JP6379764B2 - Polishing liquid and polishing method - Google Patents
Polishing liquid and polishing method Download PDFInfo
- Publication number
- JP6379764B2 JP6379764B2 JP2014141900A JP2014141900A JP6379764B2 JP 6379764 B2 JP6379764 B2 JP 6379764B2 JP 2014141900 A JP2014141900 A JP 2014141900A JP 2014141900 A JP2014141900 A JP 2014141900A JP 6379764 B2 JP6379764 B2 JP 6379764B2
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- JP
- Japan
- Prior art keywords
- polishing liquid
- polishing
- mass
- cobalt
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 238000005498 polishing Methods 0.000 title claims description 199
- 239000007788 liquid Substances 0.000 title claims description 141
- 238000000034 method Methods 0.000 title claims description 25
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- 229910017052 cobalt Inorganic materials 0.000 claims description 56
- 239000010941 cobalt Substances 0.000 claims description 56
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 38
- 239000006061 abrasive grain Substances 0.000 claims description 38
- 150000007524 organic acids Chemical class 0.000 claims description 38
- 150000001875 compounds Chemical class 0.000 claims description 32
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- 235000005985 organic acids Nutrition 0.000 claims description 28
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 26
- 235000001014 amino acid Nutrition 0.000 claims description 24
- 150000001413 amino acids Chemical class 0.000 claims description 24
- 229910052802 copper Inorganic materials 0.000 claims description 24
- 239000010949 copper Substances 0.000 claims description 24
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 19
- 125000003354 benzotriazolyl group Chemical group N1N=NC2=C1C=CC=C2* 0.000 claims description 14
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Images
Description
本発明の実施形態は、研磨液及び研磨方法に関する。 Embodiments described herein relate generally to a polishing liquid and a polishing method.
近年、半導体大規模集積回路（Ｌａｒｇｅ−Ｓｃａｌｅ Ｉｎｔｅｇｒａｔｉｏｎ。以下「ＬＳＩ」と記す。）の高集積化及び高性能化に伴って、新たな微細加工技術が開発されている。化学機械研磨（Ｃｈｅｍｉｃａｌ Ｍｅｃｈａｎｉｃａｌ Ｐｏｌｉｓｈｉｎｇ。以下「ＣＭＰ」と記す。）法もその一つである。ＣＭＰ法は、半導体デバイス製造工程、特に多層配線形成工程における層間絶縁材料の平坦化、金属プラグの形成、埋め込み配線の形成等において頻繁に利用される技術である。 2. Description of the Related Art In recent years, new microfabrication techniques have been developed along with higher integration and higher performance of semiconductor large-scale integrated circuits (Large-Scale Integration; hereinafter referred to as “LSI”). One of them is a chemical mechanical polishing (hereinafter referred to as “CMP”) method. The CMP method is a technique that is frequently used in planarization of an interlayer insulating material, formation of a metal plug, formation of a buried wiring, and the like in a semiconductor device manufacturing process, particularly in a multilayer wiring forming process.
現在は、配線材料として、主に銅、銅合金、銅の酸化物、銅合金の酸化物等の銅系金属が用いられている。通常、銅系金属を用いた埋め込み配線の形成には、いわゆるダマシン法が採用されている。ダマシン法では、まず、あらかじめ表面に凹部（例えば、溝部）及び凸部（例えば、隆起部）が形成された絶縁材料上に、銅系金属を堆積して、凹部に銅系金属を埋め込む。次いで、凸部上に堆積した銅系金属（すなわち、凹部内以外の銅系金属）をＣＭＰ法により除去して埋め込み配線を形成する。 Currently, copper-based metals such as copper, copper alloys, copper oxides and copper alloy oxides are mainly used as wiring materials. Usually, a so-called damascene method is adopted for forming a buried wiring using a copper-based metal. In the damascene method, first, a copper-based metal is deposited on an insulating material having a concave portion (for example, a groove portion) and a convex portion (for example, a raised portion) formed on the surface in advance, and the concave portion is filled with the copper-based metal. Next, the copper-based metal deposited on the convex portion (that is, the copper-based metal other than in the concave portion) is removed by CMP to form a buried wiring.
銅系金属のＣＭＰに用いられる研磨液は、必要に応じて、砥粒、酸化剤、金属溶解剤、金属防食剤等を含有する。更に、添加剤として様々な物質を添加した研磨液が検討されている。これらの研磨液によって、銅系金属に対し比較的高いＣＭＰ速度、及び、比較的低いエッチング速度が得られる場合がある（例えば、特許文献１及び２参照）。 The polishing liquid used for CMP of a copper-based metal contains abrasive grains, an oxidizing agent, a metal dissolving agent, a metal anticorrosive, and the like as necessary. Furthermore, polishing liquids to which various substances are added as additives have been studied. With these polishing liquids, a relatively high CMP rate and a relatively low etching rate may be obtained for copper-based metals (see, for example, Patent Documents 1 and 2).
ＬＳＩの潮流は、更なる高集積化及び高性能化に向かっている。それに伴い、ダマシン法による埋め込み配線にも微細化が求められている。しかし、銅系金属の凹部への埋め込みには技術的限界があり、埋め込み不良が発生する場合がある。そのため、埋め込み性の良好なバリア膜（コバルト、ルテニウム等）を用い銅系金属の埋め込み性を改善している。しかしながら、１Ｘｎｍノードが求められる最先端の半導体デバイス製造工程では、埋め込み性が良好なバリア膜を用いても銅系金属の埋め込み性が限界に近づきつつある。そこで、近年、配線材料を、銅系金属から埋め込み性の良好なコバルトへ置き換える動きが出てきている。 The trend of LSI is toward higher integration and higher performance. Along with this, miniaturization is required for embedded wiring by the damascene method. However, there is a technical limit to the embedding of the copper-based metal in the recess, and an embedding failure may occur. Therefore, the embedding property of the copper-based metal is improved by using a barrier film (such as cobalt or ruthenium) having a good embedding property. However, in a state-of-the-art semiconductor device manufacturing process that requires a 1 × nm node, the embeddability of a copper-based metal is approaching its limit even when a barrier film with good embeddability is used. Therefore, in recent years, there has been a movement to replace the wiring material from copper-based metal to cobalt having good embedding properties.
しかしながら、従来の研磨液を用いたＣＭＰでは、コバルトを高いＣＭＰ速度で研磨することは困難であることがわかった。また、コバルトは標準酸化還元電位が低く、エッチングされ易いという傾向があり、従来の研磨液を用いたＣＭＰでは、コバルトを腐食なく研磨することは困難であることがわかった。コバルトが腐食されると、形成された配線パターンに欠陥が発生し、デバイスの誤作動が引き起こされる懸念がある。 However, it has been found that in CMP using a conventional polishing liquid, it is difficult to polish cobalt at a high CMP rate. Further, cobalt has a low standard oxidation-reduction potential and tends to be easily etched, and it has been found that it is difficult to polish cobalt without corrosion by CMP using a conventional polishing liquid. When cobalt is corroded, a defect is generated in the formed wiring pattern, which may cause malfunction of the device.
上記問題点に鑑み、本発明の実施形態は、コバルト含有部を、高いＣＭＰ速度且つ低いエッチング速度で研磨可能な研磨液を提供することを目的とする。また、本発明の他の実施形態は、コバルト含有部を、高いＣＭＰ速度且つ低いエッチング速度で研磨可能な研磨方法を提供することを目的とする。 In view of the above problems, an object of an embodiment of the present invention is to provide a polishing liquid capable of polishing a cobalt-containing portion at a high CMP rate and a low etching rate. Another object of the present invention is to provide a polishing method capable of polishing a cobalt-containing portion at a high CMP rate and a low etching rate.
本発明の発明者らは、有機酸類及びベンゾトリアゾール骨格を有する化合物を含有し、ｐＨが３．０〜８．０である研磨液により、コバルトに対し、高いＣＭＰ速度と低いエッチング速度とを達成できることを見出し、種々の実施形態を含む本発明を完成するに至った。 The inventors of the present invention achieve a high CMP rate and a low etching rate with respect to cobalt by using a polishing liquid containing an organic acid and a compound having a benzotriazole skeleton and having a pH of 3.0 to 8.0. As a result, the present invention including various embodiments has been completed.
本発明の実施形態は、表面にコバルト含有部を有し、且つ、表面に銅含有部を有しない基板の、少なくとも前記コバルト含有部を研磨するための研磨液であって、（Ａ）有機酸類と、（Ｂ）ベンゾトリアゾール骨格を有する化合物とを含有し、ｐＨが３．０〜８．０である、研磨液に関する。 An embodiment of the present invention is a polishing liquid for polishing at least the cobalt-containing part of a substrate having a cobalt-containing part on the surface and no copper-containing part on the surface, and (A) an organic acid And (B) a compound having a benzotriazole skeleton, and a pH of 3.0 to 8.0.
前記研磨液の一実施形態において、前記（Ａ）有機酸類はアミノ酸を含む。 In one embodiment of the polishing liquid, the (A) organic acid contains an amino acid.
前記研磨液の一実施形態において、前記（Ｂ）ベンゾトリアゾール骨格を有する化合物は、ベンゾトリアゾール骨格を有し、且つ、親水性基を有する化合物を含む。 In one embodiment of the polishing liquid, the compound (B) having a benzotriazole skeleton includes a compound having a benzotriazole skeleton and having a hydrophilic group.
一実施形態において、前記研磨液中の硫酸及び硫酸塩の含有量は１ｐｐｍ以下である。 In one Embodiment, content of the sulfuric acid and sulfate in the said polishing liquid is 1 ppm or less.
一実施形態において、前記研磨液は、過酸化水素、過ヨウ素酸カリウム、及びオゾンからなる群より選ばれる少なくとも一種を更に含有する。 In one embodiment, the polishing liquid further contains at least one selected from the group consisting of hydrogen peroxide, potassium periodate, and ozone.
一実施形態において、前記研磨液は、研磨砥粒を更に含有する。 In one embodiment, the polishing liquid further contains polishing abrasive grains.
本発明の他の実施形態は、表面にコバルト含有部を有し、且つ、表面に銅含有部を有しない基板の、少なくとも前記コバルト含有部を、前記いずれかの研磨液を用いて研磨する、研磨方法に関する。 In another embodiment of the present invention, at least the cobalt-containing portion of a substrate having a cobalt-containing portion on the surface and not having a copper-containing portion on the surface is polished using any one of the polishing liquids. The present invention relates to a polishing method.
本発明の実施形態である研磨液によれば、コバルト含有部を、高いＣＭＰ速度且つ低いエッチング速度で研磨できる。また、本発明の他の実施形態である研磨方法によれば、コバルト含有部を、高いＣＭＰ速度且つ低いエッチング速度で研磨できる。 According to the polishing liquid according to the embodiment of the present invention, the cobalt-containing portion can be polished at a high CMP rate and a low etching rate. In addition, according to the polishing method of another embodiment of the present invention, the cobalt-containing portion can be polished at a high CMP rate and a low etching rate.
以下、本発明の実施形態である研磨液及び研磨方法について詳細に説明する。 Hereinafter, a polishing liquid and a polishing method according to embodiments of the present invention will be described in detail.
（定義）
本発明の実施形態において用いられる用語を説明する。
「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ＡがＣＭＰにより除去される速度（例えば、時間あたりの物質Ａの厚みの低減量）が大きいことと定義される。
「低いエッチング速度」とは、研磨される物質Ａが研磨液に溶解する速度（例えば、時間あたりの物質Ａの厚みの低減量）が小さいことと定義される。
(Definition)
Terms used in the embodiments of the present invention will be described.
“Polishing substance A” and “polishing substance A” are defined as removing at least a portion of substance A by polishing.
“High CMP rate” is defined as a high rate at which the material A to be polished is removed by CMP (for example, a reduction in the thickness of the material A per hour).
“Low etching rate” is defined as a small rate at which the substance A to be polished dissolves in the polishing liquid (for example, a reduction in the thickness of the substance A per hour).
「コバルト含有部」とは、コバルト原子を含む部分を意味し、「コバルト含有部」には、例えば、コバルト、コバルト合金、コバルトの酸化物、コバルト合金の酸化物等を含有する部分が含まれる。
「銅含有部」とは、銅原子を含む部分を意味し、「銅含有部」には、例えば、銅、銅合金、銅の酸化物、銅合金の酸化物等を含有する部分が含まれる。
“Cobalt-containing part” means a part containing a cobalt atom, and “cobalt-containing part” includes, for example, a part containing cobalt, a cobalt alloy, a cobalt oxide, a cobalt alloy oxide, or the like. .
The “copper-containing part” means a part containing a copper atom, and the “copper-containing part” includes, for example, a part containing copper, a copper alloy, a copper oxide, a copper alloy oxide, or the like. .
「〜」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意味する。 The numerical range indicated using “to” means a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively.
（研磨液）
本実施形態に係る研磨液は、表面にコバルト含有部を有し、且つ、表面に銅含有部を有しない基板の、少なくとも前記コバルト含有部を研磨するための研磨液である。本実施形態に係る研磨液は、例えば、半導体デバイス製造工程において用いられる。
(Polishing liquid)
The polishing liquid according to this embodiment is a polishing liquid for polishing at least the cobalt-containing part of a substrate having a cobalt-containing part on the surface and no copper-containing part on the surface. The polishing liquid according to this embodiment is used, for example, in a semiconductor device manufacturing process.
本実施形態に係る研磨液は、（Ａ）有機酸類と、（Ｂ）ベンゾトリアゾール骨格を有する化合物とを含有し、ｐＨが３．０〜８．０である。研磨液は、更に任意成分を含有してもよい。（Ａ）成分、（Ｂ）成分、及び任意成分は、ぞれぞれ、一種を単独で使用してもよく、二種類以上を併用してもよい。 The polishing liquid according to this embodiment contains (A) organic acids and (B) a compound having a benzotriazole skeleton, and has a pH of 3.0 to 8.0. The polishing liquid may further contain an optional component. As the component (A), the component (B), and the optional component, one type may be used alone, or two or more types may be used in combination.
（（Ａ）有機酸類）
本実施形態に係る研磨液は、有機酸類を含有する。有機酸類はコバルト含有部に対する溶解剤として機能すると考えられるが、これに限定されない。有機酸類には、有機酸、有機酸のエステル、及び有機酸の塩が含まれる。有機酸は酸性の官能基をもつ化合物である。但し、有機酸類には、後述するベンゾトリアゾール骨格を有する化合物又は窒素含有複素環化合物であって、酸性の官能基を持つ化合物は含まれないものとする。
((A) Organic acids)
The polishing liquid according to the present embodiment contains organic acids. Although it is thought that organic acids function as a solubilizer with respect to a cobalt containing part, it is not limited to this. Organic acids include organic acids, esters of organic acids, and salts of organic acids. An organic acid is a compound having an acidic functional group. However, the organic acids do not include compounds having a benzotriazole skeleton described later or nitrogen-containing heterocyclic compounds and compounds having an acidic functional group.
有機酸類としては、ギ酸、酢酸、プロピオン酸、酪酸、吉草酸、２−メチル酪酸、ｎ−ヘキサン酸、３，３−ジメチル酪酸、２−エチル酪酸、４−メチルペンタン酸、ｎ−ヘプタン酸、２−メチルヘキサン酸、ｎ−オクタン酸、２−エチルヘキサン酸、安息香酸、グリコ−ル酸、ジグリコール酸、サリチル酸、グリセリン酸、シュウ酸、マロン酸、コハク酸、グルタル酸、グルコン酸、アジピン酸、ピメリン酸、マレイン酸、フマル酸、フタル酸、リンゴ酸、酒石酸、クエン酸、アミノ酸等の有機酸；前記有機酸のエステル（例えば、酢酸エチル、酢酸ペンチル等）；前記有機酸の塩（例えば、酢酸アンモニウム等）などが挙げられる。 Organic acids include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, 2-methylbutyric acid, n-hexanoic acid, 3,3-dimethylbutyric acid, 2-ethylbutyric acid, 4-methylpentanoic acid, n-heptanoic acid, 2-methylhexanoic acid, n-octanoic acid, 2-ethylhexanoic acid, benzoic acid, glycolic acid, diglycolic acid, salicylic acid, glyceric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, gluconic acid, adipine Organic acids such as acids, pimelic acid, maleic acid, fumaric acid, phthalic acid, malic acid, tartaric acid, citric acid, amino acids; esters of the organic acids (for example, ethyl acetate, pentyl acetate, etc.); salts of the organic acids ( For example, ammonium acetate etc. are mentioned.
本実施形態に係る研磨液は、高いＣＭＰ速度且つ低いエッチング速度を達成する観点から、好ましくはアミノ酸を含有する。アミノ酸としては、グリシン、α−アラニン、β−アラニン（別名：３−アミノプロパン酸）、２−アミノ酪酸、ノルバリン、バリン、ロイシン、ノルロイシン、イソロイシン、アロイソロイシン、フェニルアラニン、プロリン、サルコシン、オルニチン、リシン、セリン、トレオニン、アロトレオニン、ホモセリン、チロシン、３，５−ジヨ−ド−チロシン、β−（３，４−ジヒドロキシフェニル）−アラニン、チロキシン、４−ヒドロキシ−プロリン、システイン、メチオニン、エチオニン、ランチオニン、シスタチオニン、シスチン、システイン酸、アスパラギン酸、グルタミン酸、Ｓ−（カルボキシメチル）−システイン、４−アミノ酪酸、アスパラギン、グルタミン、アザセリン、アルギニン、カナバニン、シトルリン、δ−ヒドロキシ−リシン、クレアチン、キヌレニン、ヒスチジン、１−メチル−ヒスチジン、３−メチル−ヒスチジン、エルゴチオネイン、トリプトファン等が挙げられる。 The polishing liquid according to this embodiment preferably contains an amino acid from the viewpoint of achieving a high CMP rate and a low etching rate. As amino acids, glycine, α-alanine, β-alanine (also known as 3-aminopropanoic acid), 2-aminobutyric acid, norvaline, valine, leucine, norleucine, isoleucine, alloisoleucine, phenylalanine, proline, sarcosine, ornithine, lysine , Serine, threonine, allothreonine, homoserine, tyrosine, 3,5-diiodo-tyrosine, β- (3,4-dihydroxyphenyl) -alanine, thyroxine, 4-hydroxy-proline, cysteine, methionine, ethionine, lanthionine , Cystathionine, cystine, cysteic acid, aspartic acid, glutamic acid, S- (carboxymethyl) -cysteine, 4-aminobutyric acid, asparagine, glutamine, azaserine, arginine, canavanine, citrulline, δ-hydro Sheet - lysine, creatine, kynurenine, histidine, 1-methyl - histidine, 3-methyl - histidine, ergothioneine, tryptophan, and the like.
アミノ酸の中でも、高いＣＭＰ速度と低いエッチング速度とを高度に達成する観点から、低分子量のアミノ酸が好ましい。具体的には、分子量が２００以下のアミノ酸が好ましく、１５０以下のアミノ酸がより好ましく、１００以下のアミノ酸が更に好ましい。このようなアミノ酸としては、グリシン（分子量７５）、α−アラニン（分子量８９）、β−アラニン（分子量８９）、２−アミノ酪酸（分子量１０３）、４−アミノ酪酸（分子量１０３）等が挙げられる。 Among amino acids, low molecular weight amino acids are preferred from the viewpoint of achieving a high high CMP rate and a low etching rate. Specifically, an amino acid having a molecular weight of 200 or less is preferable, an amino acid of 150 or less is more preferable, and an amino acid of 100 or less is still more preferable. Examples of such amino acids include glycine (molecular weight 75), α-alanine (molecular weight 89), β-alanine (molecular weight 89), 2-aminobutyric acid (molecular weight 103), 4-aminobutyric acid (molecular weight 103), and the like. .
有機酸類の含有量は、コバルト含有部を充分に溶解する観点から、研磨液１００質量部に対して、０．０００１質量部以上が好ましく、０．０００５質量部以上がより好ましく、０．００１質量部以上が更に好ましく、０．００５質量部以上が特に好ましく、０．０１質量部以上が極めて好ましい。また、有機酸の含有量は、エッチングを抑制する観点から、研磨液１００質量部に対して、５０質量部以下が好ましく、２５質量部以下がより好ましく、１０質量部以下が更に好ましく、５質量部以下が特に好ましく、３質量部以下が極めて好ましい。 The content of the organic acids is preferably 0.0001 parts by mass or more, more preferably 0.0005 parts by mass or more, and 0.001 parts by mass with respect to 100 parts by mass of the polishing liquid from the viewpoint of sufficiently dissolving the cobalt-containing part. Part or more is more preferable, 0.005 part by weight or more is particularly preferable, and 0.01 part by weight or more is extremely preferable. Further, the content of the organic acid is preferably 50 parts by mass or less, more preferably 25 parts by mass or less, still more preferably 10 parts by mass or less, more preferably 5 parts by mass with respect to 100 parts by mass of the polishing liquid from the viewpoint of suppressing etching. Part or less is particularly preferable, and 3 parts by mass or less is extremely preferable.
特に研磨液がアミノ酸以外の有機酸を含有する場合、アミノ酸以外の有機酸類の含有量は、コバルト含有部を充分に溶解する観点から、研磨液１００質量部に対して、０．０００１質量部以上が好ましく、０．０００５質量部以上がより好ましく、０．００１質量部以上が更に好ましく、０．００５質量部以上が特に好ましく、０．０１質量部以上が極めて好ましい。また、アミノ酸以外の有機酸の含有量は、エッチングを抑制する観点から、研磨液１００質量部に対して、５０質量部以下が好ましく、１０質量部以下がより好ましく、５質量部以下が更に好ましく、１質量部以下が特に好ましく、０．５質量部以下が極めて好ましい。 In particular, when the polishing liquid contains an organic acid other than amino acids, the content of organic acids other than amino acids is 0.0001 parts by mass or more with respect to 100 parts by mass of the polishing liquid from the viewpoint of sufficiently dissolving the cobalt-containing part. Is preferably 0.0005 parts by mass or more, more preferably 0.001 parts by mass or more, particularly preferably 0.005 parts by mass or more, and extremely preferably 0.01 parts by mass or more. Further, the content of organic acids other than amino acids is preferably 50 parts by mass or less, more preferably 10 parts by mass or less, and still more preferably 5 parts by mass or less with respect to 100 parts by mass of the polishing liquid from the viewpoint of suppressing etching. 1 part by mass or less is particularly preferable, and 0.5 part by mass or less is extremely preferable.
特に研磨液がアミノ酸を含有する場合、アミノ酸の含有量は、コバルト含有部を充分に溶解する観点から、研磨液１００質量部に対して、０．００１質量部以上が好ましく、０．０１質量部以上がより好ましく、０．０５質量部以上が更に好ましく、０．１質量部以上が特に好ましく、０．５質量部以上が極めて好ましい。また、アミノ酸の含有量は、エッチングの抑制が容易となる観点から、研磨液１００質量部に対して、５０質量部以下が好ましく、２５質量部以下がより好ましく、１０質量部以下が更に好ましく、５質量部以下が特に好ましく、３質量部以下が極めて好ましい。 In particular, when the polishing liquid contains an amino acid, the content of the amino acid is preferably 0.001 part by mass or more with respect to 100 parts by mass of the polishing liquid from the viewpoint of sufficiently dissolving the cobalt-containing part, and 0.01 part by mass The above is more preferable, 0.05 parts by mass or more is further preferable, 0.1 parts by mass or more is particularly preferable, and 0.5 parts by mass or more is extremely preferable. Further, the content of the amino acid is preferably 50 parts by mass or less, more preferably 25 parts by mass or less, still more preferably 10 parts by mass or less, with respect to 100 parts by mass of the polishing liquid from the viewpoint of easy suppression of etching. 5 parts by mass or less is particularly preferable, and 3 parts by mass or less is extremely preferable.
一実施形態において、アミノ酸の含有量は、研磨液１００質量部に対して、０．００１〜１０質量部である。これにより高いＣＭＰ速度と低いエッチング速度の両方を高度に達成できる。 In one Embodiment, content of an amino acid is 0.001-10 mass parts with respect to 100 mass parts of polishing liquid. Thereby, both a high CMP rate and a low etching rate can be achieved to a high degree.
（（Ｂ）ベンゾトリアゾール骨格を有する化合物）
本実施形態に係る研磨液は、ベンゾトリアゾール骨格を有する化合物を含有する。ベンゾトリアゾール骨格を有する化合物（以下、「ベンゾトリアゾール化合物」と記す。）は、コバルト含有部に対する保護膜形成剤、防食剤等として機能すると考えられるが、これに限定されない。高いＣＭＰ速度と低いエッチング速度とを高度に達成する観点から、好ましくはベンゾトリアゾール骨格を有し、且つ、親水性基を有する化合物（以下、「親水性基を有するベンゾトリアゾール化合物」と記す。）を含有する。親水性基としては、水酸基、アミノ基、カルボキシル基、ヒドロキシメチル基、アルコキシカルボニル基等が挙げられる。
((B) Compound having benzotriazole skeleton)
The polishing liquid according to this embodiment contains a compound having a benzotriazole skeleton. A compound having a benzotriazole skeleton (hereinafter referred to as “benzotriazole compound”) is considered to function as a protective film forming agent, an anticorrosive agent, and the like for the cobalt-containing portion, but is not limited thereto. From the viewpoint of achieving a high CMP rate and a low etching rate at a high level, a compound having a benzotriazole skeleton and having a hydrophilic group (hereinafter referred to as “benzotriazole compound having a hydrophilic group”). Containing. Examples of the hydrophilic group include a hydroxyl group, an amino group, a carboxyl group, a hydroxymethyl group, and an alkoxycarbonyl group.
ベンゾトリアゾール化合物としては、例えば、１Ｈ−ベンゾトリアゾール、５−メチル−１Ｈ−ベンゾトリアゾール（別名：トリルトリアゾール）、５−ヘキシル−１Ｈ−ベンゾトリアゾール、１−ヒドロキシ−１Ｈ−ベンゾトリアゾール、４−ヒドロキシ−１Ｈ−ベンゾトリアゾール、１−（２，３−ジヒドロキシプロピル）−１Ｈ−ベンゾトリアゾール、１−カルボキシ−１Ｈ−ベンゾトリアゾール、４−カルボキシ−１Ｈ−ベンゾトリアゾール、４−カルボキシ−１Ｈ−ベンゾトリアゾールメチルエステル、４−カルボキシ−１Ｈ−ベンゾトリアゾールブチルエステル、４−カルボキシ−１Ｈ−ベンゾトリアゾールオクチルエステル、２，３−ジカルボキシプロピル−１Ｈ−ベンゾトリアゾール、Ｎ−（１，２，３−ベンゾトリアゾリル−１−メチル）−Ｎ−（１，２，４−トリアゾリル−１−メチル）−２−エチルヘキサンアミン等が挙げられる。 Examples of the benzotriazole compound include 1H-benzotriazole, 5-methyl-1H-benzotriazole (also known as tolyltriazole), 5-hexyl-1H-benzotriazole, 1-hydroxy-1H-benzotriazole, 4-hydroxy- 1H-benzotriazole, 1- (2,3-dihydroxypropyl) -1H-benzotriazole, 1-carboxy-1H-benzotriazole, 4-carboxy-1H-benzotriazole, 4-carboxy-1H-benzotriazole methyl ester, 4-carboxy-1H-benzotriazole butyl ester, 4-carboxy-1H-benzotriazole octyl ester, 2,3-dicarboxypropyl-1H-benzotriazole, N- (1,2,3-benzotriazolyl 1-methyl)-N-(1,2,4-triazolyl-1-methyl) -2-ethylhexanoic amine.
ベンゾトリアゾール化合物の含有量は、エッチングの抑制が容易となる観点から、研磨液１００質量部に対して、０．００１質量部以上が好ましく、０．００５質量部以上がより好ましく、０．０１質量部以上が更に好ましく、０．０２質量部以上が特に好ましい。また、ベンゾトリアゾール化合物の含有量は、充分なＣＭＰ速度を得る観点から、研磨液１００質量部に対して、０．５質量部以下が好ましく、０．２質量部以下がより好ましく、０．１質量部以下が更に好ましく、０．０８質量部以下が特に好ましく、０．０５質量部以下が極めて好ましい。 The content of the benzotriazole compound is preferably 0.001 parts by mass or more, more preferably 0.005 parts by mass or more, and 0.01 masses with respect to 100 parts by mass of the polishing liquid from the viewpoint of easy etching suppression. Part or more is more preferable, and 0.02 part by mass or more is particularly preferable. The content of the benzotriazole compound is preferably 0.5 parts by mass or less, more preferably 0.2 parts by mass or less, with respect to 100 parts by mass of the polishing liquid, from the viewpoint of obtaining a sufficient CMP rate. More preferred is less than or equal to parts by mass, particularly preferred is less than or equal to 0.08 parts by mass, and most preferred is less than or equal to 0.05 parts by mass.
一実施形態において、ベンゾトリアゾール化合物の含有量は、研磨液１００質量部に対して、０．００１〜０．５質量部である。これにより高いＣＭＰ速度と低いエッチング速度の両方を高度に達成できる。 In one embodiment, content of a benzotriazole compound is 0.001-0.5 mass part with respect to 100 mass parts of polishing liquid. Thereby, both a high CMP rate and a low etching rate can be achieved to a high degree.
（金属の酸化剤）
本実施形態に係る研磨液は、金属の酸化剤（以下、「金属酸化剤」と記す。）を更に含有してもよい。金属酸化剤としては、過酸化水素（Ｈ２Ｏ２）、過ヨウ素酸カリウム、オゾン等が挙げられる。金属酸化剤の中でも、過酸化水素が好ましい。
(Metal oxidizer)
The polishing liquid according to this embodiment may further contain a metal oxidant (hereinafter referred to as “metal oxidant”). Examples of the metal oxidant include hydrogen peroxide (H 2 O 2 ), potassium periodate, ozone, and the like. Of the metal oxidants, hydrogen peroxide is preferred.
金属酸化剤を含有する場合、その含有量は、充分にコバルトが酸化され、良好なＣＭＰ速度を得る観点から、研磨液１００質量部に対して、０．１質量部以上が好ましく、０．５質量部以上がより好ましく、１質量部以上が更に好ましい。また、金属酸化剤の含有量は、被研磨面に荒れが生じることを防ぐ観点から、研磨液１００質量部に対して、１０質量部以下が好ましく、６質量部以下がより好ましく、３質量部以下が更に好ましい。 When the metal oxidant is contained, the content thereof is preferably 0.1 parts by mass or more with respect to 100 parts by mass of the polishing liquid from the viewpoint of sufficiently oxidizing cobalt and obtaining a good CMP rate. More than mass part is more preferable, and 1 mass part or more is still more preferable. In addition, the content of the metal oxidizer is preferably 10 parts by mass or less, more preferably 6 parts by mass or less, and more preferably 3 parts by mass with respect to 100 parts by mass of the polishing liquid from the viewpoint of preventing the surface to be polished from being rough. The following is more preferable.
（研磨砥粒）
本実施形態に係る研磨液は、研磨砥粒（以下、「砥粒」と記す。）を更に含有してもよい。砥粒としては、シリカ粒子、アルミナ粒子、セリア粒子、チタニア粒子、ジルコニア粒子、ゲルマニア粒子、炭化ケイ素粒子等の無機物砥粒；ポリスチレン粒子、ポリアクリル粒子、ポリ塩化ビニル粒子等の有機物砥粒；無機物砥粒と有機物砥粒の複合砥粒などが挙げられる。砥粒としては、研磨液中での分散安定性が良く、研磨時に発生する研磨傷数が少ないという観点から、無機物砥粒が好ましく、無機物砥粒のコロイドがより好ましく、コロイダルシリカ又はコロイダルアルミナが更に好ましい。
(Abrasive grains)
The polishing liquid according to this embodiment may further contain polishing abrasive grains (hereinafter referred to as “abrasive grains”). As abrasive grains, inorganic abrasive grains such as silica particles, alumina particles, ceria particles, titania particles, zirconia particles, germania particles, and silicon carbide particles; organic abrasive grains such as polystyrene particles, polyacrylic particles, and polyvinyl chloride particles; inorganic materials Examples include composite abrasive grains of abrasive grains and organic abrasive grains. As the abrasive grains, the inorganic abrasive grains are preferable, the colloid of the inorganic abrasive grains is more preferable, colloidal silica or colloidal alumina is preferable from the viewpoint of good dispersion stability in the polishing liquid and the small number of polishing scratches generated during polishing. Further preferred.
砥粒の平均粒径は、特に制限はないが、分散安定性の観点から、１００ｎｍ以下が好ましく、８０ｎｍ以下がより好ましい。また、砥粒の平均粒径は、高いＣＭＰ速度を得る観点から、１０ｎｍ以上が好ましく、２０ｎｍ以上がより好ましく、３０ｎｍ以上が更に好ましい。砥粒の「平均粒径」とは、研磨液中の砥粒の平均二次粒径を意味する。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「ＣＯＵＬＴＥＲ Ｎ４ＳＤ」、マルバーンインスツルメンツ社製「ゼータサイザー３０００ＨＳＡ」等）を使用できる。 The average particle size of the abrasive grains is not particularly limited, but is preferably 100 nm or less and more preferably 80 nm or less from the viewpoint of dispersion stability. The average grain size of the abrasive grains is preferably 10 nm or more, more preferably 20 nm or more, and further preferably 30 nm or more from the viewpoint of obtaining a high CMP rate. The “average particle diameter” of the abrasive grains means the average secondary particle diameter of the abrasive grains in the polishing liquid. In measuring the average particle size of the abrasive grains, for example, a light diffraction / scattering particle size distribution meter (for example, “COULTER N4SD” manufactured by COULTER Electronics, “Zetasizer 3000HSA” manufactured by Malvern Instruments, etc.) can be used.
本実施形態に係る研磨液において、砥粒の含有量は０〜１０質量部であることが好ましい。砥粒を含有する場合、その含有量は、研磨液中において砥粒の分散安定性が低下することを抑制する観点から、研磨液１００質量部に対して、１０質量部以下が好ましく、５質量部以下がより好ましく、１質量部以下が更に好ましく、０．５質量部以下が特に好ましい。また、砥粒を含有する場合、砥粒の含有量は、高いＣＭＰ速度を得る観点から、研磨液１００質量部に対して、０．０１質量部以上が好ましく、０．０５質量部以上がより好ましい。 In the polishing liquid according to this embodiment, the content of abrasive grains is preferably 0 to 10 parts by mass. When the abrasive grains are contained, the content is preferably 10 parts by mass or less, preferably 5 parts by mass with respect to 100 parts by mass of the polishing liquid, from the viewpoint of suppressing the dispersion stability of the abrasive grains in the polishing liquid. Part or less, more preferably 1 part by weight or less, and particularly preferably 0.5 part by weight or less. When the abrasive grains are contained, the content of the abrasive grains is preferably 0.01 parts by mass or more and more preferably 0.05 parts by mass or more with respect to 100 parts by mass of the polishing liquid from the viewpoint of obtaining a high CMP rate. preferable.
（無機酸）
本実施形態に係る研磨液は、ＣＭＰ速度を更に向上させることを目的として、無機酸類を更に含有してもよい。無機酸類には、無機酸及び無機酸の塩が含まれる。無機酸類としては、硫酸、硝酸、塩酸、リン酸、クロム酸等の無機酸；前記無機酸の塩（例えば、硫酸アンモニウム、硝酸アンモニウム等）などが挙げられる。無機酸類を含有する場合、有機酸との合計の含有量が、０．００１〜１０質量部の範囲となることが好ましい。
(Inorganic acid)
The polishing liquid according to this embodiment may further contain inorganic acids for the purpose of further improving the CMP rate. Inorganic acids include inorganic acids and salts of inorganic acids. Examples of the inorganic acids include inorganic acids such as sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, and chromic acid; salts of the inorganic acids (for example, ammonium sulfate, ammonium nitrate, and the like). When inorganic acids are contained, the total content with organic acids is preferably in the range of 0.001 to 10 parts by mass.
但し、低いエッチング速度を達成する観点からは、研磨液中の硫酸及び硫酸塩の含有量は小さいことが好ましい。硫酸及び硫酸塩の含有量を低くすることにより、コバルト含有部の活性溶解が抑制され、低いエッチング速度を実現できると考えられる。従って、研磨液中の硫酸及び硫酸塩の含有量は１ｐｐｍ以下が好ましく、０．５ｐｐｍ以下がより好ましく、０．１ｐｐｍ以下が更に好ましい。特に、硫酸及び硫酸塩の含有量を０．０００ｐｐｍとすることにより、コバルト含有部の活性溶解が抑制されるため、低いエッチング速度をより高度に達成できる。 However, from the viewpoint of achieving a low etching rate, the contents of sulfuric acid and sulfate in the polishing liquid are preferably small. By reducing the contents of sulfuric acid and sulfate, it is considered that active dissolution of the cobalt-containing part is suppressed and a low etching rate can be realized. Therefore, the content of sulfuric acid and sulfate in the polishing liquid is preferably 1 ppm or less, more preferably 0.5 ppm or less, and still more preferably 0.1 ppm or less. In particular, by setting the content of sulfuric acid and sulfate to 0.000 ppm, active dissolution of the cobalt-containing portion is suppressed, so that a low etching rate can be achieved to a higher degree.
なお、本発明の実施形態において、「硫酸及び硫酸塩の含有量」とは、研磨液が硫酸及び硫酸塩のいずれか一方を含有する場合は、当該いずれか一方の含有量をいい、研磨液が硫酸及び硫酸塩の両方を含有する場合は、両方の合計の含有量をいう。また、「硫酸塩の含有量」としては、研磨液に含まれる硫酸塩の質量を硫酸の質量に換算した値を用いる。例えば、硫酸アンモニウムの含有量は、［（研磨液に含まれる硫酸塩の質量）×（９８．１／１３２．１）］／（研磨液全体の質量）により求める。 In the embodiment of the present invention, “the content of sulfuric acid and sulfate” refers to the content of any one of the sulfuric acid and the sulfate when the polishing liquid contains either one of sulfuric acid and sulfate. In the case of containing both sulfuric acid and sulfate, it means the total content of both. Further, as the “sulfate content”, a value obtained by converting the mass of sulfate contained in the polishing liquid into the mass of sulfuric acid is used. For example, the content of ammonium sulfate is determined by [(mass of sulfate contained in polishing liquid) × (98.1 / 132.1)] / (mass of the entire polishing liquid).
研磨液中の硫酸及び硫酸塩の含有量は、イオンクロマトグラフィーにより得た硫酸イオン濃度を用いて求めることができる。また、研磨液中の硫酸及び硫酸塩の含有量は、硫酸及び硫酸塩の添加量により求めることもできる。本実施形態に係る研磨液は、少なくともいずれか一方の方法により求めた硫酸及び硫酸塩の含有量が、前記範囲であることが好ましい。 The contents of sulfuric acid and sulfate in the polishing liquid can be determined using the sulfate ion concentration obtained by ion chromatography. Further, the contents of sulfuric acid and sulfate in the polishing liquid can also be determined from the amount of sulfuric acid and sulfate added. In the polishing liquid according to this embodiment, the content of sulfuric acid and sulfate obtained by at least one of the methods is preferably within the above range.
イオンクロマトグラフィーとしては、例えば、検出器として電気伝導度検出器を用いたシステム（例えば、株式会社ダイオネクス製「ＩＣＳ−２０００」）が挙げられる。測定条件として、例えば、カラムをＡＳ２０（４ｍｍφ×２００ｍｍ）、カラム温度を３０℃、流速を１．０ｍＬ／ｍｉｎ、試料注入量を２５μＬとできる。試料は、研磨液を限外濾過、希釈等して調製できる。 Examples of the ion chromatography include a system using an electrical conductivity detector as a detector (for example, “ICS-2000” manufactured by Dionex Co., Ltd.). As measurement conditions, for example, the column can be AS20 (4 mmφ × 200 mm), the column temperature can be 30 ° C., the flow rate can be 1.0 mL / min, and the sample injection amount can be 25 μL. The sample can be prepared by ultrafiltration or dilution of the polishing liquid.
（保護膜形成剤、防食剤）
本実施形態に係る研磨液は、ベンゾトリアゾール化合物以外に、保護膜形成剤、防食剤等として機能する公知の化合物を更に含有してもよい。そのような化合物として、例えば、窒素含有複素環化合物が知られており、具体的には、トリアゾール骨格を有する化合物、ナフトトリアゾール骨格を有する化合物、ピリミジン骨格を有する化合物、イミダゾール骨格を有する化合物、グアニジン骨格を有する化合物、チアゾール骨格を有する化合物、ピラゾール骨格を有する化合物等が挙げられる。エッチングの抑制が容易となる観点から、トリアゾール骨格を有する化合物、ナフトトリアゾール骨格を有する化合物等が好ましい。
(Protective film forming agent, anticorrosive)
The polishing liquid according to this embodiment may further contain a known compound that functions as a protective film forming agent, an anticorrosive agent and the like in addition to the benzotriazole compound. As such a compound, for example, a nitrogen-containing heterocyclic compound is known. Specifically, a compound having a triazole skeleton, a compound having a naphthotriazole skeleton, a compound having a pyrimidine skeleton, a compound having an imidazole skeleton, guanidine Examples thereof include a compound having a skeleton, a compound having a thiazole skeleton, and a compound having a pyrazole skeleton. From the viewpoint of easy etching suppression, a compound having a triazole skeleton, a compound having a naphthotriazole skeleton, and the like are preferable.
トリアゾール骨格を有する化合物としては、１，２，３−トリアゾール、１，２，４−トリアゾール、３−アミノ−１Ｈ−１，２，４−トリアゾール、４−アミノ−４Ｈ−１，２，４−トリアゾール等が挙げられる。 Examples of the compound having a triazole skeleton include 1,2,3-triazole, 1,2,4-triazole, 3-amino-1H-1,2,4-triazole, 4-amino-4H-1,2,4- And triazole.
ナフトトリアゾール骨格を有する化合物としては、１Ｈ−ナフト［２，３−ｄ］トリアゾール１−アミン、１−アミノ−１Ｈ−ナフト［１，２−ｄ］トリアゾール、２−アミノ−２Ｈ−ナフト［１，２−ｄ］トリアゾール、３Ｈ−ナフト［１，２−ｄ］トリアゾール、４，９−ジヒドロ−１Ｈ−ナフト［２，３−ｄ］トリアゾール等が挙げられる。 Examples of the compound having a naphthotriazole skeleton include 1H-naphtho [2,3-d] triazole 1-amine, 1-amino-1H-naphtho [1,2-d] triazole, 2-amino-2H-naphtho [1, 2-d] triazole, 3H-naphtho [1,2-d] triazole, 4,9-dihydro-1H-naphtho [2,3-d] triazole, and the like.
ベンゾトリアゾール化合物以外に保護膜形成剤、防食剤等として機能する化合物を含む場合、当該化合物の含有量は、研磨液１００質量部に対して、それぞれ０．００１〜０．５質量部の範囲となることが好ましい。 When a compound that functions as a protective film forming agent, an anticorrosive agent or the like is included in addition to the benzotriazole compound, the content of the compound is in the range of 0.001 to 0.5 parts by mass with respect to 100 parts by mass of the polishing liquid. It is preferable to become.
（有機溶剤）
研磨液は、有機溶剤を更に含有してもよい。有機溶剤としては、例えば、エチレンカーボネート、プロピレンカーボネート、ジメチルカーボネート、ジエチルカーボネート、メチルエチルカーボネート等の炭酸エステル類；ブチルラクトン、プロピルラクトン等のラクトン類；エチレングリコール、プロピレングリコール、ジエチレングリコール、ジプロピレングリコール、トリエチレングリコール、トリプロピレングリコール等のグリコール類；テトラヒドロフラン、ジオキサン、ジメトキシエタン、ポリエチレンオキサイド、エチレングリコールモノメチルアセテート、ジエチレングリコールモノエチルエーテルアセテート、プロピレングリコールモノメチルエーテルアセテート等のエーテル類；メタノール、エタノール、プロパノール、ｎ−ブタノール、ｎ−ペンタノール、ｎ−ヘキサノール、イソプロパノール、３−メトキシ−３−メチル−１−ブタノール等のアルコール類（モノアルコール類）；アセトン、メチルエチルケトン等のケトン類；ジメチルホルムアミド、Ｎ−メチルピロリドン等のアミド類；酢酸エチル、乳酸エチル等のエステル類（炭酸エステル類及びラクトン類を除く）；スルホラン等のスルホラン類などが挙げられる。
(Organic solvent)
The polishing liquid may further contain an organic solvent. Examples of the organic solvent include carbonates such as ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, and methyl ethyl carbonate; lactones such as butyl lactone and propyl lactone; ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, Glycols such as triethylene glycol and tripropylene glycol; ethers such as tetrahydrofuran, dioxane, dimethoxyethane, polyethylene oxide, ethylene glycol monomethyl acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate; methanol, ethanol, propanol, n -Butanol, n-pentanol, n- Alcohols (monoalcohols) such as xanol, isopropanol, and 3-methoxy-3-methyl-1-butanol; ketones such as acetone and methyl ethyl ketone; amides such as dimethylformamide and N-methylpyrrolidone; ethyl acetate and ethyl lactate And the like (excluding carbonates and lactones); sulfolanes such as sulfolane.
有機溶剤を含有する場合、その含有量は、添加した各成分の溶解性を向上させる観点から、研磨液１００質量部に対し、好ましくは０．０１質量部以上、より好ましくは０．０５質量部以上、更に好ましくは０．１質量部以上である。また、有機溶剤の含有量は、研磨液を長期に亘り安定的に保管する観点から、研磨液１００質量部に対し、好ましくは５０質量部以下、より好ましくは１０質量部以下、更に好ましくは５質量部以下である。 When the organic solvent is contained, the content thereof is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass with respect to 100 parts by mass of the polishing liquid from the viewpoint of improving the solubility of each added component. As mentioned above, More preferably, it is 0.1 mass part or more. Further, the content of the organic solvent is preferably 50 parts by mass or less, more preferably 10 parts by mass or less, and still more preferably 5 parts with respect to 100 parts by mass of the polishing liquid from the viewpoint of stably storing the polishing liquid for a long period of time. It is below mass parts.
（水）
研磨液は、水を更に含有してもよい。水として、イオン交換水、蒸留水等の純水を用いることが好ましい。水を含有する場合、その含有量は、他の成分の残部でよい。
(water)
The polishing liquid may further contain water. It is preferable to use pure water such as ion exchange water or distilled water as water. When water is contained, the content may be the balance of other components.
（他の任意成分）
研磨液は、得られる効果を考慮し、更に、前記に挙げた成分以外の任意成分として、一般的な金属用研磨液に用いられる分散剤、界面活性剤等の添加剤を含有してもよい。
(Other optional ingredients)
In consideration of the effect obtained, the polishing liquid may further contain additives such as dispersants and surfactants used in general metal polishing liquids as optional components other than the components listed above. .
（ｐＨ）
本実施形態に係る研磨液のｐＨは、３．０〜８．０である。研磨液のｐＨが３．０以上であると、エッチングが抑制される。研磨液のｐＨは、エッチングの抑制が容易となる観点から、３．５以上が好ましく、４．０以上がより好ましい。また、研磨液のｐＨが８．０以下であると、充分なＣＭＰ速度が得られる。研磨液のｐＨは、充分なＣＭＰ速度を容易に得る観点から、７．０以下が好ましく、６．０以下がより好ましい。
(PH)
The pH of the polishing liquid according to this embodiment is 3.0 to 8.0. Etching is suppressed as the pH of the polishing liquid is 3.0 or more. The pH of the polishing liquid is preferably 3.5 or more and more preferably 4.0 or more from the viewpoint of easy suppression of etching. Further, when the pH of the polishing liquid is 8.0 or less, a sufficient CMP rate can be obtained. The pH of the polishing liquid is preferably 7.0 or less, more preferably 6.0 or less, from the viewpoint of easily obtaining a sufficient CMP rate.
特にｐＨを４．５〜６．０とすると、エッチング速度を抑制したまま、ＣＭＰ速度が特異的に上昇する。これにより高いＣＭＰ速度と低いエッチング速度とを高度に達成できる。 In particular, when the pH is set to 4.5 to 6.0, the CMP rate specifically increases while suppressing the etching rate. Thereby, a high CMP rate and a low etching rate can be achieved to a high degree.
本実施形態に係る研磨液について、酸又は塩基をｐＨ調整剤として用いて、ｐＨを調整してもよい。ｐＨ調整剤としては、塩酸、硝酸等の無機酸；水酸化ナトリウム、水酸化カリウム、アンモニア等の無機塩基などが挙げられる。これらの中でも、硝酸、アンモニア等がｐＨの調整が容易であるという観点から好ましい。 About the polishing liquid which concerns on this embodiment, you may adjust pH using an acid or a base as a pH adjuster. Examples of the pH adjuster include inorganic acids such as hydrochloric acid and nitric acid; inorganic bases such as sodium hydroxide, potassium hydroxide and ammonia. Among these, nitric acid, ammonia and the like are preferable from the viewpoint of easy pH adjustment.
ｐＨは、ｐＨメータ（例えば、株式会社堀場製作所製「ｐＨＭｅｔｅｒ Ｆ−５１」）を用いて測定できる。例えば、フタル酸塩ｐＨ緩衝液（ｐＨ ４．０１）と中性リン酸塩ｐＨ緩衝液（ｐＨ ６．８６）とを標準緩衝液として用いてｐＨメータを２点校正した後、ｐＨメータの電極を研磨液に入れて、２分以上経過して安定した後の値を測定する。このとき、標準緩衝液と研磨液の液温は共に２５℃とする。 The pH can be measured using a pH meter (for example, “pHMeter F-51” manufactured by Horiba, Ltd.). For example, after calibrating two pH meters using a phthalate pH buffer solution (pH 4.01) and a neutral phosphate pH buffer solution (pH 6.86) as standard buffers, Is measured in the polishing liquid after 2 minutes or more has elapsed and stabilized. At this time, both the standard buffer solution and the polishing solution are set to 25 ° C.
（研磨液セット）
上記実施形態に係る研磨液は、構成成分をスラリと添加液とに分けた複数液式の研磨液セットとして保存してもよい。スラリと、添加液とを混合して研磨液を得ることができる。スラリは、例えば、砥粒及び水を少なくとも含む。添加液は、例えば、（Ａ）有機酸類、（Ｂ）ベンゾトリアゾール骨格を有する化合物、及び金属酸化剤からなる群より選択される少なくとも一種を含む。特に、金属酸化剤として過酸化水素を用いるなど、分解し易い成分を含む場合は、構成成分を分けて保存することが好ましい。例えば、砥粒、（Ａ）有機酸類、（Ｂ）ベンゾトリアゾール骨格を有する化合物、及び水を含むスラリと、過酸化水素及び水を含む添加液とに分けて保存することが好ましい。
(Polishing liquid set)
You may preserve | save the polishing liquid which concerns on the said embodiment as a multi-liquid type polishing liquid set which divided | segmented the component into the slurry and the additive liquid. A slurry and an additive liquid can be mixed to obtain a polishing liquid. The slurry includes at least abrasive grains and water, for example. The additive liquid contains, for example, at least one selected from the group consisting of (A) organic acids, (B) a compound having a benzotriazole skeleton, and a metal oxidizing agent. In particular, when components that are easily decomposed, such as using hydrogen peroxide as a metal oxidizing agent, are included, it is preferable to store the components separately. For example, it is preferable to store the slurry separately in a slurry containing (A) an organic acid, (B) a compound having a benzotriazole skeleton, and water, and an additive solution containing hydrogen peroxide and water.
また、スラリ及び添加液は、水等の液状媒体によって希釈されて使用される、濃縮貯蔵液であってもよい。ここで、濃縮とは、液状媒体に対する各成分の含有割合が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。 Further, the slurry and the additive liquid may be a concentrated stock solution that is diluted with a liquid medium such as water. Here, the 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, and is not limited to the one that has undergone the concentration step.
（研磨方法）
本実施形態に係る研磨方法は、上記実施形態の研磨液を用いて、少なくともコバルト含有部を研磨する工程を含む。研磨方法による研磨対象は、表面にコバルト含有部を有し、且つ、表面に銅含有部を有しない基板である。研磨対象である基板として、例えば、半導体デバイスを製造するための基板が挙げられる。コバルト含有部は、コバルト原子を含有する部分であり、例えば、コバルト、コバルト合金（例えば、コバルト−ニッケル合金等）、コバルトの酸化物、及びコバルト合金の酸化物からなる群より選ばれる少なくとも一種のコバルト系金属を含む。また、前記銅含有部は、銅原子を含有する部分であり、例えば、銅、銅合金、銅の酸化物、及び銅合金の酸化物からなる群より選ばれる少なくとも一種の銅系金属を含む。研磨対象である基板は、好ましくは、表面に凸部及び凹部を有する下地層（基体、層間絶縁材料を用いて形成した層等）上に、コバルト系金属を堆積してコバルト含有部を形成し、凹部にコバルト系金属が充填された基板である。上記実施形態の研磨液を用いてこのような基板を研磨すると、下地層の凸部上に堆積したコバルト系金属が選択的に研磨により除去され、所望の平坦化されたコバルト系金属からなる配線パターンが得られる。
(Polishing method)
The polishing method according to this embodiment includes a step of polishing at least the cobalt-containing portion using the polishing liquid of the above embodiment. An object to be polished by the polishing method is a substrate having a cobalt-containing portion on the surface and not having a copper-containing portion on the surface. Examples of the substrate to be polished include a substrate for manufacturing a semiconductor device. A cobalt containing part is a part containing a cobalt atom, for example, at least 1 type chosen from the group which consists of cobalt, a cobalt alloy (for example, cobalt-nickel alloy etc.), an oxide of cobalt, and an oxide of a cobalt alloy. Contains cobalt-based metals. Moreover, the said copper containing part is a part containing a copper atom, for example, contains at least 1 type of copper-type metal chosen from the group which consists of copper, a copper alloy, a copper oxide, and a copper alloy oxide. The substrate to be polished is preferably formed by depositing a cobalt-based metal on a base layer (base, layer formed using an interlayer insulating material, etc.) having a convex portion and a concave portion on the surface to form a cobalt-containing portion. A substrate in which a concave portion is filled with a cobalt-based metal. When such a substrate is polished using the polishing liquid of the above-described embodiment, the cobalt-based metal deposited on the convex portion of the underlayer is selectively removed by polishing, and a wiring made of a desired flattened cobalt-based metal. A pattern is obtained.
研磨方法の一実施形態では、例えば、図１（ａ）に示すように、基体（図示せず）上に形成された、下地層１、バリア層２、及びコバルト含有部３を有する基板１０を研磨する。下地層１は、層間絶縁材料から構成され、表面に凸部及び凹部を有する。バリア層２は、バリア材料から構成され、下地層１の表面に追従して設けられている。コバルト含有部３は、前記凹部を埋め込むようにバリア層２を被覆している。研磨方法の一実施形態は、例えば、上記実施形態の研磨液を用いてコバルト含有部を研磨して、図１（ｂ）に示すように、下地層１の凸部上に位置するバリア層２を露出させて基板２０を得る第一の研磨工程を備える。研磨方法は、更に、前記凸部上のバリア層２を研磨して、図１（ｃ）に示すように、凸部を構成する下地層１を露出させて基板３０を得る第二の研磨工程を備えてもよい。バリア層２の研磨には、バリア層を形成する材料に応じて、公知のバリア層用の研磨液を適宜選択して用いればよい。
In one embodiment of the polishing method, for example, as shown in FIG. 1A, a
本実施形態に係る研磨方法には、例えば、基板を保持できるホルダと、研磨パッドが貼り付けられた研磨定盤とを有する、一般的な研磨装置を用いることができる。研磨定盤の研磨パッド上に上記実施形態の研磨液を供給し、基板のコバルト含有部を研磨パッドに押圧した状態で、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。 For the polishing method according to this embodiment, for example, a general polishing apparatus having a holder that can hold a substrate and a polishing surface plate to which a polishing pad is attached can be used. The polishing liquid of the above embodiment is supplied onto the polishing pad of the polishing surface plate, and the surface to be polished is polished by relatively moving the polishing surface plate and the substrate while pressing the cobalt-containing portion of the substrate against the polishing pad. To do.
研磨装置を用いる場合は、例えば、研磨される基板を保持できるホルダと、研磨パッドを貼り付け可能であり、且つ、回転数が変更可能なモータ等と接続している研磨定盤とを有する一般的な研磨装置を使用できる。研磨パッドとしては、不織布、発泡ポリウレタン、多孔質フッ素樹脂等からなるパッドが挙げられる。 In the case of using a polishing apparatus, for example, it generally has a holder that can hold a substrate to be polished, and a polishing platen that can be attached to a polishing pad and connected to a motor that can change the number of rotations. A typical polishing apparatus can be used. Examples of the polishing pad include pads made of nonwoven fabric, polyurethane foam, porous fluororesin, and the like.
研磨条件には特に制限はないが、研磨定盤の回転速度は、基板が飛び出さないように２００ｍｉｎ−１（２００ｒｐｍ）以下の低回転が好ましい。基板の研磨パッドへの押し付け圧力は、４．９〜９８ｋＰａが好ましい。同一面内でＣＭＰ速度のばらつきが少ないこと（ＣＭＰ速度の面内均一性）、及び、研磨前に存在していた凹凸が解消し平坦になり易いこと（パターンの平坦性）を満足する観点から、９．８〜４９ｋＰａがより好ましい。 The polishing conditions are not particularly limited, but the rotation speed of the polishing surface plate is preferably a low rotation of 200 min −1 (200 rpm) or less so that the substrate does not jump out. The pressure for pressing the substrate to the polishing pad is preferably 4.9 to 98 kPa. From the viewpoint of satisfying that the variation in the CMP rate is small within the same plane (in-plane uniformity of the CMP rate), and that the unevenness existing before polishing is eliminated and the surface is likely to become flat (pattern flatness). 9.8 to 49 kPa is more preferable.
研磨している間、例えば、研磨液をポンプ等で連続的に研磨パッドに供給する。この供給量に制限はないが、研磨パッドの表面が常に研磨液で覆われていることが好ましい。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。 During polishing, for example, the polishing liquid is continuously supplied to the polishing pad with a pump or the like. Although there is no restriction | limiting in this supply amount, it is preferable that the surface of a polishing pad is always covered with polishing liquid. The substrate after polishing is preferably washed in running water and then dried after removing water droplets attached to the substrate using spin drying or the like.
以下、実施例により本発明を説明する。但し、本発明はこれらの実施例に限定されるものではない。 The present invention will be described below with reference to examples. However, the present invention is not limited to these examples.
（実施例１）
［研磨液の調製］
純水に、有機溶剤として３−メトキシ−３−メチル−１−ブタノール（ＭＭＢ）、有機酸としてリンゴ酸、及びベンゾトリアゾール化合物として１−ヒドロキシ−１Ｈ−ベンゾトリアゾール（ＨＢＴＡ）をこの順に加え、撹拌して混合した。得られた溶液に、研磨砥粒としてコロイダルシリカを加えて混合した。更に、過酸化水素水（過酸化水素濃度 ３０質量％）を加えて混合した。その後、各成分の含有量が表１に示す量［質量％］となるように、純水を加えて混合し、実施例１の研磨液を得た。
Example 1
[Preparation of polishing liquid]
To pure water, 3-methoxy-3-methyl-1-butanol (MMB) as an organic solvent, malic acid as an organic acid, and 1-hydroxy-1H-benzotriazole (HBTA) as a benzotriazole compound are added in this order and stirred. And mixed. To the resulting solution, colloidal silica was added as abrasive grains and mixed. Further, hydrogen peroxide water (hydrogen peroxide concentration 30% by mass) was added and mixed. Then, pure water was added and mixed so that the content of each component would be the amount [% by mass] shown in Table 1, and the polishing liquid of Example 1 was obtained.
［砥粒の平均粒径］
砥粒の平均粒径（二次粒子の平均粒径）は、光回折散乱式粒度分布計（マルバーンインスツルメンツ社製「ゼータサイザー３０００ＨＳＡ」）を用いて測定した。具体的には、研磨液をイオン交換水で希釈して試料を調製後（散乱光強度が５００〜２０００ｃｐｓ）、前記粒度分布計の試料槽に投入し、散乱光強度から算出される電気泳動移動度として得られる値を読み取った。コロイダルシリカの平均粒径は７０ｎｍであった。
[Average grain size of abrasive grains]
The average particle size of the abrasive grains (average particle size of secondary particles) was measured using a light diffraction scattering type particle size distribution meter (“Zeta Sizer 3000HSA” manufactured by Malvern Instruments). Specifically, after preparing the sample by diluting the polishing liquid with ion-exchanged water (scattered light intensity is 500 to 2000 cps), it is put into the sample tank of the particle size distribution meter and electrophoretic movement calculated from the scattered light intensity The value obtained as a degree was read. The average particle size of the colloidal silica was 70 nm.
［研磨液のｐＨ］
研磨液のｐＨを以下の条件により測定した。
測定温度：２５℃
測定装置：株式会社堀場製作所製「ｐＨＭｅｔｅｒ Ｆ−５１」
測定方法：標準緩衝液（フタル酸塩ｐＨ緩衝液、ｐＨ：４．０１（２５℃）；中性リン酸塩ｐＨ緩衝液、ｐＨ：６．８６（２５℃））を用いて２点校正した後、電極を研磨液に入れて、２分以上経過して安定した後のｐＨを前記測定装置により測定した。
[PH of polishing liquid]
The pH of the polishing liquid was measured under the following conditions.
Measurement temperature: 25 ° C
Measuring device: “pHMeter F-51” manufactured by HORIBA, Ltd.
Measurement method: Two-point calibration using a standard buffer (phthalate pH buffer, pH: 4.01 (25 ° C.); neutral phosphate pH buffer, pH: 6.86 (25 ° C.)) Thereafter, the electrode was placed in the polishing liquid, and the pH after being stabilized after 2 minutes or more was measured with the measuring device.
［研磨特性評価］
前記で得られた研磨液の研磨特性を、以下に示す評価項目に従って評価した。
[Polishing property evaluation]
The polishing characteristics of the polishing liquid obtained above were evaluated according to the following evaluation items.
（評価項目）
（１）ＣＭＰ速度（Ｃｏ−ＲＲ（Ｒｅｍｏｖａｌ Ｒａｔｅ）［ｎｍ／ｍｉｎ］）
ＣＭＰ前後のコバルト層の厚み差を電気抵抗値から換算して求め、厚み差と研磨時間とによりＣＭＰ速度を算出した。
(Evaluation item)
(1) CMP rate (Co-RR (Removal Rate) [nm / min])
The difference in thickness of the cobalt layer before and after CMP was calculated from the electrical resistance value, and the CMP rate was calculated from the thickness difference and the polishing time.
（研磨条件）
基板：表面に厚さ１，０００ｎｍのコバルト層を形成したシリコンウエハ（８ｉｎｃｈ、ブランケットウエハ）
研磨装置：定盤直径６００ｍｍ、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（ロームアンドハース社製「ＩＣ−１０１０」）
研磨圧力：１４ｋＰａ
基板と研磨定盤との相対速度：３６ｍ／ｍｉｎ
研磨液供給量：２００ｍＬ／ｍｉｎ
研磨液の温度：２５℃
研磨時間：１ｍｉｎ
(Polishing conditions)
Substrate: Silicon wafer (8 inch, blanket wafer) with a 1,000 nm thick cobalt layer formed on the surface
Polishing device: Surface plate diameter 600 mm, rotary type Polishing pad: Foam polyurethane resin with closed cells ("IC-1010" manufactured by Rohm and Haas)
Polishing pressure: 14 kPa
Relative speed between substrate and polishing surface plate: 36 m / min
Polishing liquid supply amount: 200 mL / min
Polishing liquid temperature: 25 ° C
Polishing time: 1 min
（２）エッチング速度（Ｃｏ−ＥＲ（Ｅｔｃｈｉｎｇ Ｒａｔｅ）［ｎｍ／ｍｉｎ］）
研磨液へ浸漬前後のコバルト層の厚み差を電気抵抗値から換算して求め、厚み差と浸漬時間とによりエッチング速度を算出した。
（浸漬条件）
チップ：表面に厚さ１，０００ｎｍのコバルト層を形成したシリコンウエハ（８ｉｎｃｈ、ブランケットウエハ）を切断して得た、２０ｍｍ×２０ｍｍのチップ
研磨液容量：１００ｍＬビーカー内の１００ｍＬ
回転速度：チップを固定した撹拌羽根（回転半径１．５ｃｍ）を２００ｍｉｎ−１（ｒｐｍ）で回転
研磨液の温度：６０℃
浸漬時間：２ｍｉｎ
(2) Etching rate (Co-ER (Etching Rate) [nm / min])
The difference in thickness of the cobalt layer before and after immersion in the polishing liquid was calculated from the electrical resistance value, and the etching rate was calculated from the difference in thickness and the immersion time.
(Immersion conditions)
Chip: 20 mm × 20 mm chip obtained by cutting a silicon wafer (8 inch, blanket wafer) having a 1,000 nm thick cobalt layer formed on the surface. Polishing liquid capacity: 100 mL in a 100 mL beaker
Rotational speed: Rotating stirring blade (rotating radius 1.5 cm) with a chip fixed at 200 min −1 (rpm) Temperature of polishing liquid: 60 ° C.
Immersion time: 2 min
（実施例２〜６）
有機酸類を表１に示す有機酸類に代えた以外は、実施例１と同様に研磨液を得た。実施例１と同様に、砥粒の平均粒径及び研磨液のｐＨを測定し、また、ＣＭＰ速度及びエッチング速度を評価した。結果を表１に示す。
（比較例１及び２）
有機酸類を用いなかったか、又は、有機酸類に代えて硫酸アンモニウムを用いた以外は、実施例１と同様に研磨液を得た。実施例１と同様に、砥粒の平均粒径及び研磨液のｐＨを測定し、また、ＣＭＰ速度及びエッチング速度を評価した。結果を表１に示す。
(Examples 2 to 6)
A polishing liquid was obtained in the same manner as in Example 1 except that the organic acids were replaced with the organic acids shown in Table 1. As in Example 1, the average particle size of the abrasive grains and the pH of the polishing liquid were measured, and the CMP rate and the etching rate were evaluated. The results are shown in Table 1.
(Comparative Examples 1 and 2)
A polishing liquid was obtained in the same manner as in Example 1 except that organic acids were not used or ammonium sulfate was used in place of the organic acids. As in Example 1, the average particle size of the abrasive grains and the pH of the polishing liquid were measured, and the CMP rate and the etching rate were evaluated. The results are shown in Table 1.
実施例１〜６の研磨液は、（Ａ）有機酸類及び（Ｂ）ベンゾトリアゾール化合物を含有し、ｐＨが３．０〜８．０であることにより、高いＣＭＰ速度と低いエッチング速度とを達成できた。 The polishing liquids of Examples 1 to 6 contain (A) organic acids and (B) benzotriazole compounds, and have a pH of 3.0 to 8.0, thereby achieving a high CMP rate and a low etching rate. did it.
実施例１及び２と、実施例３〜６との比較により、有機酸類としてアミノ酸を用いることにより、高いＣＭＰ速度と低いエッチング速度とを高度に達成できることがわかる。高いＣＭＰ速度を達成できる理由としては、有機酸類に比してアミノ酸がコバルトと錯体をより形成しやすく、アミノ酸が研磨による溶出イオンを効果的に錯体化するためと推察される。一方で低いエッチング速度を達成できる理由としては、酸の添加によるｐＨの低下がアミノ酸では抑えられるため、低いｐＨによるコバルトの活性溶解が抑制できるためと推察される。このような観点から、アミノ酸は、高いＣＭＰ速度と低いエッチング速度とを高度に達成する効果を有効に発揮しているといえる。 A comparison between Examples 1 and 2 and Examples 3 to 6 shows that a high CMP rate and a low etching rate can be achieved to a high degree by using amino acids as organic acids. The reason why a high CMP rate can be achieved is presumed to be that amino acids tend to form complexes with cobalt more easily than organic acids, and amino acids effectively complex the ions eluted by polishing. On the other hand, it is assumed that the reason why the low etching rate can be achieved is that the decrease in pH due to the addition of acid can be suppressed with amino acids, so that the active dissolution of cobalt due to the low pH can be suppressed. From this point of view, it can be said that amino acids are effectively exhibiting the effect of highly achieving a high CMP rate and a low etching rate.
（実施例７〜１０）
ベンゾトリアゾール化合物を表２に示すベンゾトリアゾール化合物に代えた以外は、実施例３と同様に研磨液を得た。表中、ＣＢＴＡは４−カルボキシ−１Ｈ−ベンゾトリアゾールを、ＢＴＡは１Ｈ−ベンゾトリアゾールを表す。実施例３と同様に、砥粒の平均粒径及び研磨液のｐＨを測定し、また、ＣＭＰ速度及びエッチング速度を評価した。結果を、実施例３の結果と共に表２に示す。
(Examples 7 to 10)
A polishing liquid was obtained in the same manner as in Example 3 except that the benzotriazole compound was replaced with the benzotriazole compound shown in Table 2. In the table, CBTA represents 4-carboxy-1H-benzotriazole, and BTA represents 1H-benzotriazole. As in Example 3, the average grain size of the abrasive grains and the pH of the polishing liquid were measured, and the CMP rate and the etching rate were evaluated. The results are shown in Table 2 together with the results of Example 3.
（比較例３及び４）
ベンゾトリアゾール化合物を用いなかったか、又は、ベンゾトリアゾール化合物に代えて１，２，４−トリアゾール（１，２，４−ＴＡ）を用いた以外は、実施例３と同様に研磨液を得た。実施例３と同様に、砥粒の平均粒径及び研磨液のｐＨを測定し、また、ＣＭＰ速度及びエッチング速度を評価した。結果を表２に示す。
(Comparative Examples 3 and 4)
A polishing liquid was obtained in the same manner as in Example 3 except that the benzotriazole compound was not used or that 1,2,4-triazole (1,2,4-TA) was used instead of the benzotriazole compound. As in Example 3, the average grain size of the abrasive grains and the pH of the polishing liquid were measured, and the CMP rate and the etching rate were evaluated. The results are shown in Table 2.
実施例３及び７〜１０の研磨液は、（Ａ）有機酸類及び（Ｂ）ベンゾトリアゾール化合物を含有し、ｐＨが３．０〜８．０であることにより、高いＣＭＰ速度と低いエッチング速度とを達成できた。実施例３、７及び８の比較により、特に（Ｂ）ベンゾトリアゾール化合物として親水性基を有するベンゾトリアゾール化合物を用いることにより、高いＣＭＰ速度と低いエッチング速度との両立を高度に達成できることがわかる。また、実施例３、９及び１０の比較により、ベンゾトリアゾール化合物の含有量が大きいほど、より低いエッチング速度を達成できることがわかる。一方、比較例３の研磨液は、窒素含有複素環化合物を含有しないために、エッチング速度が高く、また、比較例４の研磨液は、（Ｂ）ベンゾトリアゾール化合物に代えてトリアゾール化合物を含有するために、ＣＭＰ速度が低く、且つ、エッチング速度が高かった。 The polishing liquids of Examples 3 and 7 to 10 contain (A) organic acids and (B) benzotriazole compounds, and have a pH of 3.0 to 8.0, so that a high CMP rate and a low etching rate are obtained. Was achieved. Comparison of Examples 3, 7 and 8 shows that, by using a benzotriazole compound having a hydrophilic group as the benzotriazole compound (B), both high CMP rate and low etching rate can be achieved at a high level. Moreover, it is understood from the comparison of Examples 3, 9 and 10 that the lower the etching rate, the higher the content of the benzotriazole compound. On the other hand, since the polishing liquid of Comparative Example 3 does not contain a nitrogen-containing heterocyclic compound, the etching rate is high, and the polishing liquid of Comparative Example 4 contains a triazole compound instead of the (B) benzotriazole compound. Therefore, the CMP rate was low and the etching rate was high.
（実施例１１）
コロイダルシリカを用いなかった以外は、実施例３と同様に研磨液を得た。実施例３と同様に、砥粒の平均粒径及び研磨液のｐＨを測定し、また、ＣＭＰ速度及びエッチング速度を評価した。結果を、実施例３の結果と共に表３に示す。
(Example 11)
A polishing liquid was obtained in the same manner as in Example 3 except that colloidal silica was not used. As in Example 3, the average grain size of the abrasive grains and the pH of the polishing liquid were measured, and the CMP rate and the etching rate were evaluated. The results are shown in Table 3 together with the results of Example 3.
実施例３及び１１の研磨液は、研磨砥粒の有無に関わらず、高いＣＭＰ速度と低いエッチング速度とを達成できた。特に、実施例３の研磨液は、研磨砥粒を含有することにより、より高いＣＭＰ速度を達成できた。 The polishing liquids of Examples 3 and 11 were able to achieve a high CMP rate and a low etching rate regardless of the presence or absence of abrasive grains. In particular, the polishing liquid of Example 3 was able to achieve a higher CMP rate by containing abrasive grains.
（実施例１２）
ｐＨ調整剤としてアンモニア水溶液（アンモニア濃度 ２５質量％）を用いて研磨液のｐＨを調整した以外は、実施例３と同様に研磨液を得た。実施例３と同様に、砥粒の平均粒径及び研磨液のｐＨを測定し、また、ＣＭＰ速度及びエッチング速度を評価した。結果を、実施例３の結果と共に表４に示す。
(Example 12)
A polishing liquid was obtained in the same manner as in Example 3 except that the pH of the polishing liquid was adjusted using an aqueous ammonia solution (ammonia concentration: 25% by mass) as a pH adjuster. As in Example 3, the average grain size of the abrasive grains and the pH of the polishing liquid were measured, and the CMP rate and the etching rate were evaluated. The results are shown in Table 4 together with the results of Example 3.
実施例３及び１２の研磨液は、（Ａ）有機酸類及び（Ｂ）ベンゾトリアゾール化合物を含有し、ｐＨが３．０〜８．０であることにより、高いＣＭＰ速度と低いエッチング速度とを達成できた。 The polishing liquids of Examples 3 and 12 contain (A) organic acids and (B) benzotriazole compounds, and have a pH of 3.0 to 8.0, thereby achieving a high CMP rate and a low etching rate. did it.
（実施例１３〜１６）
有機酸類を加えた後、更に表５に示す硫酸及び／又は硫酸塩を加えた以外は、実施例１と同様に研磨液を得た。実施例１と同様に、砥粒の平均粒径及び研磨液のｐＨを測定し、また、ＣＭＰ速度及びエッチング速度を評価した。結果を、実施例３の結果と共に表５に示す。表５中、硫酸及び硫酸アンモニウムの含有量［質量％］は、添加量に基づき求めた値であり、また、硫酸アンモニウムの含有量［質量％］は、研磨液に含まれる硫酸アンモニウムの質量を硫酸の質量に換算して求めた値である。
(Examples 13 to 16)
After adding the organic acids, a polishing liquid was obtained in the same manner as in Example 1 except that sulfuric acid and / or sulfate shown in Table 5 was further added. As in Example 1, the average particle size of the abrasive grains and the pH of the polishing liquid were measured, and the CMP rate and the etching rate were evaluated. The results are shown in Table 5 together with the results of Example 3. In Table 5, the content [mass%] of sulfuric acid and ammonium sulfate is a value determined based on the addition amount, and the content [mass%] of ammonium sulfate is the mass of ammonium sulfate contained in the polishing liquid by the mass of sulfuric acid. It is the value obtained by converting to.
実施例１３〜１６の研磨液から、無機酸類を適度に含有することにより、より高いＣＭＰ速度を達成できることがわかる。また、無機酸類の含有量が大きいほど、エッチング速度が高くなることがわかる。 It can be seen from the polishing liquids of Examples 13 to 16 that a higher CMP rate can be achieved by appropriately containing inorganic acids. Moreover, it turns out that an etching rate becomes high, so that content of inorganic acids is large.
本発明の実施形態に係る研磨液及び研磨方法は、コバルト含有部を有する基板、例えば、配線材料としてコバルト系金属を有する半導体基板のＣＭＰに好ましく用いることができる。 The polishing liquid and the polishing method according to the embodiment of the present invention can be preferably used for CMP of a substrate having a cobalt-containing portion, for example, a semiconductor substrate having a cobalt-based metal as a wiring material.
１ 下地層
２ バリア層
３ コバルト含有部
１０，２０，３０ 基板
DESCRIPTION OF SYMBOLS 1
Claims (7)
（Ａ）有機酸類と、
（Ｂ）ベンゾトリアゾール骨格を有する化合物と
を含有し、
ｐＨが４．５〜６．０であり、
前記（Ａ）有機酸類が、アミノ酸を含み、
前記（Ｂ）ベンゾトリアゾール骨格を有する化合物が、ベンゾトリアゾール骨格を有し、且つ、親水性基を有する化合物を含む、研磨液。 A polishing liquid for polishing at least the cobalt-containing part of a substrate having a cobalt-containing part on the surface and not having a copper-containing part on the surface,
(A) organic acids,
(B) a compound having a benzotriazole skeleton and
pH is 4.5-6.0 der is,
The (A) organic acid contains an amino acid,
(B) The polishing liquid in which the compound having a benzotriazole skeleton includes a compound having a benzotriazole skeleton and a hydrophilic group .
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