JP2013227168A - Colloidal silica having silica particle with unevenness on the surface, method for manufacturing the same, and polishing material using the same - Google Patents
Colloidal silica having silica particle with unevenness on the surface, method for manufacturing the same, and polishing material using the same Download PDFInfo
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Abstract
【課題】 半導体基板、磁気ディスク基板等の電子材料用基板の研磨剤として用いたときに高い研磨速度が得られるコロイダルシリカおよび、その製造方法を提供すること。
【解決手段】 本発明は、表面に凹凸のあるシリカ粒子を有するコロイダルシリカであって、大小二種類のシリカ粒子よりなるコロイダルシリカに粒子の結合剤を添加して、大きい粒子の表面に小さい粒子を結合させ、更に活性珪酸を添加して該粒子を一体化して得られる表面に凹凸のあるシリカ粒子を有するコロイダルシリカであり、その製造方法であり、さらにそれを用いた研磨剤であって、研磨加工に優れた性能を有する。
【選択図】図２PROBLEM TO BE SOLVED: To provide a colloidal silica capable of obtaining a high polishing rate when used as an abrasive for a substrate for electronic materials such as a semiconductor substrate and a magnetic disk substrate, and a method for producing the same.
SOLUTION: The present invention is a colloidal silica having silica particles with irregularities on the surface, in which a particle binder is added to colloidal silica composed of two types of large and small silica particles, so that small particles are formed on the surface of large particles. Is a colloidal silica having silica particles with irregularities on the surface obtained by adding the active silicic acid and integrating the particles, a manufacturing method thereof, and an abrasive using the colloidal silica, Excellent performance in polishing.
[Selection] Figure 2
Description
本発明は、シリコン基板、化合物半導体基板、半導体デバイス基板、磁気ディスク基板、サファイア基板、水晶基板等の電子材料用基板の研磨加工に用いられるコロイダルシリカ、その製造方法及びそれを用いた研磨剤に関する。 The present invention relates to colloidal silica used for polishing a substrate for electronic materials such as a silicon substrate, a compound semiconductor substrate, a semiconductor device substrate, a magnetic disk substrate, a sapphire substrate, and a quartz substrate, a manufacturing method thereof, and an abrasive using the same. .
従来より珪酸アルカリを原料として製造されるコロイダルシリカはシリコン基板等の電子材料用基板の研磨剤、ブラウン管製造における蛍光体の接着バインダー、電池中の電解液のゲル化剤および揺変や飛散防止剤など様々な用途に用いられてきた。このような用途に一般に使用されているコロイダルシリカのシリカ粒子の形状は真球状かそれに近いものであるため、研磨剤の用途では研磨特性の向上を目的として、また、バインダー用途では密着性や造膜性の向上を目的としてシリカ粒子の形状を球形から変化させたり，凝集させて粒子径を大きくする試みがなされてきた。 Colloidal silica produced from alkali silicate as a raw material is an abrasive for substrates for electronic materials such as silicon substrates, phosphor adhesive binders for cathode ray tube manufacturing, gelling agents for electrolytes in batteries, and anti-fluctuation and scattering agents. It has been used for various purposes. The shape of colloidal silica particles generally used for such applications is spherical or close to that of spherical particles. Therefore, in the use of abrasives, the purpose is to improve the polishing characteristics. Attempts have been made to increase the particle size by changing the shape of the silica particles from spherical or agglomerating for the purpose of improving the film properties.
例えば，特許文献１や特許文献２には、カルシウム塩等を添加してシリカ粒子を結合させて製造した球状でない細長い形状の粒子が記載されている。特許文献３には、塩基性アルミニウム塩または塩基性ジルコニウム塩を添加して製造したカチオン性シリカ粒子にアニオン性シリカ粒子を結合させて製造される扁平な粒子が開示されている。また，特許文献４にはカルシウム塩等を添加して細長い数珠状の形状の粒子を製造し，これが良好な研磨特性を有すると述べられている。
特許文献５には、単分散のコロイダルシリカにシリカ粒子の凝集剤を添加して球状の凝集二次粒子を作り、更に活性珪酸を添加して凝集粒子を一体化して得られる二次凝集コロイダルシリカが記載されており、優れた研磨性能が得られると述べられている。
特許文献６には、コロイダルシリカに電解質溶液と珪酸アルカリ溶液を同時添加して、コロイダルシリカのシリカ粒子を凝集一体化して製造される金平糖状シリカゾルとその製造方法の記載があり、金平糖状シリカゾルは研磨材として高い実用性を有する旨の記載がある。
しかしながら、特許文献１や特許文献２および特許文献４のようにカルシウム塩等を添加することによりシリカ粒子を細長い数珠状の形状とする方法は、バインダー用途では良好な性能が得られそうだが、研磨用途ではシリカ成分以外に高濃度のカルシウム塩等が不可避的に存在することから、それによる研磨対象の電子材料の汚染が問題となる。
特許文献３に記載の扁平な粒子も、短時間で粒子を大きく出来る利点はあるが、最終形状が扁平な粒子では、研磨性能に有利とはなりにくい。
特許文献５記載の二次凝集コロイダルシリカは、短時間で粒子を大きく出来る利点と高い研磨速度が得られる利点はあるが、表面の凹凸が大きすぎて被研磨面に傷ができ、良好な鏡面を得ることが難しいという欠点があった。
特許文献６記載の金平糖状シリカゾルも同様に、表面の凹凸が大きすぎて被研磨面に傷ができ、良好な鏡面を得ることが難しいという欠点があった。
For example, Patent Literature 1 and Patent Literature 2 describe non-spherical elongated particles produced by adding calcium salt or the like and bonding silica particles. Patent Document 3 discloses flat particles produced by binding anionic silica particles to cationic silica particles produced by adding a basic aluminum salt or basic zirconium salt. Patent Document 4 states that a long bead-like particle is produced by adding calcium salt or the like, and that this has good polishing characteristics.
Patent Document 5 discloses a secondary agglomerated colloidal silica obtained by adding a flocculating agent of silica particles to monodispersed colloidal silica to form spherical agglomerated secondary particles, and further adding active silicic acid to integrate the agglomerated particles. Is described, and it is stated that excellent polishing performance can be obtained.
Patent Document 6 describes a gold flat sugar-like silica sol produced by simultaneously adding an electrolyte solution and an alkali silicate solution to colloidal silica and agglomerating and integrating the silica particles of colloidal silica, and a method for producing the same. There is a description that it has high utility as an abrasive.
However, methods such as Patent Document 1, Patent Document 2 and Patent Document 4 in which silica salts are added to form a long and narrow bead shape by adding a calcium salt or the like seem to give good performance in binder applications. In use, since a high concentration of calcium salt or the like is unavoidably present in addition to the silica component, contamination of the electronic material to be polished due to this is a problem.
The flat particles described in Patent Document 3 also have an advantage that the particles can be enlarged in a short time. However, particles having a flat final shape are unlikely to be advantageous for polishing performance.
The secondary agglomerated colloidal silica described in Patent Document 5 has the advantage that particles can be enlarged in a short time and the advantage that a high polishing rate can be obtained, but the surface unevenness is too large and the surface to be polished can be scratched, resulting in a good mirror surface. There was a drawback that it was difficult to obtain.
Similarly, the gold flat sugar-like silica sol described in Patent Document 6 has the disadvantage that the surface unevenness is so large that the surface to be polished can be scratched and it is difficult to obtain a good mirror surface.
シリコン基板、化合物半導体基板、半導体デバイス基板、磁気ディスク基板、サファイア基板、水晶基板等の電子材料の研磨剤としてコロイダルシリカが使用されているが、研磨速度の高速化の要求に対応して、次第に粒径の大きいグレードが好まれるようになってきた。しかし、真球状のコロイダルシリカの場合、単一粒子のままで粒子径の大きいものを製造するには、粒子の表面に更にシリカを沈着させて粒子を成長させる、いわゆるビルドアップの工程に長い時間を必要とし、粒子の製造価格が高くなる。前記の電子材料の研磨処理においては、研磨時間の短縮化と共に、研磨費用の低減化も要求されており、従って短時間で効率的な研磨ができかつ安価な比較的大きい粒子径を持ったコロイダルシリカ、あるいは粒子径がさほど大きくなくても高速研磨の出来るコロイダルシリカが求められている。 Colloidal silica is used as a polishing agent for electronic materials such as silicon substrates, compound semiconductor substrates, semiconductor device substrates, magnetic disk substrates, sapphire substrates, and quartz substrates. In response to the demand for higher polishing speeds, Grades with a large particle size have come to be preferred. However, in the case of true spherical colloidal silica, in order to produce a single particle with a large particle size, it takes a long time to build up the particle by further depositing silica on the surface of the particle to grow the particle. And the manufacturing cost of the particles is high. In the above-described polishing treatment of electronic materials, it is required to reduce the polishing time as well as the polishing time. Therefore, colloidal having a relatively large particle size that can be efficiently polished in a short time and is inexpensive. There is a demand for silica or colloidal silica that can be polished at a high speed even if the particle diameter is not so large.
従って、本発明の目的は、このように、電子材料の研磨剤として使用されるコロイダルシリカとして、安価に製造することができ、かつ粒子形状が球形でなく比較的大きな粒子径を有する、従って研磨効率に優れた研磨剤として好適なコロイダルシリカ粒子、及びその製造方法を提供することである。 Accordingly, the object of the present invention is thus to be able to be manufactured at low cost as colloidal silica used as an abrasive for electronic materials, and the particle shape is not spherical but has a relatively large particle size, and therefore polishing. An object of the present invention is to provide colloidal silica particles suitable as an abrasive having excellent efficiency, and a method for producing the same.
このような目的を達成するために、本発明の発明者らは、鋭意研究した結果、大小二種類のシリカ粒子よりなるコロイダルシリカに、粒子の結合剤を添加して、大きい粒子の表面に小さい粒子を結合させ、更に活性珪酸を添加して該粒子を一体化して得られる表面に凹凸のあるシリカ粒子を有するコロイダルシリカを見出した。さらには、このようなシリカ粒子を含有するコロイダルシリカを得る製造方法を見出した。 In order to achieve such an object, the inventors of the present invention have intensively studied, and as a result, a particle binder is added to colloidal silica composed of two types of large and small silica particles, and the surface of a large particle is small. The present inventors found colloidal silica having silica particles having irregularities on the surface obtained by combining particles and further adding active silicic acid to integrate the particles. Furthermore, the manufacturing method which obtains the colloidal silica containing such a silica particle was discovered.
本発明の表面に凹凸のあるシリカ粒子を有するコロイダルシリカは、従来の細長い形状の粒子や細長い数珠状の形状の粒子とは異なる特異な形状を有することから、研磨剤、研磨組成物として有用であり、高速の研磨が可能となる。特にサファイア基板、水晶基板、ガラス基板等の硬質基板の研磨に有用である。 Colloidal silica having uneven silica particles on the surface of the present invention has a unique shape different from conventional elongated particles and elongated bead-shaped particles, and is therefore useful as an abrasive and polishing composition. Yes, high speed polishing is possible. In particular, it is useful for polishing hard substrates such as sapphire substrates, crystal substrates, and glass substrates.
本発明の表面に凹凸のあるシリカ粒子を有するコロイダルシリカは、シリカ粒子の表面に小さい粒子に起因した凹凸のあるシリカ粒子を含有しており、大小二種類のシリカ粒子よりなるコロイダルシリカに粒子の結合剤を添加して、大きい粒子の表面に小さい粒子を結合させ、更に活性珪酸を添加して該粒子を一体化して得られるコロイダルシリカである。前記「金平糖状」に対比して「牡丹餅(ぼたもち)状」とも呼べる粒子形状である。 The colloidal silica having uneven silica particles on the surface of the present invention contains uneven silica particles due to small particles on the surface of the silica particles, and the colloidal silica composed of two kinds of large and small silica particles Colloidal silica obtained by adding a binder to bind small particles to the surface of large particles and further adding active silicic acid to integrate the particles. In contrast to the “Golden sugar shape”, it has a particle shape that can also be referred to as “a peony shape”.
大きいシリカ粒子の粒子径が３０〜１００ｎｍであって、小さいシリカ粒子の粒子径が３〜１０ｎｍであることが好ましい。大きいシリカ粒子の粒子径が３０ｎｍより小さいと、大きいシリカ粒子同士の凝集・結合が起きてしまい、目的とする牡丹餅状粒子でない粒子が混在することになり、安定した品質が得られない。大きいシリカ粒子の粒子径が１００ｎｍより大きいと、研磨基板に傷が発生しやすくなり性能が低下する。小さいシリカ粒子の粒子径が３ｎｍより小さいと、凹凸の程度が小さくなり平滑表面のシリカ粒子との性能差が判然としなくなる。小さいシリカ粒子の粒子径が１０ｎｍより大きいと、大きい粒子への付着が起き難くなり、目的とする牡丹餅状粒子が得られ難くなる。より好ましくは、大きいシリカ粒子の粒子径が３０〜８０ｎｍであって、小さいシリカ粒子の粒子径が３〜８ｎｍである。 The particle diameter of the large silica particles is preferably 30 to 100 nm, and the particle diameter of the small silica particles is preferably 3 to 10 nm. If the particle diameter of the large silica particles is smaller than 30 nm, the large silica particles aggregate and bond with each other, and particles that are not the target peony-like particles are mixed, and stable quality cannot be obtained. If the particle diameter of the large silica particles is larger than 100 nm, scratches are likely to occur on the polishing substrate and the performance is deteriorated. If the particle diameter of the small silica particles is smaller than 3 nm, the degree of unevenness becomes small and the difference in performance from the silica particles on the smooth surface becomes unclear. When the particle diameter of the small silica particles is larger than 10 nm, adhesion to the large particles is difficult to occur, and it becomes difficult to obtain the desired peony-like particles. More preferably, the particle diameter of the large silica particles is 30 to 80 nm, and the particle diameter of the small silica particles is 3 to 8 nm.
結合剤はアルミン酸ソーダまたはハロゲン化アルミニウム化合物である。これらのアルミニウム化合物の存在で大小粒子の結合が形成される。アルミニウム化合物の使用量は大きいシリカ粒子の比表面積より算出される。例えば、５０ｎｍのシリカ粒子をＳｉＯ２として１００ｇ含有するコロイダルシリカは、比表面積が５４．４ｍ２/ｇなので全表面積は５４４０ｍ２、すなわち５．４４×１０２１ｎｍ２、シラノール基密度は８個／ｎｍ２ なので、全シラノール基は４．３５×１０２２個、全シラノール基の１０％にアルミン酸イオンＡｌ（ＯＨ）４−を結合させるとして、アルミン酸イオンの量は４．３５×１０２1個、モル量に換算して０．００７３ｍｏｌ、Ａｌ２Ｏ３として０．７４ｇのアルミン酸ソーダの使用量になる。 The binder is sodium aluminate or an aluminum halide compound. In the presence of these aluminum compounds, large and small particle bonds are formed. The amount of aluminum compound used is calculated from the specific surface area of the large silica particles. For example, colloidal silica containing 100 g of 50 nm silica particles as SiO 2 has a specific surface area of 54.4 m 2 / g, so the total surface area is 5440 m 2 , that is, 5.44 × 10 21 nm 2 , and the silanol group density is 8 / Since it is nm 2 , the total silanol group is 4.35 × 10 22 , and the amount of aluminate ion is 4.35 × 10 21 , assuming that the aluminate ion Al (OH) 4− is bonded to 10% of the total silanol group. In terms of molar amount, 0.0073 mol, and Al 2 O 3 is used as 0.74 g of sodium aluminate.
次いで、活性珪酸を添加して該粒子を一体化するのであるが、活性珪酸の添加量は大きいシリカ粒子の粒子径を基準に算出することが出来る。活性珪酸の添加量は大きいシリカ粒子の粒子径を３〜７ｎｍ増大させるのに相当するシリカを含有することが必要である。活性珪酸を添加しないと研磨性能は全く得られない。３ｎｍより少ないと研磨時に結合が壊れやすく安定した研磨性能が得られにくい。７ｎｍよりも多いと凹凸の程度が小さくなり平滑表面のシリカ粒子との性能差が判然としなくなる。より好ましくは４〜６ｎｍである。
活性珪酸は加熱下に添加する。これはコロイダルシリカのビルドアッププロセスと同じで、大小二種類のシリカ粒子と結合剤の混合液を６０ないし１００℃に加熱して、その温度を維持しつつ、活性珪酸のシリカ成分が大小粒子の結合体を被覆していくことができる添加速度で添加する。活性珪酸の添加中は液のｐＨが９〜１１を保つようにアルカリ剤を同時添加する。アルカリ剤としては苛性ソーダ、苛性カリ、水酸化テトラメチルアンモニウムなどが使用できる。
Next, the active silicic acid is added to integrate the particles. The amount of the active silicic acid added can be calculated based on the particle diameter of the large silica particles. The addition amount of active silicic acid needs to contain silica corresponding to increasing the particle diameter of large silica particles by 3 to 7 nm. If activated silica is not added, no polishing performance can be obtained. If it is less than 3 nm, the bond is easily broken during polishing, and it is difficult to obtain stable polishing performance. If it exceeds 7 nm, the degree of unevenness becomes small, and the performance difference from the silica particles on the smooth surface becomes unclear. More preferably, it is 4-6 nm.
Activated silicic acid is added under heating. This is the same as the colloidal silica build-up process, in which the mixture of two types of large and small silica particles and a binder is heated to 60 to 100 ° C., and the temperature is maintained while the silica component of the active silicic acid is composed of large and small particles. Add at an addition rate that can coat the conjugate. During the addition of the active silicic acid, an alkali agent is added simultaneously so that the pH of the liquid is maintained at 9-11. As the alkali agent, caustic soda, caustic potash, tetramethylammonium hydroxide and the like can be used.
以下に製造方法についてより詳細に記載する。出発原料となる大小二種類のコロイダルシリカとして、市販のコロイダルシリカを利用することができる。この場合は、市販品をシリカ濃度３％程度に希釈して使用する。 The production method is described in more detail below. Commercially available colloidal silica can be used as the two large and small colloidal silicas used as starting materials. In this case, a commercially available product is diluted to a silica concentration of about 3%.
この希薄なコロイダルシリカの水溶液に、シリカ粒子の結合剤を添加して結合粒子を作成する。本発明で使用される結合剤としては、ハロゲン化アルミニウム化合物や硫酸アルミニウムのようなアルミニウム化合物も使用できるが、アニオン成分の存在が好ましくない場合もあり、アルミン酸ソーダの使用が最も好ましい。 A binder of silica particles is added to the dilute colloidal silica aqueous solution to form bonded particles. As the binder used in the present invention, an aluminum compound such as an aluminum halide compound or aluminum sulfate can be used, but the presence of an anionic component may not be preferable, and use of sodium aluminate is most preferable.
次いで、得られた結合粒子に活性珪酸を添加して結合粒子を一体化する。この結合粒子の一体化とは、結合粒子の表面にシリカを沈着・被覆させて結合を確固とするもので、結合粒子のコロイド液にｐＨが８以上、好ましくはｐＨ９〜１０を保つようにアルカリ剤を添加しながら、６０〜２４０℃、好ましくは９０〜１００℃に加温した状態で、活性珪酸をその目的とする被覆厚さに相当する添加量に応じて添加し、結合粒子の表面にシリカを沈着させて、結合粒子を更に成長させ、補強するためのものである。このようにして結合粒子を成長させる方法は、元のコロイダルシリカをそのまま成長させる場合と比べて、短い時間で大きな粒子径を得ることができる。ここで使用するアルカリ剤としては、前記したものと同一のものが使用できる。 Next, activated silica is added to the obtained bonded particles to integrate the bonded particles. The integration of the binding particles is to solidify the binding by depositing and coating silica on the surface of the binding particles. Alkaline so as to maintain a pH of 8 or more, preferably pH 9 to 10 in the colloid liquid of the binding particles. While adding the agent, in a state heated to 60 to 240 ° C., preferably 90 to 100 ° C., active silicic acid is added according to the addition amount corresponding to the target coating thickness, and the surface of the binding particles is added. Silica is deposited to further grow and reinforce the binding particles. In this way, the method of growing the binding particles can obtain a large particle size in a short time compared to the case of growing the original colloidal silica as it is. As the alkali agent used here, the same one as described above can be used.
次いで、限外濾過膜によってシリカの濃度が１０〜６０％となるように濃縮する。 Subsequently, it concentrates so that the density | concentration of a silica may be 10-60% with an ultrafiltration membrane.
限外濾過膜が適用される分離は対象粒子が１ｎｍから数ミクロンであるが、溶解した高分子物質をも対象とするため、ナノメータ域では濾過精度を分画分子量で表現している。本発明によるコロイダルシリカの濃縮では、分画分子量１５０００以下の限外濾過膜を使用する。この範囲の膜を使用すると１ｎｍ以上の粒子を分離することが出来る。更に好ましくは分画分子量３０００〜１５０００の限外濾過膜を使用する。３０００未満の膜では濾過抵抗が大きすぎて処理時間が長くなり不経済であり、１５０００以上では膜細孔部にシリカ粒子が捕らえられ、かえって濾過速度の低下をまねく。膜の材質はポリスルホン、ポリアクリルニトリル、燒結金属、セラミック、カーボンなどあり、いずれも使用できるが、耐熱性や濾過速度などからポリスルホン製の膜が使用しやすい。膜の形状はスパイラル型、チューブラー型、中空糸型などあり、どれでも使用できるが、中空糸型がコンパクトで使用しやすい。 In the separation to which the ultrafiltration membrane is applied, the target particle is 1 nm to several microns, but since the dissolved polymer substance is also targeted, the filtration accuracy is expressed by the fractional molecular weight in the nanometer range. In the concentration of colloidal silica according to the present invention, an ultrafiltration membrane having a molecular weight cut-off of 15000 or less is used. When a film in this range is used, particles of 1 nm or more can be separated. More preferably, an ultrafiltration membrane having a molecular weight cutoff of 3000 to 15000 is used. When the membrane is less than 3000, the filtration resistance is too large and the treatment time becomes long, which is uneconomical. When the membrane is 15000 or more, silica particles are trapped in the pores of the membrane, and the filtration rate is lowered. The material of the membrane includes polysulfone, polyacrylonitrile, sintered metal, ceramic, and carbon, and any of them can be used. However, a membrane made of polysulfone is easy to use because of heat resistance and filtration speed. There are spiral, tubular, and hollow fiber types that can be used, but the hollow fiber type is compact and easy to use.
また、本発明は、このようにして得られる表面に凹凸のあるシリカ粒子を有するコロイダルシリカを含有する電子材料用研磨剤組成物である。本発明の一体化された結合粒子を含有するコロイダルシリカは、その表面が凹凸状をした、いわゆる牡丹餅状の形状の粒子であり、かつ電子顕微鏡写真では平均粒子径が３０ｎｍ〜１００ｎｍと比較的大きな粒子である。このような特殊な形状を有し比較的大きな粒子であるため、電子材料用の研磨加工に使用すると優れた研磨特性を発揮する。 Moreover, this invention is an abrasive | polishing agent composition for electronic materials containing the colloidal silica which has a silica particle with an unevenness | corrugation on the surface obtained in this way. The colloidal silica containing the integrated binding particles of the present invention is a so-called peony cocoon-shaped particle having an uneven surface, and has an average particle diameter of 30 nm to 100 nm in an electron micrograph. Large particles. Since it is such a special shape and relatively large particles, it exhibits excellent polishing characteristics when used for polishing processing for electronic materials.
本発明の電子材料用研磨剤組成物は、このコロイダルシリカ粒子を１〜６０重量％、好ましくは１〜３０重量％の割合で含むコロイダルシリカである。本発明の電子材料用研磨剤組成物には、研磨対象の材料の種類や研磨条件等に応じて、ｐＨ調節剤、金属溶解剤、酸化剤、キレート剤、腐食防止剤、殺菌剤などを必要に応じて加えることができる。また、研磨面やパッドの濡れ性の改善には、界面活性剤や水溶性高分子を加えることができる。更に、その他のコロイド、例えばアルミナゾル、酸化セリウムゾル、酸化ジルコニウムゾルなども加えることもでき、それらの微粒子粉体を加えることもできる。本発明の研磨剤が使用できる研磨対象材料は種々の電子材料であるが、特にシリコン基板、化合物半導体基板、半導体デバイス基板、磁気ディスク基板、サファイア基板、又は水晶基板の研磨に有用である。 The abrasive composition for electronic materials of the present invention is colloidal silica containing 1 to 60% by weight, preferably 1 to 30% by weight of the colloidal silica particles. The abrasive composition for electronic materials of the present invention requires a pH adjuster, a metal dissolving agent, an oxidizing agent, a chelating agent, a corrosion inhibitor, a disinfectant, etc., depending on the type of material to be polished and the polishing conditions. Can be added according to. In addition, a surfactant or a water-soluble polymer can be added to improve the wettability of the polished surface or pad. Furthermore, other colloids such as alumina sol, cerium oxide sol, zirconium oxide sol, etc. can be added, and fine particle powders thereof can also be added. The materials to be polished that can be used with the abrasive of the present invention are various electronic materials, and are particularly useful for polishing silicon substrates, compound semiconductor substrates, semiconductor device substrates, magnetic disk substrates, sapphire substrates, or quartz substrates.
以下に、実施例によって本発明をさらに詳細に説明する。実施例中「％」は重量基準である。粒子径は窒素吸着ＢＥＴ法による測定値である。測定装置は以下のものを使用した。
（１）ＴＥＭ観察：（株）日立製作所、透過型電子顕微鏡Ｈ−２７００型を使用した。
（２）ＢＥＴ法比表面積：（株）ユアサアイオニクス、ＮＯＶＡ−４２００ｅ型を使用した。
Hereinafter, the present invention will be described in more detail by way of examples. In the examples, “%” is based on weight. The particle diameter is a value measured by a nitrogen adsorption BET method. The following measuring apparatus was used.
(1) TEM observation: Hitachi, Ltd., transmission electron microscope H-2700 type was used.
(2) BET specific surface area: Yuasa Ionics Co., Ltd., NOVA-4200e type was used.
実施例１
脱イオン水２５８６ｇにＪＩＳ３号珪酸ソーダ（ＳｉＯ2 ：２９．０％、Ｎａ2Ｏ：９．７％、Ｈ2Ｏ：６１．３％）４１４ｇを加えて均一に混合し、ＳｉＯ2を４．０％含む希釈珪酸ソーダを作成した。この希釈珪酸ソーダを予め塩酸によって再生したＨ型強酸性陽イオン交換樹脂のカラムに通して脱アルカリし、シリカ濃度３．６％でｐＨ２．９の活性珪酸３０４０ｇを得た。
Example 1
JIS3 No. sodium silicate 2586g (SiO 2: 29.0%, Na 2 O: 9.7%, H 2 O: 61.3%) 414g added with mixing to homogeneity, the SiO 2 4. Diluted sodium silicate containing 0% was prepared. This diluted sodium silicate was passed through a column of an H-type strongly acidic cation exchange resin previously regenerated with hydrochloric acid to remove alkali, to obtain 3040 g of active silicic acid having a silica concentration of 3.6% and a pH of 2.9.
脱イオン水９１１８ｇにシリカ濃度３４％で粒子径５０ｎｍの大粒子コロイダルシリカ８８２ｇを混合し、シリカ濃度３％の希釈大粒子コロイダルシリカを得た。別途、脱イオン水１８７ｇにシリカ濃度１５％で粒子径７ｎｍの小粒子コロイダルシリカ１３ｇを混合し、シリカ濃度１％の希釈小粒子コロイダルシリカを得た。希釈大粒子コロイダルシリカに攪拌下で希釈小粒子コロイダルシリカを添加した。次に、アルミン酸ソーダ液（Ａｌ2Ｏ3：２０％、Ｎａ2Ｏ：１９％、Ｈ2Ｏ：６１％）を脱イオン水で１０倍に希釈した希釈アルミン酸ソーダ液１１２ｇを混合した。全溶液を混合し、３０分間攪拌した後、９８℃まで加熱し、この温度を１時間保った後、上記の活性珪酸３０４０ｇと１％苛性ソーダ２９５ｇを１．６時間かけて添加した。添加中は９８℃を保ち、添加終了後も９８℃に加熱して１時間この温度を保った後、５０℃まで放冷した。得られたコロイダルシリカ分散液を、分画分子量６０００の中空糸型限外濾過膜（旭化成（株）製マイクローザＵＦモジュールＳＩＰ−１０１３）を用いてポンプ循環送液による加圧濾過を行い、シリカ濃度３０％の表面に凹凸のあるシリカ約１４００ｇを得た。このコロイダルシリカはＴＥＭ映像によると粒子表面には凹凸があり、窒素吸着ＢＥＴ法による粒子径は２５ｎｍであった。 882 g of large particle colloidal silica having a silica concentration of 34% and a particle diameter of 50 nm was mixed with 9118 g of deionized water to obtain diluted large particle colloidal silica having a silica concentration of 3%. Separately, 13 g of small particle colloidal silica having a silica concentration of 15% and a particle diameter of 7 nm was mixed with 187 g of deionized water to obtain diluted small particle colloidal silica having a silica concentration of 1%. Diluted small particle colloidal silica was added to the diluted large particle colloidal silica under stirring. Next, 112 g of diluted sodium aluminate solution obtained by diluting sodium aluminate solution (Al 2 O 3 : 20%, Na 2 O: 19%, H 2 O: 61%) 10 times with deionized water was mixed. The whole solution was mixed and stirred for 30 minutes, then heated to 98 ° C. and maintained at this temperature for 1 hour, and then 3040 g of the above active silicic acid and 295 g of 1% sodium hydroxide were added over 1.6 hours. During the addition, the temperature was maintained at 98 ° C., and even after the addition was completed, the mixture was heated to 98 ° C. and maintained at this temperature for 1 hour, and then allowed to cool to 50 ° C. The obtained colloidal silica dispersion was subjected to pressure filtration by circulating pumping liquid using a hollow fiber type ultrafiltration membrane (Microsa UF module SIP-1013 manufactured by Asahi Kasei Co., Ltd.) having a molecular weight cut off of 6000, and silica. About 1400 g of silica with irregularities on the surface with a concentration of 30% was obtained. According to the TEM image, the colloidal silica had irregularities on the particle surface, and the particle diameter by the nitrogen adsorption BET method was 25 nm.
得られた表面に凹凸のあるシリカ粒子の４００００倍のＴＥＭ写真を図１に示す。 FIG. 1 shows a 40000 times TEM photograph of the obtained silica particles having irregularities on the surface.
実施例２
脱イオン水７３３ｇにＪＩＳ３号珪酸ソーダ（ＳｉＯ2 ：２９．０％、Ｎａ2Ｏ：９．７％、Ｈ2Ｏ：６１．３％）１１７ｇを加えて均一に混合し、ＳｉＯ2を４．０％含む希釈珪酸ソーダを作成した。この希釈珪酸ソーダを予め塩酸によって再生したＨ型強酸性陽イオン交換樹脂のカラムに通して脱アルカリし、シリカ濃度３．５％でｐＨ２．９の活性珪酸９００ｇを得た。
Example 2
JIS3 No. sodium silicate 733g (SiO 2: 29.0%, Na 2 O: 9.7%, H 2 O: 61.3%) 117g added with mixing to homogeneity, the SiO 2 4. Diluted sodium silicate containing 0% was prepared. This diluted sodium silicate was passed through a column of an H-type strongly acidic cation exchange resin previously regenerated with hydrochloric acid to remove alkali, thereby obtaining 900 g of active silicic acid having a silica concentration of 3.5% and a pH of 2.9.
脱イオン水２７８３ｇにシリカ濃度４１％で粒子径８０ｎｍの大粒子コロイダルシリカ２１７ｇを混合し、シリカ濃度３％の希釈大粒子コロイダルシリカを得た。別途、脱イオン水２８０ｇにシリカ濃度１５％で粒子径７ｎｍの小粒子コロイダルシリカ２０ｇを混合し、シリカ濃度１％の希釈小粒子コロイダルシリカを得た。希釈大粒子コロイダルシリカに攪拌下で希釈小粒子コロイダルシリカを添加した。次に、塩化アルミニウム６水和物（ＡｌＣｌ3・６Ｈ2Ｏ）２．６ｇを脱イオン水２３．４ｇに溶解させた溶解液２６ｇを混合した。全溶液を混合し、３０分間攪拌した後、９８℃まで加熱し、この温度を１時間保った後、活性珪酸９００ｇと１％苛性ソーダ８１ｇを１．６時間かけて添加した。添加中は９８℃を保ち、添加終了後も９８℃に加熱して１時間この温度を保った後、５０℃まで放冷した。得られたコロイダルシリカ分散液を、分画分子量６０００の中空糸型限外濾過膜（旭化成（株）製マイクローザＵＦモジュールＳＩＰ−１０１３）を用いてポンプ循環送液による加圧濾過を行い、シリカ濃度３０％の表面に凹凸のあるシリカ約４００ｇを得た。このコロイダルシリカはＴＥＭ映像によると粒子表面には凹凸があり、窒素吸着ＢＥＴ法による粒子径は２４ｎｍであった。 217 g of large particle colloidal silica having a silica concentration of 41% and a particle diameter of 80 nm was mixed with 2783 g of deionized water to obtain diluted large particle colloidal silica having a silica concentration of 3%. Separately, 280 g of deionized water was mixed with 20 g of small particle colloidal silica having a silica concentration of 15% and a particle diameter of 7 nm to obtain diluted small particle colloidal silica having a silica concentration of 1%. Diluted small particle colloidal silica was added to the diluted large particle colloidal silica under stirring. Next, 26 g of a solution obtained by dissolving 2.6 g of aluminum chloride hexahydrate (AlCl 3 .6H 2 O) in 23.4 g of deionized water was mixed. The whole solution was mixed and stirred for 30 minutes, then heated to 98 ° C. and maintained at this temperature for 1 hour, and then 900 g of active silicic acid and 81 g of 1% sodium hydroxide were added over 1.6 hours. During the addition, the temperature was maintained at 98 ° C, and even after the addition was completed, the mixture was heated to 98 ° C and maintained at this temperature for 1 hour, and then allowed to cool to 50 ° C. The obtained colloidal silica dispersion was subjected to pressure filtration by circulating pumping liquid using a hollow fiber type ultrafiltration membrane (Microsa UF module SIP-1013 manufactured by Asahi Kasei Co., Ltd.) having a molecular weight cut off of 6000, and silica. About 400 g of silica with irregularities on the surface with a concentration of 30% was obtained. According to a TEM image, the colloidal silica had irregularities on the particle surface, and the particle diameter by the nitrogen adsorption BET method was 24 nm.
得られた表面に凹凸のあるシリカ粒子の５００００倍のＴＥＭ写真を図２に示す。 FIG. 2 shows a 50,000 times TEM photograph of the obtained silica particles having irregularities on the surface.
実施例３
実施例１〜２で得た本発明のコロイダルシリカ及び市販のコロイダルシリカを用いて、表１に示す研磨剤組成物を調製した。
Example 3
The abrasive | polishing agent composition shown in Table 1 was prepared using the colloidal silica of this invention and the commercially available colloidal silica which were obtained in Examples 1-2.
これらの研磨剤組成物１〜３を用いて、下記の研磨条件で、シリコン単結晶(シリコン矩形ミラーウェハー、方位：<100>±1゜)の研磨試験を行った。これらの結果を表２に示す。
＜研磨条件＞
研磨機 ； 片面研磨機研磨パッド； ロデール(株)製ＳＵＢＡ４００
定盤回転数； １５０ｒｐｍ自転数 ； １００ｒｐｍ
加工圧力； ２３０ｇ／ｃｍ2
研磨時間； １０分
研磨液供給量；２０ｍｌ／分
＜研磨性能の評価＞
研磨速度；加工完了後のシリコンを洗浄・乾燥し、加工前後の重量減から研磨速度を求めた。
研磨痕 ；暗室で目視により研磨痕の有無を判定した。
Using these abrasive compositions 1 to 3, a polishing test of a silicon single crystal (silicon rectangular mirror wafer, orientation: <100> ± 1 °) was performed under the following polishing conditions. These results are shown in Table 2.
<Polishing conditions>
Polishing machine; Single-side polishing machine Polishing pad; SUBA400 manufactured by Rodel Corporation
Surface plate rotation speed: 150 rpm Autorotation speed: 100 rpm
Processing pressure: 230 g / cm 2
Polishing time: 10 minutes Polishing liquid supply amount: 20 ml / min <Evaluation of polishing performance>
Polishing speed: The silicon after processing was washed and dried, and the polishing speed was determined from the weight loss before and after processing.
Polishing marks: The presence or absence of polishing marks was determined visually in a dark room.
表２に示したように，本発明のコロイダルシリカを使用した研磨材組成物（Ｎｏ．１〜３）の研磨速度は、市販のコロイダルシリカを使用したものと比べ１１〜１７％の向上が得られた。 As shown in Table 2, the polishing rate of the abrasive composition (Nos. 1 to 3) using the colloidal silica of the present invention is improved by 11 to 17% compared to that using a commercially available colloidal silica. It was.
Claims (8)
The polishing agent according to claim 7, wherein the electronic material substrate is a silicon substrate, a compound semiconductor substrate, a semiconductor device substrate, a magnetic disk substrate, a sapphire substrate, or a quartz substrate.
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| JP2019522896A (en) * | 2016-05-19 | 2019-08-15 | ドンジン セミケム カンパニー リミテッドＤｏｎｇｊｉｎ Ｓｅｍｉｃｈｅｍ Ｃｏ．， Ｌｔｄ． | Slurry composition for chemical-mechanical polishing |
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| JP2023505180A (en) * | 2019-12-04 | 2023-02-08 | スリーエム イノベイティブ プロパティズ カンパニー | Microparticle slurry and its manufacturing method |
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