JP5412706B2 - Polishing material and polishing method for copper film and insulating material film - Google Patents
Polishing material and polishing method for copper film and insulating material film Download PDFInfo
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- JP5412706B2 JP5412706B2 JP2006258796A JP2006258796A JP5412706B2 JP 5412706 B2 JP5412706 B2 JP 5412706B2 JP 2006258796 A JP2006258796 A JP 2006258796A JP 2006258796 A JP2006258796 A JP 2006258796A JP 5412706 B2 JP5412706 B2 JP 5412706B2
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- 238000005498 polishing Methods 0.000 title claims description 106
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims description 73
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Description
本発明は、銅膜及び絶縁材料膜用研磨材及び研磨方法に関するものであり、特に高性能配線板の銅配線形成に適した化学機械研磨（以下、ＣＭＰという）工程で使用する研磨材およびそれを用いた研磨方法に関する。 The present invention relates to a polishing material for a copper film and an insulating material film, and a polishing method, and more particularly to a polishing material used in a chemical mechanical polishing (hereinafter referred to as CMP) process suitable for forming a copper wiring of a high performance wiring board. The present invention relates to a polishing method using stencil.
ＬＳＩを高性能化するために、配線材料として従来のアルミニウム合金配線に替わって銅合金配線の利用が進んでいる。銅合金配線は従来のアルミニウム合金配線の形成で頻繁に用いられたドライエッチング法による微細加工が困難であるため、あらかじめ溝を形成してある絶縁膜上に銅合金薄膜を堆積して埋め込み、溝部以外の銅合金薄膜をＣＭＰにより除去して埋め込み配線を形成する、いわゆるダマシン法が主に採用されている（特許文献１）。銅や銅合金等の金属膜を研磨する金属ＣＭＰの一般的な方法は、円形の研磨定盤（プラテン）上に研磨パッドを貼り付け、研磨パッド表面を金属膜用研磨材で浸し、基板の金属膜を形成した面を押し付けて、その裏面から所定の圧力（以下研磨圧力と記す）を加えた状態で研磨定盤を回し、研磨材と金属膜の凸部との機械的摩擦によって凸部の金属膜を除去するものである。 In order to improve the performance of LSIs, the use of copper alloy wiring as a wiring material is progressing instead of conventional aluminum alloy wiring. Since copper alloy wiring is difficult to be finely processed by the dry etching method frequently used in the formation of conventional aluminum alloy wiring, a copper alloy thin film is deposited and embedded on an insulating film in which grooves have been formed in advance. A so-called damascene method is mainly employed in which a copper alloy thin film other than the above is removed by CMP to form a buried wiring (Patent Document 1). A general method of metal CMP for polishing a metal film such as copper or copper alloy is to apply a polishing pad on a circular polishing platen (platen), immerse the polishing pad surface with a metal film polishing material, and The surface on which the metal film is formed is pressed, and the polishing platen is rotated with a predetermined pressure (hereinafter referred to as polishing pressure) applied from the back surface, and the convex portion is caused by mechanical friction between the abrasive and the convex portion of the metal film. The metal film is removed.
ＣＭＰ処理に用いられる金属膜用研磨材は、一般には酸化剤及び砥粒からなっている。酸化剤によって金属膜の表面を酸化し、その酸化層を砥粒によって削り取るのが基本的なメカニズムと考えられている。凹部の金属膜表面の酸化層は研磨パッドにあまり触れず、砥粒による削り取りの効果が及ばないので、ＣＭＰ処理の進行とともに凸部の酸化層が除去されて基板表面は平坦化される。また、必要に応じてさらに酸などの酸化金属溶解剤、金属膜表面に対する保護膜形成剤が添加される。酸化金属溶解剤を添加すると研磨速度を向上させることが可能であり、併せて金属膜表面に対する保護膜形成剤を添加すると凹部の金属膜表面に保護膜を形成するので、実用的な研磨速度を保ちつつ平坦性を確保することができる（特許文献２）。 The metal film abrasive used in the CMP process is generally composed of an oxidizing agent and abrasive grains. It is considered that the basic mechanism is to oxidize the surface of the metal film with an oxidizing agent and scrape the oxidized layer with abrasive grains. Since the oxide layer on the surface of the metal film in the concave portion does not touch the polishing pad so much and the effect of scraping off by the abrasive grains does not reach, the oxide layer in the convex portion is removed and the substrate surface is flattened as the CMP process proceeds. Further, if necessary, a metal oxide solubilizer such as an acid and a protective film forming agent for the metal film surface are added. Adding a metal oxide solubilizer can improve the polishing rate, and adding a protective film forming agent for the metal film surface also forms a protective film on the concave metal film surface, so a practical polishing rate can be achieved. Flatness can be ensured while maintaining (Patent Document 2).
近年、ＬＳＩの製造に続いてパッケージ等の高性能・微細配線板においても、高精度の配線形成が可能なＣＭＰ法の適用が検討されている。ＬＳＩの製造において使用される銅または銅合金等の金属膜の厚さは１μｍ程度であるのに対し、高性能・微細配線版に使用される金属膜の厚さは１０μｍ程度と厚いため、研磨速度０．５μｍ／ｍｉｎ程度の従来のＬＳＩ用の研磨材を使用すると（特許文献３）、ＣＭＰ処理に時間がかかり、生産性が悪くなるという問題があった。
本発明は、銅および銅合金膜を２μｍ／ｍｉｎ以上の高い研磨速度で研磨することが可能で、高性能配線板などの厚い銅膜の研磨が必要とされる製品の製造においても、短時間で研磨処理が可能で十分な生産性を確保できる研磨材及び研磨方法を提供するものである。 The present invention makes it possible to polish copper and copper alloy films at a high polishing rate of 2 μm / min or more, and in a short time even in the manufacture of products that require polishing of thick copper films such as high-performance wiring boards. Therefore, the present invention provides an abrasive and a polishing method that can be polished and can ensure sufficient productivity.
本発明は、（１）水、砥粒、酸化剤、無機酸及びアミノ酸を含有し、ｐＨが１．５以上３．５以下である研磨材であって、該研磨材のｐＨを４まで増加するのに要する水酸化カリウムの量が研磨材１ｋｇ当たり０．０５ｍｏｌ以上であることを特徴とする銅膜及び絶縁材料膜用研磨材に関する。 The present invention is (1) an abrasive containing water, abrasive grains, an oxidizing agent, an inorganic acid and an amino acid and having a pH of 1.5 or more and 3.5 or less, and the pH of the abrasive is increased to 4. The present invention relates to an abrasive for a copper film and an insulating material film, characterized in that the amount of potassium hydroxide required for the treatment is 0.05 mol or more per kg of the abrasive.
また、本発明は、（２）前記砥粒が、平均粒径１００ｎｍ以下のコロイダルシリカであることを特徴とする前記（１）記載の銅膜及び絶縁材料膜用研磨材に関する。 The present invention also relates to (2) the abrasive for copper film and insulating material film according to (1), wherein the abrasive grains are colloidal silica having an average particle diameter of 100 nm or less.
また、本発明は、（３）前記酸化剤が、過酸化水素、過硫酸または過硫酸塩より選ばれた少なくとも１種の酸化剤であることを特徴とする前記（１）記載の銅膜及び絶縁材料膜用研磨材に関する。 Moreover, this invention is (3) The copper film as described in said (1) characterized by the said oxidizing agent being at least 1 sort (s) of oxidizing agent chosen from hydrogen peroxide, persulfuric acid, or persulfate. The present invention relates to an insulating material film abrasive.
また、本発明は、（４）前記無機酸が、硫酸またはリン酸もしくはそれらの混合物であることを特徴とする前記（１）記載の銅膜及び絶縁材料膜用研磨材に関する。 The present invention also relates to (4) the abrasive for copper film and insulating material film according to (1), wherein the inorganic acid is sulfuric acid, phosphoric acid or a mixture thereof.
また、本発明は、（５）前記アミノ酸が、２５℃における第一段の酸解離指数が２以上３以下であることを特徴とする前記（１）記載の銅膜及び絶縁材料膜用研磨材に関する。 In addition, the present invention provides: (5) The polishing material for copper film and insulating material film according to (1), wherein the amino acid has a first-stage acid dissociation index of 2 to 3 at 25 ° C. About.
また、本発明は、（６）銅表面に対する保護膜形成剤を含有することを特徴とする前記（１）〜（５）のいずれか一項に記載の銅膜及び絶縁材料膜用研磨材に関する。 The present invention also relates to (6) a polishing agent for a copper film and an insulating material film according to any one of (1) to (5) above, which contains a protective film forming agent for the copper surface. .
また、本発明は、（７）前記保護膜形成剤が、ベンゾトリアゾ−ル及びその誘導体から選ばれた少なくとも１種の保護膜形成剤であることを特徴とする前記（６）記載の銅膜及び絶縁材料膜用研磨材に関する。 The present invention is also directed to (7) the copper film according to (6), wherein the protective film forming agent is at least one protective film forming agent selected from benzotriazole and derivatives thereof. The present invention relates to an insulating material film abrasive.
また、本発明は、（８）水溶性高分子を含有することを特徴とする前記（１）〜（７）のいずれか一項に記載の銅膜及び絶縁材料膜用研磨材に関する。 Moreover, this invention relates to the abrasive | polishing material for copper films as described in any one of said (1)-(7) characterized by containing water-soluble polymer (8).
また、本発明は、（９）前記（１）〜（８）のいずれか一項に記載の銅膜及び絶縁材料膜用研磨材を用いて、銅膜及び絶縁材料膜が形成された基板を含む被研磨膜を研磨することを特徴とする研磨方法に関する。 In addition, the present invention provides (9) a substrate on which a copper film and an insulating material film are formed using the copper film and the insulating material film abrasive according to any one of (1) to (8). The present invention relates to a polishing method comprising polishing a film to be polished.
本発明の研磨材として、ｐＨが１．５〜３．５の緩衝溶液を得ることができる。このため被研磨物である銅および銅合金が研磨材中に溶解してもｐＨ変動が起こりにくく、高い研磨速度を維持することができる。本発明の研磨材及び研磨方法は、高い研磨速度と金属膜上の表面粗さの抑制が可能であり、生産性の向上と、製品歩留まりの向上を両立できるので、高性能配線板等の製造工程に適用できる。 As the abrasive of the present invention, a buffer solution having a pH of 1.5 to 3.5 can be obtained. For this reason, even if copper and a copper alloy, which are objects to be polished, are dissolved in the polishing material, pH fluctuation hardly occurs, and a high polishing rate can be maintained. The polishing material and polishing method of the present invention can suppress the surface roughness on the metal film with a high polishing rate, and can improve productivity and increase the product yield. Applicable to process.
本発明の銅膜及び絶縁材料膜用研磨材は、水、砥粒、酸化剤、無機酸及びアミノ酸を含有し、ｐＨが１．５以上３．５以下である研磨材であって、該研磨材のｐＨを４まで増加するのに要する水酸化カリウムの量が研磨材１ｋｇ当たり０．０５ｍｏｌ以上であることを特徴とする。 The abrasive for copper film and insulating material film of the present invention is an abrasive containing water, abrasive grains, oxidant, inorganic acid and amino acid, and having a pH of 1.5 or more and 3.5 or less. The amount of potassium hydroxide required to increase the pH of the material to 4 is 0.05 mol or more per kg of the abrasive.
本発明の銅膜及び絶縁材料膜用研磨材のｐＨは、銅膜のＣＭＰによる研磨速度が大きく、銅膜に腐食を生じさせないという点でｐＨ１．５以上３．５以下であり、ｐＨ２以上ｐＨ３以下が好ましい。ｐＨ１．５未満では、銅膜の表面粗さが大きくなり、また、ｐＨ３．５を超えるとＣＭＰによる研磨速度が遅くなり実用的な研磨材とはなり得ない。本発明では、無機酸及びアミノ酸の配合量を適宜選択することにより研磨材のｐＨを上記範囲に調整する。無機酸は一般的に強酸であり、多量に添加するとｐＨが低下してしまいｐＨを所望の範囲に調整するのは困難であるが、アミノ酸を添加することによりｐＨを所望の範囲に容易に調整することができる。 The pH of the polishing material for copper film and insulating material film of the present invention is pH 1.5 or more and 3.5 or less, pH 2 or more and pH 3 in that the polishing rate by CMP of the copper film is large and the copper film is not corroded. The following is preferred. If the pH is less than 1.5, the surface roughness of the copper film becomes large. If the pH exceeds 3.5, the polishing rate by CMP becomes slow and cannot be a practical abrasive. In the present invention, the pH of the abrasive is adjusted to the above range by appropriately selecting the blending amounts of inorganic acid and amino acid. Inorganic acids are generally strong acids, and when added in large amounts, the pH drops and it is difficult to adjust the pH to the desired range, but it is easy to adjust the pH to the desired range by adding amino acids. can do.
本発明の銅膜及び絶縁材料膜用研磨材は、研磨材のｐＨを４まで増加するのに要する水酸化カリウムの量が研磨材１ｋｇ当たり０．０５ｍｏｌ以上である。該水酸化カリウムの量が０．０５ｍｏｌ未満では、研磨速度が低下してしまう。該水酸化カリウムの量を研磨材１ｋｇ当たり０．０５ｍｏｌ以上とする方法は、添加する無機酸の配合量を適宜選択することにより行なわれる。 In the abrasive for copper film and insulating material film of the present invention, the amount of potassium hydroxide required to increase the pH of the abrasive to 4 is 0.05 mol or more per kg of abrasive. If the amount of potassium hydroxide is less than 0.05 mol, the polishing rate will decrease. The method of setting the amount of potassium hydroxide to 0.05 mol or more per 1 kg of the abrasive is performed by appropriately selecting the blending amount of the inorganic acid to be added.
ＣＭＰ処理中には被研磨物である銅膜が研磨され、研磨材中に銅イオンとして溶解する。無機酸の配合量が少ないと、銅膜の溶解により水素イオンが消費され研磨材のｐＨが上昇し、研磨速度が低下してしまう。一方、無機酸の配合量が充分であると、研磨材はｐＨ緩衝作用を有するため、銅イオンが多量に溶解しても、ｐＨの上昇は抑制され、研磨速度は低下することなく安定した研磨が可能になる。そのために必要な研磨材中の無機酸の量は、研磨速度、研磨中における研磨材流量にもよるが８インチの円盤状の基板を研磨する場合には、研磨材のｐＨを４まで増加するのに要する水酸化カリウムの量として研磨材１ｋｇ当たり０．０５ｍｏｌ以上に相当する量である。 During the CMP process, the copper film that is the object to be polished is polished and dissolved as copper ions in the polishing material. If the amount of the inorganic acid is small, hydrogen ions are consumed by dissolution of the copper film, the pH of the abrasive is increased, and the polishing rate is decreased. On the other hand, if the amount of the inorganic acid is sufficient, the abrasive has a pH buffering action, so even if a large amount of copper ions are dissolved, the increase in pH is suppressed, and stable polishing without decreasing the polishing rate. Is possible. The amount of inorganic acid in the polishing material required for that purpose increases the pH of the polishing material to 4 when polishing an 8-inch disk-shaped substrate, although it depends on the polishing rate and the polishing material flow rate during polishing. The amount of potassium hydroxide required for this is an amount corresponding to 0.05 mol or more per kg of the abrasive.
本発明における砥粒は、シリカ、アルミナ、ジルコニア、セリア、チタニア、炭化珪素等の無機物砥粒、ポリスチレン、ポリアクリル、ポリ塩化ビニル等の有機物砥粒のいずれでもよいが、研磨材中での分散安定性が良く、ＣＭＰにより発生する研磨傷（スクラッチ）の発生数の少ない、平均粒径が１００ｎｍ以下のコロイダルシリカ、コロイダルアルミナが好ましく、平均粒径１００ｎｍ以下のコロイダルシリカがより好ましい。コロイダルシリカはシリコンアルコキシドの加水分解または珪酸ナトリウムのイオン交換による製造方法が知られており、コロイダルアルミナは硝酸アルミニウムの加水分解による製造方法が知られている。 The abrasive grains in the present invention may be any of inorganic abrasive grains such as silica, alumina, zirconia, ceria, titania and silicon carbide, and organic abrasive grains such as polystyrene, polyacryl and polyvinyl chloride, but dispersed in the abrasive. Colloidal silica and colloidal alumina having an average particle size of 100 nm or less are preferred, and colloidal silica having an average particle size of 100 nm or less is more preferred, since the stability is good and the number of polishing scratches (scratches) generated by CMP is small. Colloidal silica is known for its production by hydrolysis of silicon alkoxide or ion exchange of sodium silicate, and colloidal alumina is known for its production by hydrolysis of aluminum nitrate.
本発明における砥粒の配合量は、研磨材全重量に対して０．１質量％〜１０質量％であることが好ましく、１質量％〜５質量％であることがより好ましい。砥粒の配合量が０．１質量％未満である場合は、物理的な研削作用が小さいため研磨速度が低下する傾向にあり、１０質量％を超える場合は、研磨速度は飽和し、それ以上加えても研磨速度の増加は認められない傾向にある。 The blending amount of the abrasive grains in the present invention is preferably 0.1% by mass to 10% by mass, and more preferably 1% by mass to 5% by mass with respect to the total weight of the abrasive. When the blending amount of the abrasive grains is less than 0.1% by mass, the polishing rate tends to decrease because the physical grinding action is small, and when it exceeds 10% by mass, the polishing rate is saturated and beyond. Even when added, the polishing rate tends not to increase.
本発明における酸化剤としては、過酸化水素（Ｈ２Ｏ２）、過硫酸、過硫酸アンモニウム、過硫酸カリウム等の過硫酸塩、過ヨウ素酸、過ヨウ素酸カリウム等が挙げられ、これらの中でも過酸化水素、過硫酸、過硫酸塩が好ましく、過酸化水素がより好ましい。 Examples of the oxidizing agent in the present invention include hydrogen sulfate (H 2 O 2 ), persulfates such as persulfuric acid, ammonium persulfate, and potassium persulfate, periodic acid, potassium periodate, and the like. Hydrogen oxide, persulfuric acid and persulfate are preferable, and hydrogen peroxide is more preferable.
本発明における酸化剤の配合量は、研磨材全重量に対して、０．１ｍｏｌ／ｋｇ〜５ｍｏｌ／ｋｇであることが好ましく、０．５ｍｏｌ／ｋｇ〜４ｍｏｌ／ｋｇであることがより好ましい。酸化剤の配合量が０．１ｍｏｌ／ｋｇ未満である場合は、研磨速度が低下する傾向にあり、５ｍｏｌ／ｋｇを超える場合も研磨速度が低下する傾向にある。 The blending amount of the oxidizing agent in the present invention is preferably 0.1 mol / kg to 5 mol / kg, and more preferably 0.5 mol / kg to 4 mol / kg with respect to the total weight of the abrasive. When the blending amount of the oxidizing agent is less than 0.1 mol / kg, the polishing rate tends to decrease, and when it exceeds 5 mol / kg, the polishing rate tends to decrease.
本発明における無機酸としては、硝酸、塩酸、臭化水素酸、ヨウ化水素酸、硫酸、リン酸等が挙げられ、これらの中でも硫酸またはリン酸もしくは硫酸とリン酸の混合物がＣＭＰによる研磨速度が大きく、銅および銅合金膜の表面粗さを低減できるという点で好ましい。 Examples of the inorganic acid in the present invention include nitric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, phosphoric acid, etc. Among these, sulfuric acid or phosphoric acid or a mixture of sulfuric acid and phosphoric acid is a polishing rate by CMP. Is preferable in that the surface roughness of the copper and copper alloy films can be reduced.
本発明における無機酸の配合量は、研磨材のｐＨを４まで増加するのに要する水酸化カリウムの量が研磨材１ｋｇ当たり０．０５ｍｏｌ以上となる量である。 The blending amount of the inorganic acid in the present invention is such that the amount of potassium hydroxide required to increase the pH of the abrasive to 4 is 0.05 mol or more per 1 kg of the abrasive.
本発明におけるアミノ酸としては、グリシン、アラニン、バリン、ロイシン、イソロイシン、セリン、トレオニン、システイン、シスチン、メチオニン、アスパラギン酸、グルタミン酸、リシン、アルギニン、フェニルアラニン、チロシン、ヒスチジン、トリプトファン、プロリン、オキシプロリン等が挙げられる。これらの中でも、２５℃における第一段の酸解離指数（ｐＫ１）が２以上３以下であるアミノ酸が、銅膜及び絶縁材料膜用研磨材のｐＨを１．５以上４以下に調整しやすいという点で好ましい。具体的にはアラニン、アルギニン、イソロイシン、グリシン、グルタミン酸、トリプトファン、トレオニン、バリン、メチオニン、リシン、ロイシン、セリン、チロシン、フェニルアラニン等が好ましく、グリシンが特に好ましい。なお、本発明における酸解離指数（ｐＫａ）とは、酸解離定数の逆数の対数値で、例えば「化学便覧基礎編」改定４版（平成５年９月３０日発行）、丸善株式会社、ＩＩ−３１７〜３２１頁に詳細な記載がある。 Examples of amino acids in the present invention include glycine, alanine, valine, leucine, isoleucine, serine, threonine, cysteine, cystine, methionine, aspartic acid, glutamic acid, lysine, arginine, phenylalanine, tyrosine, histidine, tryptophan, proline, oxyproline and the like. Can be mentioned. Among these, the amino acid whose first-stage acid dissociation index (pK1) at 25 ° C. is 2 or more and 3 or less is easy to adjust the pH of the abrasive for the copper film and the insulating material film to 1.5 or more and 4 or less. This is preferable. Specifically, alanine, arginine, isoleucine, glycine, glutamic acid, tryptophan, threonine, valine, methionine, lysine, leucine, serine, tyrosine, phenylalanine and the like are preferable, and glycine is particularly preferable. The acid dissociation index (pKa) in the present invention is a logarithmic value of the reciprocal of the acid dissociation constant. For example, “Basic Manual of Chemistry” revised 4th edition (issued on September 30, 1993), Maruzen Co., Ltd., II There are detailed descriptions on pages 317 to 321.
本発明の研磨材は、銅表面に対する保護膜形成剤を含有することが好ましい。保護膜形成剤としては特に限定されず、例えば、ベンゾトリアゾール（ＢＴＡ）、ＢＴＡ誘導体、例えばＢＴＡのベンゼン環の一つの水素原子をメチル基で置換したもの（トリルトリアゾール）もしくはカルボキシル基等で置換したもの（ベンゾトリアゾール−４−カルボン酸およびベンゾトリアゾール−４−カルボン酸のメチル、エチル、プロピル、ブチル及びオクチルエステル）、トリアゾール、キナルジン酸、アントニル酸、サリチルアルドキシム等が挙げられる。これらの中でも、ＢＴＡもしくはその誘導体もしくはそれらの混合物であることが好ましい。 The abrasive of the present invention preferably contains a protective film forming agent for the copper surface. The protective film forming agent is not particularly limited. For example, benzotriazole (BTA), BTA derivative, for example, one hydrogen atom of the benzene ring of BTA is substituted with a methyl group (tolyltriazole) or a carboxyl group is substituted. And the like (methyl, ethyl, propyl, butyl and octyl esters of benzotriazole-4-carboxylic acid and benzotriazole-4-carboxylic acid), triazole, quinaldic acid, anthonylic acid, salicylaldoxime and the like. Among these, BTA or a derivative thereof or a mixture thereof is preferable.
本発明における保護膜形成剤の配合量は、研磨材全重量に対して、０．０５質量％から１質量％であることが好ましく、０．１質量％〜０．５質量％であることがより好ましい。保護膜形成剤の配合量が０．０５質量％未満では研磨表面の表面粗さが大きくなる傾向があり、１質量％を超えると研磨速度が小さくなる傾向がある。 The blending amount of the protective film forming agent in the present invention is preferably 0.05% by mass to 1% by mass, and preferably 0.1% by mass to 0.5% by mass with respect to the total weight of the abrasive. More preferred. When the blending amount of the protective film forming agent is less than 0.05% by mass, the surface roughness of the polishing surface tends to increase, and when it exceeds 1% by mass, the polishing rate tends to decrease.
また、本発明の研磨材は、水溶性高分子を含有することが好ましい。水溶性高分子としては特に限定されず、例えば、ポリアクリル酸、ポリアクリル酸アンモニウム塩、ポリアクリル酸ナトリウム塩、ポリメタクリル酸、ポリメタクリル酸アンモニウム塩、ポリメタクリル酸ナトリウム塩、ポリアクリルアミド等のカルボキシル基を持つモノマーを基本構成単位とするポリマーおよびその塩、ポリビニルアルコール、ポリビニルピロリドン等のビニル基を持つモノマーを基本構成単位とするポリマーが挙げられる。これらの中でも、ポリアクリル酸もしくはその塩、ポリメタクリル酸もしくはその塩であることが好ましい。これら水溶性高分子の重量平均分子量は５００以上であることが好ましい。これらの水溶性高分子を添加することにより、研磨速度および平坦性（銅膜／縁膜性樹膜間段差）が向上する傾向にある。 The abrasive of the present invention preferably contains a water-soluble polymer. The water-soluble polymer is not particularly limited, and examples thereof include polyacrylic acid, polyacrylic acid ammonium salt, polyacrylic acid sodium salt, polymethacrylic acid, polymethacrylic acid ammonium salt, polymethacrylic acid sodium salt, and polyacrylamide. Examples thereof include a polymer having a monomer having a group as a basic structural unit and a salt thereof, a polymer having a monomer having a vinyl group such as polyvinyl alcohol and polyvinylpyrrolidone as a basic structural unit. Among these, polyacrylic acid or a salt thereof, and polymethacrylic acid or a salt thereof are preferable. These water-soluble polymers preferably have a weight average molecular weight of 500 or more. The addition of these water-soluble polymers tends to improve the polishing rate and flatness (step between the copper film / rim film dendrite).
本発明における水溶性高分子の配合量は、研磨材全重量に対して、０．０１質量％〜２．０質量％とすることが好ましく、０．１質量％〜１．０質量％とすることがより好ましい。水溶性高分子の配合量が０．０１質量％未満では、研磨速度を向上させる作用は認められにくく、２．０質量％を超えると、砥粒の分散安定性を低下させる傾向がある。 The blending amount of the water-soluble polymer in the present invention is preferably 0.01% by mass to 2.0% by mass, and 0.1% by mass to 1.0% by mass with respect to the total weight of the abrasive. It is more preferable. If the blending amount of the water-soluble polymer is less than 0.01% by mass, the effect of improving the polishing rate is hardly recognized, and if it exceeds 2.0% by mass, the dispersion stability of the abrasive tends to be lowered.
本発明の研磨材は、砥粒が水中にスラリー状に分散したものである。水の配合量は前述した各種成分の合計量に対する残分となる。 The abrasive of the present invention is one in which abrasive grains are dispersed in water in a slurry form. The amount of water added is the remainder relative to the total amount of the various components described above.
本発明の研磨方法は、上記本発明の研磨材を用いて銅膜及び絶縁材料膜を含む被研磨膜が形成された基板を研磨することを特徴とする。研磨対象である被研磨膜は銅膜及び絶縁材料膜であり、これらそれぞれの膜は単層でも積層でも構わない。銅膜としては銅または銅合金である。銅膜はスパッタ法やメッキ法などの公知の方法により成膜される。 The polishing method of the present invention is characterized in that a substrate on which a film to be polished including a copper film and an insulating material film is formed is polished using the polishing material of the present invention. The target films to be polished are a copper film and an insulating material film, and each of these films may be a single layer or a stacked layer. The copper film is copper or a copper alloy. The copper film is formed by a known method such as sputtering or plating.
基板としては、半導体装置製造に係る基板、例えば回路素子と配線パターンが形成された段階の半導体基板、回路素子が形成された段階の半導体基板等の半導体基板上に、絶縁層が形成された基板などが挙げられる。 As the substrate, a substrate related to semiconductor device manufacture, for example, a substrate in which an insulating layer is formed on a semiconductor substrate such as a semiconductor substrate in which a circuit element and a wiring pattern are formed, a semiconductor substrate in a stage in which a circuit element is formed, etc. Etc.
被研磨膜の研磨は化学機械研磨により行なわれ、具体的には、被研磨面が形成された基板を研磨定盤の研磨布（パッド）上に押圧した状態で、本発明の研磨材を供給しながら研磨定盤と基板とを相対的に動かすことによって被研磨面を研磨する。他に、金属製または樹脂製のブラシを被研磨面に接触させる方法、研磨材を所定の圧力で吹きつける方法が挙げられる。 Polishing of the film to be polished is performed by chemical mechanical polishing. Specifically, the polishing material of the present invention is supplied in a state where the substrate on which the surface to be polished is formed is pressed onto the polishing cloth (pad) of the polishing surface plate. The surface to be polished is polished by relatively moving the polishing platen and the substrate. In addition, there are a method in which a metal or resin brush is brought into contact with the surface to be polished, and a method in which an abrasive is sprayed at a predetermined pressure.
研磨する装置としては、例えば研磨布により研磨する場合、研磨される基板を保持できるホルダと、回転数が変更可能なモータ等に接続し、研磨布を貼り付けられる定盤とを有する一般的な研磨装置が使用できる。例えば、株式会社荏原製作所製研磨装置：型番ＥＰＯ１１１が使用できる。 As an apparatus for polishing, for example, when polishing with a polishing cloth, a general apparatus having a holder that can hold a substrate to be polished and a surface plate that is connected to a motor that can change the number of rotations and to which the polishing cloth is attached. A polishing apparatus can be used. For example, a polishing apparatus manufactured by Ebara Corporation: model number EPO111 can be used.
研磨布としては、一般的な不織布、発泡ポリウレタン、多孔質フッ素樹脂などが使用でき、特に制限がない。研磨条件には制限はないが、定盤の回転速度は基板が飛び出さないように２００ｒｐｍ以下の低回転が好ましい。被研磨面を有する基板の研磨布への押し付け圧力（研磨圧力）が１〜１００ｋＰａであることが好ましく、ＣＭＰ速度の被研磨面内均一性及びパターンの平坦性を満足するためには、５〜５０ｋＰａであることがより好ましい。 As an abrasive cloth, a general nonwoven fabric, a polyurethane foam, a porous fluororesin, etc. can be used, and there is no restriction | limiting in particular. The polishing conditions are not limited, but the rotation speed of the surface plate is preferably low rotation of 200 rpm or less so that the substrate does not jump out. The pressing pressure of the substrate having the surface to be polished on the polishing cloth (polishing pressure) is preferably 1 to 100 kPa, and in order to satisfy the uniformity of the polishing surface within the CMP rate and the flatness of the pattern, 5 to More preferably, it is 50 kPa.
研磨している間、研磨布には研磨材をポンプ等で連続的に供給する。この供給量に制限はないが、研磨布の表面が常に研磨材で覆われていることが好ましい。 During polishing, the abrasive is continuously supplied to the polishing cloth with a pump or the like. The supply amount is not limited, but it is preferable that the surface of the polishing pad is always covered with an abrasive.
研磨終了後の基板は、流水中でよく洗浄後、スピンドライ等を用いて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。研磨布の表面状態を常に同一にしてＣＭＰを行うために、研磨の前に研磨布のコンディショニング工程を入れるのが好ましい。例えば、ダイヤモンド粒子のついたドレッサを用いて少なくとも水を含む液で研磨布のコンディショニングを行う。続いて本発明によるＣＭＰ研磨工程を実施し、さらに、基板洗浄工程を加えるのが好ましい。 The substrate after polishing is preferably washed in running water and then dried after removing water droplets adhering to the substrate using spin drying or the like. In order to perform CMP with the surface state of the polishing cloth always the same, it is preferable to perform a conditioning process of the polishing cloth before polishing. For example, the polishing cloth is conditioned with a liquid containing at least water using a dresser with diamond particles. Subsequently, it is preferable to perform a CMP polishing process according to the present invention, and further add a substrate cleaning process.
以下、実施例により本発明を説明する。本発明はこれらの実施例により制限されるものではない。 Hereinafter, the present invention will be described by way of examples. The present invention is not limited by these examples.
（実施例１）
（銅および銅合金用研磨材の作製方法）
硫酸０．０５ｍｏｌ（濃度９６％の硫酸５．１ｇ）、グリシン２５ｇ、ベンゾトリアゾール３ｇ、平均粒径７０ｎｍのコロイダルシリカ２０ｇに水６４６．９ｇを加えて溶解し、過酸化水素水（試薬特級、３０％水溶液）３００ｇを加え銅膜及び絶縁材料膜用研磨材（Ａ）を作製した。
Example 1
(Method for producing abrasive for copper and copper alloy)
A solution of 646.9 g of water in 0.05 mol of sulfuric acid (5.1 g of 96% sulfuric acid), 25 g of glycine, 3 g of benzotriazole and 20 g of colloidal silica having an average particle size of 70 nm was dissolved in hydrogen peroxide (special grade, 30 % Aqueous solution) 300 g was added to produce a copper film and an insulating material film abrasive (A).
なお、コロイダルシリカは、常法に従いテトラエトキシシランのアンモニア溶液中での加水分解により作製した。 Colloidal silica was prepared by hydrolysis of tetraethoxysilane in an ammonia solution according to a conventional method.
研磨材（Ａ）のｐＨは２．６であった。また、研磨材（Ａ）のｐＨを４まで増加するのに要する水酸化カリウムの量は研磨材（Ａ）１ｋｇ当たり０．０９ｍｏｌ／ｋｇであった。 The pH of the abrasive (A) was 2.6. The amount of potassium hydroxide required to increase the pH of the abrasive (A) to 4 was 0.09 mol / kg per kg of the abrasive (A).
上記研磨材（Ａ）を定盤に貼り付けたパッドに滴下しながら、下記に示す基板を使用し、下記に示す研磨条件でＣＭＰ処理を行い、下記に示す評価を行った。 While dripping the above-mentioned abrasive (A) onto a pad attached to a surface plate, the following substrate was used, CMP treatment was performed under the following polishing conditions, and the following evaluation was performed.
（評価基板）
基板１：ガラスエポキシ基板上に厚さ１８μｍの銅膜を形成した直径（φ）８インチのブランケット基板。
(Evaluation board)
Substrate 1: A blanket substrate having a diameter (φ) of 8 inches in which a copper film having a thickness of 18 μm is formed on a glass epoxy substrate.
基板２：ガラスエポキシ基板上に感光性の永久レジストを使用して深さ５μｍ、溝幅１００μｍのストライプ状のパターンを形成後、スパッタ法によって厚さ０．２μｍの銅のメッキシード層を形成し、続いてめっき法により厚さ１０μｍの銅膜を形成した、直径（φ）８インチのパターン形成基板。 Substrate 2: A striped pattern having a depth of 5 μm and a groove width of 100 μm is formed on a glass epoxy substrate using a photosensitive permanent resist, and then a copper plating seed layer having a thickness of 0.2 μm is formed by sputtering. Subsequently, a pattern forming substrate having a diameter (φ) of 8 inches, in which a copper film having a thickness of 10 μm is formed by plating.
（研磨条件）
研磨装置：定盤寸法６００ｍｍφ、ロータリータイプ
研磨パッド：独立気泡を持つ発泡ポリウレタン樹脂
研磨圧力：３５ｋＰａ
基板と研磨定盤との相対速度：７０ｍ／ｍｉｎ
研磨材流量：２００ｍｌ／ｍｉｎ
（評価項目および評価方法）
ＣＭＰによる銅研磨速度：基板１のＣＭＰ処理前後での膜厚差をシート抵抗変化から換算して求め、研磨時間とから算出した。
(Polishing conditions)
Polishing device: Surface plate size 600mmφ, Rotary type Polishing pad: Polyurethane resin with closed cells Polishing pressure: 35kPa
Relative speed between substrate and polishing surface plate: 70 m / min
Abrasive flow rate: 200ml / min
(Evaluation items and evaluation methods)
Copper polishing rate by CMP: The film thickness difference between before and after the CMP treatment of the substrate 1 was calculated from the sheet resistance change, and calculated from the polishing time.
表面粗さ（算術平均粗さＲａ）：基板１のＣＭＰ処理後の銅膜表面粗さをＡＦＭ（原子間力顕微鏡）で測定した。 Surface roughness (arithmetic mean roughness Ra): The surface roughness of the copper film after the CMP treatment of the substrate 1 was measured with an AFM (atomic force microscope).
銅膜／縁膜性樹膜間段差：基板２のＣＭＰ処理後の銅膜／縁膜性樹膜間境界段差を触針式の段差計で評価した。 Step difference between copper film / rim film dendrite: The step difference between the copper film / edge film dendrite after the CMP process of the substrate 2 was evaluated with a stylus type step meter.
評価の結果、銅膜の研磨速度は２．２μｍ／ｍｉｎ、表面粗さはＲａで２．７ｎｍ、銅膜／縁膜性樹膜間段差は０．３５μｍであった。 As a result of the evaluation, the polishing rate of the copper film was 2.2 μm / min, the surface roughness Ra was 2.7 nm, and the step between the copper film / rim film dendritic film was 0.35 μm.
（実施例２）
リン酸を０．０２ｍｏｌ（濃度８５％のリン酸２．３ｇ）をさらに加え、水の添加量を６４４．６ｇとすること以外は実施例１と同様に操作して銅膜及び絶縁材料膜用研磨材（Ｂ）を作製した。
(Example 2)
0.02 mol of phosphoric acid (2.3 g of phosphoric acid with a concentration of 85%) was further added, and the operation was performed in the same manner as in Example 1 except that the amount of water added was 644.6 g. An abrasive (B) was produced.
研磨材（Ｂ）のｐＨは２．５であった。また、研磨材（Ｂ）のｐＨを４まで増加するのに要する水酸化カリウムの量は研磨材（Ｂ）１ｋｇ当たり０．１１ｍｏｌ／ｋｇであった。 The pH of the abrasive (B) was 2.5. The amount of potassium hydroxide required to increase the pH of the abrasive (B) to 4 was 0.11 mol / kg per kg of the abrasive (B).
研磨材（Ｂ）を使用して実施例１と同様にＣＭＰ処理を行い、評価を行った。評価の結果、銅膜の研磨速度は２．７μｍ／ｍｉｎ、表面粗さはＲａで１．３ｎｍ、銅膜／縁膜性樹膜間段差は０．２８μｍであり、研磨速度が増加し表面粗さおよび銅膜／縁膜性樹膜間段差が向上した。 CMP was performed in the same manner as in Example 1 using the abrasive (B), and evaluation was performed. As a result of the evaluation, the polishing rate of the copper film was 2.7 μm / min, the surface roughness was 1.3 nm in Ra, and the step difference between the copper film / rim film dendritic film was 0.28 μm. And the step between the copper film / rim film dendritic membrane was improved.
（実施例３）
重量平均分子量２万のポリアクリル酸５ｇをさらに加え、水の添加量を６３９．６ｇとすること以外は実施例２と同様に操作して銅膜及び絶縁材料膜用研磨材（Ｃ）を作製した。
(Example 3)
A polishing material (C) for a copper film and an insulating material film was produced in the same manner as in Example 2 except that 5 g of polyacrylic acid having a weight average molecular weight of 20,000 was further added and the amount of water added was 639.6 g. did.
研磨材（Ｃ）のｐＨは２．５であった。また、研磨材（Ｃ）のｐＨを４まで増加するのに要する水酸化カリウムの量は研磨材（Ｃ）１ｋｇ当たり０．１２ｍｏｌ／ｋｇであった。 The pH of the abrasive (C) was 2.5. The amount of potassium hydroxide required to increase the pH of the abrasive (C) to 4 was 0.12 mol / kg per kg of the abrasive (C).
研磨材（Ｃ）を使用して実施例１と同様にＣＭＰ処理を行い、評価を行った。評価の結果、銅膜の研磨速度は２．９μｍ／ｍｉｎ、表面粗さはＲａで１．１ｎｍ、銅膜／縁膜性樹膜間段差は０．１９μｍであり、研磨速度が増加し表面粗さおよび銅膜／縁膜性樹膜間段差が向上した。 CMP was performed in the same manner as in Example 1 using the abrasive (C), and evaluation was performed. As a result of the evaluation, the polishing rate of the copper film was 2.9 μm / min, the surface roughness was 1.1 nm in terms of Ra, and the step difference between the copper film / rim film dendritic film was 0.19 μm. And the step between the copper film / rim film dendritic membrane was improved.
（比較例１）
グリシンを添加しないこと、水の添加量を６６４．６ｇとすること以外は実施例１と同様に操作して銅膜及び絶縁材料膜用研磨材（Ｄ）を作製した。
(Comparative Example 1)
A polishing material (D) for a copper film and an insulating material film was produced in the same manner as in Example 1 except that glycine was not added and the amount of water added was 664.6 g.
研磨材（Ｄ）のｐＨは１．２であった。また、研磨材（Ｄ）のｐＨを４まで増加するのに要する水酸化カリウムの量は研磨材（Ｄ）１ｋｇ当たり０．０９ｍｏｌ／ｋｇであった。 The pH of the abrasive (D) was 1.2. Further, the amount of potassium hydroxide required to increase the pH of the abrasive (D) to 4 was 0.09 mol / kg per 1 kg of the abrasive (D).
研磨材（Ｄ）を使用して実施例１と同様にＣＭＰ処理を行い、評価を行った。評価の結果、銅膜の研磨速度は２．１μｍ／ｍｉｎ、表面粗さはＲａで３５．６ｎｍ、銅膜／縁膜性樹膜間段差は１．２μｍであり、研磨速度の大きな変化は見られなかったが、表面粗さおよび銅膜／縁膜性樹膜間段差が低下した。 CMP was performed in the same manner as in Example 1 using the abrasive (D), and evaluation was performed. As a result of the evaluation, the polishing rate of the copper film was 2.1 μm / min, the surface roughness was 35.6 nm in Ra, and the step between the copper film / rim film dendritic film was 1.2 μm. Although not, the surface roughness and the step between the copper film / rim film dendrite decreased.
（比較例２）
硫酸の添加量を０．０１ｍｏｌ（濃度９６％の硫酸１．０２ｇ）とすること以外は実施例１と同様に操作して銅膜及び絶縁材料膜用研磨材（Ｅ）を作製した。
(Comparative Example 2)
A polishing material (E) for copper film and insulating material film was produced in the same manner as in Example 1 except that the addition amount of sulfuric acid was 0.01 mol (1.02 g of sulfuric acid having a concentration of 96%).
研磨材（Ｅ）のｐＨは３．３であった。また、研磨材（Ｅ）のｐＨを４まで増加するのに要する水酸化カリウムの量は研磨材（Ｅ）１ｋｇ当たり０．０１８ｍｏｌ／ｋｇであった。 The pH of the abrasive (E) was 3.3. The amount of potassium hydroxide required to increase the pH of the abrasive (E) to 4 was 0.018 mol / kg per kg of the abrasive (E).
研磨材（Ｅ）を使用して実施例１と同様にＣＭＰ処理を行い、評価を行った。評価の結果、銅膜の研磨速度は０．８μｍ／ｍｉｎ、表面粗さはＲａで２．１ｎｍ、銅膜／縁膜性樹膜間段差は０．３μｍであり、研磨速度が大幅に低下した。 CMP was performed in the same manner as in Example 1 using the abrasive (E), and evaluation was performed. As a result of the evaluation, the polishing rate of the copper film was 0.8 μm / min, the surface roughness was 2.1 nm in Ra, and the step difference between the copper film / rim film dendritic film was 0.3 μm, and the polishing rate was greatly reduced. .
Claims (9)
前記アミノ酸の２５℃における第一段の酸解離指数が、２以上３以下であり、かつ、
前記無機酸の配合量は、前記研磨材のｐＨを４まで増加するのに要する水酸化カリウムの量が研磨材１ｋｇ当たり０．０５ｍｏｌ以上となる量であることを特徴とする銅膜及び絶縁材料膜用研磨材。 For polishing a substrate on which a film to be polished, including a copper film and an insulating material film, containing water, abrasive grains, an oxidizing agent, an inorganic acid, and an amino acid and having a pH of 1.5 to 3.5 is formed. Abrasive,
The first-stage acid dissociation index of the amino acid at 25 ° C. is 2 or more and 3 or less, and
The amount of the inorganic acid, the copper film and insulating material, wherein the amount of potassium hydroxide required to increase the pH of the abrasive until 4 is an amount to be abrasive 1kg per 0.05mol more Membrane abrasive.
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