JP2014187268A - Cmp polishing agent, and method for polishing substrate - Google Patents
Cmp polishing agent, and method for polishing substrate Download PDFInfo
- Publication number
- JP2014187268A JP2014187268A JP2013061991A JP2013061991A JP2014187268A JP 2014187268 A JP2014187268 A JP 2014187268A JP 2013061991 A JP2013061991 A JP 2013061991A JP 2013061991 A JP2013061991 A JP 2013061991A JP 2014187268 A JP2014187268 A JP 2014187268A
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- Prior art keywords
- polishing
- mass
- cmp
- silica
- abrasive
- Prior art date
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Landscapes
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
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Abstract
Description
本発明は、ＣＭＰ研磨剤及び該ＣＭＰ研磨剤を用いた基板の研磨方法に関する。特に、半導体素子製造技術である、基板表面の平坦化工程に用いられるＣＭＰ研磨剤及びその製造方法、並びに該ＣＭＰ研磨剤を用いた基板の研磨方法に関する。さらに詳しくは、シャロートレンチ分離絶縁材料、プリメタル絶縁材料、層間絶縁材料等の平坦化工程において使用されるＣＭＰ研磨剤及び該ＣＭＰ研磨剤を用いた基板の研磨方法に関する。 The present invention relates to a CMP abrasive and a method for polishing a substrate using the CMP abrasive. In particular, the present invention relates to a CMP polishing agent used in a planarization process of a substrate surface, which is a semiconductor element manufacturing technique, a manufacturing method thereof, and a substrate polishing method using the CMP polishing agent. More specifically, the present invention relates to a CMP abrasive used in a planarization process of a shallow trench isolation insulating material, a premetal insulating material, an interlayer insulating material, and the like, and a substrate polishing method using the CMP abrasive.
近年の半導体素子製造工程では、高密度化・微細化のための加工技術の重要性がますます高まっている。加工技術の一つであるＣＭＰ（ケミカル・メカニカル・ポリッシング：化学機械研磨）技術は、半導体素子製造工程において、シャロートレンチ・アイソレーション（ＳＴＩ）の形成、プリメタル絶縁材料や層間絶縁材料の平坦化、プラグの形成、埋め込み金属配線の形成等に必須の技術となっている。 In recent semiconductor device manufacturing processes, the importance of processing technology for higher density and miniaturization is increasing. CMP (Chemical Mechanical Polishing) technology, which is one of the processing technologies, is the formation of shallow trench isolation (STI), planarization of premetal insulating materials and interlayer insulating materials in the semiconductor device manufacturing process, This technology is essential for forming plugs and buried metal wiring.
ＣＭＰ研磨剤として最も多用されているのは、砥粒として、ヒュームドシリカ、コロイダルシリカ等のシリカ（酸化ケイ素）粒子を含むシリカ系ＣＭＰ研磨剤である。シリカ系ＣＭＰ研磨剤は汎用性が高いことが特徴であり、砥粒濃度、ｐＨ、添加剤等を適切に選択することで、絶縁材料や導電材料を問わず幅広い種類の材料を研磨できる。 The most frequently used CMP abrasive is a silica-based CMP abrasive containing silica (silicon oxide) particles such as fumed silica and colloidal silica as abrasive grains. Silica-based CMP abrasives are characterized by high versatility, and a wide variety of materials can be polished regardless of insulating materials and conductive materials by appropriately selecting the abrasive concentration, pH, additives, and the like.
一方で、主に酸化ケイ素材料等の絶縁材料を対象とした、砥粒としてセリウム化合物粒子を含むＣＭＰ研磨剤の需要も拡大している。例えば、酸化セリウム（セリア）粒子を砥粒として含む酸化セリウム系ＣＭＰ研磨剤は、シリカ系ＣＭＰ研磨剤よりも低い砥粒濃度でも高速に酸化ケイ素材料を研磨できる（例えば、下記特許文献１、２参照）。 On the other hand, the demand for CMP abrasives containing cerium compound particles as abrasive grains, mainly for insulating materials such as silicon oxide materials, is also expanding. For example, a cerium oxide-based CMP abrasive containing cerium oxide (ceria) particles as abrasive grains can polish a silicon oxide material at high speed even with a lower abrasive concentration than a silica-based CMP abrasive (for example, Patent Documents 1 and 2 below). reference).
近年、半導体素子製造工程では、微細化が更に進行しており、研磨時に発生する研磨傷に対する要求が、より厳格となってきている。この課題に対し、前記のような酸化セリウム系ＣＭＰ研磨剤に含まれる酸化セリウム粒子の平均粒径を小さくする試みがなされている。しかし、平均粒径を小さくすると機械的作用が低下するため、研磨速度が低下してしまう問題がある。 In recent years, in the semiconductor element manufacturing process, further miniaturization has progressed, and the demand for polishing flaws occurring during polishing has become more stringent. In response to this problem, attempts have been made to reduce the average particle size of the cerium oxide particles contained in the cerium oxide-based CMP abrasive. However, if the average particle size is made small, the mechanical action is lowered, so that there is a problem that the polishing rate is lowered.
この問題に対し、４価の金属水酸化物粒子を砥粒として用いたＣＭＰ研磨剤が検討されており、この技術は下記特許文献３に開示されている。この技術は、４価の金属水酸化物粒子の化学的作用を活かし、かつ機械的作用を極力小さくすることによって、砥粒により生じる研磨傷の低減と、研磨速度の向上とを両立させたものである。 In order to solve this problem, a CMP abrasive using tetravalent metal hydroxide particles as an abrasive has been studied. This technique is disclosed in Patent Document 3 below. This technology uses both the chemical action of tetravalent metal hydroxide particles and minimizes the mechanical action, thereby reducing both polishing scratches caused by abrasive grains and improving the polishing rate. It is.
しかしながら、従来のＣＭＰ研磨剤よりも絶縁材料に対する研磨速度の更なる向上が求められているのが現状である。研磨速度を向上させるためには、一般に種々の添加剤が加えられるが、このようなアプローチには限界がある。 However, the current situation is that further improvement in the polishing rate for the insulating material is required as compared with the conventional CMP abrasive. In order to improve the polishing rate, various additives are generally added, but such an approach has its limitations.
本発明は、このような技術的課題を解決しようとするものであり、絶縁材料に対する研磨速度を向上させることが可能なＣＭＰ研磨剤及び該ＣＭＰ研磨剤を用いた基板の研磨方法を提供することを目的とする。 The present invention is intended to solve such a technical problem, and provides a CMP polishing agent capable of improving the polishing rate for an insulating material and a method for polishing a substrate using the CMP polishing agent. With the goal.
前記課題を解決するために、本発明の発明者らは、砥粒そのものが有する研磨能力を更に向上させることを検討し、特定成分を含有する混合粒子を砥粒として用いることを着想し、本発明の完成に至った。 In order to solve the above-mentioned problems, the inventors of the present invention studied to further improve the polishing ability of the abrasive grains themselves, and conceived that mixed particles containing a specific component are used as abrasive grains. The invention has been completed.
すなわち、本発明の実施態様の一つは、水及び砥粒を含み、ｐＨが５．５〜７．３であり、前記砥粒は、シリカ及びセリウム水酸化物を含み、前記セリウム水酸化物粒子の含有量が、セリウム水酸化物粒子とシリカ粒子の合計に対して２５〜９８質量％であり、前記シリカのシラノール基密度が５．０個／ｎｍ２以下である、ＣＭＰ研磨剤に関する。 That is, one embodiment of the present invention includes water and abrasive grains, and has a pH of 5.5 to 7.3, and the abrasive grains include silica and cerium hydroxide, and the cerium hydroxide It is related with CMP abrasive | polishing agent whose content of particle | grains is 25-98 mass% with respect to the sum total of a cerium hydroxide particle | grain and a silica particle, and the silanol group density of the said silica is 5.0 piece / nm < 2 > or less.
このようなＣＭＰ研磨剤によれば、従来のＣＭＰ研磨剤に比して、絶縁材料（例えば酸化ケイ素材料）に対する研磨速度を向上させることができる。特に、本発明のＣＭＰ研磨剤によれば、砥粒としてシリカ粒子及びセリウム水酸化物粒子をそれぞれ単独で又は両者を組み合わせて使用した従来のＣＭＰ研磨剤と比較して、絶縁材料に対する研磨速度を顕著に向上させることができる。 According to such a CMP abrasive, the polishing rate for an insulating material (for example, a silicon oxide material) can be improved as compared with a conventional CMP abrasive. In particular, according to the CMP abrasive of the present invention, the polishing rate for the insulating material is higher than that of a conventional CMP abrasive using silica particles and cerium hydroxide particles alone or in combination as abrasive grains. It can be remarkably improved.
本発明のＣＭＰ研磨剤において、前記シリカの平均二次粒子径が６５ｎｍ以下であることが好ましい。これにより、絶縁材料に対する研磨速度を更に向上させることができる。 In the CMP abrasive slurry of the present invention, the average secondary particle diameter of the silica is preferably 65 nm or less. Thereby, the polishing rate for the insulating material can be further improved.
また、本発明の実施態様の一つは、水及び砥粒を含み、ｐＨが５．５〜７．３であり、前記砥粒は、シリカ及びセリウム水酸化物を含み、前記セリウム水酸化物粒子の含有量が、セリウム水酸化物粒子とシリカ粒子の合計に対して２５〜９８質量％であり、前記シリカの平均二次粒子径が６５ｎｍ以下である、ＣＭＰ研磨剤に関する。 Also, one embodiment of the present invention includes water and abrasive grains, and has a pH of 5.5 to 7.3, and the abrasive grains include silica and cerium hydroxide, and the cerium hydroxide The CMP abrasive | polishing agent whose content of particle | grains is 25-98 mass% with respect to the sum total of a cerium hydroxide particle | grain and a silica particle, and the average secondary particle diameter of the said silica is 65 nm or less.
このようなＣＭＰ研磨剤によれば、従来のＣＭＰ研磨剤に比して、絶縁材料（例えば酸化ケイ素材料）に対する研磨速度を向上させることができる。特に、本発明のＣＭＰ研磨剤によれば、砥粒としてシリカ粒子及び酸化セリウム粒子をそれぞれ単独で又は両者を組み合わせて使用した従来のＣＭＰ研磨剤と比較して、絶縁材料に対する研磨速度をより向上させることができる。 According to such a CMP abrasive, the polishing rate for an insulating material (for example, a silicon oxide material) can be improved as compared with a conventional CMP abrasive. In particular, according to the CMP polishing agent of the present invention, the polishing rate for the insulating material is further improved as compared with the conventional CMP polishing agent using silica particles and cerium oxide particles alone or in combination as abrasive grains. Can be made.
本発明の実施態様において、前記セリウム水酸化物は、４価のセリウム塩と、塩基性化合物との反応物であることが好ましい。これにより、絶縁材料に対する研磨速度をより向上させることができる。 In an embodiment of the present invention, the cerium hydroxide is preferably a reaction product of a tetravalent cerium salt and a basic compound. Thereby, the grinding | polishing speed | rate with respect to an insulating material can be improved more.
同様の観点で、前記セリウム水酸化物は、セリウムに結合した陰イオン基（但し水酸化物イオンを除く）を含むことが好ましい。前記陰イオン基としては、硝酸イオン基又は硫酸イオン基が好ましい。すなわち、前記セリウム水酸化物は、セリウムに結合した硝酸イオン基又はセリウムに結合した硫酸イオン基を含むことが好ましい。 From the same viewpoint, the cerium hydroxide preferably contains an anion group (excluding hydroxide ions) bonded to cerium. The anionic group is preferably a nitrate ion group or a sulfate ion group. That is, the cerium hydroxide preferably contains a nitrate ion group bonded to cerium or a sulfate ion group bonded to cerium.
また、前記セリウム水酸化物の平均一次粒子径が１０ｎｍ以下であることが好ましい。これにより、絶縁材料に対する研磨速度を更に向上させることができる。 Moreover, it is preferable that the average primary particle diameter of the said cerium hydroxide is 10 nm or less. Thereby, the polishing rate for the insulating material can be further improved.
本発明のＣＭＰ研磨剤は、さらに水溶性ポリマを含むことが好ましい。このようなＣＭＰ研磨剤によれば、絶縁材料に対する研磨速度を更に向上させることができる。 The CMP abrasive of the present invention preferably further contains a water-soluble polymer. According to such a CMP abrasive, the polishing rate for the insulating material can be further improved.
前記水溶性ポリマは、ポリグリセリン類及びポリアリルアミン類からなる群から選択される少なくとも一種であることが好ましい。このようなＣＭＰ研磨剤によれば、絶縁材料に対する研磨速度を更に向上させることができる。 The water-soluble polymer is preferably at least one selected from the group consisting of polyglycerols and polyallylamines. According to such a CMP abrasive, the polishing rate for the insulating material can be further improved.
また、本発明は、少なくとも表面に酸化ケイ素を含む被研磨材料を研磨する研磨方法への前記ＣＭＰ研磨剤の使用に関する。すなわち、本発明のＣＭＰ研磨剤は、酸化ケイ素を含む被研磨材料を研磨するために用いられることが好ましい。 The present invention also relates to the use of the CMP abrasive in a polishing method for polishing a material to be polished containing at least silicon oxide on the surface. That is, it is preferable that the CMP abrasive | polishing agent of this invention is used in order to grind | polish the to-be-polished material containing a silicon oxide.
本発明の実施態様の一つは、酸化ケイ素を有する基板を用意するステップと、研磨パッドを用意するステップと、前記ＣＭＰ研磨剤を用意するステップと、前記基板の酸化ケイ素の少なくとも一部を除去するステップを含む、酸化ケイ素を有する基板の研磨方法に関する。 One embodiment of the present invention includes a step of preparing a substrate having silicon oxide, a step of preparing a polishing pad, a step of preparing the CMP abrasive, and removing at least a portion of the silicon oxide on the substrate. And a method for polishing a substrate having silicon oxide.
このような構成の研磨方法によれば、従来のＣＭＰ研磨剤に比して、絶縁材料（例えば酸化ケイ素材料）を、高い研磨速度で研磨できる。特に、本発明のＣＭＰ研磨剤によれば、砥粒としてシリカ粒子及び酸化セリウム粒子をそれぞれ単独で又は両者を組み合わせて使用した従来のＣＭＰ研磨剤と比較して、絶縁材料を高い研磨速度で研磨できる。 According to the polishing method having such a configuration, an insulating material (for example, a silicon oxide material) can be polished at a higher polishing rate than a conventional CMP abrasive. In particular, according to the CMP abrasive of the present invention, the insulating material is polished at a higher polishing rate than conventional CMP abrasives using silica particles and cerium oxide particles alone or in combination as abrasive grains. it can.
本発明によれば、絶縁材料に対する研磨速度を向上させることが可能なＣＭＰ研磨剤及び該ＣＭＰ研磨剤を用いた基板の研磨方法を提供できる。また、本発明によれば、特に、シャロートレンチ分離絶縁、プリメタル絶縁材料、層間絶縁材料等を平坦化するＣＭＰ技術において、絶縁材料を高速に研磨できるＣＭＰ研磨剤及び該ＣＭＰ研磨剤を用いた基板の研磨方法を提供できる。 ADVANTAGE OF THE INVENTION According to this invention, the polishing method of the board | substrate using the CMP abrasive | polishing agent which can improve the grinding | polishing rate with respect to an insulating material, and this CMP abrasive | polishing agent can be provided. In addition, according to the present invention, in particular, in a CMP technique for planarizing shallow trench isolation insulation, pre-metal insulation material, interlayer insulation material, etc., a CMP abrasive that can polish the insulation material at high speed and a substrate using the CMP abrasive Can be provided.
以下、本発明の一実施形態に係るＣＭＰ研磨剤及び該ＣＭＰ研磨剤を用いた基板の研磨方法について詳細に説明する。 Hereinafter, the CMP abrasive | polishing agent which concerns on one Embodiment of this invention, and the grinding | polishing method of the board | substrate using this CMP abrasive | polishing agent are demonstrated in detail.
本実施形態に係るＣＭＰ研磨剤は、ｐＨが５．５〜７．３であり、前記砥粒は、シリカ粒子及びセリウム水酸化物粒子を含み、前記のセリウム水酸化物粒子の含有量が、セリウム水酸化物粒子とシリカ粒子の合計に対して２５〜９８質量％であり、前記シリカ粒子のシラノール基密度が５．０個／ｎｍ２以下である。以下、各成分について順に説明する。 The CMP abrasive according to this embodiment has a pH of 5.5 to 7.3, the abrasive grains include silica particles and cerium hydroxide particles, and the content of the cerium hydroxide particles is It is 25-98 mass% with respect to the sum total of a cerium hydroxide particle | grain and a silica particle, The silanol group density of the said silica particle is 5.0 piece / nm < 2 > or less. Hereinafter, each component will be described in order.
（定義）
本実施形態の説明において、「物質Ａを研磨する」及び「物質Ａの研磨」とは、物質Ａの少なくとも一部を研磨により除去することと定義される。「高いＣＭＰ速度」とは、研磨される物質がＣＭＰ研磨により除去される速度（例えば、時間あたりの厚みの低減量）が大きいことと定義される。
(Definition)
In the description of this embodiment, “polishing the substance A” and “polishing the substance A” are defined as removing at least a part of the substance A by polishing. “High CMP rate” is defined as a high rate at which the material being polished is removed by CMP polishing (eg, a reduction in thickness per hour).
また、本実施形態の説明において「スラリー」及び「研磨液」とは、研磨時に被研磨材料に触れる組成物であり、水及び砥粒を少なくとも含んでいる。また、砥粒の含有量を所定量に調整した「水分散液」とは、所定量の砥粒と水とを含む液を意味する。 In the description of this embodiment, “slurry” and “polishing liquid” are compositions that come into contact with the material to be polished during polishing, and contain at least water and abrasive grains. Further, the “aqueous dispersion” in which the content of abrasive grains is adjusted to a predetermined amount means a liquid containing a predetermined amount of abrasive grains and water.
また、「〜」を用いて示された数値範囲は、「〜」の前後に記載される数値をそれぞれ最小値及び最大値として含む範囲を示す。 Moreover, the numerical value range shown using "to" shows the range which includes the numerical value described before and behind "to" as a minimum value and a maximum value, respectively.
（砥粒）
本実施形態のＣＭＰ研磨剤は、砥粒として、シリカ粒子及びセリウム水酸化物粒子を含有する混合砥粒を含む。このような粒子は、ヒュームドシリカやコロイダルシリカ等のシリカ粒子、酸化セリウム粒子、セリウム水酸化物等の４価の金属水酸化物粒子などを単独で使用、又は、単純に複数種の粒子を混合して使用する従来のＣＭＰ研磨剤と比較して、絶縁材料に対して高い研磨速度を示す。
(Abrasive grains)
The CMP abrasive | polishing agent of this embodiment contains the mixed abrasive grain containing a silica particle and a cerium hydroxide particle as an abrasive grain. As such particles, silica particles such as fumed silica and colloidal silica, tetravalent metal hydroxide particles such as cerium oxide particles, cerium hydroxide, etc. are used alone, or a plurality of types of particles are simply used. Compared with a conventional CMP abrasive used in combination, the insulating material exhibits a higher polishing rate.
ここで、混合砥粒とは、シリカ粒子とセリウム水酸化物粒子とが、単純な分散処理で分散されたものとして定義される。これらの粒子は、水等の媒体中でいくらか凝集する可能性はあるが、例えば、シリカ粒子とセリウム水酸化物粒子とが強固に付着又は結合した複合粒子とは明確に区別される。
混合砥粒における、セリウム水酸化物粒子の含有量は、シリカ粒子とセリウム水酸化物粒子の合計を１００質量％とした場合、２５〜９８質量％である。これにより、従来のＣＭＰ研磨剤に比して、絶縁材料（例えば酸化ケイ素材料）に対する研磨速度を向上させることが可能となる。
Here, the mixed abrasive grains are defined as silica particles and cerium hydroxide particles dispersed by a simple dispersion process. These particles may have some agglomeration in a medium such as water, but are clearly distinguished from, for example, composite particles in which silica particles and cerium hydroxide particles are firmly attached or bonded.
The content of the cerium hydroxide particles in the mixed abrasive is 25 to 98% by mass when the total of the silica particles and the cerium hydroxide particles is 100% by mass. This makes it possible to improve the polishing rate for an insulating material (for example, a silicon oxide material) as compared with a conventional CMP abrasive.
混合砥粒に用いるシリカ粒子としては、シラノール基密度が５．０個／ｎｍ２以下であれば、特に制限はなく、具体的には、コロイダルシリカやヒュームドシリカ等のシリカ粒子などが挙げられ、中でもコロイダルシリカ粒子が好ましい。また、シリカ粒子として、表面修飾をしていないシリカ粒子、シリカの表面にある水酸基をカチオン基、アニオン基、ノニオン基等で修飾したシリカ粒子、シリカの表面にある水酸基をアルコキシ基で置換したシリカ粒子などを使用できる。
また、シリカ粒子のシラノール基密度は、４．０個／ｎｍ２以下が好ましく、３．０個／ｎｍ２以下がより好ましく、２．０個／ｎｍ２以下が更に好ましい。シラノール基密度が５．０個／ｎｍ２以下であることにより、従来のＣＭＰ研磨剤に比して、絶縁材料（例えば酸化ケイ素材料）に対する研磨速度を向上させることが可能となる。
The silica particles used in the mixed abrasive are not particularly limited as long as the silanol group density is 5.0 particles / nm 2 or less, and specific examples include silica particles such as colloidal silica and fumed silica. Of these, colloidal silica particles are preferred. Further, as silica particles, silica particles that are not surface-modified, silica particles in which a hydroxyl group on the surface of the silica is modified with a cation group, an anion group, nonionic group, etc., silica in which the hydroxyl group on the surface of the silica is substituted with an alkoxy group Particles can be used.
Moreover, the silanol group density of the silica particles is preferably 4.0 pieces / nm 2 or less, more preferably 3.0 pieces / nm 2 or less, more preferably 2.0 pieces / nm 2 or less. When the silanol group density is 5.0 / nm 2 or less, the polishing rate for the insulating material (for example, silicon oxide material) can be improved as compared with the conventional CMP abrasive.
ＣＭＰ研磨剤中の砥粒の平均粒径の下限は、研磨速度が低くなりすぎることを避ける点で、５ｎｍ以上が好ましく、１０ｎｍ以上がより好ましく、２０ｎｍ以上が更に好ましい。また、砥粒の平均粒径の上限は、研磨する材料に傷がつきにくくなる点で、４００ｎｍ以下が好ましく、３００ｎｍ以下がより好ましく、２５０ｎｍ以下が更に好ましい。 The lower limit of the average grain size of the abrasive grains in the CMP abrasive is preferably 5 nm or more, more preferably 10 nm or more, and still more preferably 20 nm or more, in order to avoid the polishing rate becoming too low. Further, the upper limit of the average grain size of the abrasive grains is preferably 400 nm or less, more preferably 300 nm or less, and further preferably 250 nm or less in that the material to be polished is less likely to be damaged.
「砥粒の平均粒径」とは、ＣＭＰ研磨剤中の砥粒の平均二次粒子径を意味する。砥粒の平均粒径の測定に際しては、例えば、光回折散乱式粒度分布計（例えば、ＣＯＵＬＴＥＲ Ｅｌｅｃｔｒｏｎｉｃｓ社製、商品名：ＣＯＵＬＴＥＲ Ｎ４ＳＤや、マルバーンインスツルメンツ社製、商品名：ゼータサイザー３０００ＨＳＡ）を使用できる。具体的には、粒子径毎の存在比率を分布としてグラフにしたときに、分布の極大値となる値を平均二次粒子径としている。 The “average grain size of the abrasive grains” means the average secondary particle diameter of the abrasive grains in the CMP abrasive. In measuring the average particle size of the abrasive grains, for example, a light diffraction / scattering particle size distribution meter (for example, COULTER Electronics, trade name: COULTER N4SD, Malvern Instruments, trade name: Zeta Sizer 3000HSA) can be used. . Specifically, when the abundance ratio for each particle diameter is graphed as a distribution, the value that is the maximum value of the distribution is the average secondary particle diameter.
なお、砥粒に含まれる混合粒子において、セリウム水酸化物粒子の平均一次粒径は、シリカ粒子の平均二次粒径よりも小さいことが好ましい。
また、シリカ粒子の平均二次粒子径は、６５ｎｍ以下である。そして、セリウム水酸化物粒子の平均一次粒子径は、１０ｎｍ以下であることが好ましい。これにより、絶縁材料に対する研磨速度を更に向上させることができる。
In the mixed particles contained in the abrasive grains, the average primary particle size of the cerium hydroxide particles is preferably smaller than the average secondary particle size of the silica particles.
The average secondary particle diameter of the silica particles is 65 nm or less. And it is preferable that the average primary particle diameter of a cerium hydroxide particle is 10 nm or less. Thereby, the polishing rate for the insulating material can be further improved.
ここで、シリカ粒子の平均二次粒径子は、前記「砥粒の平均粒径」とは異なる。平均二次粒径の測定に際しては、例えば、光回折散乱式粒度分布計（例えば、ＣＯＵＬＴＥＲ Ｅｌｅｃｔｒｏｎｉｃｓ社製、商品名：ＣＯＵＬＴＥＲ Ｎ４ＳＤや、マルバーンインスツルメンツ社製、商品名：ゼータサイザー３０００ＨＳＡ）を使用できる。具体的には、粒子径毎の存在比率を分布としてグラフにしたときに、分布の極大値となる値を平均二次粒子径としている。 Here, the average secondary particle size of the silica particles is different from the “average particle size of the abrasive grains”. For the measurement of the average secondary particle size, for example, a light diffraction scattering type particle size distribution meter (for example, COULTER Electronics, trade name: COULTER N4SD, Malvern Instruments, trade name: Zeta Sizer 3000HSA) can be used. Specifically, when the abundance ratio for each particle diameter is graphed as a distribution, the value that is the maximum value of the distribution is the average secondary particle diameter.
ここで、セリウム水酸化物粒子の平均一次粒子径は、粒子一つ一つのサイズを意味し、前記「砥粒の平均粒径」とは異なる。各粒子の平均粒径は、走査型電子顕微鏡で観測して得られたＳＥＭ画像から測定できる。具体的には例えば、粒子のＳＥＭ画像について、粒子を無作為に複数個（例えば２０個）選び出す。選び出した粒子について、ＳＥＭで表示される縮尺を基準に粒径を測定する。粒径は粒子の最長径とその垂直二等分線の積の平方根として求めることができる。得られた測定値の平均値を粒子の平均一次粒子径とする。 Here, the average primary particle diameter of the cerium hydroxide particles means the size of each particle, and is different from the above-mentioned “average particle diameter of abrasive grains”. The average particle diameter of each particle can be measured from an SEM image obtained by observation with a scanning electron microscope. Specifically, for example, a plurality of particles (for example, 20 particles) are randomly selected from the SEM image of the particles. About the selected particle | grains, a particle size is measured on the basis of the reduced scale displayed by SEM. The particle size can be determined as the square root of the product of the longest diameter of the particle and its perpendicular bisector. The average value of the measured values obtained is taken as the average primary particle diameter of the particles.
砥粒の含有量（濃度）の下限は、更に好適な研磨速度を得ることができる点で、ＣＭＰ研磨剤の全質量を基準として０．０１質量％以上が好ましく、０．０５質量％以上がより好ましい。また、砥粒の含有量の上限は、砥粒の凝集を抑制できる点で、ＣＭＰ研磨剤の全質量を基準として２０質量％以下が好ましく、１５質量％以下がより好ましく、１０質量％以下が更に好ましい。 The lower limit of the content (concentration) of the abrasive grains is preferably 0.01% by mass or more, more preferably 0.05% by mass or more based on the total mass of the CMP abrasive in that a more suitable polishing rate can be obtained. More preferred. Further, the upper limit of the content of the abrasive grains is preferably 20% by mass or less, more preferably 15% by mass or less, and more preferably 10% by mass or less based on the total mass of the CMP abrasive in terms of suppressing aggregation of the abrasive grains. Further preferred.
（セリウム水酸化物）
本実施形態のＣＭＰ研磨剤は、砥粒として、セリウム水酸化物を含む。ここで、セリウム水酸化物とは、セリウム（Ｃｅ４＋）と、少なくとも一つの水酸化物イオン（ＯＨ−）とを含む化合物として定義される。すなわち、「セリウム水酸化物」という語句は、当然水酸化セリウム（Ｃｅ（ＯＨ）４）を含むが、水酸化物イオン以外の陰イオン成分（例えば硝酸イオンＮＯ３−及び硫酸イオンＳＯ４ ２−）が含まれることを排除しない。すなわち、砥粒は、セリウムに結合した陰イオン基（例えば、硝酸基（ＮＯ３−）、硫酸基（ＳＯ４ ２−））を含有する粒子を含んでいてもよい。特に、絶縁材料に対して高い研磨速度を示す観点では、セリウムに結合した陰イオン基を含有する粒子を含むことが好ましい。
(Cerium hydroxide)
The CMP abrasive | polishing agent of this embodiment contains a cerium hydroxide as an abrasive grain. Here, cerium hydroxide is defined as a compound containing cerium (Ce 4+ ) and at least one hydroxide ion (OH − ). That is, the phrase “cerium hydroxide” naturally includes cerium hydroxide (Ce (OH) 4 ), but anionic components other than hydroxide ions (eg, nitrate ion NO 3− and sulfate ion SO 4 2−). ) Is not excluded. That is, the abrasive grains may include particles containing an anion group (for example, nitrate group (NO 3− ), sulfate group (SO 4 2− )) bonded to cerium. In particular, from the viewpoint of showing a high polishing rate for the insulating material, it is preferable to include particles containing an anion group bonded to cerium.
セリウム水酸化物の作製工程において、セリウム水酸化物粒子は、以下の製造方法により製造できる。セリウム水酸化物の作製工程では、セリウム水酸化物の前駆体を含む第１の成分（反応成分）と、前記前駆体と反応して、セリウム水酸化物粒子を析出させることが可能な第２の成分と、を含む水溶液中で前記前駆体と第２の成分とを反応させてセリウム水酸化物粒子を析出させる。 In the production process of cerium hydroxide, cerium hydroxide particles can be produced by the following production method. In the cerium hydroxide production step, a first component (reaction component) containing a cerium hydroxide precursor and a second component capable of precipitating cerium hydroxide particles by reacting with the precursor. The cerium hydroxide particles are precipitated by reacting the precursor and the second component in an aqueous solution containing the component.
セリウム水酸化物の前駆体としては、例えば４価のセリウム塩が挙げられ、第２の成分としては、例えば塩基性化合物が挙げられる。また、セリウム水酸化物の前駆体が４価のセリウム塩であり、且つ、前記反応液が第２の成分として塩基性化合物を含有するアルカリ液であることが好ましい。 Examples of the cerium hydroxide precursor include a tetravalent cerium salt, and examples of the second component include a basic compound. Moreover, it is preferable that the precursor of cerium hydroxide is a tetravalent cerium salt, and the reaction solution is an alkaline solution containing a basic compound as the second component.
４価のセリウム塩としては、従来公知のものを特に制限なく使用でき、例えば、Ｃｅ（ＮＯ３）４、Ｃｅ（ＳＯ４）２、Ｃｅ（ＮＨ４）２（ＮＯ３）６、Ｃｅ（ＮＨ４）４（ＳＯ４）４が挙げられる。 As the tetravalent cerium salt, conventionally known ones can be used without any particular limitation. For example, Ce (NO 3 ) 4 , Ce (SO 4 ) 2 , Ce (NH 4 ) 2 (NO 3 ) 6 , Ce (NH 4) 4 (SO 4) 4 and the like.
アルカリ液としては、従来公知のものを特に制限なく使用できる。アルカリ液中の塩基性化合物としては、例えば、イミダゾール、テトラメチルアンモニウムヒドロキシド（ＴＭＡＨ）、グアニジン、トリエチルアミン、ピリジン、ピペリジン、ピロリジン又はキトサン等の有機塩基、アンモニア、水酸化カリウム、水酸化ナトリウム又は水酸化カルシウム等の無機塩基が挙げられる。これらのうちアンモニア、イミダゾールが好ましい。 A conventionally well-known thing can be especially used as an alkaline liquid without a restriction | limiting. Examples of the basic compound in the alkaline solution include organic bases such as imidazole, tetramethylammonium hydroxide (TMAH), guanidine, triethylamine, pyridine, piperidine, pyrrolidine or chitosan, ammonia, potassium hydroxide, sodium hydroxide or water. An inorganic base such as calcium oxide can be used. Of these, ammonia and imidazole are preferred.
水酸化セリウムの前駆体を含む第１の成分の前駆体溶液における濃度は、製造効率の観点から、０．００１ｍｏｌ／Ｌ以上が好ましく、０．００５ｍｏｌ／Ｌ以上がより好ましい。第１の成分の濃度は、粒子の凝集を防ぐと共に研磨速度を更に高める観点から、１．５ｍｏｌ／Ｌ以下が好ましく、１．０ｍｏｌ／Ｌ以下がより好ましい。 The concentration of the first component containing the cerium hydroxide precursor in the precursor solution is preferably 0.001 mol / L or more, and more preferably 0.005 mol / L or more, from the viewpoint of production efficiency. The concentration of the first component is preferably 1.5 mol / L or less, more preferably 1.0 mol / L or less, from the viewpoint of preventing particle aggregation and further increasing the polishing rate.
反応液（例えばアルカリ液）における第２の成分（例えば塩基性化合物）の濃度は、製造時間の短縮の観点から、０．１ｍｏｌ／Ｌ以上が好ましく、０．３ｍｏｌ／Ｌ以上がより好ましい。第２の成分の濃度は、研磨速度を更に高める観点から、２０ｍｏｌ／Ｌ以下が好ましく、１５ｍｏｌ／Ｌ以下がより好ましい。 The concentration of the second component (eg, basic compound) in the reaction solution (eg, alkaline solution) is preferably 0.1 mol / L or more, more preferably 0.3 mol / L or more, from the viewpoint of shortening the production time. From the viewpoint of further increasing the polishing rate, the concentration of the second component is preferably 20 mol / L or less, and more preferably 15 mol / L or less.
前駆体溶液と反応液との混合速度の制御により、研磨速度を更に高めることができる。混合速度は、２Ｌの溶液を撹拌する混合スケールの場合、例えば０．５ｍＬ／ｍｉｎ以上が好ましく、５０ｍＬ／ｍｉｎ以下が好ましい。 By controlling the mixing rate of the precursor solution and the reaction solution, the polishing rate can be further increased. In the case of a mixing scale for stirring a 2 L solution, the mixing speed is preferably 0.5 mL / min or more, for example, and preferably 50 mL / min or less.
撹拌羽の回転速度（撹拌速度）は、全長４ｃｍの撹拌羽を用いて２Ｌの溶液を撹拌する混合スケールの場合、例えば、３０〜８００ｍｉｎ―１であることが好ましい。回転速度の上限は、液面が上昇しすぎることを抑制する点で、７００ｍｉｎ―１以下が好ましく、６００ｍｉｎ―１以下がより好ましい。 In the case of a mixing scale in which a 2 L solution is stirred using a stirring blade having a total length of 4 cm, the rotation speed (stirring speed) of the stirring blade is preferably, for example, 30 to 800 min- 1 . The upper limit of the rotation speed, in that to prevent the liquid level too high, preferably 700Min -1 or less, 600 min -1 or less is more preferable.
前駆体溶液と反応液とを混合して得られる水溶液の液温は、反応系に温度計を設置して読み取れる反応系内の温度が０〜７０℃であることが好ましい。前記水溶液の液温は、粒子の凝集を防ぐと共に研磨速度を更に高める観点から、６０℃以下がより好ましく、５５℃以下が更に好ましい。前記水溶液の液温は、液の凍結を防ぐ観点から、０℃以上が好ましい。 The temperature of the aqueous solution obtained by mixing the precursor solution and the reaction solution is preferably 0 to 70 ° C. in the reaction system, which can be read by installing a thermometer in the reaction system. The liquid temperature of the aqueous solution is more preferably 60 ° C. or lower, and further preferably 55 ° C. or lower, from the viewpoint of preventing particle aggregation and further increasing the polishing rate. The liquid temperature of the aqueous solution is preferably 0 ° C. or higher from the viewpoint of preventing the liquid from freezing.
なお、セリウム水酸化物は、第１の成分を含む前駆体溶液と、第２の成分を含む反応液とを混合し、前記前駆体と第２の成分とを反応させて得ることもできる。 The cerium hydroxide can also be obtained by mixing a precursor solution containing the first component and a reaction solution containing the second component, and reacting the precursor and the second component.
本実施形態のＣＭＰ研磨剤の製造方法は、セリウム水酸化物粒子作製工程の後に、前記方法で合成した粒子を洗浄してセリウム水酸化物粒子から金属不純物を除去する洗浄工程を更に備えていることが好ましい。セリウム水酸化物粒子の洗浄は、遠心分離等で固液分離を数回繰り返す方法等が使用できる。 The manufacturing method of the CMP abrasive | polishing agent of this embodiment is further equipped with the washing | cleaning process of removing the metal impurity from a cerium hydroxide particle by wash | cleaning the particle | grains synthesize | combined by the said method after the cerium hydroxide particle preparation process. It is preferable. For washing the cerium hydroxide particles, a method of repeating solid-liquid separation several times by centrifugation or the like can be used.
本実施形態のＣＭＰ研磨剤の製造方法は、前記で得られたセリウム水酸化物の粒子同士が凝集している場合、洗浄工程の後、適切な方法で水中に分散させる分散工程を更に備えていることが好ましい。水酸化セリウム粒子を主な分散媒である水中に分散させる方法としては、通常の撹拌機による分散処理の他に、ホモジナイザ、超音波分散機、湿式ボールミル等による機械的な分散、遠心分離、透析、限外ろ過、イオン交換樹脂等による夾雑イオンの除去等を用いることができる。分散方法、粒径制御方法については、例えば、「分散技術大全集」〔株式会社情報機構、２００５年７月〕第３章「各種分散機の最新開発動向と選定基準」に記述されている方法を用いることができる。 The manufacturing method of the CMP abrasive | polishing agent of this embodiment is further equipped with the dispersion | distribution process of disperse | distributing in water by an appropriate method after the washing | cleaning process, when the particles of the cerium hydroxide obtained above are aggregated. Preferably it is. As a method of dispersing cerium hydroxide particles in water, which is the main dispersion medium, in addition to dispersion processing with a normal stirrer, mechanical dispersion with a homogenizer, ultrasonic disperser, wet ball mill, etc., centrifugation, dialysis For example, ultrafiltration, removal of contaminating ions with an ion exchange resin, or the like can be used. Regarding the dispersion method and the particle size control method, for example, the method described in “The Complete Collection of Dispersion Technology” [Information Organization Co., Ltd., July 2005] Chapter 3, “Latest Development Trends and Selection Criteria of Various Dispersers” Can be used.
（添加剤）
本実施形態のＣＭＰ研磨剤は、添加剤を更に含んでいてもよい。ここで、「添加剤」とは、複合粒子の分散性、研磨特性、保存安定性等を調整するために、水や砥粒以外に含まれる物質を指す。
(Additive)
The CMP abrasive | polishing agent of this embodiment may further contain the additive. Here, the “additive” refers to a substance contained other than water and abrasive grains in order to adjust the dispersibility, polishing characteristics, storage stability, and the like of the composite particles.
前記添加剤としては、水溶性高分子（水溶性ポリマ）、カルボン酸、アミノ酸、両性界面活性剤、陰イオン性界面活性剤、非イオン性界面活性剤、陽イオン性界面活性剤等が挙げられる。これらは単独で又は二種類以上組み合わせて使用できる。 Examples of the additive include water-soluble polymers (water-soluble polymers), carboxylic acids, amino acids, amphoteric surfactants, anionic surfactants, nonionic surfactants, and cationic surfactants. . These can be used alone or in combination of two or more.
前記のうち水溶性高分子（水溶性ポリマ）は、複合粒子の分散性を向上させ、研磨速度を更に向上させると共に、平坦性や面内均一性を向上させる効果を有する。ここで、「水溶性」とは、水：１００ｇに対して、０．１ｇ以上溶解すれば水溶性であるとする。 Among these, the water-soluble polymer (water-soluble polymer) has the effect of improving the dispersibility of the composite particles, further improving the polishing rate, and improving flatness and in-plane uniformity. Here, “water-soluble” means water-soluble if dissolved in 0.1 g or more per 100 g of water.
水溶性高分子（水溶性ポリマ）の具体例としては、特に制限はなく、例えば、アルギン酸、ペクチン酸、カルボキシメチルセルロース、寒天、カードラン、キトサン、キトサン誘導体、デキストラン、プルラン等の多糖類；ポリアスパラギン酸、ポリグルタミン酸、ポリリシン、ポリリンゴ酸、ポリアミド酸、ポリマレイン酸、ポリイタコン酸、ポリフマル酸、ポリ（ｐ−スチレンカルボン酸）、ポリアミド酸アンモニウム塩、ポリアミド酸ナトリウム塩、ポリグリオキシル酸等のポリカルボン酸及びその塩；ポリビニルアルコール、ポリビニルピロリドン、ポリアクロレイン等のビニル系ポリマ；アクリル酸、メタクリル酸、アクリルアミド、ジメチルアクリルアミド等のアクリル系モノマを単量体成分として含む組成物を重合させて得られるアクリル系ポリマ；ポリグリセリン、ポリエチレングリコール、ポリオキシプロピレン、ポリオキシエチレン−ポリオキシプロピレン縮合物、エチレンジアミンのポリオキシエチレン−ポリオキシプロピレンブロックポリマー、ポリアリルアミン類が挙げられる。前記水溶性高分子（水溶性ポリマ）が、分子中に酸性置換基又は塩基性置換基を含む場合、それぞれの置換基の一部が塩を構成していても良く、例えば、酸のアンモニウム塩、ナトリウム塩、カリウム塩が挙げられる。 Specific examples of the water-soluble polymer (water-soluble polymer) are not particularly limited. For example, polysaccharides such as alginic acid, pectic acid, carboxymethylcellulose, agar, curdlan, chitosan, chitosan derivatives, dextran, and pullulan; polyasparagine Polycarboxylic acids such as acid, polyglutamic acid, polylysine, polymalic acid, polyamic acid, polymaleic acid, polyitaconic acid, polyfumaric acid, poly (p-styrenecarboxylic acid), polyamic acid ammonium salt, polyamic acid sodium salt, polyglyoxylic acid, and the like Its salt; vinyl polymer such as polyvinyl alcohol, polyvinyl pyrrolidone and polyacrolein; obtained by polymerizing a composition containing an acrylic monomer such as acrylic acid, methacrylic acid, acrylamide and dimethylacrylamide as a monomer component. That acrylic polymers; polyglycerin, polyethylene glycol, polyoxypropylene, polyoxyethylene - polyoxypropylene condensate, polyoxyethylene ethylenediamine - polyoxypropylene block polymers, polyallyl amines and the like. When the water-soluble polymer (water-soluble polymer) contains an acidic substituent or a basic substituent in the molecule, a part of each substituent may form a salt. For example, an ammonium salt of an acid , Sodium salt and potassium salt.
また、ポリビニルアルコールに官能基を導入した、ポリビニルアルコール誘導体も利用できる。例えば、反応型ポリビニルアルコール（例えば、日本合成化学工業株式会社製、商品名：ゴーセファイマーＺ、ゴーセファイマーは登録商標）、カチオン化ポリビニルアルコール（例えば、日本合成化学工業株式会社製、商品名：ゴーセファイマーＫ）、アニオン化ポリビニルアルコール（例えば、日本合成化学工業株式会社製、商品名：ゴーセランＬ、ゴーセナールＴ、ゴーセラン及びゴーセナールは登録商標）、親水基変性ポリビニルアルコール（例えば、日本合成化学工業株式会社製、商品名：エコマティは登録商標）が挙げられる。また、複数の水溶性高分子（水溶性ポリマ）を併用して用いてもよい。 Moreover, the polyvinyl alcohol derivative which introduce | transduced the functional group into polyvinyl alcohol can also be utilized. For example, reactive polyvinyl alcohol (for example, manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name: GOHSEFIMAR Z, GOSEFIMER is a registered trademark), cationized polyvinyl alcohol (for example, manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name) : Goosefimmer K), anionized polyvinyl alcohol (for example, manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name: Goseiran L, Goosenal T, Gooselan and Gousenal are registered trademarks), hydrophilic group-modified polyvinyl alcohol (for example, Nippon Synthetic Chemical) Manufactured by Kogyo Co., Ltd., trade name: Ecomati is a registered trademark). A plurality of water-soluble polymers (water-soluble polymers) may be used in combination.
カルボン酸は、ｐＨを安定化させる効果があり、具体的には、例えば、ギ酸、酢酸、プロピオン酸、酪酸、吉草酸、カプロン酸、乳酸等が挙げられる。 Carboxylic acid has an effect of stabilizing pH, and specific examples include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, and lactic acid.
アミノ酸は、複合粒子の分散性を向上させ、被研磨材料（例えば酸化ケイ素材料）の研磨速度を更に向上させる効果を有する。アミノ酸としては、具体的には、例えば、アルギニン、リシン、アスパラギン酸、グルタミン酸、アスパラギン、グルタミン、ヒスチジン、プロリン、チロシン、トリプトファン、セリン、トレオニン、グリシン、アラニン、β−アラニン、メチオニン、システイン、フェニルアラニン、ロイシン、バリン、イソロイシンが挙げられる。 The amino acid has the effect of improving the dispersibility of the composite particles and further improving the polishing rate of the material to be polished (for example, silicon oxide material). Specific examples of amino acids include arginine, lysine, aspartic acid, glutamic acid, asparagine, glutamine, histidine, proline, tyrosine, tryptophan, serine, threonine, glycine, alanine, β-alanine, methionine, cysteine, phenylalanine, Examples include leucine, valine, and isoleucine.
両性界面活性剤は、混合粒子の分散性を向上させ、被研磨材料（例えば酸化ケイ素材料）の研磨速度を更に向上させる効果を有する。両性界面活性剤としては、具体的には、例えば、ベタイン、β−アラニンベタイン、ラウリルベタイン、ステアリルベタイン、ラウリルジメチルアミンオキサイド、２−アルキル−Ｎ−カルボキシメチル−Ｎ−ヒドロキシエチルイミダゾリニウムベタイン、ラウリン酸アミドプロピルベタイン、ヤシ油脂肪酸アミドプロピルベタイン、ラウリルヒドロキシスルホベタインが挙げられる。中でも、両性界面活性剤としては、分散性安定性が向上する観点から、ベタイン、β−アラニンベタイン、ラウリン酸アミドプロピルベタインが更に好ましい。 The amphoteric surfactant has the effect of improving the dispersibility of the mixed particles and further improving the polishing rate of the material to be polished (for example, silicon oxide material). Specific examples of the amphoteric surfactant include betaine, β-alanine betaine, lauryl betaine, stearyl betaine, lauryl dimethylamine oxide, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, Examples thereof include lauric acid amidopropyl betaine, coconut oil fatty acid amidopropyl betaine, and lauryl hydroxysulfobetaine. Among these, as the amphoteric surfactant, betaine, β-alanine betaine, and amide propyl betaine laurate are more preferable from the viewpoint of improving dispersibility stability.
陰イオン性界面活性剤は、研磨特性の平坦性や面内均一性を調整する効果を有する。陰イオン性界面活性剤としては、例えば、ラウリル硫酸トリエタノールアミン、ラウリル硫酸アンモニウム、ポリオキシエチレンアルキルエーテル硫酸トリエタノールアミン、特殊ポリカルボン酸型高分子分散剤が挙げられる。 The anionic surfactant has an effect of adjusting the flatness and in-plane uniformity of the polishing characteristics. Examples of the anionic surfactant include lauryl sulfate triethanolamine, ammonium lauryl sulfate, polyoxyethylene alkyl ether sulfate triethanolamine, and special polycarboxylic acid type polymer dispersants.
非イオン性界面活性剤は、研磨特性の平坦性や面内均一性を調整する効果を有する。非イオン性界面活性剤としては、例えば、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンセチルエーテル、ポリオキシエチレンステアリルエーテル、ポリオキシエチレンオレイルエーテル、ポリオキシエチレン高級アルコールエーテル、ポリオキシエチレンオクチルフェニルエーテル、ポリオキシエチレンノニルフェニルエーテル、ポリオキシアルキレンアルキルエーテル、ポリオキシエチレン誘導体、ポリオキシエチレンソルビタンモノラウレート、ポリオキシエチレンソルビタンモノパルミテート、ポリオキシエチレンソルビタンモノステアレート、ポリオキシエチレンソルビタントリステアレート、ポリオキシエチレンソルビタンモノオレエート、ポリオキシエチレンソルビタントリオレエート、テトラオレイン酸ポリオキシエチレンソルビット、ポリエチレングリコールモノラウレート、ポリエチレングリコールモノステアレート、ポリエチレングリコールジステアレート、ポリエチレングリコールモノオレエート、ポリオキシエチレンアルキルアミン、ポリオキシエチレン硬化ヒマシ油、２−ヒドロキシエチルメタクリレート、アルキルアルカノールアミドが挙げられる。 The nonionic surfactant has an effect of adjusting the flatness and in-plane uniformity of the polishing characteristics. Nonionic surfactants include, for example, polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene higher alcohol ether, polyoxyethylene octylphenyl ether, polyoxyethylene Oxyethylene nonylphenyl ether, polyoxyalkylene alkyl ether, polyoxyethylene derivatives, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan tristearate, poly Oxyethylene sorbitan monooleate, polyoxyethylene sorbitan trioleate, tetraoleic acid polio Siethylene sorbit, polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol distearate, polyethylene glycol monooleate, polyoxyethylene alkylamine, polyoxyethylene hydrogenated castor oil, 2-hydroxyethyl methacrylate, alkylalkanolamide Is mentioned.
陽イオン性界面活性剤は、研磨特性の平坦性や面内均一性を調整する効果を有する。陽イオン性界面活性剤としては、例えば、ココナットアミンアセテート、ステアリルアミンアセテートが挙げられる。 The cationic surfactant has an effect of adjusting the flatness and in-plane uniformity of the polishing characteristics. Examples of the cationic surfactant include coconut amine acetate and stearyl amine acetate.
ＣＭＰ研磨剤が前記添加剤を含む場合、これら添加剤の含有量（添加量）の下限は、砥粒の分散性、研磨特性、保存安定性を更に向上させることができることから、ＣＭＰ研磨剤の全質量を基準として０．０１質量％以上が好ましい。添加剤の含有量の上限は、砥粒の沈降を防ぐ観点から、ＣＭＰ研磨剤の全質量を基準として２０質量％以下が好ましい。
（水）
本実施形態のＣＭＰ研磨剤は、水を含有する。水としては、特に制限はないが、脱イオン水、超純水が好ましい。水の含有量は、他の含有成分の含有量の残部でよく、特に限定されない。
（ｐＨ）
本実施形態のＣＭＰ研磨剤のｐＨは、５．５〜７．３である。ｐＨが５．５〜７．３の範囲内であれば、ＣＭＰ研磨剤としての保存安定性や研磨速度に優れている。よって、研磨速度が充分に確保できる傾向があり、実用的なＣＭＰ研磨剤となり易い。
When the CMP abrasive contains the additive, the lower limit of the content (addition amount) of these additives can further improve the dispersibility, polishing characteristics, and storage stability of the abrasive grains. 0.01 mass% or more is preferable on the basis of the total mass. The upper limit of the content of the additive is preferably 20% by mass or less based on the total mass of the CMP abrasive from the viewpoint of preventing the settling of the abrasive grains.
(water)
The CMP abrasive | polishing agent of this embodiment contains water. Although there is no restriction | limiting in particular as water, Deionized water and ultrapure water are preferable. The content of water is not particularly limited, and may be the remainder of the content of other components.
(PH)
The pH of the CMP abrasive | polishing agent of this embodiment is 5.5-7.3. When the pH is in the range of 5.5 to 7.3, the storage stability and polishing rate as a CMP abrasive are excellent. Therefore, there is a tendency that a sufficient polishing rate can be secured, and it is easy to become a practical CMP abrasive.
ｐＨは、酸性分又はアンモニア、水酸化ナトリウム、水酸化カリウム、ＴＭＡＨ、イミダゾール等のアルカリ成分の添加によって調整可能である。また、ｐＨを安定化させるため、ＣＭＰ研磨剤に緩衝液を添加してもよい。このような緩衝液としては、例えば、酢酸塩緩衝液、フタル酸塩緩衝液が挙げられる。 The pH can be adjusted by adding an acidic component or an alkaline component such as ammonia, sodium hydroxide, potassium hydroxide, TMAH, imidazole or the like. In order to stabilize the pH, a buffer solution may be added to the CMP abrasive. Examples of such a buffer include an acetate buffer and a phthalate buffer.
ＣＭＰ研磨剤のｐＨは、ｐＨメーター（例えば、電気化学計器株式会社製、型番：ＰＨＬ−４０）で測定できる。ｐＨの測定値としては、標準緩衝液（フタル酸塩ｐＨ緩衝液 ｐＨ：４．０１（２５℃）、中性りん酸塩ｐＨ緩衝液 ｐＨ：６．８６（２５℃）、ホウ酸塩ｐＨ緩衝液 ｐＨ：９．１８（２５℃））を用いて、３点校正した後、電極をＣＭＰ研磨剤に入れて、２分以上経過して安定した後の値を採用する。 The pH of the CMP abrasive can be measured with a pH meter (for example, model number: PHL-40, manufactured by Electrochemical Instrument Co., Ltd.). As the pH measurement value, standard buffer solution (phthalate pH buffer solution pH: 4.01 (25 ° C), neutral phosphate pH buffer solution pH: 6.86 (25 ° C), borate pH buffer solution After calibrating three points using the liquid pH: 9.18 (25 ° C.), the electrode is placed in a CMP abrasive and the value after 2 minutes or more has been stabilized is adopted.
本実施形態のＣＭＰ研磨剤の製造方法は、洗浄工程や分散工程の後に、水が添加されてＣＭＰ研磨剤となる濃縮スラリと、水とを混合して、砥粒の含有量（濃度）が調整されたＣＭＰ研磨剤を得る濃度調整工程を更に備えていてもよい。これにより、被研磨材料の種類によって砥粒濃度を容易に調節できるほか、保管・輸送が更に容易になる。濃縮スラリにおける砥粒の含有量は、ＣＭＰ研磨剤として使用される砥粒の含有量よりも高い含有量に調整されており、濃度調整工程において濃縮スラリが水で希釈されて、所望の砥粒の含有量に調整される。濃縮スラリは、洗浄工程や分散工程において調製されてもよく、洗浄工程や分散工程の後に別途調製されてもよい。なお、本実施形態のＣＭＰ研磨剤の製造方法では、濃度調整工程を行うことなく、複合粒子作製工程、洗浄工程又は分散工程において得られたスラリをそのまま研磨に用いてもよい。なお、濃縮とは、液状媒体に対する各成分の含有割合が、使用時（ＰＯＵ：Ｐｏｉｎｔ−Ｏｆ−Ｕｓｅ）の研磨液における含有割合より多いことを意味し、濃縮工程を経たものに限定されない。 The manufacturing method of the CMP abrasive | polishing agent of this embodiment mixes the concentrated slurry which water is added and becomes a CMP abrasive | polishing agent after a washing | cleaning process and a dispersion | distribution process, and content (concentration) of an abrasive grain is mixed. You may further provide the density | concentration adjustment process of obtaining the adjusted CMP abrasive | polishing agent. This makes it possible to easily adjust the abrasive grain concentration depending on the type of material to be polished, and further facilitates storage and transportation. The content of the abrasive grains in the concentrated slurry is adjusted to a content higher than the content of the abrasive grains used as the CMP abrasive, and the concentrated slurry is diluted with water in the concentration adjusting step to obtain desired abrasive grains. The content is adjusted. The concentrated slurry may be prepared in a washing step or a dispersion step, or may be separately prepared after the washing step or the dispersion step. Note that in the CMP abrasive manufacturing method of the present embodiment, the slurry obtained in the composite particle preparation process, the cleaning process, or the dispersion process may be used for polishing without performing the concentration adjustment process. Concentration means that the content ratio of each component with respect to the liquid medium is larger than the content ratio in the polishing liquid at the time of use (POU: Point-Of-Use), and is not limited to the one that has undergone the concentration step.
本実施形態のＣＭＰ研磨剤は、前記の各工程において前記含有成分を混合することにより得ることができる。前記含有成分である添加剤は、例えば分散工程や濃度調整工程において砥粒と混合される。ＣＭＰ研磨剤を構成する含有成分の割合は、上述した各含有成分の好適な含有量になるように調製好ましい。ＣＭＰ研磨剤を構成する含有成分の割合を前記の範囲にすることで、絶縁材料の研磨速度を更に向上させることができる。 The CMP abrasive | polishing agent of this embodiment can be obtained by mixing the said component in each said process. The additive as the component is mixed with the abrasive grains in, for example, a dispersion step or a concentration adjustment step. The proportion of the components constituting the CMP abrasive is preferably adjusted so as to be a suitable content of each component described above. The polishing rate of the insulating material can be further improved by setting the ratio of the components constituting the CMP abrasive to the above range.
（基板の研磨方法）
以上説明したＣＭＰ研磨剤を用いることで、被研磨材料（例えば絶縁材料層）を有する基板の被研磨材料を良好な研磨速度で研磨可能となる。
(Substrate polishing method)
By using the CMP abrasive described above, the material to be polished of the substrate having the material to be polished (for example, the insulating material layer) can be polished at a good polishing rate.
本実施形態の基板の研磨方法は、本実施形態のＣＭＰ研磨剤の製造方法によりＣＭＰ研磨剤を調製する研磨剤調製工程と、被研磨材料を有する基板と研磨パッドとの間に前記ＣＭＰ研磨剤を供給しながら、基板の被研磨材料を研磨パッドで研磨する研磨工程を備える。研磨工程では、被研磨材料を有する基板の該被研磨材料（被研磨面）を研磨定盤の研磨パッドに対向させると共に被研磨材料を研磨パッドに押圧した状態で、前記ＣＭＰ研磨剤を被研磨材料と研磨パッドとの間に供給しながら、基板の裏面（被研磨面と反対の面）に所定の圧力を加えた状態で、基板と研磨定盤とを相対的に動かして被研磨材料を研磨するのが好ましい。 The substrate polishing method of this embodiment includes an abrasive preparation step of preparing a CMP abrasive by the CMP abrasive manufacturing method of this embodiment, and the CMP abrasive between the substrate having the material to be polished and the polishing pad. A polishing step of polishing the material to be polished on the substrate with a polishing pad. In the polishing step, the CMP abrasive is polished while the material to be polished (surface to be polished) of the substrate having the material to be polished is opposed to the polishing pad of the polishing platen and the material to be polished is pressed against the polishing pad. While supplying the material between the material and the polishing pad, with the predetermined pressure applied to the back surface of the substrate (the surface opposite to the surface to be polished), the substrate and the polishing platen are relatively moved to move the material to be polished. It is preferable to polish.
研磨装置としては、例えば、回転数を変更可能なモータが取り付けてあり、研磨パッド（パッド）を貼り付け可能な定盤と、基板を保持するホルダーとを有する一般的な研磨装置が使用できる。研磨パッドとしては、特に制限はないが、一般的な不織布、発泡ポリウレタン、多孔質フッ素樹脂等を使用できる。研磨条件には、特に制限はないが、基板が飛び出さないように、定盤の回転速度を２００ｍｉｎ−１以下の低回転に好ましい。 As the polishing apparatus, for example, a general polishing apparatus having a motor capable of changing the number of rotations and having a surface plate on which a polishing pad (pad) can be attached and a holder for holding the substrate can be used. Although there is no restriction | limiting in particular as a polishing pad, A general nonwoven fabric, a foaming polyurethane, a porous fluororesin, etc. can be used. The polishing conditions are not particularly limited, but the rotation speed of the surface plate is preferable for low rotation of 200 min −1 or less so that the substrate does not jump out.
研磨パッドに押し当てた基板へ加える圧力（研磨圧力）は、４〜１００ｋＰａであることが好ましく、基板面内の均一性及びパターンの平坦性に優れる見地から、６〜６０ｋＰａであることがより好ましい。 The pressure applied to the substrate pressed against the polishing pad (polishing pressure) is preferably 4 to 100 kPa, and more preferably 6 to 60 kPa from the viewpoint of excellent uniformity in the substrate surface and flatness of the pattern. .
研磨している間、研磨パッドの表面には、ＣＭＰ研磨剤をポンプ等で連続的に供給してもよい。この供給量に制限はないが、研磨パッドの表面が常にＣＭＰ研磨剤で覆われていることが好ましい。 During polishing, a CMP abrasive may be continuously supplied to the surface of the polishing pad with a pump or the like. Although the supply amount is not limited, it is preferable that the surface of the polishing pad is always covered with a CMP abrasive.
研磨される基板としては、半導体素子製造に係る基板、例えば、シャロートレンチ分離パターン、ゲートパターン、配線パターンが形成された半導体基板上に被研磨材料が形成された基板が挙げられる。そして、被研磨材料は、これらのパターンの上に形成された絶縁材料、例えば、酸化ケイ素材料、ポリシリコン材料が挙げられる。なお、被研磨材料は、単一の材料であってもよく、複数の材料であってもよい。複数の材料が基板表面に露出している場合、それらを被研磨材料と見なすことができる。 Examples of the substrate to be polished include a substrate for manufacturing a semiconductor element, for example, a substrate in which a material to be polished is formed on a semiconductor substrate on which a shallow trench isolation pattern, a gate pattern, and a wiring pattern are formed. Examples of the material to be polished include insulating materials formed on these patterns, such as silicon oxide materials and polysilicon materials. The material to be polished may be a single material or a plurality of materials. If multiple materials are exposed on the substrate surface, they can be considered as materials to be polished.
このような半導体基板上に形成された酸化ケイ素材料やポリシリコン材料を前記ＣＭＰ研磨剤で研磨することによって、酸化ケイ素材料の表面の凹凸を解消し、半導体基板全面にわたって平滑な面とできる。このように、本実施形態のＣＭＰ研磨剤は、少なくとも表面に酸化ケイ素を含む被研磨材料（被研磨面）を研磨するために使用されることが好ましい。 By polishing the silicon oxide material or the polysilicon material formed on such a semiconductor substrate with the CMP abrasive, unevenness on the surface of the silicon oxide material can be eliminated and a smooth surface can be formed over the entire surface of the semiconductor substrate. Thus, it is preferable that the CMP abrasive | polishing agent of this embodiment is used in order to grind | polish the to-be-polished material (surface to be polished) which contains a silicon oxide at least on the surface.
少なくとも表面に酸化ケイ素を含む被研磨材料（例えば酸化ケイ素材料）と、該被研磨材料の下層に配置された研磨停止層とを備える基板を研磨対象とする場合、研磨停止層は、ポリシリコン材料、窒化ケイ素材料等であることが好ましい。酸化ケイ素よりも研磨速度が低い研磨停止層が露出した時に研磨が停止することにより、被研磨材料（例えば酸化ケイ素材料）が過剰に研磨されることを防止でき、被研磨材料の研磨後の平坦性を向上させることができる。 When a substrate including a material to be polished (for example, silicon oxide material) containing at least silicon oxide on the surface and a polishing stopper layer disposed under the material to be polished is a polishing target, the polishing stopper layer is a polysilicon material. A silicon nitride material or the like is preferable. By stopping polishing when a polishing stopper layer having a lower polishing rate than silicon oxide is exposed, it is possible to prevent the material to be polished (for example, silicon oxide material) from being excessively polished, and to flatten the polished material after polishing. Can be improved.
また、本実施形態のＣＭＰ研磨剤は、シャロートレンチ分離にも好適に使用できる。シャロートレンチ分離に使用するためには、研磨停止層に対する酸化ケイ素を含む材料（例えば酸化ケイ素材料）の研磨速度の選択比が１００以上であることが好ましい。選択比が１００未満では、酸化ケイ素を含む材料（例えば酸化ケイ素材料）に対する研磨速度と研磨停止層に対する研磨速度との差が小さく、シャロートレンチ分離をする際、所定の位置で研磨を停止し難くなる傾向があるためである。選択比が１００以上であれば、研磨の停止が容易になり、シャロートレンチ分離に更に好適である。また、シャロートレンチ分離に使用するためには、研磨時に傷の発生が少ないことが好ましい。 Moreover, the CMP abrasive | polishing agent of this embodiment can be used conveniently also for shallow trench isolation | separation. In order to use for shallow trench isolation, it is preferable that the selection ratio of the polishing rate of the material containing silicon oxide (for example, silicon oxide material) to the polishing stopper layer is 100 or more. When the selection ratio is less than 100, the difference between the polishing rate for the material containing silicon oxide (for example, silicon oxide material) and the polishing rate for the polishing stopper layer is small, and it is difficult to stop polishing at a predetermined position when performing shallow trench isolation. This is because there is a tendency to become. If the selection ratio is 100 or more, polishing can be easily stopped, which is more suitable for shallow trench isolation. In addition, for use in shallow trench isolation, it is preferable that scratches are less likely to occur during polishing.
更に、本実施形態のＣＭＰ研磨剤は、プリメタル絶縁材料の研磨にも使用できる。プリメタル絶縁材料として、酸化ケイ素の他、例えば、リン−シリケートガラスやボロン−リン−シリケートガラスが使用され、更に、シリコンオキシフロリド、フッ化アモルファスカーボンも使用できる。 Furthermore, the CMP abrasive | polishing agent of this embodiment can be used also for grinding | polishing of a premetal insulating material. As the premetal insulating material, for example, phosphorus-silicate glass or boron-phosphorus-silicate glass is used in addition to silicon oxide, and silicon oxyfluoride and fluorinated amorphous carbon can also be used.
研磨パッドとしては、一般的な不織布、発泡体、非発泡体等が使用でき、材質としてはポリウレタン、アクリル、ポリエステル、アクリル−エステル共重合体、ポリテトラフルオロエチレン、ポリプロピレン、ポリエチレン、ポリ４−メチルペンテン、セルロース、セルロースエステル、ナイロン（商標名）、アラミド等のポリアミド、ポリイミド、ポリイミドアミド、ポリシロキサン共重合体、オキシラン化合物、フェノール樹脂、ポリスチレン、ポリカーボネート、エポキシ樹脂等の樹脂が使用できる。 As the polishing pad, general nonwoven fabrics, foams, non-foams, etc. can be used, and the materials are polyurethane, acrylic, polyester, acrylic-ester copolymer, polytetrafluoroethylene, polypropylene, polyethylene, poly-4-methyl. Resins such as pentene, cellulose, cellulose ester, nylon (trade name), polyamide such as aramid, polyimide, polyimide amide, polysiloxane copolymer, oxirane compound, phenol resin, polystyrene, polycarbonate, and epoxy resin can be used.
特に、研磨速度や平坦性の観点から、研磨パッドの材質としては発泡ポリウレタン、非発泡ポリウレタンが好ましい。また、研磨パッドには、研磨剤がたまるような溝加工を施すことが好ましい。 In particular, from the viewpoint of polishing speed and flatness, the material of the polishing pad is preferably foamed polyurethane or non-foamed polyurethane. Further, the polishing pad is preferably subjected to groove processing so that the abrasive is accumulated.
研磨終了後の半導体基板は、流水中で良く洗浄して基板に付着した粒子を除去好ましい。洗浄には、純水以外に希フッ酸やアンモニア水を併用してもよく、洗浄効率を高めるためにブラシを併用してもよい。 The semiconductor substrate after polishing is preferably washed well under running water to remove particles adhering to the substrate. For cleaning, dilute hydrofluoric acid or ammonia water may be used in addition to pure water, and a brush may be used in combination to increase cleaning efficiency.
また、洗浄後はスピンドライヤ等を用いて半導体基板上に付着した水滴を払い落としてから乾燥させることが好ましい。 In addition, after washing, it is preferable to dry after removing water droplets adhering to the semiconductor substrate using a spin dryer or the like.
本実施形態の研磨剤及び研磨方法は、酸化ケイ素材料のような絶縁材料以外の材料にも適用できる。例えば、Ｈｆ系、Ｔｉ系、Ｔａ系酸化物等の高誘電率材料、シリコン、アモルファスシリコン、ＳｉＣ、ＳｉＧｅ、Ｇｅ、ＧａＮ、ＧａＰ、ＧａＡｓ、有機半導体等の半導体材料、ＧｅＳｂＴｅ等の相変化材料、ＩＴＯ等の無機導電材料、ポリイミド系、ポリベンゾオキサゾール系、アクリル系、エポキシ系、フェノール系等のポリマ樹脂材料が挙げられる。 The abrasive and the polishing method of this embodiment can also be applied to materials other than insulating materials such as silicon oxide materials. For example, high dielectric constant materials such as Hf-based, Ti-based, and Ta-based oxides, semiconductor materials such as silicon, amorphous silicon, SiC, SiGe, Ge, GaN, GaP, GaAs, and organic semiconductors, phase change materials such as GeSbTe, Inorganic conductive materials such as ITO, polymer resin materials such as polyimide, polybenzoxazole, acrylic, epoxy, and phenol are listed.
以下、本発明を実施例により更に詳細に説明するが、本発明はこれらの実施例に限定されるものではない。
本発明で用いたコロイダルシリカに含まれるシリカ粒子を表１に記載する。表１中のシリカはシリカ粒子を表す。
EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited to these Examples.
Table 1 shows the silica particles contained in the colloidal silica used in the present invention. Silica in Table 1 represents silica particles.
まず、シリカ粒子やセリウム水酸化物粒子を単独で、又は単に混ぜ合わせたＣＭＰ研磨剤の製造法及び諸特性について実施例１及び比較例１〜２に示す。
＜実施例１＞
（セリウム水酸化物粒子の合成（合成例１））
３１１ｇのＣｅ（ＮＨ４）２（ＮＯ３）６を２２７７ｇの純水に溶解して、前駆体液を得た。次に、前駆体液を４０℃に調整すると共に混合液を５００ｍｉｎ―１で撹拌しながら、１３６８ｇのイミダゾール（５．０質量％水溶液）を２．７ｍＬ／ｍｉｎで混合液に滴下して、黄白色の粒子を作製した。この分散液から限外濾過法で粒子を単離することにより、粒子を洗浄した。
First, Example 1 and Comparative Examples 1 and 2 show the manufacturing method and various characteristics of a CMP abrasive in which silica particles and cerium hydroxide particles are used alone or simply mixed together.
<Example 1>
(Synthesis of cerium hydroxide particles (Synthesis Example 1))
311 g of Ce (NH 4 ) 2 (NO 3 ) 6 was dissolved in 2277 g of pure water to obtain a precursor liquid. Next, while adjusting the precursor liquid to 40 ° C. and stirring the mixed liquid at 500 min −1 , 1368 g of imidazole (5.0 mass% aqueous solution) was dropped into the mixed liquid at 2.7 mL / min to give a yellowish white color. Particles were produced. The particles were washed by isolating the particles from this dispersion by ultrafiltration.
得られた粒子を一部抽出してＴＥＭ（透過型電子顕微鏡）にて観察したところ、単独に存在する粒子の粒径がおよそ２〜４ｎｍ程度の「単独粒子」が観察された。前記単独粒子は「セリウム水酸化物の単独粒子」であった。
（濃縮スラリの調製）
前記洗浄後の粒子に純水を加え、濃縮スラリ（混合粒子濃度：１．０質量％）を調製した。
（水及びシリカ／セリウム水酸化物混合粒子及び水溶性ポリマを含むスラリの調整）
シリカ粒子１（表１中の「シリカ１」）のコロイダルシリカ分散液（シリカ粒子含有量：２０質量％）０．５質量％（シリカ粒子として０．１質量％相当）と、前記調整後の濃縮スラリ０．１質量％とポリマ添加剤（ポリグリセリン（阪本薬品工業株式会社製、ポリグリセリン＃７５０）５．０質量％、ポリアリルアミン（ニットーボーメディカル株式会社製、ＰＡＡ−０１）０．０１質量％）１０質量％と水８９質量％とを混合することにより、シリカ粒子とセリウム水酸化物粒子とを０．１質量％ずつ含有するＣＭＰ研磨液を調整した。さらに、１０質量％イミダゾール水溶液でｐＨ６．０に調整することによりＣＭＰ研磨液を調整した。
＜測定方法＞
本実施例及び比較例において、ＣＭＰ研磨剤のｐＨは、下記の方法に従って測定した。
（ｐＨ測定）
測定温度：２５±５℃
ｐＨ：電気化学計器株式会社製、型番：ＰＨＬ−４０で測定した。
（基板の研磨）
前記ＣＭＰ研磨剤を用いて、下記の研磨条件で基板の研磨を行った。
（ＣＭＰ研磨条件）
研磨装置：ＡＰＰＬＩＥＤ ＭＡＴＥＲＩＡＬＳ社製、商品名：Ｍｉｒｒａ
ＣＭＰ研磨剤流量：２００ｍＬ／ｍｉｎ
研磨される基板：Ｓｉ基板上に、厚さ１０００ｎｍの酸化ケイ素（ＳｉＯ２）をプラズマＣＶＤ法により形成したシリコン基板（アドバンテック株式会社製，製品名：８インチ Ｐ−ＴＥＯＳウエハー １ミクロン ２５枚）
研磨パッド：独立気泡を持つ発泡ポリウレタン樹脂（ローム・アンド・ハース・ジャパン株式会社製、型番：ＩＣ１０１０）
研磨圧力：３１．４ｋＰａ（４ｐｓｉ）
基板と研磨定盤との相対速度：８０ｍ／ｍｉｎ
研磨時間：１分／枚
洗浄：ＣＭＰ処理後、超音波水による洗浄を行った後、スピンドライヤで乾燥させた。
（研磨品評価項目：研磨速度）
前記条件で研磨及び洗浄した基板に対して、酸化ケイ素層に対する研磨速度（ＳｉＯ２ＲＲ）を求めた。具体的には、研磨前後での前記酸化ケイ素層の材料厚差を、光干渉式材料厚測定装置を用いて測定し、次式より求めた。
（ＳｉＯ２ＲＲ）＝（研磨前後での酸化ケイ素層の材料厚差（Å））／（研磨時間（分））
このＣＭＰ研磨剤について、ｐＨを測定したところ、ｐＨは６．０であった。また、ＣＭＰ研磨剤の酸化ケイ素層に対する研磨速度を求めたところ、６６１７Å／ｍｉｎであった。
When a part of the obtained particles was extracted and observed with a TEM (transmission electron microscope), “single particles” having a particle size of about 2 to 4 nm alone were observed. The single particles were “single particles of cerium hydroxide”.
(Preparation of concentrated slurry)
Pure water was added to the washed particles to prepare a concentrated slurry (mixed particle concentration: 1.0 mass%).
(Preparation of slurry containing water and silica / cerium hydroxide mixed particles and water-soluble polymer)
0.5% by mass (corresponding to 0.1% by mass as silica particles) of a colloidal silica dispersion (silica particle content: 20% by mass) of silica particles 1 (“Silica 1” in Table 1), 0.1% by mass of concentrated slurry and polymer additive (polyglycerin (manufactured by Sakamoto Pharmaceutical Co., Ltd., polyglycerin # 750) 5.0% by mass, polyallylamine (manufactured by Nitto Bo Medical Co., Ltd., PAA-01) 0.01% by mass %) A CMP polishing liquid containing silica particles and cerium hydroxide particles in an amount of 0.1% by mass was prepared by mixing 10% by mass and 89% by mass of water. Further, the CMP polishing liquid was adjusted by adjusting the pH to 6.0 with a 10 mass% imidazole aqueous solution.
<Measurement method>
In this example and comparative examples, the pH of the CMP abrasive was measured according to the following method.
(PH measurement)
Measurement temperature: 25 ± 5 ° C
pH: Measured by Electrochemical Instrument Co., Ltd., model number: PHL-40.
(Polishing the substrate)
Using the CMP abrasive, the substrate was polished under the following polishing conditions.
(CMP polishing conditions)
Polishing device: Made by APPLIED MATERIALS, product name: Mirra
CMP abrasive flow rate: 200 mL / min
Substrate to be polished: A silicon substrate in which silicon oxide (SiO 2 ) having a thickness of 1000 nm is formed on a Si substrate by a plasma CVD method (manufactured by Advantech Co., Ltd., product name: 8 inch P-TEOS wafer 1 micron 25 sheets)
Polishing pad: Polyurethane resin with closed cells (Rohm and Haas Japan, model number: IC1010)
Polishing pressure: 31.4 kPa (4 psi)
Relative speed between substrate and polishing surface plate: 80 m / min
Polishing time: 1 minute / sheet Cleaning: After CMP treatment, cleaning with ultrasonic water was performed, followed by drying with a spin dryer.
(Polished product evaluation item: Polishing speed)
The polishing rate (SiO 2 RR) for the silicon oxide layer was determined for the substrate polished and cleaned under the above conditions. Specifically, the difference in material thickness of the silicon oxide layer before and after polishing was measured using an optical interference type material thickness measuring device, and obtained from the following formula.
(SiO 2 RR) = (Material thickness difference of silicon oxide layer before and after polishing (Å)) / (Polishing time (min))
The pH of the CMP abrasive was measured and found to be 6.0. Further, the polishing rate for the silicon oxide layer of the CMP abrasive was determined to be 6617 Å / min.
＜比較例１＞
（セリウム水酸化物粒子の合成）
合成例１と同様にして、セリウム水酸化物を得た。また、合成例１と同様の洗浄及び調製を行い、セリウム水酸化物粒子濃度が１．０質量％の濃縮スラリを調製した。
（セリウム水酸化物混合粒子及び水溶性ポリマを含むスラリの調整）
前記調整後の濃縮スラリ０．２質量％と前記ポリマ添加剤（ポリグリセリン（阪本薬品工業株式会社製、ポリグリセリン＃７５０）５．０質量％、ポリアリルアミン（ニットーボーメディカル株式会社製、ＰＡＡ−０１）０．０１質量％）１０質量％と水８９質量％とを混合することにより、水酸化セリウム粒子を０．５質量％ずつ含有するＣＭＰ研磨液を調整した。さらに、１０質量％イミダゾール水溶液でｐＨ６．０に調整し、ＣＭＰ研磨液を調整した。
<Comparative Example 1>
(Synthesis of cerium hydroxide particles)
Cerium hydroxide was obtained in the same manner as in Synthesis Example 1. Moreover, washing | cleaning and preparation similar to the synthesis example 1 were performed, and the concentrated slurry whose cerium hydroxide particle density | concentration is 1.0 mass% was prepared.
(Preparation of slurry containing cerium hydroxide mixed particles and water-soluble polymer)
0.2% by mass of the concentrated slurry after adjustment and 5.0% by mass of the polymer additive (polyglycerin (manufactured by Sakamoto Yakuhin Kogyo Co., Ltd., polyglycerin # 750), polyallylamine (manufactured by Nitto Bo Medical Co., Ltd., PAA-01) ) 0.01% by mass) A CMP polishing liquid containing 0.5% by mass of cerium hydroxide particles was prepared by mixing 10% by mass and 89% by mass of water. Further, the pH was adjusted to 6.0 with a 10% by mass imidazole aqueous solution to prepare a CMP polishing liquid.
このＣＭＰ研磨剤について、ｐＨを測定したところ、ｐＨは６．０であった。また、ＣＭＰ研磨剤の酸化ケイ素層に対する研磨速度を求めたところ、５６２４Å／ｍｉｎであった。 The pH of the CMP abrasive was measured and found to be 6.0. Further, the polishing rate of the CMP abrasive for the silicon oxide layer was determined to be 5624 Å / min.
＜比較例２＞
シリカ１（コロイダルシリカ分散液、シリカ粒子濃度：２０質量％）を１．０質量％（シリカ粒子として０．２質量％相当）と、前記ポリマ添加剤（ポリグリセリン（阪本薬品工業株式会社製、ポリグリセリン＃７５０）５．０質量％、ポリアリルアミン（ニットーボーメディカル株式会社製、ＰＡＡ−０１）０．０１質量％）１０質量％と水８９質量％とを混合して、シリカ粒子を０．２質量％含有するＣＭＰ研磨剤を調製した。さらに、１０質量％イミダゾール水溶液でｐＨ６．０に調整し、ＣＭＰ研磨液を調整した。ＣＭＰ研磨剤の酸化ケイ素層に対する研磨速度を求めたところ６０Å／ｍｉｎであった。
前記の実施例１と比較例１〜２について表２にまとめて示す。表２中のシリカ１はシリカ粒子１を表す。
<Comparative example 2>
Silica 1 (colloidal silica dispersion, silica particle concentration: 20% by mass) is 1.0% by mass (corresponding to 0.2% by mass as silica particles) and the polymer additive (polyglycerin (manufactured by Sakamoto Pharmaceutical Co., Ltd., Polyglycerin # 750) 5.0% by mass, polyallylamine (manufactured by Nitto Bo Medical Co., Ltd., 0.01% by mass) 10% by mass and water 89% by mass are mixed with 0.2% silica particles. A CMP abrasive containing mass% was prepared. Further, the pH was adjusted to 6.0 with a 10% by mass imidazole aqueous solution to prepare a CMP polishing liquid. When the polishing rate for the silicon oxide layer of the CMP abrasive was determined, it was 60 Å / min.
Table 2 summarizes Example 1 and Comparative Examples 1-2. Silica 1 in Table 2 represents silica particles 1.
表２から明らかなように酸化ケイ素層の研磨速度は、シリカ・セリウム水酸化物の混合粒子を含むＣＭＰ研磨剤を用いることで顕著に向上した。すなわち、実施例１と比較例１〜２との対比から、シリカ・セリウム水酸化物の混合粒子を含むＣＭＰ研磨剤は、シリカ粒子やセリウム水酸化物粒子を単独と比較して研磨速度に優れていた。
次に、シリカ粒子及びセリウム水酸化物粒子の混合比率が異なる混合粒子を調整し、ｐＨを６．０に調整したＣＭＰ研磨剤の製造法及び諸特性について実施例２〜４及び比較例３〜４に示す。
As apparent from Table 2, the polishing rate of the silicon oxide layer was significantly improved by using a CMP abrasive containing mixed particles of silica and cerium hydroxide. That is, from the comparison between Example 1 and Comparative Examples 1 and 2, the CMP abrasives containing mixed particles of silica and cerium hydroxide are superior in polishing rate compared to silica particles and cerium hydroxide particles alone. It was.
Next, Examples 2 to 4 and Comparative Examples 3 to 4 were prepared for the manufacturing method and various characteristics of CMP abrasives prepared by adjusting mixed particles having different mixing ratios of silica particles and cerium hydroxide particles and adjusting the pH to 6.0. 4 shows.
＜実施例２＞
合成例１と同様にしてセリウム水酸化物粒子を得た。次いで、合成例１と同様の洗浄及び調製を行い、セリウム水酸化物粒子濃度が１．０質量％の濃縮スラリを調製した。シリカ粒子１（表１中の「シリカ１」）のコロイダルシリカ分散液（シリカ粒子含有量：２０質量％）０．０５質量％（シリカ粒子として０．０１質量％相当）と、前記調整後の濃縮スラリ０．１９質量％と前記ポリマ添加剤（ポリグリセリン（阪本薬品工業株式会社製、ポリグリセリン＃７５０）５．０質量％、ポリアリルアミン（ニットーボーメディカル株式会社製、ＰＡＡ−０１）０．０１質量％）１０質量％と水８９質量％とを混合した。さらに、１０質量％イミダゾール水溶液でｐＨ６．０に調整することによりＣＭＰ研磨液を調整した。ＣＭＰ研磨剤の酸化ケイ素層に対する研磨速度を求めたところ５９０９Å／ｍｉｎであった。
<Example 2>
Cerium hydroxide particles were obtained in the same manner as in Synthesis Example 1. Next, washing and preparation similar to those of Synthesis Example 1 were performed to prepare a concentrated slurry having a cerium hydroxide particle concentration of 1.0 mass%. Colloidal silica dispersion of silica particles 1 (“Silica 1” in Table 1) (silica particle content: 20% by mass) 0.05% by mass (corresponding to 0.01% by mass as silica particles), 0.19% by mass of concentrated slurry and the above polymer additive (polyglycerin (manufactured by Sakamoto Pharmaceutical Co., Ltd., polyglycerin # 750) 5.0% by mass, polyallylamine (manufactured by Nitto Bo Medical Co., Ltd., PAA-01) 0.01 (Mass%) 10 mass% and water 89 mass% were mixed. Further, the CMP polishing liquid was adjusted by adjusting the pH to 6.0 with a 10 mass% imidazole aqueous solution. When the polishing rate for the silicon oxide layer of the CMP abrasive was determined, it was 5909 kg / min.
＜実施例３＞
合成例１と同様にしてセリウム水酸化物粒子を得た。次いで、合成例１と同様の洗浄及び調製を行い、セリウム水酸化物粒子濃度が１．０質量％の濃縮スラリを調製した。シリカ粒子１（表１中の「シリカ１」）のコロイダルシリカ分散液（シリカ粒子含有量：２０質量％）０．２５質量％（シリカ粒子として０．０５質量％相当）と、前記調整後の濃縮スラリ０．１５質量％と前記ポリマ添加剤（ポリグリセリン（阪本薬品工業株式会社製、ポリグリセリン＃７５０）５．０質量％、ポリアリルアミン（ニットーボーメディカル株式会社製、ＰＡＡ−０１）０．０１質量％）１０質量％と水８９質量％とを混合した。さらに、１０質量％イミダゾール水溶液でｐＨ６．０に調整することによりＣＭＰ研磨液を調整した。ＣＭＰ研磨剤の酸化ケイ素層に対する研磨速度を求めたところ６０７９Å／ｍｉｎであった。
<Example 3>
Cerium hydroxide particles were obtained in the same manner as in Synthesis Example 1. Next, washing and preparation similar to those of Synthesis Example 1 were performed to prepare a concentrated slurry having a cerium hydroxide particle concentration of 1.0 mass%. 0.25% by mass (corresponding to 0.05% by mass as silica particles) of colloidal silica dispersion (silica particle content: 20% by mass) of silica particles 1 (“Silica 1” in Table 1), 0.15% by mass of concentrated slurry and the above polymer additive (polyglycerin (manufactured by Sakamoto Pharmaceutical Co., Ltd., polyglycerin # 750) 5.0% by mass, polyallylamine (manufactured by Nitto Bo Medical Co., Ltd., PAA-01) 0.01 (Mass%) 10 mass% and water 89 mass% were mixed. Further, the CMP polishing liquid was adjusted by adjusting the pH to 6.0 with a 10 mass% imidazole aqueous solution. The polishing rate of the CMP abrasive to the silicon oxide layer was determined to be 6079 kg / min.
＜実施例４＞
合成例１と同様にしてセリウム水酸化物粒子を得た。次いで、合成例１と同様の洗浄及び調製を行い、セリウム水酸化物粒子濃度が１．０質量％の濃縮スラリを調製した。シリカ粒子１（表１中の「シリカ１」）のコロイダルシリカ分散液（シリカ粒子含有量：２０質量％）０．７５質量％（シリカ粒子として０．１５質量％相当）と、前記調整後の濃縮スラリ０．０５質量％と前記ポリマ添加剤（ポリグリセリン（阪本薬品工業株式会社製、ポリグリセリン＃７５０）５．０質量％、ポリアリルアミン（ニットーボーメディカル株式会社製、ＰＡＡ−０１）０．０１質量％）１０質量％と水８９質量％とを混合した。さらに、１０質量％イミダゾール水溶液でｐＨ６．０に調整することによりＣＭＰ研磨液を調整した。ＣＭＰ研磨剤の酸化ケイ素層に対する研磨速度を求めたところ５６４０Å／ｍｉｎであった。
<Example 4>
Cerium hydroxide particles were obtained in the same manner as in Synthesis Example 1. Next, washing and preparation similar to those of Synthesis Example 1 were performed to prepare a concentrated slurry having a cerium hydroxide particle concentration of 1.0 mass%. 0.75% by mass (corresponding to 0.15% by mass as silica particles) of colloidal silica dispersion (silica particle content: 20% by mass) of silica particles 1 (“Silica 1” in Table 1), 0.05% by weight of concentrated slurry and the above polymer additive (polyglycerin (manufactured by Sakamoto Pharmaceutical Co., Ltd., polyglycerin # 750) 5.0% by weight, polyallylamine (manufactured by Nitto Bo Medical Co., Ltd., PAA-01) 0.01 (Mass%) 10 mass% and water 89 mass% were mixed. Further, the CMP polishing liquid was adjusted by adjusting the pH to 6.0 with a 10 mass% imidazole aqueous solution. When the polishing rate for the silicon oxide layer of the CMP abrasive was determined, it was 5640 Å / min.
＜比較例３＞
合成例１と同様にしてセリウム水酸化物粒子を得た。次いで、合成例１と同様の洗浄及び調製を行い、セリウム水酸化物粒子濃度が１．０質量％の濃縮スラリを調製した。シリカ粒子１（表１中の「シリカ１」）のコロイダルシリカ分散液（シリカ粒子含有量：２０質量％）０．９０質量％（シリカ粒子として０．１８質量％相当）と、前記調整後の濃縮スラリ０．０２質量％と前記ポリマ添加剤（ポリグリセリン（阪本薬品工業株式会社製、ポリグリセリン＃７５０）５．０質量％、ポリアリルアミン（ニットーボーメディカル株式会社製、ＰＡＡ−０１）０．０１質量％）１０質量％と水８９質量％とを混合した。さらに、１０質量％イミダゾール水溶液でｐＨ６．０に調整することによりＣＭＰ研磨液を調整した。ＣＭＰ研磨剤の酸化ケイ素層に対する研磨速度を求めたところ２７１９Å／ｍｉｎであった。
<Comparative Example 3>
Cerium hydroxide particles were obtained in the same manner as in Synthesis Example 1. Next, washing and preparation similar to those of Synthesis Example 1 were performed to prepare a concentrated slurry having a cerium hydroxide particle concentration of 1.0 mass%. Colloidal silica dispersion (silica particle content: 20% by mass) of silica particles 1 (“Silica 1” in Table 1) 0.90% by mass (corresponding to 0.18% by mass as silica particles), 0.02% by mass of concentrated slurry and the above-mentioned polymer additive (polyglycerin (manufactured by Sakamoto Pharmaceutical Co., Ltd., polyglycerin # 750) 5.0% by mass, polyallylamine (manufactured by Nitto Bo Medical Co., Ltd., PAA-01) 0.01 (Mass%) 10 mass% and water 89 mass% were mixed. Further, the CMP polishing liquid was adjusted by adjusting the pH to 6.0 with a 10 mass% imidazole aqueous solution. The polishing rate of the CMP abrasive to the silicon oxide layer was determined to be 2719 Å / min.
＜比較例４＞
合成例１と同様にしてセリウム水酸化物粒子を得た。次いで、合成例１と同様の洗浄及び調製を行い、セリウム水酸化物粒子濃度が１質量％の濃縮スラリを調製した。シリカ粒子１（表１中の「シリカ１」）のコロイダルシリカ分散液（シリカ粒子含有量：２０質量％）０．９５質量％（シリカ粒子として０．１９質量％相当）と、前記調整後の濃縮スラリ０．０１質量％と前記ポリマ添加剤（ポリグリセリン（阪本薬品工業株式会社製、ポリグリセリン＃７５０）５．０質量％、ポリアリルアミン（ニットーボーメディカル株式会社製、ＰＡＡ−０１）０．０１質量％）１０質量％と水８９質量％とを混合した。さらに、１０質量％イミダゾール水溶液でｐＨ６．０に調整することによりＣＭＰ研磨液を調整した。ＣＭＰ研磨剤の酸化ケイ素層に対する研磨速度を求めたところ２３２７Å／ｍｉｎであった。
実施例１〜４と比較例１〜４について表３にまとめて示す。表３中のシリカ１はシリカ粒子１を表す。
<Comparative example 4>
Cerium hydroxide particles were obtained in the same manner as in Synthesis Example 1. Next, washing and preparation similar to those of Synthesis Example 1 were performed to prepare a concentrated slurry having a cerium hydroxide particle concentration of 1% by mass. Colloidal silica dispersion (silica particle content: 20% by mass) of silica particles 1 (“Silica 1” in Table 1) 0.95% by mass (equivalent to 0.19% by mass as silica particles), 0.01% by weight of concentrated slurry and the above polymer additive (polyglycerin (manufactured by Sakamoto Pharmaceutical Co., Ltd., polyglycerin # 750) 5.0% by weight, polyallylamine (manufactured by Nitto Bo Medical Co., Ltd., PAA-01) 0.01 (Mass%) 10 mass% and water 89 mass% were mixed. Further, the CMP polishing liquid was adjusted by adjusting the pH to 6.0 with a 10 mass% imidazole aqueous solution. The polishing rate of the CMP abrasive to the silicon oxide layer was determined to be 2327 Å / min.
Examples 3 to 4 and Comparative Examples 1 to 4 are shown together in Table 3. Silica 1 in Table 3 represents silica particles 1.
表３から明らかなように酸化ケイ素層の研磨速度は、セリウム水酸化物粒子の割合が２５〜９５質量％のときにセリウム水酸化物粒子単体と比較して研磨速度に優れていた。
次に、シリカ・セリウム水酸化物の混合粒子を含み、ｐＨの異なるＣＭＰ研磨剤の製造法及び諸特性について実施例５及び比較例５〜７に示す。
As apparent from Table 3, the polishing rate of the silicon oxide layer was superior to that of the cerium hydroxide particles alone when the ratio of the cerium hydroxide particles was 25 to 95% by mass.
Next, Example 5 and Comparative Examples 5 to 7 show the manufacturing method and various characteristics of CMP abrasives containing mixed particles of silica and cerium hydroxide and having different pHs.
＜実施例５＞
合成例１と同様にしてセリウム水酸化物粒子を得た。次いで、合成例１と同様の洗浄及び調製を行い、セリウム水酸化物粒子濃度が１．０質量％の濃縮スラリを調製した。シリカ粒子１（表１中の「シリカ１」）のコロイダルシリカ分散液（シリカ粒子含有量：２０質量％）０．５質量％（シリカ粒子として０．１質量％相当）と、前記ポリマ添加剤（ポリグリセリン（阪本薬品工業株式会社製、ポリグリセリン＃７５０）５．０質量％、ポリアリルアミン（ニットーボーメディカル株式会社製、ＰＡＡ−０１）０．０１質量％）１０質量％と水８９質量％とを混合した。さらに、１０質量％イミダゾール水溶液でｐＨ７．０に調整することによりＣＭＰ研磨液を調整した。ＣＭＰ研磨剤の酸化ケイ素層に対する研磨速度を求めたところ６２３６Å／ｍｉｎであった。
<Example 5>
Cerium hydroxide particles were obtained in the same manner as in Synthesis Example 1. Next, washing and preparation similar to those of Synthesis Example 1 were performed to prepare a concentrated slurry having a cerium hydroxide particle concentration of 1.0 mass%. 0.5% by mass (corresponding to 0.1% by mass as silica particles) of a colloidal silica dispersion (silica particle content: 20% by mass) of silica particles 1 (“Silica 1” in Table 1), and the polymer additive (Polyglycerin (manufactured by Sakamoto Pharmaceutical Co., Ltd., polyglycerin # 750) 5.0% by mass, polyallylamine (manufactured by Nitto Bo Medical Co., Ltd., 0.01% by mass) 10% by mass and water 89% by mass Were mixed. Further, the CMP polishing liquid was adjusted by adjusting the pH to 7.0 with a 10% by mass imidazole aqueous solution. The polishing rate of the CMP abrasive to the silicon oxide layer was determined to be 6236 Å / min.
＜比較例５＞
合成例１と同様にしてセリウム水酸化物粒子を得た。次いで、合成例１と同様の洗浄及び調製を行い、セリウム水酸化物粒子濃度が１．０質量％の濃縮スラリを調製した。シリカ粒子１（表１中の「シリカ１」）のコロイダルシリカ分散液（シリカ粒子含有量：２０質量％）０．５質量％（シリカ粒子として０．１質量％相当）と、前記調整後の濃縮スラリ０．１質量％と前記ポリマ添加剤（ポリグリセリン（阪本薬品工業株式会社製、ポリグリセリン＃７５０）５．０質量％、ポリアリルアミン（ニットーボーメディカル株式会社製、ＰＡＡ−０１）０．０１質量％）１０質量％と水８９質量％とを混合した。さらに、１０質量％の酢酸水溶液でｐＨ３．０に調整することによりＣＭＰ研磨液を調整した。ＣＭＰ研磨剤の酸化ケイ素層に対する研磨速度を求めたところ０Å／ｍｉｎであった。
<Comparative Example 5>
Cerium hydroxide particles were obtained in the same manner as in Synthesis Example 1. Next, washing and preparation similar to those of Synthesis Example 1 were performed to prepare a concentrated slurry having a cerium hydroxide particle concentration of 1.0 mass%. 0.5% by mass (corresponding to 0.1% by mass as silica particles) of a colloidal silica dispersion (silica particle content: 20% by mass) of silica particles 1 (“Silica 1” in Table 1), 0.1% by mass of concentrated slurry and the above polymer additive (polyglycerin (manufactured by Sakamoto Yakuhin Kogyo Co., Ltd., polyglycerin # 750) 5.0% by mass, polyallylamine (manufactured by Nitto Bo Medical Co., Ltd., PAA-01) 0.01 (Mass%) 10 mass% and water 89 mass% were mixed. Further, the CMP polishing liquid was adjusted by adjusting the pH to 3.0 with a 10 mass% acetic acid aqueous solution. When the polishing rate for the silicon oxide layer of the CMP abrasive was determined, it was 0 Å / min.
＜比較例６＞
合成例１と同様にしてセリウム水酸化物粒子を得た。次いで、合成例１と同様の洗浄及び調製を行い、セリウム水酸化物粒子濃度が１．０質量％の濃縮スラリを調製した。シリカ粒子１（表１中の「シリカ１」）のコロイダルシリカ分散液（シリカ粒子含有量：２０質量％）０．５質量％（シリカ粒子として０．１質量％相当）と、前記調整後の濃縮スラリ０．１質量％と前記ポリマ添加剤（ポリグリセリン（阪本薬品工業株式会社製、ポリグリセリン＃７５０）５．０質量％、ポリアリルアミン（ニットーボーメディカル株式会社製、ＰＡＡ−０１）０．０１質量％）１０質量％と水８９質量％とを混合した。さらに、１０質量％イミダゾール水溶液でｐＨ５．０に調整することによりＣＭＰ研磨液を調整した。ＣＭＰ研磨剤の酸化ケイ素層に対する研磨速度を求めたところ４５２６Å／ｍｉｎであった。
<Comparative Example 6>
Cerium hydroxide particles were obtained in the same manner as in Synthesis Example 1. Next, washing and preparation similar to those of Synthesis Example 1 were performed to prepare a concentrated slurry having a cerium hydroxide particle concentration of 1.0 mass%. 0.5% by mass (corresponding to 0.1% by mass as silica particles) of a colloidal silica dispersion (silica particle content: 20% by mass) of silica particles 1 (“Silica 1” in Table 1), 0.1% by mass of concentrated slurry and the above polymer additive (polyglycerin (manufactured by Sakamoto Yakuhin Kogyo Co., Ltd., polyglycerin # 750) 5.0% by mass, polyallylamine (manufactured by Nitto Bo Medical Co., Ltd., PAA-01) 0.01 (Mass%) 10 mass% and water 89 mass% were mixed. Further, the CMP polishing liquid was adjusted by adjusting the pH to 5.0 with a 10 mass% imidazole aqueous solution. When the polishing rate of the CMP abrasive for the silicon oxide layer was determined, it was 4526 Å / min.
＜比較例７＞
合成例１と同様にしてセリウム水酸化物粒子を得た。次いで、合成例１と同様の洗浄及び調製を行い、セリウム水酸化物粒子濃度が１．０質量％の濃縮スラリを調製した。シリカ粒子１（表１中の「シリカ１」）のコロイダルシリカ分散液（シリカ粒子含有量：２０質量％）０．５質量％（シリカ粒子として０．１質量％相当）と、前記調整後の濃縮スラリ０．１質量％と前記ポリマ添加剤（ポリグリセリン（阪本薬品工業株式会社製、ポリグリセリン＃７５０）５．０質量％、ポリアリルアミン（ニットーボーメディカル株式会社製、ＰＡＡ−０１）０．０１質量％）１０質量％と水８９質量％とを混合した。さらに、１０質量％イミダゾール水溶液でｐＨ８．０に調整することによりＣＭＰ研磨液を調整した。ＣＭＰ研磨剤の酸化ケイ素層に対する研磨速度を求めたところ１４８８Å／ｍｉｎであった。
前記の実施例１及び実施例５と比較例５〜７について表４にまとめて示す。表４中のシリカ１はシリカ粒子１を表す。
<Comparative Example 7>
Cerium hydroxide particles were obtained in the same manner as in Synthesis Example 1. Next, washing and preparation similar to those of Synthesis Example 1 were performed to prepare a concentrated slurry having a cerium hydroxide particle concentration of 1.0 mass%. 0.5% by mass (corresponding to 0.1% by mass as silica particles) of a colloidal silica dispersion (silica particle content: 20% by mass) of silica particles 1 (“Silica 1” in Table 1), 0.1% by mass of concentrated slurry and the above polymer additive (polyglycerin (manufactured by Sakamoto Yakuhin Kogyo Co., Ltd., polyglycerin # 750) 5.0% by mass, polyallylamine (manufactured by Nitto Bo Medical Co., Ltd., PAA-01) 0.01 (Mass%) 10 mass% and water 89 mass% were mixed. Further, the CMP polishing liquid was adjusted by adjusting the pH to 8.0 with a 10 mass% imidazole aqueous solution. When the polishing rate of the CMP abrasive for the silicon oxide layer was determined, it was 1488 Å / min.
Table 4 summarizes the above-mentioned Examples 1 and 5 and Comparative Examples 5 to 7. Silica 1 in Table 4 represents silica particles 1.
表４から明らかなように酸化ケイ素層の研磨速度は、ｐＨ６．０〜７．０のときにセリウム水酸化物粒子単体と比較して研磨速度に優れていた。
次に、異なるシリカを用いてシリカ・セリウム水酸化物の混合粒子を調整し、ｐＨを６付近に調整したＣＭＰ研磨剤の製造法及び諸特性について実施例６〜９及び比較例８に示す。
As apparent from Table 4, the polishing rate of the silicon oxide layer was superior to that of the cerium hydroxide particles alone when the pH was 6.0 to 7.0.
Next, Examples 6 to 9 and Comparative Example 8 show the manufacturing method and various characteristics of a CMP abrasive in which mixed silica / cerium hydroxide particles are prepared using different silicas, and the pH is adjusted to around 6.
＜実施例６＞
合成例１と同様にしてセリウム水酸化物粒子を得た。次いで、合成例１と同様の洗浄及び調製を行い、セリウム水酸化物粒子濃度が１．０質量％の濃縮スラリを調製した。シリカ粒子２（表５中の「シリカ２」）のコロイダルシリカ分散液（シリカ粒子含有量：２０質量％）０．５質量％（シリカ粒子として０．１質量％相当）と、前記調整後の濃縮スラリ０．１質量％と前記ポリマ添加剤（ポリグリセリン（阪本薬品工業株式会社製、ポリグリセリン＃７５０）５．０質量％、ポリアリルアミン（ニットーボーメディカル株式会社製、ＰＡＡ−０１）０．０１質量％）１０質量％と水８９質量％とを混合した。さらに、１０質量％イミダゾール水溶液でｐＨ６．０に調整することによりＣＭＰ研磨液を調整した。ＣＭＰ研磨剤の酸化ケイ素層に対する研磨速度を求めたところ６７７５Å／ｍｉｎであった。
<Example 6>
Cerium hydroxide particles were obtained in the same manner as in Synthesis Example 1. Next, washing and preparation similar to those of Synthesis Example 1 were performed to prepare a concentrated slurry having a cerium hydroxide particle concentration of 1.0 mass%. 0.5% by mass (corresponding to 0.1% by mass as silica particles) of a colloidal silica dispersion (silica particle content: 20% by mass) of silica particles 2 (“Silica 2” in Table 5); 0.1% by mass of concentrated slurry and the above polymer additive (polyglycerin (manufactured by Sakamoto Yakuhin Kogyo Co., Ltd., polyglycerin # 750) 5.0% by mass, polyallylamine (manufactured by Nitto Bo Medical Co., Ltd., PAA-01) 0.01 (Mass%) 10 mass% and water 89 mass% were mixed. Further, the CMP polishing liquid was adjusted by adjusting the pH to 6.0 with a 10 mass% imidazole aqueous solution. When the polishing rate for the silicon oxide layer of the CMP abrasive was determined, it was 6775 kg / min.
＜実施例７＞
合成例１と同様にしてセリウム水酸化物を得た。次いで、合成例１と同様の洗浄及び調製を行い、セリウム水酸化物粒子濃度が１．０質量％の濃縮スラリを調製した。シリカ粒子３（表５中の「シリカ３」）のコロイダルシリカ分散液（シリカ粒子含有量：２０質量％）０．５質量％（シリカ粒子として０．１質量％相当）と、前記調整後の濃縮スラリ０．１質量％と前記ポリマ添加剤（ポリグリセリン（阪本薬品工業株式会社製、ポリグリセリン＃７５０）５．０質量％、ポリアリルアミン（ニットーボーメディカル株式会社製、ＰＡＡ−０１）０．０１質量％）１０質量％と水８９質量％とを混合した。さらに、１０質量％イミダゾール水溶液でｐＨ６．０に調整することによりＣＭＰ研磨液を調整した。ＣＭＰ研磨剤の酸化ケイ素層に対する研磨速度を求めたところ６０８６Å／ｍｉｎであった。
<Example 7>
Cerium hydroxide was obtained in the same manner as in Synthesis Example 1. Next, washing and preparation similar to those of Synthesis Example 1 were performed to prepare a concentrated slurry having a cerium hydroxide particle concentration of 1.0 mass%. 0.5% by mass (corresponding to 0.1% by mass as silica particles) of a colloidal silica dispersion (silica particle content: 20% by mass) of silica particles 3 (“Silica 3” in Table 5), 0.1% by mass of concentrated slurry and the above polymer additive (polyglycerin (manufactured by Sakamoto Yakuhin Kogyo Co., Ltd., polyglycerin # 750) 5.0% by mass, polyallylamine (manufactured by Nitto Bo Medical Co., Ltd., PAA-01) 0.01 (Mass%) 10 mass% and water 89 mass% were mixed. Further, the CMP polishing liquid was adjusted by adjusting the pH to 6.0 with a 10 mass% imidazole aqueous solution. The polishing rate of the CMP abrasive to the silicon oxide layer was determined to be 6086 Å / min.
＜実施例８＞
合成例１と同様にしてセリウム水酸化物粒子を得た。次いで、合成例１と同様の洗浄及び調製を行い、セリウム水酸化物粒子濃度が１．０質量％の濃縮スラリを調製した。シリカ粒子４（表５中の「シリカ４」）のコロイダルシリカ分散液（シリカ粒子含有量：２０質量％）０．５質量％（シリカ粒子として０．１質量％相当）と、前記調整後の濃縮スラリ０．１質量％と前記ポリマ添加剤（ポリグリセリン（阪本薬品工業株式会社製、ポリグリセリン＃７５０）５．０質量％、ポリアリルアミン（ニットーボーメディカル株式会社製、ＰＡＡ−０１）０．０１質量％）１０質量％と水８９質量％とを混合した。さらに、１０質量％イミダゾール水溶液でｐＨ６．０に調整することによりＣＭＰ研磨液を調整した。ＣＭＰ研磨剤の酸化ケイ素層に対する研磨速度を求めたところ６３０６Å／ｍｉｎであった。
<Example 8>
Cerium hydroxide particles were obtained in the same manner as in Synthesis Example 1. Next, washing and preparation similar to those of Synthesis Example 1 were performed to prepare a concentrated slurry having a cerium hydroxide particle concentration of 1.0 mass%. Colloidal silica dispersion (silica particle content: 20% by mass) of silica particles 4 (“Silica 4” in Table 5) 0.5% by mass (equivalent to 0.1% by mass as silica particles), 0.1% by mass of concentrated slurry and the above polymer additive (polyglycerin (manufactured by Sakamoto Yakuhin Kogyo Co., Ltd., polyglycerin # 750) 5.0% by mass, polyallylamine (manufactured by Nitto Bo Medical Co., Ltd., PAA-01) 0.01 (Mass%) 10 mass% and water 89 mass% were mixed. Further, the CMP polishing liquid was adjusted by adjusting the pH to 6.0 with a 10 mass% imidazole aqueous solution. When the polishing rate for the silicon oxide layer of the CMP abrasive was determined, it was 6306 Å / min.
＜実施例９＞
合成例１と同様にしてセリウム水酸化物粒子を得た。次いで、合成例１と同様の洗浄及び調製を行い、セリウム水酸化物粒子濃度が１．０質量％の濃縮スラリを調製した。シリカ粒子５（表５中の「シリカ５」）のコロイダルシリカ分散液（シリカ粒子含有量：２０質量％）０．５質量％（シリカ粒子として０．１質量％相当）と、前記調整後の濃縮スラリ０．１質量％と前記ポリマ添加剤（ポリグリセリン（阪本薬品工業株式会社製、ポリグリセリン＃７５０）５．０質量％、ポリアリルアミン（ニットーボーメディカル株式会社製、ＰＡＡ−０１）０．０１質量％）１０質量％と水８９質量％とを混合した。さらに、１０質量％イミダゾール水溶液でｐＨ６．０に調整することによりＣＭＰ研磨液を調整した。ＣＭＰ研磨剤の酸化ケイ素層に対する研磨速度を求めたところ６１３１Å／ｍｉｎであった。
<Example 9>
Cerium hydroxide particles were obtained in the same manner as in Synthesis Example 1. Next, washing and preparation similar to those of Synthesis Example 1 were performed to prepare a concentrated slurry having a cerium hydroxide particle concentration of 1.0 mass%. 0.5% by mass (corresponding to 0.1% by mass as silica particles) of a colloidal silica dispersion (silica particle content: 20% by mass) of silica particles 5 (“Silica 5” in Table 5), 0.1% by mass of concentrated slurry and the above polymer additive (polyglycerin (manufactured by Sakamoto Yakuhin Kogyo Co., Ltd., polyglycerin # 750) 5.0% by mass, polyallylamine (manufactured by Nitto Bo Medical Co., Ltd., PAA-01) 0.01 (Mass%) 10 mass% and water 89 mass% were mixed. Further, the CMP polishing liquid was adjusted by adjusting the pH to 6.0 with a 10 mass% imidazole aqueous solution. When the polishing rate for the silicon oxide layer of the CMP abrasive was determined, it was 6131 Å / min.
＜比較例８＞
合成例１と同様にしてセリウム水酸化物粒子を得た。次いで、合成例１と同様の洗浄及び調製を行い、セリウム水酸化物粒子濃度が１．０質量％の濃縮スラリを調製した。シリカ粒子６（表５中の「シリカ６」）のコロイダルシリカ分散液（シリカ粒子含有量：２０質量％）０．５質量％（シリカ粒子として０．１質量％相当）と、前記調整後の濃縮スラリ０．１質量％と前記ポリマ添加剤（ポリグリセリン（阪本薬品工業株式会社製、ポリグリセリン＃７５０）５．０質量％、ポリアリルアミン（ニットーボーメディカル株式会社製、ＰＡＡ−０１）０．０１質量％）１０質量％と水８９質量％とを混合した。さらに、１０質量％イミダゾール水溶液でｐＨ６．０に調整することによりＣＭＰ研磨液を調整した。ＣＭＰ研磨剤の酸化ケイ素層に対する研磨速度を求めたところ５１７２Å／ｍｉｎであった。
前記の実施例１及び実施例６〜９と比較例８について表５にまとめて示す。表５中のシリカ１〜６は、シリカ粒子１〜６を表す。
<Comparative Example 8>
Cerium hydroxide particles were obtained in the same manner as in Synthesis Example 1. Next, washing and preparation similar to those of Synthesis Example 1 were performed to prepare a concentrated slurry having a cerium hydroxide particle concentration of 1.0 mass%. Colloidal silica dispersion (silica particle content: 20% by mass) of silica particles 6 (“Silica 6” in Table 5) 0.5% by mass (corresponding to 0.1% by mass as silica particles), 0.1% by mass of concentrated slurry and the above polymer additive (polyglycerin (manufactured by Sakamoto Yakuhin Kogyo Co., Ltd., polyglycerin # 750) 5.0% by mass, polyallylamine (manufactured by Nitto Bo Medical Co., Ltd., PAA-01) 0.01 (Mass%) 10 mass% and water 89 mass% were mixed. Further, the CMP polishing liquid was adjusted by adjusting the pH to 6.0 with a 10 mass% imidazole aqueous solution. When the polishing rate for the silicon oxide layer of the CMP abrasive was determined, it was 5172 Å / min.
Table 5 summarizes Example 1 and Examples 6 to 9 and Comparative Example 8 described above. Silica 1-6 in Table 5 represent silica particles 1-6.
表２に示すように、本実施形態のＣＭＰ研磨剤であるシリカ粒子及びセリウム水酸化物粒子を含有する混合砥粒は、シリカ粒子単体（比較例２）及びセリウム水酸化物粒子単体（比較例１）と比較して、酸化ケイ素層に対する研磨速度が速く、優れていることが明らかとなった。
また、表３〜表５に示すように、セリウム水酸化物粒子の割合が２５質量％未満の比較例３〜４、ＣＭＰ研磨剤のｐＨが５．５〜７．３の範囲外の比較例５〜７、平均二次粒子径が６５ｎｍ超かつシラノール基密度が５．０個／ｎｍ２超のシリカ粒子を使用した比較例８と比較しても、酸化ケイ素層に対する研磨速度が速く、優れていることが明らかとなった。
本発明のＣＭＰ研磨剤によれば、シャロートレンチ分離絶縁材料、プリメタル絶縁材料、層間絶縁材料等を平坦化するＣＭＰ技術において、これらの絶縁材料を高速に研磨できる。また本発明のＣＭＰ研磨剤によれば、絶縁材料に対する研磨速度を向上させつつ、絶縁材料を低研磨傷で研磨することもできる。
As shown in Table 2, the mixed abrasives containing silica particles and cerium hydroxide particles, which are the CMP abrasives of this embodiment, are silica particles alone (Comparative Example 2) and cerium hydroxide particles alone (Comparative Example). Compared with 1), the polishing rate for the silicon oxide layer was faster and was found to be excellent.
Moreover, as shown in Tables 3 to 5, Comparative Examples 3 to 4 in which the ratio of cerium hydroxide particles is less than 25% by mass, and Comparative Examples outside the range where the pH of the CMP abrasive is 5.5 to 7.3. 5-7, even average secondary particle diameter as compared with Comparative example 8 65nm ultra and silanol group density using 5.0 pieces / nm 2 greater than the silica particles, fast polishing rate of the silicon oxide layer, excellent It became clear that.
According to the CMP polishing agent of the present invention, these insulating materials can be polished at high speed in the CMP technique for flattening the shallow trench isolation insulating material, the premetal insulating material, the interlayer insulating material and the like. Moreover, according to the CMP abrasive | polishing agent of this invention, an insulating material can also be grind | polished with a low grinding | polishing damage | wound, improving the polishing rate with respect to an insulating material.
本発明は、シャロートレンチ分離絶縁材料、プリメタル絶縁材料、層間絶縁材料等を平坦化するＣＭＰ技術において、絶縁材料を高速かつ低研磨傷で研磨できるＣＭＰ研磨剤及び該ＣＭＰ研磨剤を用いた基板の研磨方法を提供できる。 The present invention relates to a CMP technique for planarizing shallow trench isolation insulating materials, pre-metal insulating materials, interlayer insulating materials, etc., and a CMP polishing agent capable of polishing the insulating material at high speed with low polishing scratches and a substrate using the CMP polishing agent. A polishing method can be provided.
Claims (11)
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