be low, and it is difficult to maintain a practical polishing rate.
  • the particle diameter of manganese oxide which is an abrasive particle, is not particularly limited, but in order to achieve smoother surface accuracy, the 50% diameter D 50 in the volume-based integrated fraction of laser diffraction / scattering particle diameter distribution measurement is It is preferably 1 ⁇ m or less, and more preferably 0.5 ⁇ m or less.
  • the polishing slurry is adjusted to pH 4 or more. This is because the higher the pH, the higher the polishing rate, and even if the content of the abrasive particles is low, a polishing rate equal to or higher than that of cerium oxide can be realized.
  • the pH is preferably pH 5 or more, more preferably pH 7 or more. A pH exceeding 13 is undesirable because it may adversely affect the polishing machine and the operator during polishing.
  • the pH is usually about 4.7 to 4.9, so that it can be used as an abrasive slurry without adjusting the pH. Preparation may be performed.
  • the chemical solution used for pH adjustment is not particularly limited, but it is preferable to use potassium salt such as potassium hydroxide or potassium pyrophosphate, ammonium salt such as ammonium polyacrylate, or ammonia in order to suppress adverse effects on the object to be polished. In particular, potassium salt is preferred.
  • water or a mixed liquid of water and an organic solvent can be used as the aqueous liquid in which the abrasive particles are dispersed.
  • the mixed solution is a mixture of at least one organic solvent having solubility in water within the range of solubility in water and containing at least 1% of water.
  • the organic solvent include alcohol and ketone.
  • alcohols that can be used as the organic solvent include methanol (methyl alcohol), ethanol (ethyl alcohol), 1-propanol (n-propyl alcohol), 2-propanol (iso-propyl alcohol, IPA), 2-methyl-1- Examples include propanol (iso-butyl alcohol), 2-methyl-2-propanol (tert-butyl alcohol), 1-butanol (n-butyl alcohol), 2-butanol (sec-butyl alcohol), and the like.
  • Polyhydric alcohols include 1,2-ethanediol (ethylene glycol), 1,2-propanediol (propylene glycol), 1,3-propanediol (trimethylene glycol), 1,2,3-propanetriol. (Glycerin).
  • ketones examples include propanone (acetone) and 2-butanone (methyl ethyl ketone, MEK).
  • tetrahydrofuran (THF), N, N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), 1,4-dioxane and the like can be used.
  • polishing slurry of the present invention even when manganese oxide is used as the polishing particles, it is possible to provide a polishing technique that can realize a polishing speed and polishing surface accuracy equivalent to or higher than those of cerium oxide.
  • Embodiments of the present invention will be described with reference to examples and comparative examples. First, the relationship between the polishing performance and the polishing particle concentration in the polishing slurry was tested.
  • Examples 1 to 3 Comparative Examples 1 and 2
  • Manganese dioxide MnO 2 (FMH, average particle diameter D 50 3 ⁇ m, manufactured by Tosoh Corporation) was wet-pulverized to an average particle diameter D 50 of 0.41 ⁇ m. After pulverization, it was calcined at 850 ° C. for 2 hours to obtain dimanganese trioxide Mn 2 O 3 . The average particle size D 50 after firing was 1.85. Thereafter, wet pulverization was performed again to obtain an average particle diameter D 50 of 0.51 ⁇ m.
  • This dimanganese trioxide (specific surface area of 32 m 2 / g) was dispersed as abrasive particles in water, which is an aqueous liquid, to prepare polishing slurries with various concentrations shown in Table 1.
  • the pH of each slurry was adjusted to the pH shown in Table 1 using potassium hydroxide.
  • the average particle diameter D 50 of Mn 2 O 3 was measured with a laser diffraction / scattering particle diameter distribution measuring apparatus (LA920, manufactured by Horiba, Ltd.).
  • soda lime glass (diameter 50 mm) was polished with each polishing slurry, and polishing characteristics were examined. Prior to the polishing treatment, the average surface roughness of the glass was measured within a range of 10 ⁇ m ⁇ 10 ⁇ m with an AFM (Atomic Force Microscope: Nanoscope IIIa manufactured by Veeco).
  • MH-N15A lat grooved manufactured by Nitta Haas Co., Ltd. was used as a polishing pad, the load was 8.2 kPa, the rotation speed was 60 rpm, and the polishing time was 30 minutes. After the polishing treatment, the polished surface was washed with water, and the attached slurry was removed and dried. The surface roughness was measured by AFM at any five points on the dry polished surface. The results of the average surface roughness measurement (range of 10 ⁇ m ⁇ 10 ⁇ m) are shown in Table 1. Further, the weight of the soda lime glass before and after polishing was measured, and the polishing rate was calculated from the surface area of the surface to be polished and the specific gravity of the glass, using the difference in weight as the amount of polishing. Table 1 shows the calculated polishing speed.
  • the polishing slurry (Examples 1 to 3) in which dimanganese trioxide as an abrasive particle is less than 10 wt% has a polishing rate comparable to that of the cerium oxide abrasive slurry (Reference Examples 3 to 5).
  • the surface roughness after polishing was smoother than that of a slurry of the same concentration of cerium oxide abrasive.
  • the polishing rate was not improved so much, but the surface roughness increased.
  • the polishing particles of Comparative Examples 3 to 7 were dimanganese dioxide, it was confirmed that the surface roughness after polishing could be finished smoothly but the polishing speed was slow.
  • Examples 4 to 8, Comparative Example 8 Next, the relationship of the polishing performance to the pH of the polishing slurry was tested.
  • a polishing slurry having a slurry concentration of 4 wt% was prepared in the same manner as in Examples 1 to 3, and then adjusted to the pH shown in Table 2 with potassium hydroxide.
  • the same substrate as in Examples 1 to 3 was polished under the same conditions. The results are shown in Table 2.
  • the polishing rate was improved by increasing the pH of the polishing slurry.
  • the polishing rate was comparable to that of the cerium oxide-based abrasive, and at a pH of 7 or more (Examples 5 to 8), the polishing rate was higher than that of the cerium oxide-based abrasive. This is presumably because the hydroxyl groups in the polishing slurry increased by raising the pH, and the chemical reactivity with the glass as the material to be polished increased.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)

Abstract

Disclosed is a polishing treatment technology that uses polishing particles consisting of manganese oxide and exhibits polishing characteristics equivalent to those of cerium oxide: namely, good polishing speed and polishing-surface precision. The disclosed polishing slurry for polishing substrates is characterized by polishing particles that consist primarily of manganese(III) oxide and constitute less than 10% of the weight of the polishing slurry. The polishing slurry is further characterized by a pH of at least 4. This polishing slurry can maintain a polishing speed and polishing-surface precision at least equivalent to those exhibited by cerium oxide.

Description

研摩スラリー及びその研摩方法Polishing slurry and polishing method thereof
　本発明は、三酸化二マンガンを主成分とする研摩スラリーとそのスラリーを用いた研摩方法に関し、特にガラスを研摩する際に好適な研摩スラリーに関する。 The present invention relates to a polishing slurry containing dimanganese trioxide as a main component and a polishing method using the slurry, and particularly to a polishing slurry suitable for polishing glass.
　ハードディスク等のガラス基板や液晶用ガラス等を研摩する研摩粒子としては、高い研摩速度でガラスを研摩できる酸化セリウムが広く用いられている。酸化セリウムは、産出国が中国等に限定されているのに対し、ハードディスクや薄型テレビ等の生産拡大に伴い需要増大の見込みとなっているため、将来的に供給不足の問題があるとされている。このため、酸化セリウムと同等の研摩粒子の開発が求められており、その研摩粒子の１つとして酸化マンガンが知られている（引用文献１～３）。 As a polishing particle for polishing a glass substrate such as a hard disk or a glass for liquid crystal, cerium oxide capable of polishing the glass at a high polishing speed is widely used. Although cerium oxide is produced only in China and other countries, demand is expected to increase with the expansion of production of hard disks and flat-screen TVs. Yes. Therefore, development of abrasive particles equivalent to cerium oxide has been demanded, and manganese oxide is known as one of the abrasive particles (cited documents 1 to 3).
　これら酸化マンガンを用いた研摩処理では、酸化セリウムを用いる場合と同様に、水性液中に研摩粒子を分散させた研摩スラリーによって研摩対象の基材表面を研摩する手法が採用できる。研摩スラリーでは、研摩粒子の濃度が高いほど、基材と研摩粒子との接触頻度を増大できるため、基材の研摩速度を向上できると考えられている。かかる観点から、研摩粒子として酸化マンガンを用いる場合にも、研摩速度を向上させるため、研摩スラリー中の酸化マンガン濃度を高く設定する傾向にある。例えば、特許文献１では、酸化マンガン濃度を１０ｗｔ％としている。 In the polishing treatment using these manganese oxides, as in the case of using cerium oxide, a method of polishing the surface of the substrate to be polished with a polishing slurry in which polishing particles are dispersed in an aqueous liquid can be employed. In the polishing slurry, it is considered that the higher the concentration of the abrasive particles, the greater the contact frequency between the substrate and the abrasive particles, so that the polishing rate of the substrate can be improved. From this point of view, when manganese oxide is used as the abrasive particles, the manganese oxide concentration in the polishing slurry tends to be set high in order to improve the polishing rate. For example, in Patent Document 1, the manganese oxide concentration is 10 wt%.
特開平１０－７２５７８号公報Japanese Patent Laid-Open No. 10-72578 特開平１０－６０４１５号公報Japanese Patent Laid-Open No. 10-60415 特開２００６－１２１１１１号公報JP 2006-121111 A
　しかしながら、研摩スラリー中の酸化マンガン濃度を高くすると、研摩速度は大きくなるものの、基材表面に研摩粒子が滞留しやすくなり、研摩面の面精度が低下しやすい傾向となる。このような背景から、本発明は、研摩粒子を酸化マンガンとした場合にも、研摩速度と研摩面精度の高さをいずれも維持できる研摩処理技術の提供を目的とする。 However, when the manganese oxide concentration in the polishing slurry is increased, the polishing rate increases, but the polishing particles tend to stay on the surface of the base material, and the surface accuracy of the polishing surface tends to decrease. From such a background, an object of the present invention is to provide a polishing treatment technique that can maintain both the polishing speed and the high accuracy of the polishing surface even when the polishing particles are made of manganese oxide.
　上記課題を解決すべく、本発明者等は、酸化マンガンを研摩粒子として用い水性液に分散させた研摩スラリーについて鋭意研究したところ、研摩粒子の濃度が低い場合であっても、研摩粒子の化学的な特性により、研摩速度を高くすることができることを見出し、本発明を想到するに至った。 In order to solve the above-mentioned problems, the present inventors have conducted intensive research on an abrasive slurry in which manganese oxide is used as abrasive particles and dispersed in an aqueous liquid. Even when the concentration of the abrasive particles is low, the chemistry of the abrasive particles has been reduced. The inventors have found that the polishing speed can be increased due to the specific characteristics, and have come up with the present invention.
　本発明は、基材を研摩するための研摩スラリーにおいて、研摩粒子は三酸化二マンガンを主成分とし、研摩粒子の含有量は、研摩スラリーに対して１０重量％未満であり、研摩スラリーのｐＨはｐＨ４以上であることを特徴とする研摩スラリーに関する。従来より酸化マンガンが優れた研摩材であることは知られているものの、この酸化マンガンの中でも、特に三酸化二マンガン（Ｍｎ２Ｏ３）を１０重量％未満の低濃度でスラリー中に分散させ、かつスラリーｐＨをｐＨ４以上にすると、従来の研摩材に匹敵する研摩性能が実現できるのである。 The present invention relates to a polishing slurry for polishing a substrate. The polishing particles are mainly composed of dimanganese trioxide, and the content of the polishing particles is less than 10% by weight with respect to the polishing slurry. Relates to a polishing slurry having a pH of 4 or more. Although it is known that manganese oxide is an excellent abrasive material, manganese manganese oxide (Mn 2 O 3 ) is dispersed in the slurry at a low concentration of less than 10% by weight. When the slurry pH is 4 or more, polishing performance comparable to that of conventional abrasives can be realized.
　本発明の研摩スラリーによれば、研摩粒子の含有量を１０重量％（ｗｔ％）未満という低濃度としても、酸化セリウムと同程度の研摩速度を維持できることに加え、基材の研摩面も平滑に研摩処理できる。特に、研摩する基材が、ソーダ（ライム）ガラスや石英ガラス、液晶用ガラスのようにＳｉを成分に含む基材である場合や、ＳｉＯ２膜のような表面酸化膜を備えた基材である場合、酸化セリウムの研摩速度に匹敵する研摩材料が提供されていなかったところ、本発明によれば、研摩スラリーのｐＨを調整することにより、酸化セリウムより高い研摩速度も実現できる。 According to the polishing slurry of the present invention, it is possible to maintain a polishing rate comparable to that of cerium oxide even when the content of abrasive particles is as low as less than 10% by weight (wt%), and the polished surface of the substrate is also smooth. Can be polished. In particular, when the substrate to be polished is a substrate containing Si as a component such as soda (lime) glass, quartz glass, or liquid crystal glass, or a substrate having a surface oxide film such as a SiO 2 film. In some cases, a polishing material comparable to the polishing rate of cerium oxide has not been provided. According to the present invention, a polishing rate higher than that of cerium oxide can also be realized by adjusting the pH of the polishing slurry.
　以下、本発明の研摩スラリーについて詳細に説明する。本発明の研摩スラリーは、研摩粒子として三酸化二マンガンを主成分とする。本発明によると、酸化セリウムを用いた場合と同等以上の研摩速度を維持しつつ、研摩面精度も良好なものとなるのは、三酸化二マンガンが、基材であるガラスと化学的作用を生じ、原子レベルでガラスの表面部分を除去できるためと考えられる。ここで、本発明において「研摩粒子が三酸化二マンガンを主成分とする」とは、研摩スラリーに用いる研摩粒子のＸ線回折測定において、三酸化二マンガンの最大Ｘ線ピークに対して、他の酸化物のＸ線ピークが１０％以下であるものをいう。 Hereinafter, the polishing slurry of the present invention will be described in detail. The polishing slurry of the present invention contains dimanganese trioxide as a main component as polishing particles. According to the present invention, while maintaining a polishing speed equivalent to or higher than that when cerium oxide is used, the polished surface accuracy is also good because dimanganese trioxide has a chemical action with the glass substrate. This is considered to be because the surface portion of the glass can be removed at the atomic level. Here, in the present invention, “the abrasive particles are mainly composed of dimanganese trioxide” means that, in the X-ray diffraction measurement of the abrasive particles used in the polishing slurry, The oxide has an X-ray peak of 10% or less.
　そして、本発明において、研摩スラリー中の研摩粒子含有量は１０重量％未満である。１０重量％以上としても、研摩速度はほとんど速くならず、むしろ研摩面の面精度が低下する傾向となる。研摩粒子の含有量は、５重量％以下が好ましく、３重量％以下がより好ましい。研摩速度と研摩面精度のバランスの良い研摩スラリーとなるからである。また、含有量は１重量％以上が好ましく、１重量％未満では、研摩速度が低い傾向となり、実用的な研摩速度を維持しにくい。 In the present invention, the abrasive particle content in the polishing slurry is less than 10% by weight. Even if it is 10% by weight or more, the polishing speed is hardly increased, but the surface accuracy of the polished surface tends to be lowered. The content of the abrasive particles is preferably 5% by weight or less, and more preferably 3% by weight or less. This is because the polishing slurry has a good balance between the polishing speed and the polishing surface accuracy. The content is preferably 1% by weight or more, and if it is less than 1% by weight, the polishing rate tends to be low, and it is difficult to maintain a practical polishing rate.
　研摩粒子である酸化マンガンの粒子径は特に制限されないが、より平滑な面精度を実現するためには、レーザ回折・散乱法粒子径分布測定の体積基準の積算分率における５０％径Ｄ５０が１μｍ以下であることが好ましく、０．５μｍ以下がより好ましい。 The particle diameter of manganese oxide, which is an abrasive particle, is not particularly limited, but in order to achieve smoother surface accuracy, the 50% diameter D 50 in the volume-based integrated fraction of laser diffraction / scattering particle diameter distribution measurement is It is preferably 1 μm or less, and more preferably 0.5 μm or less.
　また、研摩スラリーはｐＨ４以上とする。ｐＨの高いほど研摩速度を向上できるため、研摩粒子の含有量を低濃度としても、酸化セリウムと同等以上の研摩速度を実現できるからである。このためｐＨは、好ましくはｐＨ５以上であり、より好ましくはｐＨ７以上である。ｐＨは１３を超えると、研摩の際、研摩機や作業者に対し悪影響を与える場合があるため望ましくない。 Also, the polishing slurry is adjusted to pH 4 or more. This is because the higher the pH, the higher the polishing rate, and even if the content of the abrasive particles is low, a polishing rate equal to or higher than that of cerium oxide can be realized. For this reason, the pH is preferably pH 5 or more, more preferably pH 7 or more. A pH exceeding 13 is undesirable because it may adversely affect the polishing machine and the operator during polishing.
　研摩粒子として三酸化二マンガンを水に分散させた場合、通常ｐＨはｐＨ４．７～４．９程度となるので、特にｐＨ調整せずに研摩スラリーとして使用できるが、より好ましいｐＨ範囲にするため調製を行ってもよい。ｐＨ調整に用いる薬液は特に制限はないが、研摩対象への悪影響を抑制するため、水酸化カリウム又はピロリン酸カリウム等のカリウム塩、ポリアクリル酸アンモニウム等のアンモニウム塩、若しくはアンモニアを用いることが好ましく、特にカリウム塩が好ましい。 When dimanganese trioxide is dispersed in water as abrasive particles, the pH is usually about 4.7 to 4.9, so that it can be used as an abrasive slurry without adjusting the pH. Preparation may be performed. The chemical solution used for pH adjustment is not particularly limited, but it is preferable to use potassium salt such as potassium hydroxide or potassium pyrophosphate, ammonium salt such as ammonium polyacrylate, or ammonia in order to suppress adverse effects on the object to be polished. In particular, potassium salt is preferred.
　本発明の研摩スラリーにおいて、研摩粒子を分散させる水性液としては、水、又は水と有機溶媒との混合液を用いることができる。混合液は、水に対し溶解度がある少なくとも１種以上の有機溶媒を、水に対し溶解度の範囲内で混合したものであり、水を少なくとも１％含むのをいう。この有機溶媒としては、アルコールやケトン等が挙げられる。 In the polishing slurry of the present invention, water or a mixed liquid of water and an organic solvent can be used as the aqueous liquid in which the abrasive particles are dispersed. The mixed solution is a mixture of at least one organic solvent having solubility in water within the range of solubility in water and containing at least 1% of water. Examples of the organic solvent include alcohol and ketone.
　有機溶媒として使用可能なアルコールとしては、メタノール（メチルアルコール）、エタノール（エチルアルコール）、１－プロパノール（ｎ－プロピルアルコール）、２－プロパノール（ｉｓｏ－プロピルアルコール、ＩＰＡ）、２－メチル－１－プロパノール（ｉｓｏ－ブチルアルコール）、２－メチル－２－プロパノール（ｔｅｒｔ－ブチルアルコール）、１－ブタノール（ｎ－ブチルアルコール）、２－ブタノール（ｓｅｃ－ブチルアルコール）等が挙げられる。また、多価アルコールとしては、１，２－エタンジオール（エチレングリコール）、１，２－プロパンジオール（プロピレングリコール）、１，３－プロパンジオール（トリメチレングリコール）、１，２，３－プロパントリオール（グリセリン）が挙げられる。 Examples of alcohols that can be used as the organic solvent include methanol (methyl alcohol), ethanol (ethyl alcohol), 1-propanol (n-propyl alcohol), 2-propanol (iso-propyl alcohol, IPA), 2-methyl-1- Examples include propanol (iso-butyl alcohol), 2-methyl-2-propanol (tert-butyl alcohol), 1-butanol (n-butyl alcohol), 2-butanol (sec-butyl alcohol), and the like. Polyhydric alcohols include 1,2-ethanediol (ethylene glycol), 1,2-propanediol (propylene glycol), 1,3-propanediol (trimethylene glycol), 1,2,3-propanetriol. (Glycerin).
　また、ケトンとしては、プロパノン（アセトン）、２－ブタノン（メチルエチルケトン、ＭＥＫ）等が挙げられる。その他、テトラヒドロフラン（ＴＨＦ）、Ｎ，Ｎ－ジメチルホルムアミド（ＤＭＦ）、ジメチルスルホキシド（ＤＭＳＯ）、１，４－ジオキサン等も使用できる。 Examples of ketones include propanone (acetone) and 2-butanone (methyl ethyl ketone, MEK). In addition, tetrahydrofuran (THF), N, N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), 1,4-dioxane and the like can be used.
　本発明の研摩スラリーによれば、研摩粒子として酸化マンガンを用いた場合にも、酸化セリウムと同等以上の研摩速度と研摩面精度を実現可能な研摩処理技術を提供できる。 According to the polishing slurry of the present invention, even when manganese oxide is used as the polishing particles, it is possible to provide a polishing technique that can realize a polishing speed and polishing surface accuracy equivalent to or higher than those of cerium oxide.
　本発明の実施形態について、実施例及び比較例を参照して説明する。まず、研摩スラリー中の研摩粒子濃度に対する研摩性能の関係について試験した。 Embodiments of the present invention will be described with reference to examples and comparative examples. First, the relationship between the polishing performance and the polishing particle concentration in the polishing slurry was tested.
[実施例１～実施例３、比較例１、２]
二酸化マンガンＭｎＯ２（ＦＭＨ、平均粒径Ｄ５０　３μｍ、東ソー（株）製）を湿式粉砕して、平均粒径Ｄ５０　０．４１μｍとした。粉砕後、８５０℃で２時間焼成して三酸化二マンガンＭｎ２Ｏ３とした。焼成後の平均粒径Ｄ５０は１．８５μｍであった。その後、再度湿式粉砕し、平均粒径Ｄ５０　０．５１μｍとした。この三酸化二マンガン（比表面積３２ｍ２／ｇ）を研摩粒子として、水性液である水に分散させて、表１に示す各濃度の研摩スラリーを作製した。各スラリーのｐＨは、水酸化カリウムを用いて表１に示すｐＨに調整した。尚、Ｍｎ２Ｏ３の平均粒径Ｄ５０は、レーザ回折・散乱法粒子径分布測定装置（堀場製作所製　ＬＡ９２０）により測定した。 [Examples 1 to 3, Comparative Examples 1 and 2]
Manganese dioxide MnO 2 (FMH, average particle diameter D 50 3 μm, manufactured by Tosoh Corporation) was wet-pulverized to an average particle diameter D 50 of 0.41 μm. After pulverization, it was calcined at 850 ° C. for 2 hours to obtain dimanganese trioxide Mn 2 O 3 . The average particle size D 50 after firing was 1.85. Thereafter, wet pulverization was performed again to obtain an average particle diameter D 50 of 0.51 μm. This dimanganese trioxide (specific surface area of 32 m 2 / g) was dispersed as abrasive particles in water, which is an aqueous liquid, to prepare polishing slurries with various concentrations shown in Table 1. The pH of each slurry was adjusted to the pH shown in Table 1 using potassium hydroxide. The average particle diameter D 50 of Mn 2 O 3 was measured with a laser diffraction / scattering particle diameter distribution measuring apparatus (LA920, manufactured by Horiba, Ltd.).
　そして、各研摩スラリーでソーダライムガラス（直径５０ｍｍ）を研摩し、研摩特性を調べた。研摩処理前に、ＡＦＭ（原子間力顕微鏡：Ｖｅｅｃｏ社製　ＮａｎｏｓｃｏｐｅIIIａ）にて、ガラスの平均表面粗さを１０μｍ×１０μｍの範囲で測定したところ、Ｒａ　１８ｎｍであった。 And soda lime glass (diameter 50 mm) was polished with each polishing slurry, and polishing characteristics were examined. Prior to the polishing treatment, the average surface roughness of the glass was measured within a range of 10 μm × 10 μm with an AFM (Atomic Force Microscope: Nanoscope IIIa manufactured by Veeco).
　研摩処理条件としては、ニッタ・ハース（株）製、ＭＨ－Ｎ１５Ａ（格子状溝入）を研摩パットとして用い、荷重を８．２ｋＰａ、回転速度を６０ｒｐｍとし、研摩時間を３０分間とした。研摩処理後、研摩面を水洗し、付着したスラリーを除去し乾燥した。その乾燥した研摩表面の任意の五個所について、ＡＦＭにより表面粗さを測定した。その平均表面粗さ測定（１０μｍ×１０μｍの範囲）の結果を表１に示す。また、研摩前と研摩後のソーダライムガラスの重量を測定し、その重量差を研摩量として、被研摩面の表面積とガラスの比重から研摩速度を算出した。算出した研摩速度を表１に示す。 As polishing conditions, MH-N15A (lattice grooved) manufactured by Nitta Haas Co., Ltd. was used as a polishing pad, the load was 8.2 kPa, the rotation speed was 60 rpm, and the polishing time was 30 minutes. After the polishing treatment, the polished surface was washed with water, and the attached slurry was removed and dried. The surface roughness was measured by AFM at any five points on the dry polished surface. The results of the average surface roughness measurement (range of 10 μm × 10 μm) are shown in Table 1. Further, the weight of the soda lime glass before and after polishing was measured, and the polishing rate was calculated from the surface area of the surface to be polished and the specific gravity of the glass, using the difference in weight as the amount of polishing. Table 1 shows the calculated polishing speed.
[比較例３～７]
　実施例１と同じ二酸化マンガンＭｎＯ２（東ソー（株）、ＦＭＨ、平均粒径Ｄ５０　３μｍ）を用い、湿式粉砕して平均粒径Ｄ５０　０．４１μｍとした後、この二酸化マンガンをそのまま研摩粒子として、水性液である水に分散させ、表１に示す各濃度の研摩スラリーを作製した。各スラリーのｐＨは、水酸化カリウムを用いて表１に示すｐＨに調整した。そして、実施例１～３と同条件により、その研摩特性を調べた。比較例３～７の各研摩スラリーの結果を表１に示す。尚、ＭｎＯ２の平均粒径Ｄ５０は、レーザ回折・散乱法粒子径分布測定装置（堀場製作所製　ＬＡ９２０）により測定した。 [Comparative Examples 3 to 7]
The same manganese dioxide MnO 2 (Tosoh Corp., FMH, average particle size D 50 3 μm) as in Example 1 was wet pulverized to an average particle size D 50 of 0.41 μm. As a result, the slurry was dispersed in water as an aqueous liquid to prepare polishing slurries having various concentrations shown in Table 1. The pH of each slurry was adjusted to the pH shown in Table 1 using potassium hydroxide. The polishing characteristics were examined under the same conditions as in Examples 1 to 3. The results of each polishing slurry of Comparative Examples 3 to 7 are shown in Table 1. The average particle diameter D 50 of MnO 2 was measured by a laser diffraction / scattering particle diameter distribution measuring apparatus (LA920 manufactured by Horiba, Ltd.).
[参考例１～５]
　酸化セリウムを主成分とする酸化セリウム系研摩材（平均粒径０．５μｍ、比表面積８ｍ２／ｇ、ミレークＭ６０、三井金属鉱業株式会社製）を用いて、実施例１～３と同条件で同じ基材について研摩処理を行った。結果を表１に示す。尚、研摩スラリーのｐＨは調整せずに研摩処理を行った。 [Reference Examples 1 to 5]
Using a cerium oxide-based abrasive containing cerium oxide as a main component (average particle size 0.5 μm, specific surface area 8 m 2 / g, Mirake M60, manufactured by Mitsui Mining & Smelting Co., Ltd.) under the same conditions as in Examples 1 to 3. The same substrate was polished. The results are shown in Table 1. The polishing treatment was performed without adjusting the pH of the polishing slurry.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　表１より、研摩粒子である三酸化二マンガンが１０ｗｔ％未満の研摩スラリー（実施例１～３）は、酸化セリウム系研摩材のスラリー（参考例３～５）と、同程度の研摩速度を維持できることに加え、同濃度の酸化セリウム系研摩材のスラリーよりも、研摩後の面粗さが平滑となった。一方、三酸化二マンガンを１０ｗｔ％以上の高濃度（比較例１、２）としても、研摩速度はあまり向上しない一方、面粗さが大きくなった。また、比較例３～７の研摩粒子が二酸化二マンガンである場合は、研摩後の面粗さを平滑に仕上げることができるものの、研摩速度が遅いことが確認された。 From Table 1, the polishing slurry (Examples 1 to 3) in which dimanganese trioxide as an abrasive particle is less than 10 wt% has a polishing rate comparable to that of the cerium oxide abrasive slurry (Reference Examples 3 to 5). In addition to being able to be maintained, the surface roughness after polishing was smoother than that of a slurry of the same concentration of cerium oxide abrasive. On the other hand, even when the concentration of dimanganese trioxide was set to a high concentration of 10 wt% or more (Comparative Examples 1 and 2), the polishing rate was not improved so much, but the surface roughness increased. Further, when the polishing particles of Comparative Examples 3 to 7 were dimanganese dioxide, it was confirmed that the surface roughness after polishing could be finished smoothly but the polishing speed was slow.
[実施例４～８、比較例８]
次に、研摩スラリーのｐＨに対する研摩性能の関係について試験した。実施例１～３と同様の方法で、スラリー濃度４ｗｔ％の研摩スラリーを作製した後、水酸化カリウムで表２に示すｐＨとなるよう調整した。各スラリーについて、実施例１～３と同一の基板を、同条件で研摩処理した。結果を表２に示す。 [Examples 4 to 8, Comparative Example 8]
Next, the relationship of the polishing performance to the pH of the polishing slurry was tested. A polishing slurry having a slurry concentration of 4 wt% was prepared in the same manner as in Examples 1 to 3, and then adjusted to the pH shown in Table 2 with potassium hydroxide. For each slurry, the same substrate as in Examples 1 to 3 was polished under the same conditions. The results are shown in Table 2.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　表２より、研摩スラリーのｐＨを上昇させると、研摩速度が向上することが分かった。ｐＨ４以上（実施例４～８）で、酸化セリウム系研摩材と同程度の研摩速度となり、ｐＨ７以上（実施例５～８）では、酸化セリウム系研摩材よりも高い研摩速度となった。これは、ｐＨを上げることにより研摩スラリー中の水酸基が増え、被研摩材であるガラスとの化学的な反応性が増したためと考えられる。 From Table 2, it was found that the polishing rate was improved by increasing the pH of the polishing slurry. At a pH of 4 or more (Examples 4 to 8), the polishing rate was comparable to that of the cerium oxide-based abrasive, and at a pH of 7 or more (Examples 5 to 8), the polishing rate was higher than that of the cerium oxide-based abrasive. This is presumably because the hydroxyl groups in the polishing slurry increased by raising the pH, and the chemical reactivity with the glass as the material to be polished increased.
　本発明によれば、酸化セリウム研摩材を使用した場合と同等のガラス研摩処理技術を提供できる。 According to the present invention, it is possible to provide a glass polishing treatment technique equivalent to the case where a cerium oxide abrasive is used.

Claims (4)

  1. 　基材を研摩するための研摩スラリーにおいて、
    　研摩粒子は三酸化二マンガンを主成分とし、研摩粒子の含有量は、研摩スラリーに対して１０重量％未満であり、研摩スラリーのｐＨはｐＨ４以上であることを特徴とする研摩スラリー。     In a polishing slurry for polishing a substrate,
    A polishing slurry characterized in that the abrasive particles are mainly composed of dimanganese trioxide, the content of the abrasive particles is less than 10% by weight with respect to the polishing slurry, and the pH of the polishing slurry is pH 4 or more.
  2. 　基材がガラスである請求項１記載の研摩スラリー。 The polishing slurry according to claim 1, wherein the substrate is glass.
  3. 　研摩粒子が三酸化二マンガンを主成分とし、研摩粒子の含有量が、研摩スラリーに対して１０重量％未満である研摩スラリーを用いて、ｐＨをｐＨ４以上に維持して基材を研摩することを特徴とする基材の研摩方法。 Abrasive particles are composed mainly of dimanganese trioxide, and the abrasive particles are less than 10% by weight based on the abrasive slurry, and the substrate is polished while maintaining the pH at pH 4 or higher. A polishing method for a substrate characterized by the above.
  4. 　基材がガラスである請求項３記載の基材の研摩方法。 The method for polishing a substrate according to claim 3, wherein the substrate is glass.
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JPH10180619A (en) * 1996-12-27 1998-07-07 Fujitsu Ltd Grinding agent, grinding method and manufacture of semiconductor device
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CN103740329B (en) * 2014-01-09 2015-03-25 上海华明高纳稀土新材料有限公司 Cerium oxide polishing powder and preparation method thereof

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