JP2011119380A - Abrasive for copper and chemical mechanical polishing method - Google Patents
Abrasive for copper and chemical mechanical polishing method Download PDFInfo
- Publication number
- JP2011119380A JP2011119380A JP2009274246A JP2009274246A JP2011119380A JP 2011119380 A JP2011119380 A JP 2011119380A JP 2009274246 A JP2009274246 A JP 2009274246A JP 2009274246 A JP2009274246 A JP 2009274246A JP 2011119380 A JP2011119380 A JP 2011119380A
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- Prior art keywords
- acid
- mol
- abrasive
- copper
- polishing
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Landscapes
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
Abstract
Description
本発明は、化学的機械的研磨方法（ＣＭＰ）、及びその方法に用いる銅用の研磨剤に関する。 The present invention relates to a chemical mechanical polishing method (CMP) and a polishing agent for copper used in the method.
ＬＳＩの高性能化に伴い、ＬＳＩ製造工程における微細加工技術として、予め溝を形成した絶縁膜上に、銅を電気めっき法により埋め込んだ後、配線形成のために溝部以外の過剰な銅を化学的機械的研磨方法（ＣＭＰ）を用いて除去することにより配線を形成する、いわゆるダマシン法が従来使用されている。一般に、ＣＭＰで使用する研磨剤は、酸化剤及び固体粒子からなり、必要に応じて保護膜形成剤、酸化金属用溶解剤等が添加されている。固体粒子としては、特許文献１〜４等に記載されているように、数十ｎｍ程度のシリカ、アルミナ、ジルコニア、セリア等の微粒子が知られている。また酸化剤としては、特許文献５〜９等に記載されているように、過酸化水素、硝酸鉄、フェリシアン化カリウム、過硫酸アンモニウム等が知られている。 Along with the higher performance of LSIs, as a microfabrication technology in the LSI manufacturing process, copper is embedded in an insulating film in which grooves have been previously formed by electroplating, and then excess copper other than the grooves is chemically formed for wiring formation. A so-called damascene method is conventionally used in which wiring is formed by removal using a mechanical mechanical polishing method (CMP). In general, an abrasive used in CMP is composed of an oxidizing agent and solid particles, and a protective film forming agent, a dissolving agent for metal oxide, and the like are added as necessary. As solid particles, fine particles such as silica, alumina, zirconia, and ceria of about several tens of nm are known as described in Patent Documents 1 to 4 and the like. As the oxidizing agent, as described in Patent Documents 5 to 9 and the like, hydrogen peroxide, iron nitrate, potassium ferricyanide, ammonium persulfate, and the like are known.
生産性の向上の観点からＣＭＰによる銅の研磨速度の向上が求められている。研磨速度を向上させる従来の方法として、酸化金属溶解剤を添加することが有効とされる。固体砥粒によって削り取られた金属酸化物の粒を研磨剤に溶解させることで固体砥粒による削り取りの効果が増加するためと考えられる。それ以外の方法として、添加されている酸化剤の濃度を増加させることも知られている。また、特許文献１０には水に不溶な銅化合物と可溶な銅化合物を銅配線上に形成させる方法、特許文献１１にはアミノ酸を添加する方法、特許文献１２には鉄（III）化合物を含ませる方法、特許文献１３にはアルミニウム、チタン、クロム、鉄、コバルト、ニッケル、銅、亜鉛、ゲルマニウム、ジルコニウム、モリブデン、錫、アンチモン、タンタル、タングステン、鉛、セリウムの多価金属を含有させることにより研磨速度を向上させる方法が開示されている。その一方、研磨速度を向上させてしまうと金属配線部の中央が皿のように窪むディッシング現象を生じ、平坦性を悪化させてしまうという問題点がある。それを防止するために、通常は、表面保護の作用を示す化合物が添加される。これは、銅表面に緻密な保護膜を形成することにより、酸化剤による銅のイオン化を抑制して銅の研磨剤中への過剰な溶解を防止するためである。一般的に、この作用を示す化合物としては、ベンゾトリアゾール（ＢＴＡ）をはじめとするキレート剤が知られている。これに関しては、特許文献１４〜１７等に記載されている。 From the viewpoint of improving productivity, it is required to improve the polishing rate of copper by CMP. As a conventional method for improving the polishing rate, it is effective to add a metal oxide solubilizer. It is considered that the effect of scraping by the solid abrasive grains is increased by dissolving the metal oxide grains scraped by the solid abrasive grains in the abrasive. As another method, it is also known to increase the concentration of the added oxidizing agent. Patent Document 10 discloses a method of forming a water-insoluble copper compound and a soluble copper compound on a copper wiring, Patent Document 11 includes a method of adding an amino acid, and Patent Document 12 includes an iron (III) compound. The method of inclusion, Patent Document 13 contains a polyvalent metal such as aluminum, titanium, chromium, iron, cobalt, nickel, copper, zinc, germanium, zirconium, molybdenum, tin, antimony, tantalum, tungsten, lead, and cerium. Discloses a method for improving the polishing rate. On the other hand, if the polishing rate is increased, there is a problem that the dishing phenomenon in which the center of the metal wiring part is depressed like a dish is caused, and the flatness is deteriorated. In order to prevent this, a compound that exhibits a surface protecting action is usually added. This is because a dense protective film is formed on the copper surface to suppress the ionization of copper by the oxidizing agent and prevent excessive dissolution of the copper in the abrasive. In general, chelating agents such as benzotriazole (BTA) are known as compounds exhibiting this action. This is described in Patent Documents 14 to 17 and the like.
一般的に、ディッシングの低減を目的としてＢＴＡをはじめとするキレート剤を添加すると、研磨すべき部分にも保護皮膜が形成されるために研磨速度が極端に低下する。これを解決するために種々の添加剤が検討されている。例えば、特許文献１８に記載されているヘテロポリ酸及び有機高分子を含むものがある。このヘテロポリ酸は溶解速度が速いため、有機高分子化合物を添加して溶解速度を抑制し、ディッシングの発生を防止している。この有機高分子としてポリビニルアルコール、ポリアクリルアミド、ポリアクリル酸をはじめとするアクリレート、ポリビニルアセテート等のポリビニルエステル類、ポリアリルアミン等が含まれている。 In general, when a chelating agent such as BTA is added for the purpose of reducing dishing, a protective film is also formed on the portion to be polished, so that the polishing rate is extremely reduced. In order to solve this, various additives have been studied. For example, there is one containing a heteropolyacid and an organic polymer described in Patent Document 18. Since this heteropolyacid has a high dissolution rate, an organic polymer compound is added to suppress the dissolution rate and prevent dishing. Examples of the organic polymer include polyvinyl alcohol, polyacrylamide, acrylates such as polyacrylic acid, polyvinyl esters such as polyvinyl acetate, polyallylamine, and the like.
また、特許文献１９には抑制剤とアミノ酸とを併用する方法、特許文献２０にはアミノ酢酸又はアミド硫酸とＢＴＡ等保護膜形成剤とを使用する方法、特許文献２１にはカルボキシル基を１つ有するα−オキシ酸と保護膜形成剤のバランスをとる方法、特許文献２２には銅と水不溶性錯体を形成するヘテロ環化合物（第１錯化剤）、及び銅と水難溶性ないし可溶性錯体を形成し、錯形成後に１個以上の配位子が余るヘテロ環化合物（第２錯化剤）を含む方法等が開示されている。一般に、ＬＳＩの製造で使用される銅の膜厚は約１μｍ程度であり、研磨速度は特許文献２３に記載されるように０．５μｍ／分程度となるようなスラリーが使用される。 Patent Document 19 uses a method of using an inhibitor and an amino acid together, Patent Document 20 uses a method of using aminoacetic acid or amidosulfuric acid and a protective film forming agent such as BTA, and Patent Document 21 has one carboxyl group. A method for balancing the α-oxyacid having a protective film forming agent, Patent Document 22 forms a heterocyclic compound (first complexing agent) that forms a water-insoluble complex with copper, and forms a water-insoluble or soluble complex with copper. In addition, a method including a heterocyclic compound (second complexing agent) in which one or more ligands remain after complex formation is disclosed. Generally, a copper film used in the manufacture of LSI has a thickness of about 1 μm, and a slurry having a polishing rate of about 0.5 μm / min as described in Patent Document 23 is used.
生産性の向上の観点から、研磨速度が数μｍ／分の高速の研磨剤が求められている。このレベルでの研磨速度を有する従来技術として、特許文献２４に記載されている銅及び銅合金用研磨剤並びにそれを用いた研磨方法があるが、さらなる改良の余地があった。この研磨剤は、無機酸、アミノ酸、保護膜形成剤、砥粒及び酸化剤を含み、ｐＨが１．５〜４と示されている。使用する酸は硫酸、リン酸等であり、アミノ酸としては、ｐＫａ（第一酸解離定数の逆数の対数）が２〜３のアミノ酸、例えばグリシン、アラニン、バリン、ロイシン、プロリン等が有効であることが開示されている。 From the viewpoint of improving productivity, a high-speed abrasive having a polishing rate of several μm / min is demanded. As a prior art having a polishing rate at this level, there is a polishing agent for copper and copper alloy and a polishing method using the same described in Patent Document 24, but there is room for further improvement. This abrasive contains an inorganic acid, an amino acid, a protective film forming agent, abrasive grains and an oxidizing agent, and has a pH of 1.5 to 4. Acids to be used are sulfuric acid, phosphoric acid, and the like. As amino acids, amino acids having pKa (logarithm of the reciprocal of the first acid dissociation constant) of 2 to 3, such as glycine, alanine, valine, leucine, and proline are effective. It is disclosed.
ところで、電子機器の小型化、高性能化のためには、近年、薄型で占有面積が小さく、高密度に集約され、さらに高速動作が可能な半導体デバイスが求められてきている。このような要求に対して、従来の配線技術では性能の限界に近づきつつある。そのため、次世代の技術として、ＩＣチップの裏面と表面に電極を有するシリコン貫通電極（ＴＳＶ：Through Silicon Via）が開発された。このチップを積層させてチップ間をダイレクトに接合させるシステムインパッケージ（ＳｉＰ：System in Package）が知られている。 Incidentally, in order to reduce the size and increase the performance of electronic devices, in recent years, there has been a demand for semiconductor devices that are thin, occupy a small area, are integrated with high density, and can operate at high speed. In response to such demand, the conventional wiring technology is approaching the limit of performance. Therefore, as a next generation technology, a through silicon via (TSV) having electrodes on the back and front surfaces of the IC chip has been developed. A system in package (SiP) in which the chips are stacked and directly joined between the chips is known.
ＴＳＶの作製において、Ｖｉａ内にＣｕを充填する場合、半導体デバイスの配線工程と同様にＣｕシード層をスパッタリング法で形成し、その上に電気めっきでＣｕを充填する。しかし、直径数十μｍのＶｉａ内にＣｕを電気めっきで充填する場合、現状のめっき技術では１０μｍ以上の不要なＣｕがシリコン基板上に成膜される。そのＣｕは、化学的機械的研磨方法（ＣＭＰ）を使用して除去する。この際、数十μｍまで薄化したチップを積層させるため、上下の貫通電極間の接触不良を防止するためには電極表面の平滑性が重要となる。チップ同士の接合工程で使用される金バンプの溶着による追随量を考慮しても、許容されるディシング量は、０．３μｍ以下にする必要があると考えられている。さらに、半導体デバイスで使用されるＣｕ−ＣＭＰプロセスでの研磨速度は１μｍ／分程度であり、現状のＣＭＰプロセスをＣｕ研磨量が１０μｍのシステムインパッケージに用いると、多くの時間を要し、生産性が低下する。このような背景から、ＳｉＰのＣｕ研磨に適した、５μｍ／分以上の高速かつ高平坦性を兼ね備えた新規なＣＭＰ用研磨剤の開発が求められている。 In the production of TSV, when Cu is filled in the Via, a Cu seed layer is formed by sputtering as in the wiring process of the semiconductor device, and Cu is filled thereon by electroplating. However, when Cu is filled in a via having a diameter of several tens of μm by electroplating, unnecessary Cu of 10 μm or more is formed on a silicon substrate by the current plating technique. The Cu is removed using a chemical mechanical polishing method (CMP). At this time, since the chips thinned to several tens of μm are stacked, smoothness of the electrode surface is important in order to prevent poor contact between the upper and lower through electrodes. Considering the follow-up amount due to the welding of gold bumps used in the chip-to-chip bonding process, it is considered that the allowable dicing amount needs to be 0.3 μm or less. Furthermore, the polishing rate in the Cu-CMP process used in semiconductor devices is about 1 μm / min. If the current CMP process is used for a system-in-package with a Cu polishing amount of 10 μm, a lot of time is required for production. Sex is reduced. Against this background, development of a new CMP polishing agent suitable for SiP Cu polishing, which has a high speed of 5 μm / min or more and high flatness has been demanded.
本発明は、銅膜を高速かつ高平滑に研磨することができ、高性能配線板やＴＳＶ等の厚い金属膜の研磨が必要とされる用途においても短時間の研磨処理が可能であり十分な生産性を確保できる銅用研磨剤、及びその研磨剤を用いる化学的機械的研磨方法を提供することを目的とする。 The present invention can polish a copper film at high speed and with high smoothness, and can perform a short-time polishing process even in applications requiring polishing of thick metal films such as high-performance wiring boards and TSVs. It is an object of the present invention to provide a copper abrasive capable of ensuring productivity and a chemical mechanical polishing method using the abrasive.
本発明者は、上記課題に関して検討した結果、無機酸、及びアミノ酸等の種類、並びに保護膜形成剤、酸化剤等の添加量を制御するとともに、さらに有機酸を添加してｐＨを適切に制御することにより銅を高い速度で研磨できる研磨剤が得られることを見出し、本発明を完成した。すなわち、本発明の要旨は以下の通りである。 As a result of studying the above problems, the present inventor controls the types of inorganic acid and amino acid, and the addition amount of a protective film forming agent, an oxidizing agent, etc., and further controls the pH by adding an organic acid. As a result, it was found that an abrasive capable of polishing copper at a high speed was obtained, and the present invention was completed. That is, the gist of the present invention is as follows.
（１）無機酸、アミノ酸、保護膜形成剤、砥粒、酸化剤、有機酸及び水を含み、無機酸が少なくとも硫酸及びリン酸の両方を含む銅用研磨剤であって、研磨剤のｐＨがアミノ酸及び有機酸のｐＫａより大きく、かつ４．０以下である前記銅用研磨剤。
（２）無機酸の添加量が０．０８〜１．０ｍｏｌ／ｋｇ、アミノ酸の添加量が０．２０〜２．０ｍｏｌ／ｋｇ、保護膜形成剤の添加量が０．０２〜０．２ｍｏｌ／ｋｇ、及び有機酸の添加量が０．０２〜１．０ｍｏｌ／ｋｇである上記（１）に記載の銅用研磨剤。
（３）無機酸の添加量（ｍｏｌ／ｋｇ）／保護膜形成剤の添加量（ｍｏｌ／ｋｇ）の値が、２．０以上である上記（１）又は（２）に記載の銅用研磨剤。
（４）保護膜形成剤が、ベンゾトリアゾール又はその誘導体を含む上記（１）〜（３）のいずれかに記載の銅用研磨剤。
（５）酸化剤が、過酸化水素、過硫酸及び過硫酸塩よりなる群から選択される少なくとも１種を含む上記（１）〜（４）のいずれかに記載の銅用研磨剤。
（６）上記（１）〜（５）のいずれかに記載の銅用研磨剤を用いて、研磨面と被研磨面とを相対運動させて研磨を行う化学的機械的研磨方法。
（７）研磨を行う際の圧力が、５〜５０ｋＰａである上記（６）に記載の化学的機械的研磨方法。
(1) An abrasive for copper containing an inorganic acid, an amino acid, a protective film forming agent, abrasive grains, an oxidizing agent, an organic acid and water, and the inorganic acid contains at least both sulfuric acid and phosphoric acid, and the pH of the abrasive The abrasive for copper, wherein is greater than the pKa of amino acids and organic acids and not more than 4.0.
(2) The amount of inorganic acid added is 0.08 to 1.0 mol / kg, the amount of amino acid added is 0.20 to 2.0 mol / kg, and the amount of protective film forming agent added is 0.02 to 0.2 mol / kg. Polishing agent for copper as described in said (1) whose addition amount of kg and organic acid is 0.02-1.0 mol / kg.
(3) Polishing for copper as described in said (1) or (2) whose value of the addition amount (mol / kg) of inorganic acid / addition amount (mol / kg) of a protective film formation agent is 2.0 or more Agent.
(4) The copper polishing slurry according to any one of (1) to (3) above, wherein the protective film forming agent contains benzotriazole or a derivative thereof.
(5) The copper abrasive | polishing agent in any one of said (1)-(4) in which an oxidizing agent contains at least 1 sort (s) selected from the group which consists of hydrogen peroxide, a persulfuric acid, and a persulfate.
(6) A chemical mechanical polishing method in which polishing is performed by relatively moving a polishing surface and a surface to be polished using the copper polishing slurry according to any one of (1) to (5) above.
(7) The chemical mechanical polishing method according to the above (6), wherein the pressure during polishing is 5 to 50 kPa.
なお、本発明においては、特に断りがない限り、銅には銅を含む金属（銅合金）も含むものとする。また、本発明において銅用研磨剤とは、銅からなる金属膜、銅を含む金属膜（銅合金膜等）、又はそれらの金属膜と他の金属膜との積層膜を研磨するための研磨剤をいう。 In the present invention, unless otherwise specified, copper includes a metal containing copper (copper alloy). In the present invention, the abrasive for copper is a polishing for polishing a metal film made of copper, a metal film containing copper (such as a copper alloy film), or a laminated film of these metal films and other metal films. An agent.
本発明によれば、銅を通常の研磨剤よりも格段に高速で研磨することが可能である。特に、銅に対する研磨速度が４μｍ／分を超えるような研磨剤が得られるため、高性能配線板や、ＴＳＶ等の作製等、短時間で大量に銅を研磨する用途に最適な研磨剤、及びそれを用いた化学的機械的研磨方法を提供することができる。 According to the present invention, copper can be polished at a much higher speed than a normal abrasive. In particular, since an abrasive with a polishing rate exceeding 4 μm / min for copper can be obtained, an optimum abrasive for use in polishing copper in a large amount in a short time, such as production of high-performance wiring boards and TSVs, and the like, and A chemical mechanical polishing method using the same can be provided.
本発明は、無機酸、アミノ酸、保護膜形成剤、砥粒、酸化剤、有機酸及び水を含み、無機酸が少なくとも硫酸及びリン酸の両方を含む銅用研磨剤であって、研磨剤のｐＨがアミノ酸及び有機酸のｐＫａ（第一酸解離定数の逆数の対数）より大きく、かつ４．０以下であることを特徴とする。以下、各成分に関して詳細に説明する。 The present invention is an abrasive for copper containing an inorganic acid, an amino acid, a protective film forming agent, abrasive grains, an oxidizing agent, an organic acid and water, wherein the inorganic acid contains at least both sulfuric acid and phosphoric acid, The pH is larger than pKa (logarithm of the reciprocal of the first acid dissociation constant) of amino acids and organic acids and 4.0 or less. Hereinafter, each component will be described in detail.
（無機酸）
本発明の銅用研磨剤は無機酸を含有する。無機酸としては、硫酸とリン酸との混合物を用いると、研磨の高速化が可能になり、さらに表面粗さを低減できるという点で非常に有効である。硫酸又はリン酸単独では研磨の高速化及び高平坦化は困難である。硝酸単独の場合、硝酸とリン酸とを混合させた場合、リン酸と硫酸以外の無機酸とを混合させた場合等は、いずれも高速化かつ高平坦化は困難である。硫酸とリン酸との混合比は特に制約はないが、両者が少なくとも混合されることが必要条件である。また、リン酸、硫酸が存在していれば、それ以外の酸、例えば硝酸等が存在していても効果は得られる。
(Inorganic acid)
The copper abrasive | polishing agent of this invention contains an inorganic acid. As the inorganic acid, use of a mixture of sulfuric acid and phosphoric acid is very effective in that the polishing can be speeded up and the surface roughness can be reduced. With sulfuric acid or phosphoric acid alone, it is difficult to increase the speed and flatness of polishing. In the case of nitric acid alone, when nitric acid and phosphoric acid are mixed, or when inorganic acid other than phosphoric acid and sulfuric acid is mixed, it is difficult to increase the speed and flatness. The mixing ratio of sulfuric acid and phosphoric acid is not particularly limited, but it is a necessary condition that they are mixed at least. If phosphoric acid and sulfuric acid are present, the effect can be obtained even if other acids such as nitric acid are present.
無機酸の添加量は、研磨速度に優れるという点で、銅用研磨剤全体に対して０．０８〜１．０ｍｏｌ／ｋｇ、特に０．０９〜１．０ｍｏｌ／ｋｇとすることが好ましい。また、保護膜形成剤の添加量との比率も重要であり、無機酸の合計添加量（ｍｏｌ／ｋｇ）／保護膜形成剤の合計添加量（ｍｏｌ／ｋｇ）の値が、２．０以上であることが好ましい。 The amount of the inorganic acid added is preferably 0.08 to 1.0 mol / kg, particularly 0.09 to 1.0 mol / kg, based on the entire polishing slurry for copper, in that the polishing rate is excellent. The ratio of the protective film forming agent to the added amount is also important, and the value of the total added amount of inorganic acid (mol / kg) / the total added amount of protective film forming agent (mol / kg) is 2.0 or more. It is preferable that
（アミノ酸）
本発明の銅用研磨剤は、アミノ酸を含有する。本発明におけるアミノ酸は、銅との化合物を形成させる目的で使用される。このようなアミノ酸としては、水に溶解するものであれば使用することができ、具体的には、グリシン、アラニン、バリン、システイン、アスパラギン酸、ヒドロキシプロリン、トレオニン、セリン、グルタミン酸、プロリン、メオチニン、イソロイシン、ロイシン、チロシン、フェニルアラニン、リシン、トリプトファン、ヒスチジン、アルギニン等が挙げられる。いずれのアミノ酸でも使用可能であるが、研磨剤溶液のｐＨとの兼ね合いが重要であり、使用するアミノ酸は、そのアミノ酸のｐＫａが銅用研磨剤のｐＨより小さいことが条件となる。例えば、研磨剤のｐＨを２．２０に調整した場合、プロリン（ｐＫａ：１．９５）は使用することが可能であるが、グリシン（ｐＫａ：２．３５）は使用することができない。しかし溶液のｐＨを２．５０に調整した場合は、グリシンも使用可能となる。
(amino acid)
The abrasive | polishing agent for copper of this invention contains an amino acid. The amino acid in the present invention is used for the purpose of forming a compound with copper. As such an amino acid, it can be used as long as it is soluble in water. Specifically, glycine, alanine, valine, cysteine, aspartic acid, hydroxyproline, threonine, serine, glutamic acid, proline, metinin, Examples include isoleucine, leucine, tyrosine, phenylalanine, lysine, tryptophan, histidine, and arginine. Any amino acid can be used, but the balance with the pH of the abrasive solution is important, and the amino acid to be used is required to have a pKa of the amino acid smaller than the pH of the copper abrasive. For example, when the pH of the abrasive is adjusted to 2.20, proline (pKa: 1.95) can be used, but glycine (pKa: 2.35) cannot be used. However, when the pH of the solution is adjusted to 2.50, glycine can also be used.
アミノ酸の添加量は、アミノ酸の種類によって異なるが、通常、銅用研磨剤全体に対して０．２０〜２．０ｍｏｌ／ｋｇ、特に０．５〜１．０ｍｏｌ／ｋｇとすることが好ましい。 The amount of amino acid added varies depending on the type of amino acid, but it is usually preferably 0.20 to 2.0 mol / kg, particularly preferably 0.5 to 1.0 mol / kg, based on the total amount of the copper abrasive.
（保護膜形成剤）
また、本発明の銅用研磨剤は、保護膜形成剤を含有する。保護膜形成剤とは、銅表面に対して保護膜を形成する作用を有する物質であり、研磨進行時には研磨によって除去されるいわゆる反応層を形成しているものと推察され、銅が研磨されるのを防ぐための保護膜を形成するものではない。保護膜形成剤としては、複素環化合物を用いることが好ましい。複素環化合物は、ヘテロ原子を１個以上含んだ複素環を有する化合物である。ヘテロ原子とは、炭素原子、又は水素原子以外の原子、すなわち窒素原子、硫黄原子、酸素原子、セレン原子、リン原子、ホウ素原子等を意味し、好ましくは窒素原子、酸素原子、硫黄原子である。複素環化合物の複素環の環員数は特に限定はないが、単環化合物であっても縮合環を有する多環化合物であっても良い。単環の場合の員数は好ましくは５〜７である。縮合環を有する場合の環数は、好ましくは２〜４である。
(Protective film forming agent)
Moreover, the abrasive | polishing agent for copper of this invention contains a protective film formation agent. The protective film forming agent is a substance that has a function of forming a protective film on the copper surface, and is presumed to form a so-called reaction layer that is removed by polishing when the polishing proceeds, and copper is polished. It does not form a protective film for preventing this. As the protective film forming agent, a heterocyclic compound is preferably used. A heterocyclic compound is a compound having a heterocyclic ring containing one or more heteroatoms. The heteroatom means an atom other than a carbon atom or a hydrogen atom, that is, a nitrogen atom, a sulfur atom, an oxygen atom, a selenium atom, a phosphorus atom, a boron atom, etc., preferably a nitrogen atom, an oxygen atom, or a sulfur atom. . The number of members of the heterocyclic ring of the heterocyclic compound is not particularly limited, but it may be a monocyclic compound or a polycyclic compound having a condensed ring. The number of members in the case of a single ring is preferably 5-7. When it has a condensed ring, the number of rings is preferably 2 to 4.
複素環として具体的には、トリアゾール環、テトラゾール環、キノリン環、イミダゾール環、ピラゾール環、ピリジン環、ベンズイミダゾール環、ピロール環、チオフェン環、フラン環、ピラン環、チオピラン環、チアゾール環、イソチアゾール環、オキサゾール環、イソオキサゾール環、ピラジン環、ピリミジン環、ピリダジン環、ピロリジン環、ピラゾリジン環、イミダゾリジン環、イソオキサゾリジン環、イソチアゾリジン環、ピペリジン環、ピペラジン環、モルホリン環、チオモルホリン環、クロマン環、チオクロマン環、イソクロマン環、イソチオクロマン環、インドリン環、イソインドリン環、ピリンジン環、インドリジン環、インドール環、インダゾール環、プリン環、キノリジン環、イソキノリン環、キノリン環、ナフチリジン環、フタラジン環、キノキサリン環、キナゾリン環、シンノリン環、プテリジン環、アクリジン環、ペリミジン環、フェナントロリン環、カルバゾール環、カルボリン環、フェナジン環、アンチリジン環、チアジアゾール環、オキサジアゾール環、トリアジン環、テトラゾール環、ベンズオキサゾール環、ベンズチアゾール環、ベンズチアジアゾール環、ベンズフロキサン環、ナフトイミダゾール環、テトラアザインデン環等が挙げられるが、特にトリアゾール環、テトラゾール環が好ましい。 Specific examples of the heterocyclic ring include triazole ring, tetrazole ring, quinoline ring, imidazole ring, pyrazole ring, pyridine ring, benzimidazole ring, pyrrole ring, thiophene ring, furan ring, pyran ring, thiopyran ring, thiazole ring, isothiazole. Ring, oxazole ring, isoxazole ring, pyrazine ring, pyrimidine ring, pyridazine ring, pyrrolidine ring, pyrazolidine ring, imidazolidine ring, isoxazolidine ring, isothiazolidine ring, piperidine ring, piperazine ring, morpholine ring, thiomorpholine ring, chroman Ring, thiochroman ring, isochroman ring, isothiochroman ring, indoline ring, isoindoline ring, pyrindine ring, indolizine ring, indole ring, indazole ring, purine ring, quinolidine ring, isoquinoline ring, quinoline ring, naphthyl Ring, phthalazine ring, quinoxaline ring, quinazoline ring, cinnoline ring, pteridine ring, acridine ring, perimidine ring, phenanthroline ring, carbazole ring, carboline ring, phenazine ring, anti-lysine ring, thiadiazole ring, oxadiazole ring, triazine ring , Tetrazole ring, benzoxazole ring, benzthiazole ring, benzthiadiazole ring, benzfuroxan ring, naphthimidazole ring, tetraazaindene ring, etc., among which triazole ring and tetrazole ring are particularly preferable.
本発明で使用する複素環化合物は、１又はそれ以上の置換基を有しても良い。好ましい置換基としては、例えばハロゲン原子（フッ素原子、塩素原子、臭素原子、又はヨウ素原子）、直鎖、分岐又は環状のアルキル基、アルケニル基、アルキニル基、アリール基、ヘテロ環基、アシル基、アルコキシカルボニル基、アリールオキシカルボニル基、ヘテロ環オキシカルボニル基、カルバモイル基、Ｎ−ヒドロキシカルバモイル基、Ｎ−アシルカルバモイル基、Ｎ−スルホニルカルバモイル基、Ｎ−カルバモイルカルバモイル基、チオカルバモイル基、Ｎ−スルファモイルカルバモイル基、カルバゾイル基、オキサリル基、オキサモイル基、シアノ基、カルボンイミドイル基、ホルミル基、ヒドロキシ基、アルコキシ基、アリールオキシ基、ヘテロ環オキシ基、アシルオキシ基、（アルコキシもしくはアリールオキシ）カルボニルオキシ基、カルバモイルオキシ基、スルホニルオキシ基、（アルキル、アリール、又はヘテロ環）アミノ基、アシルアミノ基、スルホンアミド基、ウレイド基、チオウレイド基、Ｎ−ヒドロキシウレイド基、イミド基、（アルコキシもしくはアリールオキシ）カルボニルアミノ基、スルファモイルアミノ基、セミカルバジド基、チオセミカルバジド基、ヒドラジノ基、アンモニオ基、オキサモイルアミノ基、Ｎ−（アルキルもしくはアリール）スルホニルウレイド基、Ｎ−アシルウレイド基、Ｎ−アシルスルファモイルアミノ基、ヒドロキシアミノ基、ニトロ基、４級化された窒素原子を含むヘテロ環基（例えばピリジニオ基、イミダゾリオ基、キノリニオ基、イソキノリニオ基）、イソシアノ基、イミノ基、メルカプト基、（アルキル、アリール、又はヘテロ環）チオ基、（アルキル、アリール、又はヘテロ環）ジチオ基、（アルキル又はアリール）スルホニル基、（アルキル又はアリール）スルフィニル基、スルホ基又はその塩、スルファモイル基又はその塩、ホスフィノ基、ホスフィニル基、ホスフィニルオキシ基、ホスフィニルアミノ基、シリル基等が挙げられる。 The heterocyclic compound used in the present invention may have one or more substituents. Preferable substituents include, for example, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom), a linear, branched or cyclic alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an acyl group, Alkoxycarbonyl group, aryloxycarbonyl group, heterocyclic oxycarbonyl group, carbamoyl group, N-hydroxycarbamoyl group, N-acylcarbamoyl group, N-sulfonylcarbamoyl group, N-carbamoylcarbamoyl group, thiocarbamoyl group, N-sulfa Moylcarbamoyl group, carbazoyl group, oxalyl group, oxamoyl group, cyano group, carbonimidoyl group, formyl group, hydroxy group, alkoxy group, aryloxy group, heterocyclic oxy group, acyloxy group, (alkoxy or aryloxy) cal Nyloxy group, carbamoyloxy group, sulfonyloxy group, (alkyl, aryl, or heterocyclic) amino group, acylamino group, sulfonamide group, ureido group, thioureido group, N-hydroxyureido group, imide group, (alkoxy or aryloxy) ) Carbonylamino group, sulfamoylamino group, semicarbazide group, thiosemicarbazide group, hydrazino group, ammonio group, oxamoylamino group, N- (alkyl or aryl) sulfonylureido group, N-acylureido group, N-acylsulfa group Moylamino group, hydroxyamino group, nitro group, heterocyclic group containing a quaternized nitrogen atom (for example, pyridinio group, imidazolio group, quinolinio group, isoquinolinio group), isocyano group, imino group, mercapto group, (alkoxy group) , Aryl, or heterocyclic) thio group, (alkyl, aryl, or heterocyclic) dithio group, (alkyl or aryl) sulfonyl group, (alkyl or aryl) sulfinyl group, sulfo group or salt thereof, sulfamoyl group or salt thereof, A phosphino group, a phosphinyl group, a phosphinyloxy group, a phosphinylamino group, a silyl group, etc. are mentioned.
本発明で使用される複素環化合物の具体例としては、例えば以下のものが挙げられるが、これに限定されるものではない。すなわち、ベンゾトリアゾール又はその誘導体、１、２、３、４−テトラゾール、３−アミノ−１、２、４−トリアゾール等を使用することができる。それ以外にも、アントニル酸、サリチルアルドキシム等も有効である。特に好ましいのはベンゾトリアゾ−ル又はその誘導体である。ベンゾトリアゾ−ル又はその誘導体の例としては、無置換のベンゾトリアゾール、１−ヒドロキシベンゾトリアゾール、４−ヒドロキシベンゾトリアゾール、２，３−ジカルボキシトリアゾール、２，３−ジカルボキシプロピルトリアゾール、４−カルボキシル−１Ｈ−ベンゾトリアゾール、４−メトキシカルボニル−１Ｈ−ベンゾトリアゾール、４−ブトキシカルボニル−１Ｈ−ベンゾトリアゾール、メチル−１Ｈ−ベンゾトリアゾール等の置換ベンゾトリアゾールを挙げることができる。以上のような複素環化合物は、いずれかを単独で用いても良いし、二種以上を混合して用いても良い。 Specific examples of the heterocyclic compound used in the present invention include, but are not limited to, the following. That is, benzotriazole or a derivative thereof, 1,2,3,4-tetrazole, 3-amino-1,2,4-triazole and the like can be used. In addition, anthonylic acid and salicylaldoxime are also effective. Particularly preferred is benzotriazole or a derivative thereof. Examples of benzotriazole or derivatives thereof include unsubstituted benzotriazole, 1-hydroxybenzotriazole, 4-hydroxybenzotriazole, 2,3-dicarboxytriazole, 2,3-dicarboxypropyltriazole, 4-carboxyl- Examples thereof include substituted benzotriazoles such as 1H-benzotriazole, 4-methoxycarbonyl-1H-benzotriazole, 4-butoxycarbonyl-1H-benzotriazole, and methyl-1H-benzotriazole. Any of the above heterocyclic compounds may be used alone, or two or more of them may be used in combination.
保護膜形成剤の添加量は、金属表面の粗さを小さくするという観点から、銅用研磨剤全量に対して０．０２〜０．２ｍｏｌ／ｋｇとすることが好ましい。 The addition amount of the protective film forming agent is preferably 0.02 to 0.2 mol / kg with respect to the total amount of the polishing slurry for copper, from the viewpoint of reducing the roughness of the metal surface.
（酸化剤）
また、本発明の銅用研磨剤は、酸化剤を含有する。酸化剤としては、銅を酸化できる化合物であれば特に限定されるものではないが、具体的には、過酸化水素、過酸化物、硝酸塩、ヨウ素酸塩、過ヨウ素酸塩、次亜塩素酸塩、亜塩素酸塩、過硫酸塩、鉄（III）塩等を挙げることができる。過酸化水素がより好ましく用いられる。これらの酸化剤は、いずれかを単独で用いても良く、複数を組み合わせて使用しても良い。
(Oxidant)
Moreover, the abrasive | polishing agent for copper of this invention contains an oxidizing agent. The oxidizing agent is not particularly limited as long as it is a compound that can oxidize copper, and specifically, hydrogen peroxide, peroxide, nitrate, iodate, periodate, hypochlorous acid. Salt, chlorite, persulfate, iron (III) salt and the like. Hydrogen peroxide is more preferably used. Any of these oxidizing agents may be used alone or in combination of two or more.
酸化剤の添加量は、銅用研磨剤全体に対して０．１質量％以上であることが好ましく、０．２質量％以上であることがより好ましい。過剰の添加は、逆に研磨速度を低下させる場合があるため、上限を２０質量％とすることが好ましい。 The addition amount of the oxidizing agent is preferably 0.1% by mass or more, and more preferably 0.2% by mass or more, based on the entire abrasive for copper. Since excessive addition may reduce the polishing rate, the upper limit is preferably 20% by mass.
（有機酸）
また、本発明の銅用研磨剤は、有機酸を含有する。有機酸は、本発明におけるアミノ酸と同様に銅との化合物を形成させる目的で使用される。このような有機酸としては、基本的には水に溶解するものであれば使用することができるが、銅用研磨剤のｐＨとの兼ね合いが重要であり、使用する有機酸は、その化合物のｐＫａが銅用研磨剤のｐＨより小さいことが条件となる。また、使用できる有機酸は、そのｐＫａが４．０より小さいものに限定される。使用可能な有機酸の具体例として、例えばクエン酸（ｐＫａ：２．９０）、酒石酸（ｐＫａ：２．８２）、マレイン酸（ｐＫａ：１．７５）、マロン酸（ｐＫａ：２．６５）、リンゴ酸（ｐＫａ：３．２４）、フマル酸（ｐＫａ：２．８５）、ベンゼンスルホン酸（ｐＫａ：０．７０）、ｐ−トルエンスルホン酸（ｐＫａ：−０．８）、サリチル酸（ｐＫａ：２．８１）等を挙げることができる。
(Organic acid)
Moreover, the abrasive | polishing agent for copper of this invention contains an organic acid. The organic acid is used for the purpose of forming a compound with copper in the same manner as the amino acid in the present invention. As such an organic acid, it can be used as long as it is basically soluble in water, but the balance with the pH of the copper abrasive is important. The condition is that pKa is smaller than the pH of the abrasive for copper. Moreover, the organic acid which can be used is limited to the thing whose pKa is smaller than 4.0. Specific examples of organic acids that can be used include, for example, citric acid (pKa: 2.90), tartaric acid (pKa: 2.82), maleic acid (pKa: 1.75), malonic acid (pKa: 2.65), Malic acid (pKa: 3.24), fumaric acid (pKa: 2.85), benzenesulfonic acid (pKa: 0.70), p-toluenesulfonic acid (pKa: -0.8), salicylic acid (pKa: 2) .81) and the like.
有機酸の添加量は、過剰に添加すると研磨剤のｐＨが低下し、その場合、別途ＮＨ３やＫＯＨ等のアルカリを添加してｐＨを挙げる必要があるため好ましくない。通常、銅用研磨剤全体に対して０．０２〜１．０ｍｏｌ／ｋｇ、特に０．１〜０．５ｍｏｌ／ｋｇとすることが好ましい。 When the organic acid is added in excess, the pH of the polishing agent is lowered, and in that case, it is necessary to add an alkali such as NH 3 or KOH separately to increase the pH, which is not preferable. Usually, it is preferable to set it as 0.02-1.0 mol / kg with respect to the whole abrasive | polishing agent for copper, especially 0.1-0.5 mol / kg.
（砥粒）
本発明の銅用研磨剤は砥粒を含有する。砥粒としては特に制限はなく、好ましい砥粒としては、例えば、シリカ（フュームドシリカ、コロイダルシリカ、合成シリカ等）、アルミナ、ジルコニア、セリア、チタニア等の無機系の砥粒の他、ポリスチレン、アクリル樹脂等の有機系砥粒等を使用することができる。研磨速度と研磨後の表面粗さを低く抑え、またスクラッチ発生を低く抑えるという観点から、砥粒の平均粒径は１００ｎｍ以下であることが好ましく、平均粒径が１００ｎｍ以下であるコロイダルシリカ、コロイダルアルミナが特に好ましく用いられる。
(Abrasive grains)
The abrasive | polishing agent for copper of this invention contains an abrasive grain. The abrasive grains are not particularly limited, and preferable abrasive grains include, for example, silica (fumed silica, colloidal silica, synthetic silica, etc.), alumina, zirconia, ceria, titania and other inorganic abrasive grains, polystyrene, Organic abrasive grains such as acrylic resin can be used. From the viewpoint of suppressing the polishing rate and the surface roughness after polishing, and suppressing the occurrence of scratches, the average particle size of the abrasive grains is preferably 100 nm or less, and colloidal silica or colloidal having an average particle size of 100 nm or less. Alumina is particularly preferably used.
砥粒の添加量は、平坦性向上と研磨速度向上との両立という観点から適宜設定される。一般的には、銅用研磨剤全体に対して０．００５〜１０質量％、特に０．０２〜２．０質量％とすることが好ましい。 The addition amount of the abrasive grains is appropriately set from the viewpoint of achieving both flatness improvement and polishing rate improvement. Generally, it is preferable to set it as 0.005-10 mass% with respect to the whole abrasive | polishing agent for copper, especially 0.02-2.0 mass%.
（銅用研磨剤のｐＨ）
銅用研磨剤のｐＨは、硫酸等の無機酸、又はアンモニア等のアルカリで調整されるが、他の物質を使用しても良い。本発明において、銅用研磨剤のｐＨは、使用するアミノ酸及び有機酸のｐＫａよりも大きいことが条件である。これは、銅用研磨剤のｐＨがアミノ酸及び有機酸のｐＫａよりも小さい場合、銅と反応生成物を形成しにくくなるためである。また、銅用研磨剤の上限のｐＨは４．０である。これは、４．０より大きい場合、保護膜形成剤の作用が非常に強くなり、強固な皮膜を形成するために、極端に研磨速度が低下するためである。
(PH of abrasive for copper)
The pH of the copper abrasive is adjusted with an inorganic acid such as sulfuric acid or an alkali such as ammonia, but other substances may be used. In the present invention, the condition is that the pH of the copper abrasive is higher than the pKa of the amino acid and organic acid used. This is because it is difficult to form a reaction product with copper when the pH of the copper abrasive is lower than the pKa of amino acids and organic acids. Moreover, the upper limit pH of the abrasive for copper is 4.0. This is because when it is larger than 4.0, the action of the protective film forming agent becomes very strong, and the polishing rate is extremely reduced in order to form a strong film.
（それ以外の添加剤）
本発明の銅用研磨剤には、必要に応じて、例えば界面活性剤や親水性ポリマーを含有させることができる。これらの化合物は、いずれも被研磨面の接触角を低下させる作用を有し、均一な研磨を促す作用を有する。界面活性剤及び／又は親水性ポリマーは単独で用いても良く、２種類以上を併用しても良い。
(Other additives)
If necessary, the abrasive for copper of the present invention can contain, for example, a surfactant or a hydrophilic polymer. These compounds all have an action of reducing the contact angle of the surface to be polished, and an action of promoting uniform polishing. Surfactants and / or hydrophilic polymers may be used alone or in combination of two or more.
界面活性剤の例としては、硫酸エステル塩、リン酸エステル塩等のアニオン性界面活性剤、脂肪族アミン塩等のカチオン性界面活性剤、アミノカルボン酸塩、アルキルアミンオキサイド等の両性界面活性剤が挙げられる。また、親水性ポリマーとしては、ポリエチレングリコール、ポリアクリルアミド、ポリビニルアルコール、ポリビニルピロリドン等が挙げられる。界面活性剤及び親水性ポリマーの添加量は、特に限定されるものではないが、一般的には銅用研磨剤全体に対して界面活性剤及び親水性ポリマーの合計量が０．５質量％以下とすることが好ましい。 Examples of surfactants include anionic surfactants such as sulfate ester salts and phosphate ester salts, cationic surfactants such as aliphatic amine salts, and amphoteric surfactants such as aminocarboxylates and alkylamine oxides. Is mentioned. Examples of the hydrophilic polymer include polyethylene glycol, polyacrylamide, polyvinyl alcohol, polyvinyl pyrrolidone and the like. The addition amount of the surfactant and the hydrophilic polymer is not particularly limited, but generally the total amount of the surfactant and the hydrophilic polymer is 0.5% by mass or less with respect to the entire polishing slurry for copper. It is preferable that
（化学的機械的研磨方法）
本発明の銅用研磨剤は、例えばシリコン貫通ビア（ＴＳＶ：Through Silicon Vias）形成時に適用することを目的としている。ＴＳＶは、作製プロセスの違いによりいくつかの異なった構造を有するが、基本的には２種類に分類することができる。すなわち、シリコンデバイスを作製する際の基本的なウエハプロセス（前工程−回路素子と配線の作製工程）に対して、このプロセスの前にＴＳＶを作製するのがＶｉａ Ｆｉｒｓｔプロセス、ウエハプロセス完了後にＴＳＶを作製するのがＶｉａ Ｌａｓｔプロセスである。この二つのプロセスによる基本的なビア構造においては、チップの厚さは５０μｍ程度となるので、ビアの長さはバンプの長さを考慮して７０μｍ程度となる。ビアの直径は、Ｖｉａ Ｌａｓｔプロセスの場合には３０〜４０μｍ、Ｖｉａ Ｆｉｒｓｔプロセスの場合には微細加工が可能となるために３〜２０μｍの細さになる。ビアとシリコンチップは約１μｍ厚のＳｉＯ２で絶縁され、内部はＶｉａ Ｆｉｒｓｔプロセスではポリシリコン、Ｖｉａ ＬａｓｔプロセスではＣｕで充填される。Ｃｕは、ポリシリコンと比較して抵抗率が低いために有利であるが、ウエハプロセス中にＴＳＶを作製するＶｉａ Ｆｉｒｓｔプロセスでは、ウエハが高温になるために導電体としてＣｕを使用することはできない。
(Chemical mechanical polishing method)
The copper abrasive | polishing agent of this invention aims at applying, for example at the time of through-silicon-via (TSV: Through Silicon Vias) formation. TSVs have several different structures depending on the manufacturing process, but can basically be classified into two types. That is, for a basic wafer process (preparation process—circuit element and wiring fabrication process) for fabricating a silicon device, a TSV is fabricated before this process, and a TSV is completed after the wafer process is completed. Is the Via Last process. In the basic via structure by these two processes, the thickness of the chip is about 50 μm, and the length of the via is about 70 μm in consideration of the length of the bump. The diameter of the via is 30 to 40 μm in the case of the Via Last process and 3 to 20 μm in the case of the Via First process because fine processing is possible. The via and the silicon chip are insulated by SiO 2 having a thickness of about 1 μm, and the inside is filled with polysilicon in the Via First process and Cu in the Via Last process. Cu is advantageous because it has a lower resistivity than polysilicon, but the Via First process for producing TSV during the wafer process cannot use Cu as a conductor because the wafer becomes hot. .
ビア内にＣｕを充填する場合、半導体デバイスの配線工程の場合と同様にＣｕシード層をスパッタリング法で形成し、その上に電気めっきでＣｕを充填する。しかし、直径数十μｍのビアをＣｕ電気めっきで充填する場合、現状のめっき技術では１０μｍ以上の不要なＣｕがシリコン基板上に成膜される。そのＣｕは、化学的機械的研磨方法（ＣＭＰ）により除去される。この際、数十μｍまで薄化したチップを積層させるため、上下の貫通電極間の接触不良を防止するために電極表面の平滑性が重要となる。 When Cu is filled in the via, a Cu seed layer is formed by sputtering as in the case of the wiring process of the semiconductor device, and Cu is filled thereon by electroplating. However, when a via having a diameter of several tens of μm is filled by Cu electroplating, unnecessary Cu of 10 μm or more is formed on a silicon substrate by the current plating technique. The Cu is removed by a chemical mechanical polishing method (CMP). At this time, since the chips thinned to several tens of μm are stacked, the smoothness of the electrode surface is important in order to prevent poor contact between the upper and lower through electrodes.
本発明の化学的機械的研磨方法によれば、研磨する基板の銅層と研磨定盤のパッドの表面との間に本発明の銅用研磨剤を連続的に供給しながら、圧力を付与した状態で、研磨面である研磨定盤と被研磨面である基板とを相対的に動かすことにより研磨を行うことができる。 According to the chemical mechanical polishing method of the present invention, pressure was applied while continuously supplying the copper abrasive of the present invention between the copper layer of the substrate to be polished and the surface of the pad of the polishing surface plate. In this state, polishing can be performed by relatively moving a polishing platen serving as a polishing surface and a substrate serving as a surface to be polished.
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、回転数が変更可能なモータ等に接続していて研磨布を貼り付けられる定盤と研磨される基板を保持できるホルダとを有する一般的な研磨装置を使用することができる。研磨布としては、一般的な不織布、発泡ポリウレタン、多孔質フッ素樹脂等を用いることができ特に限定されるものではない。研磨条件は適宜設定されるが、定盤の回転速度は基板が飛び出さないように２００ｍｉｎ−１以下の低回転に設定することが好ましい。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）は、１〜１００ｋＰａとすることが好ましく、被研磨面内におけるＣＭＰ速度の均一性及びパターンの平坦性を満足するためには、５〜５０ｋＰａとすることがより好ましい。研磨している間、研磨布には本発明の銅用研磨剤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銅用研磨剤で覆われていることが好ましい。研磨終了後の基板は、流水中でよく洗浄した後、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。また、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有していても良い。例えば、ダイヤモンド粒子の付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化学的機械的研磨を行い、さらに、基板洗浄を行うことが好ましい。 As an apparatus for polishing, for example, when polishing with a polishing cloth, a general apparatus having a surface plate to which a polishing cloth is attached and a holder that can hold a substrate to be polished is connected to a motor or the like whose rotation speed can be changed. A polishing apparatus can be used. As an abrasive cloth, a general nonwoven fabric, a foamed polyurethane, a porous fluororesin, etc. can be used, and it is not specifically limited. The polishing conditions are set as appropriate, but the rotation speed of the surface plate is preferably set to a low rotation of 200 min −1 or less so that the substrate does not jump out. The pressing pressure (polishing pressure) of the substrate having the surface to be polished to the polishing cloth is preferably 1 to 100 kPa. In order to satisfy the uniformity of the CMP rate and the flatness of the pattern in the surface to be polished, It is more preferable to set it as 5-50 kPa. During polishing, the polishing slurry for copper of the present invention is continuously supplied to the polishing cloth with a pump or the like. Although there is no restriction | limiting in this supply amount, It is preferable that the surface of polishing cloth is always covered with the abrasive | polishing agent for copper. 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. Further, in order to perform CMP with the surface state of the polishing cloth always the same, a polishing cloth conditioning step may be provided 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 chemical mechanical polishing according to the present invention and to perform substrate cleaning.
以下、実施例及び比較例により本発明を詳細に説明するが、これらに限定されるものではない。 EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention in detail, it is not limited to these.
以下の実施例及び比較例において、銅用研磨剤を用いて化学的機械的研磨を行う際の研磨条件は次の通りである。
（研磨条件）
研磨装置：定盤寸法は直径６００ｍｍφ、ロータリータイプ
研磨パッド：独立気泡を有する発泡ウレタン樹脂
研磨圧力：３５ｋＰａ
研磨定盤／ヘッド回転速度：９３ｒｐｍ／８７ｒｐｍ
研磨剤流量：２００ｍｌ／分
基板：直径８インチ（２０．３ｃｍ）、シリコン上に２０μｍ厚の銅膜
In the following examples and comparative examples, the polishing conditions for performing chemical mechanical polishing using a copper abrasive are as follows.
(Polishing conditions)
Polishing apparatus: plate dimensions diameter 600 mm phi, a rotary type Polishing pad: foam urethane resin polishing pressure having closed cells: 35 kPa
Polishing surface plate / head rotation speed: 93 rpm / 87 rpm
Abrasive flow rate: 200 ml / min Substrate: 8 inch diameter (20.3 cm), 20 μm thick copper film on silicon
（研磨速度の評価方法）
ＣＭＰによる研磨速度は、基板のＣＭＰ前後での膜厚差をシート抵抗変化から換算して求めた。
(Evaluation method of polishing rate)
The polishing rate by CMP was obtained by converting the film thickness difference between before and after the CMP of the substrate from the change in sheet resistance.
（実施例１）
無機酸として硫酸０．０５ｍｏｌ／ｋｇ、リン酸０．０５ｍｏｌ／ｋｇ（無機酸の合計添加量０．１０ｍｏｌ／ｋｇ）、アミノ酸としてグリシン０．２０ｍｏｌ／ｋｇ、保護膜形成剤としてベンゾトリアゾール（ＢＴＡ）０．０３ｍｏｌ／ｋｇ、酸化剤として過酸化水素９質量％、有機酸としてシュウ酸０．２０ｍｏｌ／ｋｇ、砥粒としてコロイダルシリカ１．００質量％を含み、ｐＨを２．５０（少量のＮＨ３で調整）としたスラリー状の銅用研磨剤を用いて化学的機械的研磨（ＣＭＰ）を実施した。表１に示すように、４００００Å／分という良好な研磨速度を示した。無機酸と保護膜形成剤の添加量（ｍｏｌ／ｋｇ）の比は３．３３であり、２．００より大きい値を示す。また、使用した研磨剤のｐＨは２．５０であり、ｐＨ＞グリシンのｐＫａ及びシュウ酸のｐＫａの関係を満たしている。
Example 1
0.05 mol / kg sulfuric acid as inorganic acid, 0.05 mol / kg phosphoric acid (total addition amount of inorganic acid 0.10 mol / kg), 0.20 mol / kg as amino acid, benzotriazole (BTA) as protective film forming agent 0.03 mol / kg, hydrogen peroxide 9% by mass as an oxidant, oxalic acid 0.20 mol / kg as an organic acid, colloidal silica 1.00% by mass as an abrasive, pH 2.50 (a small amount of NH 3 Chemical mechanical polishing (CMP) was performed using the slurry-like copper abrasive prepared in (1). As shown in Table 1, a good polishing rate of 40000 Å / min was shown. The ratio of the addition amount (mol / kg) of the inorganic acid to the protective film forming agent is 3.33, which is larger than 2.00. Moreover, the pH of the used abrasive | polishing agent is 2.50, and satisfy | fills the relationship of pKa of pH> glycine and pKa of oxalic acid.
（実施例２）
無機酸として硫酸０．０５ｍｏｌ／ｋｇ、リン酸０．１５ｍｏｌ／ｋｇ（無機酸の合計添加量０．２０ｍｏｌ／ｋｇ）、アミノ酸としてグリシン０．４０ｍｏｌ／ｋｇ、保護膜形成剤としてＢＴＡ０．０５ｍｏｌ／ｋｇ、酸化剤として過酸化水素９質量％、有機酸としてシュウ酸０．２０ｍｏｌ／ｋｇ、砥粒としてコロイダルシリカ１．００質量％を含み、ｐＨを２．５０（少量のＮＨ３で調整）としたスラリー状の銅用研磨剤を用いてＣＭＰを実施した。本研磨剤は、上記実施例１と比較してリン酸、グリシン及びＢＴＡの濃度を増加させている。また、硫酸とリン酸の添加量の比を変えている。表１に示すように、４３０００Å／分という良好な研磨速度を示した。無機酸と保護膜形成剤の添加量（ｍｏｌ／ｋｇ）の比は４．００であり、２．００より大きい値を示す。また、使用した研磨剤のｐＨは２．５０であり、ｐＨ＞グリシンのｐＫａ及びシュウ酸のｐＫａの関係を満たしている。
(Example 2)
0.05 mol / kg sulfuric acid as inorganic acid, 0.15 mol / kg phosphoric acid (total addition amount of inorganic acid 0.20 mol / kg), 0.40 mol / kg as amino acid, 0.05 mol / kg BTA as protective film forming agent In addition, 9% by mass of hydrogen peroxide as an oxidizing agent, 0.20 mol / kg of oxalic acid as an organic acid, 1.00% by mass of colloidal silica as abrasive grains, and a pH of 2.50 (adjusted with a small amount of NH 3 ). CMP was performed using a slurry-like abrasive for copper. This abrasive | polishing agent has increased the density | concentration of phosphoric acid, glycine, and BTA compared with the said Example 1. FIG. Moreover, the ratio of the addition amount of sulfuric acid and phosphoric acid is changed. As shown in Table 1, a good polishing rate of 43,000 Å / min was shown. The ratio of the added amount of the inorganic acid and the protective film forming agent (mol / kg) is 4.00, which is larger than 2.00. Moreover, the pH of the used abrasive | polishing agent is 2.50, and satisfy | fills the relationship of pKa of pH> glycine and pKa of oxalic acid.
（実施例３）
無機酸として硫酸０．１５ｍｏｌ／ｋｇ、リン酸０．１５ｍｏｌ／ｋｇ（無機酸の合計添加量０．３０ｍｏｌ／ｋｇ）、アミノ酸としてグリシン０．９５ｍｏｌ／ｋｇ、保護膜形成剤としてＢＴＡ０．１０ｍｏｌ／ｋｇ、酸化剤として過酸化水素９質量％、有機酸としてシュウ酸０．２０ｍｏｌ／ｋｇ、砥粒としてコロイダルシリカ１．００質量％を含み、ｐＨを２．５０（少量のＮＨ３で調整）としたスラリー状の銅用研磨剤を用いてＣＭＰを実施した。本研磨剤は、上記実施例１と比較して硫酸、リン酸、グリシン及びＢＴＡの濃度を増加させている。硫酸とリン酸の添加量の比は同じである。表１に示すように、６００００Å／分という良好な研磨速度を示した。無機酸と保護膜形成剤の添加量（ｍｏｌ／ｋｇ）の比は３．００であり、２．００より大きい値を示す。また、使用した研磨剤のｐＨは２．５０であり、ｐＨ＞グリシンのｐＫａ及びシュウ酸のｐＫａの関係を満たしている。
(Example 3)
Sulfuric acid 0.15 mol / kg, phosphoric acid 0.15 mol / kg (total addition amount of inorganic acid 0.30 mol / kg) as amino acid, glycine 0.95 mol / kg as amino acid, BTA 0.10 mol / kg as protective film forming agent In addition, 9% by mass of hydrogen peroxide as an oxidizing agent, 0.20 mol / kg of oxalic acid as an organic acid, 1.00% by mass of colloidal silica as abrasive grains, and a pH of 2.50 (adjusted with a small amount of NH 3 ). CMP was performed using a slurry-like abrasive for copper. This abrasive | polishing agent is making the density | concentration of a sulfuric acid, phosphoric acid, glycine, and BTA increase compared with the said Example 1. The ratio of the addition amount of sulfuric acid and phosphoric acid is the same. As shown in Table 1, a good polishing rate of 60000 Å / min was shown. The ratio of the addition amount (mol / kg) of the inorganic acid to the protective film forming agent is 3.00, which is larger than 2.00. Moreover, the pH of the used abrasive | polishing agent is 2.50, and satisfy | fills the relationship of pKa of pH> glycine and pKa of oxalic acid.
（実施例４）
無機酸として硫酸０．１５ｍｏｌ／ｋｇ、リン酸０．０５ｍｏｌ／ｋｇ（無機酸の合計添加量０．２０ｍｏｌ／ｋｇ）、アミノ酸としてグリシン０．４０ｍｏｌ／ｋｇ、保護膜形成剤としてＢＴＡ０．０５ｍｏｌ／ｋｇ、酸化剤として過酸化水素９質量％、有機酸としてシュウ酸０．２０ｍｏｌ／ｋｇ、砥粒としてコロイダルシリカ１．００質量％を含み、ｐＨを２．５０（少量のＮＨ３で調整）としたスラリー状の銅用研磨剤を用いてＣＭＰを実施した。本研磨剤では、上記実施例２の場合と硫酸、及びリン酸の添加量を逆転させている。表１に示すように、４５０００Å／分という良好な研磨速度を示した。無機酸と保護膜形成剤の添加量（ｍｏｌ／ｋｇ）の比は４．００であり、２．００より大きい値を示す。また、使用した研磨剤のｐＨは２．５０であり、ｐＨ＞グリシンのｐＫａ及びシュウ酸のｐＫａの関係を満たしている。
Example 4
Inorganic acid 0.15 mol / kg, phosphoric acid 0.05 mol / kg (total amount of inorganic acid added 0.20 mol / kg), amino acid glycine 0.40 mol / kg, protective film forming agent BTA 0.05 mol / kg In addition, 9% by mass of hydrogen peroxide as an oxidizing agent, 0.20 mol / kg of oxalic acid as an organic acid, 1.00% by mass of colloidal silica as abrasive grains, and a pH of 2.50 (adjusted with a small amount of NH 3 ). CMP was performed using a slurry-like abrasive for copper. In this abrasive | polishing agent, the addition amount of a sulfuric acid and phosphoric acid is reversed with the case of the said Example 2. FIG. As shown in Table 1, a good polishing rate of 45000 Å / min was shown. The ratio of the added amount of the inorganic acid and the protective film forming agent (mol / kg) is 4.00, which is larger than 2.00. Moreover, the pH of the used abrasive | polishing agent is 2.50, and satisfy | fills the relationship of pKa of pH> glycine and pKa of oxalic acid.
（実施例５）
無機酸として硫酸０．１５ｍｏｌ／ｋｇ、リン酸０．１５ｍｏｌ／ｋｇ（無機酸の合計添加量０．３０ｍｏｌ／ｋｇ）、アミノ酸としてグリシン０．９５ｍｏｌ／ｋｇ、保護膜形成剤としてＢＴＡ０．１０ｍｏｌ／ｋｇ、酸化剤として過酸化水素９質量％、有機酸としてベンゼンスルホン酸０．２０ｍｏｌ／ｋｇ、砥粒としてコロイダルシリカ１．００質量％を含み、ｐＨを２．５０（少量ＮＨ３で調整）としたスラリー状の銅用研磨剤を用いてＣＭＰを実施した。本研磨剤は、上記実施例３における有機酸をシュウ酸からベンゼンスルホン酸に代えた場合に相当する。表１に示すように、６５０００Å／分という良好な研磨速度を示した。無機酸と保護膜形成剤の添加量（ｍｏｌ／ｋｇ）の比は３．００であり、２．００より大きい値を示す。また、使用した研磨剤のｐＨは２．５０であり、ｐＨ＞グリシンのｐＫａ及びベンゼンスルホン酸のｐＫａの関係を満たしている。
(Example 5)
Sulfuric acid 0.15 mol / kg, phosphoric acid 0.15 mol / kg (total addition amount of inorganic acid 0.30 mol / kg) as amino acid, glycine 0.95 mol / kg as amino acid, BTA 0.10 mol / kg as protective film forming agent In addition, hydrogen peroxide 9% by mass as an oxidant, benzenesulfonic acid 0.20 mol / kg as an organic acid, colloidal silica 1.00% by mass as an abrasive, and pH 2.50 (adjusted with a small amount of NH 3 ). CMP was performed using a slurry-like abrasive for copper. This abrasive corresponds to the case where the organic acid in Example 3 is changed from oxalic acid to benzenesulfonic acid. As shown in Table 1, a good polishing rate of 65000 Å / min was shown. The ratio of the addition amount (mol / kg) of the inorganic acid to the protective film forming agent is 3.00, which is larger than 2.00. Moreover, the pH of the used abrasive | polishing agent is 2.50, and satisfy | fills the relationship of pKa of pH> glycine and pKa of benzenesulfonic acid.
（実施例６）
無機酸として硫酸０．１５ｍｏｌ／ｋｇ、リン酸０．１５ｍｏｌ／ｋｇ（無機酸の合計添加量０．３０ｍｏｌ／ｋｇ）、アミノ酸としてグリシン０．９５ｍｏｌ／ｋｇ、保護膜形成剤としてＢＴＡ０．１０ｍｏｌ／ｋｇ、酸化剤として過酸化水素９質量％、有機酸としてマレイン酸０．２０ｍｏｌ／ｋｇ、砥粒としてコロイダルシリカ１．００質量％を含み、ｐＨを２．５０（少量のＮＨ３で調整）としたスラリー状の銅用研磨剤を用いてＣＭＰを実施した。本研磨剤は、上記実施例３における有機酸をシュウ酸からマレイン酸に代えた場合に相当する。表１に示すように、５２０００Å／分という良好な研磨速度を示した。無機酸と保護膜形成剤の添加量（ｍｏｌ／ｋｇ）の比は、３．００であり、２．００より大きい値を示す。また、使用したスラリーのｐＨは２．５０であり、ｐＨ＞グリシンのｐＫａ及びマレイン酸のｐＫａの関係を満たしている。
(Example 6)
Sulfuric acid 0.15 mol / kg, phosphoric acid 0.15 mol / kg (total addition amount of inorganic acid 0.30 mol / kg) as amino acid, glycine 0.95 mol / kg as amino acid, BTA 0.10 mol / kg as protective film forming agent In addition, hydrogen peroxide 9% by mass as an oxidizing agent, maleic acid 0.20 mol / kg as an organic acid, colloidal silica 1.00% by mass as abrasive grains, and pH 2.50 (adjusted with a small amount of NH 3 ). CMP was performed using a slurry-like abrasive for copper. This abrasive corresponds to the case where the organic acid in Example 3 is changed from oxalic acid to maleic acid. As shown in Table 1, a good polishing rate of 52000 kg / min was shown. The ratio of the addition amount (mol / kg) of the inorganic acid to the protective film forming agent is 3.00, which is larger than 2.00. The pH of the used slurry is 2.50, and the relationship of pH> pKa of glycine and pKa of maleic acid is satisfied.
（実施例７）
無機酸として硫酸０．１５ｍｏｌ／ｋｇ、リン酸０．１５ｍｏｌ／ｋｇ（無機酸の合計添加量０．３０ｍｏｌ／ｋｇ）、アミノ酸としてグリシン０．９５ｍｏｌ／ｋｇ、保護膜形成剤としてＢＴＡ０．１０ｍｏｌ／ｋｇ、酸化剤として過酸化水素９質量％、有機酸としてリンゴ酸０．２０ｍｏｌ／ｋｇ、砥粒としてコロイダルシリカ１．００質量％を含み、ｐＨを３．５０（少量のＮＨ３で調整）としたスラリー状の銅用研磨剤を用いてＣＭＰを実施した。本研磨剤は、上記実施例３における有機酸をシュウ酸からリンゴ酸に代えた場合に相当する。表１に示すように、５００００Å／分という良好な研磨速度を示した。無機酸と保護膜形成剤の添加量（ｍｏｌ／ｋｇ）の比は３．００であり、２．００より大きい値を示す。また、使用した研磨剤のｐＨは３．５０であり、ｐＨ＞グリシンのｐＫａ及びリンゴ酸のｐＫａの関係を満たしている。リンゴ酸のｐＫａは３．２４であるため、上記の関係を維持するべく研磨剤のｐＨを３．５０に上げている。
(Example 7)
Sulfuric acid 0.15 mol / kg, phosphoric acid 0.15 mol / kg (total addition amount of inorganic acid 0.30 mol / kg) as amino acid, glycine 0.95 mol / kg as amino acid, BTA 0.10 mol / kg as protective film forming agent In addition, 9% by mass of hydrogen peroxide as an oxidizing agent, 0.20 mol / kg of malic acid as an organic acid, 1.00% by mass of colloidal silica as abrasive grains, and a pH of 3.50 (adjusted with a small amount of NH 3 ). CMP was performed using a slurry-like abrasive for copper. This abrasive corresponds to the case where the organic acid in Example 3 is changed from oxalic acid to malic acid. As shown in Table 1, a good polishing rate of 50000 Å / min was shown. The ratio of the addition amount (mol / kg) of the inorganic acid to the protective film forming agent is 3.00, which is larger than 2.00. Moreover, the pH of the used abrasive | polishing agent is 3.50, and satisfy | fills the relationship of pKa of pH> glycine and pKa of malic acid. Since the pKa of malic acid is 3.24, the pH of the abrasive is raised to 3.50 to maintain the above relationship.
（実施例８）
無機酸として硫酸０．１５ｍｏｌ／ｋｇ、リン酸０．１５ｍｏｌ／ｋｇ（無機酸の合計添加量０．３０ｍｏｌ／ｋｇ）、アミノ酸としてプロリン０．９５ｍｏｌ／ｋｇ、保護膜形成剤としてＢＴＡ０．１０ｍｏｌ／ｋｇ、酸化剤として過酸化水素９質量％、有機酸としてシュウ酸０．２０ｍｏｌ／ｋｇ、砥粒としてコロイダルシリカ１．００質量％を含み、ｐＨを２．２０（少量のＨ２ＳＯ４で調整）としたスラリー状の銅用研磨剤を用いてＣＭＰを実施した。本研磨剤は、上記実施例３におけるアミノ酸をグリシンからプロリンに代えた場合に相当する。表１に示すように、７００００Å／分という良好な研磨速度を示した。無機酸と保護膜形成剤の添加量（ｍｏｌ／ｋｇ）の比は３．００であり、２．００より大きい値を示す。また、使用した研磨剤のｐＨは２．２０であり、ｐＨ＞プロリンのｐＫａ及びシュウ酸のｐＫａの関係を満たしている。プロリンのｐＫａは１．９５であり、グリシンの２．３５と比較して小さいために研磨剤のｐＨを下げることが可能となる。
(Example 8)
Sulfuric acid 0.15 mol / kg, phosphoric acid 0.15 mol / kg (total addition amount of inorganic acid 0.30 mol / kg), amino acid proline 0.95 mol / kg, protective film forming agent BTA 0.10 mol / kg In addition, it contains 9% by mass of hydrogen peroxide as an oxidizing agent, 0.20 mol / kg of oxalic acid as an organic acid, and 1.00% by mass of colloidal silica as abrasive grains, and has a pH of 2.20 (adjusted with a small amount of H 2 SO 4 ) CMP was performed using the slurry-like copper polishing agent. This abrasive corresponds to the case where the amino acid in Example 3 is changed from glycine to proline. As shown in Table 1, a good polishing rate of 70000 Å / min was shown. The ratio of the addition amount (mol / kg) of the inorganic acid to the protective film forming agent is 3.00, which is larger than 2.00. Moreover, the pH of the used abrasive | polishing agent is 2.20, and satisfy | fills the relationship of pKa of pH> proline and pKa of oxalic acid. Since pKa of proline is 1.95, which is smaller than 2.35 of glycine, the pH of the abrasive can be lowered.
（実施例９）
無機酸として硫酸０．１５ｍｏｌ／ｋｇ、リン酸０．１５ｍｏｌ／ｋｇ（無機酸の合計添加量０．３０ｍｏｌ／ｋｇ）、アミノ酸としてアラニン０．９５ｍｏｌ／ｋｇ、保護膜形成剤としてＢＴＡ０．１０ｍｏｌ／ｋｇ、酸化剤として過酸化水素９質量％、有機酸としてシュウ酸０．２０ｍｏｌ／ｋｇ、砥粒としてコロイダルシリカ１．００質量％を含み、ｐＨを２．５０（少量のＮＨ３で調整）としたスラリー状の銅用研磨剤を用いてＣＭＰを実施した。本研磨剤は、上記実施例３におけるアミノ酸をグリシンからアラニンに代えた場合に相当する。表１に示すように、６８０００Å／分という良好な研磨速度を示した。無機酸と保護膜形成剤の添加量（ｍｏｌ／ｋｇ）の比は３．００であり、２．００より大きい値を示す。また、使用した研磨剤のｐＨは２．５０であり、ｐＨ＞アラニンのｐＫａ及びシュウ酸のｐＫａの関係を満たしている。
Example 9
Sulfuric acid 0.15 mol / kg, phosphoric acid 0.15 mol / kg (total addition amount of inorganic acid 0.30 mol / kg), amino acid alanine 0.95 mol / kg, protective film forming agent BTA 0.10 mol / kg In addition, 9% by mass of hydrogen peroxide as an oxidizing agent, 0.20 mol / kg of oxalic acid as an organic acid, 1.00% by mass of colloidal silica as abrasive grains, and a pH of 2.50 (adjusted with a small amount of NH 3 ). CMP was performed using a slurry-like abrasive for copper. This abrasive corresponds to the case where the amino acid in Example 3 is changed from glycine to alanine. As shown in Table 1, a good polishing rate of 68000 kg / min was shown. The ratio of the addition amount (mol / kg) of the inorganic acid to the protective film forming agent is 3.00, which is larger than 2.00. Moreover, the pH of the used abrasive | polishing agent is 2.50, and satisfy | fills the relationship of pKa of pH> alanine and pKa of oxalic acid.
（実施例１０）
無機酸として硫酸０．１５ｍｏｌ／ｋｇ、リン酸０．１５ｍｏｌ／ｋｇ（無機酸の合計添加量０．３０ｍｏｌ／ｋｇ）、アミノ酸としてプロリン０．９５ｍｏｌ／ｋｇ、保護膜形成剤としてＢＴＡ０．１０ｍｏｌ／ｋｇ、酸化剤として過酸化水素９質量％、有機酸としてベンゼンスルホン酸０．２０ｍｏｌ／ｋｇ、砥粒としてコロイダルシリカ１．００質量％を含み、ｐＨを２．００（少量のＨ２ＳＯ４で調整）としたスラリー状の銅用研磨剤を用いてＣＭＰを実施した。本研磨剤は、上記実施例３におけるアミノ酸をグリシンからプロリンに代え、さらに有機酸をシュウ酸からベンゼンスルホン酸に代えた場合に相当する。表１に示すように、７２０００Å／分という良好な研磨速度を示した。無機酸と保護膜形成剤の添加量（ｍｏｌ／ｋｇ）の比は３．００であり、２．００より大きい値を示す。また、使用した研磨剤のｐＨは２．００であり、ｐＨ＞プロリンのｐＫａ及びベンゼンスルホン酸のｐＫａの関係を満たしている。プロリンのｐＫａは１．９５であり、グリシンの２．３５と比較して小さいために研磨剤のｐＨを下げることが可能となる。
(Example 10)
Sulfuric acid 0.15 mol / kg, phosphoric acid 0.15 mol / kg (total addition amount of inorganic acid 0.30 mol / kg), amino acid proline 0.95 mol / kg, protective film forming agent BTA 0.10 mol / kg In addition, it contains 9% by mass of hydrogen peroxide as an oxidizing agent, 0.20 mol / kg of benzenesulfonic acid as an organic acid, and 1.00% by mass of colloidal silica as abrasive grains, and has a pH of 2.00 (adjusted with a small amount of H 2 SO 4) . CMP was performed using the slurry-like copper polishing slurry. This abrasive corresponds to the case where the amino acid in Example 3 is changed from glycine to proline, and the organic acid is changed from oxalic acid to benzenesulfonic acid. As shown in Table 1, a good polishing rate of 72000 kg / min was exhibited. The ratio of the addition amount (mol / kg) of the inorganic acid to the protective film forming agent is 3.00, which is larger than 2.00. Moreover, the pH of the used abrasive | polishing agent is 2.00, and satisfies the relationship of pH> pKa of proline and pKa of benzenesulfonic acid. Since pKa of proline is 1.95, which is smaller than 2.35 of glycine, the pH of the abrasive can be lowered.
（実施例１１）
無機酸として硫酸０．１５ｍｏｌ／ｋｇ、リン酸０．１５ｍｏｌ／ｋｇ（無機酸の合計添加量０．３０ｍｏｌ／ｋｇ）、アミノ酸としてグリシン０．９５ｍｏｌ／ｋｇ、保護膜形成剤としてＢＴＡ０．１０ｍｏｌ／ｋｇ、酸化剤として過酸化水素９質量％、有機酸としてシュウ酸０．０５ｍｏｌ／ｋｇ、砥粒としてコロイダルシリカ１．００質量％を含み、ｐＨを２．５０（少量のＮＨ３で調整）としたスラリー状の銅用研磨剤を用いてＣＭＰを実施した。本研磨剤は、上記実施例３におけるシュウ酸の添加量を０．２ｍｏｌ／ｋｇから０．０５ｍｏｌ／ｋｇに低減させた場合に相当する。表１に示すように、若干研磨速度は低下したものの５２０００Å／分という良好な研磨速度を示した。無機酸と保護膜形成剤の添加量（ｍｏｌ／ｋｇ）の比は３．００であり、２．００より大きい値を示す。また、使用した研磨剤のｐＨは２．５０であり、ｐＨ＞グリシンのｐＫａ及びシュウ酸のｐＫａの関係を満たしている。
(Example 11)
Sulfuric acid 0.15 mol / kg, phosphoric acid 0.15 mol / kg (total addition amount of inorganic acid 0.30 mol / kg) as amino acid, glycine 0.95 mol / kg as amino acid, BTA 0.10 mol / kg as protective film forming agent In addition, 9% by mass of hydrogen peroxide as an oxidizing agent, 0.05 mol / kg of oxalic acid as an organic acid, 1.00% by mass of colloidal silica as abrasive grains, and a pH of 2.50 (adjusted with a small amount of NH 3 ). CMP was performed using a slurry-like abrasive for copper. This abrasive | polishing agent is equivalent to the case where the addition amount of the oxalic acid in the said Example 3 is reduced from 0.2 mol / kg to 0.05 mol / kg. As shown in Table 1, although the polishing rate was slightly reduced, a good polishing rate of 52,000 kg / min was shown. The ratio of the addition amount (mol / kg) of the inorganic acid to the protective film forming agent is 3.00, which is larger than 2.00. Moreover, the pH of the used abrasive | polishing agent is 2.50, and satisfy | fills the relationship of pKa of pH> glycine and pKa of oxalic acid.
（実施例１２）
無機酸として硫酸０．１０ｍｏｌ／ｋｇ、リン酸０．１０ｍｏｌ／ｋｇ、硝酸０．１０ｍｏｌ／ｋｇ（無機酸の合計添加量０．３０ｍｏｌ／ｋｇ）、アミノ酸としてグリシン０．９５ｍｏｌ／ｋｇ、保護膜形成剤としてＢＴＡ０．１０ｍｏｌ／ｋｇ、酸化剤として過酸化水素９質量％、有機酸としてシュウ酸０．２０ｍｏｌ／ｋｇ、砥粒としてコロイダルシリカ１．００質量％を含み、ｐＨを２．５０（少量のＮＨ３で調整）としたスラリー状の銅用研磨剤を用いてＣＭＰを実施した。本研磨剤は、上記実施例３における無機酸の種類を変更し、硝酸を追加した場合に相当する。無機酸の合計添加量は実施例３と同様に０．３０ｍｏｌ／ｋｇとした。表１に示すように、６２０００Å／分という良好な研磨速度を示した。無機酸と保護膜形成剤の添加量（ｍｏｌ／ｋｇ）の比は３．００であり、２．００より大きい値を示す。また、使用した研磨剤のｐＨは２．５０であり、ｐＨ＞グリシンのｐＫａ及びシュウ酸のｐＫａの関係を満たしている。
(Example 12)
0.10 mol / kg of sulfuric acid as inorganic acid, 0.10 mol / kg of phosphoric acid, 0.10 mol / kg of nitric acid (total addition amount of inorganic acid 0.30 mol / kg), 0.95 mol / kg of glycine as amino acid, protective film formation BTA 0.10 mol / kg as an agent, hydrogen peroxide 9% by mass as an oxidizing agent, oxalic acid 0.20 mol / kg as an organic acid, colloidal silica 1.00% by mass as an abrasive, pH 2.50 (a small amount) CMP was carried out using a slurry-like copper abrasive prepared as adjusted with NH 3 . This abrasive | polishing agent is equivalent to the case where the kind of inorganic acid in the said Example 3 is changed, and nitric acid is added. The total amount of inorganic acid added was 0.30 mol / kg as in Example 3. As shown in Table 1, a good polishing rate of 62000 kg / min was shown. The ratio of the addition amount (mol / kg) of the inorganic acid to the protective film forming agent is 3.00, which is larger than 2.00. Moreover, the pH of the used abrasive | polishing agent is 2.50, and satisfy | fills the relationship of pKa of pH> glycine and pKa of oxalic acid.
（実施例１３）
無機酸として硫酸０．０２ｍｏｌ／ｋｇ、リン酸０．０２ｍｏｌ／ｋｇ（無機酸の合計添加量０．０４ｍｏｌ／ｋｇ）、アミノ酸としてグリシン０．９５ｍｏｌ／ｋｇ、保護膜形成剤としてＢＴＡ０．１０ｍｏｌ／ｋｇ、酸化剤として過酸化水素９質量％、有機酸としてシュウ酸０．２０ｍｏｌ／ｋｇ、砥粒としてコロイダルシリカ１．００質量％を含み、ｐＨを２．５０（少量のＮＨ３で調整）としたスラリー状の銅用研磨剤を用いてＣＭＰを実施した。本研磨剤は、上記実施例３における無機酸の合計添加量を低下させた場合に相当し、無機酸の合計添加量は０．０４ｍｏｌ／ｋｇである。表２に示すように、研磨速度は１８０００Å／分に低下したものの、極めてディッシング量が少なく平坦性に優れていた。無機酸と保護膜形成剤の添加量（ｍｏｌ／ｋｇ）の比は０．４０であり、２．００より小さい値を示す。
(Example 13)
Inorganic acid 0.02 mol / kg, phosphoric acid 0.02 mol / kg (total addition amount of inorganic acid 0.04 mol / kg), amino acid glycine 0.95 mol / kg, protective film forming agent BTA 0.10 mol / kg In addition, 9% by mass of hydrogen peroxide as an oxidizing agent, 0.20 mol / kg of oxalic acid as an organic acid, 1.00% by mass of colloidal silica as abrasive grains, and a pH of 2.50 (adjusted with a small amount of NH 3 ). CMP was performed using a slurry-like abrasive for copper. This abrasive | polishing agent is equivalent to the case where the total addition amount of the inorganic acid in the said Example 3 is reduced, and the total addition amount of an inorganic acid is 0.04 mol / kg. As shown in Table 2, although the polishing rate was reduced to 18000 kg / min, the dishing amount was very small and the flatness was excellent. The ratio of the added amount of the inorganic acid to the protective film forming agent (mol / kg) is 0.40, which is smaller than 2.00.
（比較例１）
無機酸として硫酸０．１５ｍｏｌ／ｋｇ、リン酸０．０５ｍｏｌ／ｋｇ（無機酸の合計添加量０．２０ｍｏｌ／ｋｇ）、アミノ酸としてグリシン０．４０ｍｏｌ／ｋｇ、保護膜形成剤としてＢＴＡ０．０５ｍｏｌ／ｋｇ、酸化剤として過酸化水素９質量％、砥粒としてコロイダルシリカ１．００質量％を含み、ｐＨを２．５０（少量のＮＨ３で調整）としたスラリー状の銅用研磨剤を用いてＣＭＰを実施した。本研磨剤は、上記実施例４の研磨剤から有機酸であるシュウ酸を取り除いた組成に相当する。表２に示すように、研磨速度は２５０００Å／分に低下した。
(Comparative Example 1)
Inorganic acid 0.15 mol / kg, phosphoric acid 0.05 mol / kg (total amount of inorganic acid added 0.20 mol / kg), amino acid glycine 0.40 mol / kg, protective film forming agent BTA 0.05 mol / kg CMP using a slurry of copper abrasive containing 9% by mass of hydrogen peroxide as an oxidizing agent, 1.00% by mass of colloidal silica as abrasive grains, and having a pH of 2.50 (adjusted with a small amount of NH 3 ) Carried out. This abrasive corresponds to a composition obtained by removing oxalic acid, which is an organic acid, from the abrasive of Example 4 above. As shown in Table 2, the polishing rate decreased to 25000 Å / min.
（比較例２）
無機酸として硫酸０．１５ｍｏｌ／ｋｇ（無機酸の合計添加量０．１５ｍｏｌ／ｋｇ）、アミノ酸としてグリシン０．９５ｍｏｌ／ｋｇ、保護膜形成剤としてＢＴＡ０．１０ｍｏｌ／ｋｇ、酸化剤として過酸化水素９質量％、有機酸としてシュウ酸０．２０ｍｏｌ／ｋｇ、砥粒としてコロイダルシリカ１．００質量％を含み、ｐＨを２．５０（少量のＮＨ３で調整）としたスラリー状の銅用研磨剤を用いてＣＭＰを実施した。本研磨剤は、上記実施例３の研磨剤からリン酸を取り除いた組成に相当する。表２に示すように、研磨速度は２００００Å／分に低下した。無機酸と保護膜形成剤の添加量（ｍｏｌ／ｋｇ）の比は１．５０であり、２．００より小さい値を示す。
(Comparative Example 2)
Sulfuric acid 0.15 mol / kg as inorganic acid (total addition amount of inorganic acid 0.15 mol / kg), glycine 0.95 mol / kg as amino acid, BTA 0.10 mol / kg as protective film forming agent, hydrogen peroxide 9 as oxidizing agent A slurry of copper for polishing comprising a mass%, 0.20 mol / kg of oxalic acid as an organic acid, 1.00 mass% of colloidal silica as an abrasive, and a pH of 2.50 (adjusted with a small amount of NH 3 ) CMP was performed. This abrasive corresponds to the composition obtained by removing phosphoric acid from the abrasive of Example 3 above. As shown in Table 2, the polishing rate was reduced to 20000 kg / min. The ratio of the addition amount (mol / kg) of the inorganic acid to the protective film forming agent is 1.50, which is smaller than 2.00.
（比較例３）
無機酸としてリン酸０．１５ｍｏｌ／ｋｇ（無機酸の合計添加量０．１５ｍｏｌ／ｋｇ）、アミノ酸としてグリシン０．９５ｍｏｌ／ｋｇ、保護膜形成剤としてＢＴＡ０．１０ｍｏｌ／ｋｇ、酸化剤として過酸化水素９質量％、有機酸としてシュウ酸０．２０ｍｏｌ／ｋｇ、砥粒としてコロイダルシリカ１．００質量％を含み、ｐＨを２．５０（少量のＮＨ３で調整）としたスラリー状の銅用研磨剤を用いてＣＭＰを実施した。本研磨剤は、上記実施例３の研磨剤から硫酸を取り除いた組成に相当する。表２に示すように、研磨速度は１８０００Å／分に低下した。無機酸と保護膜形成剤の添加量（ｍｏｌ／ｋｇ）の比は１．５０であり、２．００より小さい値を示す。
(Comparative Example 3)
Phosphoric acid 0.15 mol / kg as inorganic acid (total addition amount of inorganic acid 0.15 mol / kg), glycine 0.95 mol / kg as amino acid, BTA 0.10 mol / kg as protective film forming agent, hydrogen peroxide as oxidizing agent Slurry abrasive for copper containing 9% by mass, 0.20 mol / kg oxalic acid as organic acid, 1.00% by mass colloidal silica as abrasive grains, and having a pH of 2.50 (adjusted with a small amount of NH 3 ) CMP was performed using This abrasive corresponds to a composition obtained by removing sulfuric acid from the abrasive of Example 3 above. As shown in Table 2, the polishing rate was reduced to 18000 kg / min. The ratio of the addition amount (mol / kg) of the inorganic acid to the protective film forming agent is 1.50, which is smaller than 2.00.
（比較例４）
無機酸として硝酸０．３０ｍｏｌ／ｋｇ（無機酸の合計添加量０．３０ｍｏｌ／ｋｇ）、アミノ酸としてグリシン０．９５ｍｏｌ／ｋｇ、保護膜形成剤としてＢＴＡ０．１０ｍｏｌ／ｋｇ、酸化剤として過酸化水素９質量％、有機酸としてシュウ酸０．２０ｍｏｌ／ｋｇ、砥粒としてコロイダルシリカ１．００質量％を含み、ｐＨを２．５０（少量のＮＨ３で調整）としたスラリー状の銅用研磨剤を用いてＣＭＰを実施した。本研磨剤は、上記実施例３における無機酸を硫酸及びリン酸から硝酸に変更した場合に相当する。無機酸の合計添加量は０．３０ｍｏｌ／ｋｇであり、実施例３と同一とした。表２に示すように、研磨速度は２９０００Å／分に低下した。無機酸と保護膜形成剤の添加量（ｍｏｌ／ｋｇ）の比は３．００であり、２．００より大きい値を示すが、研磨速度が低下したのは硝酸の影響である。
(Comparative Example 4)
Nitric acid 0.30 mol / kg as inorganic acid (total addition amount of inorganic acid 0.30 mol / kg), glycine 0.95 mol / kg as amino acid, BTA 0.10 mol / kg as protective film forming agent, hydrogen peroxide 9 as oxidizing agent A slurry of copper for polishing comprising a mass%, 0.20 mol / kg of oxalic acid as an organic acid, 1.00 mass% of colloidal silica as an abrasive, and a pH of 2.50 (adjusted with a small amount of NH 3 ) CMP was performed. This abrasive corresponds to the case where the inorganic acid in Example 3 is changed from sulfuric acid and phosphoric acid to nitric acid. The total amount of inorganic acid added was 0.30 mol / kg, which was the same as in Example 3. As shown in Table 2, the polishing rate was reduced to 29000 kg / min. The ratio of the addition amount (mol / kg) of the inorganic acid to the protective film forming agent is 3.00 and shows a value larger than 2.00, but the polishing rate was lowered due to the influence of nitric acid.
（比較例５）
無機酸として硫酸０．１５ｍｏｌ／ｋｇ、硝酸０．１５ｍｏｌ／ｋｇ（無機酸の合計添加量０．３０ｍｏｌ／ｋｇ）、アミノ酸としてグリシン０．９５ｍｏｌ／ｋｇ、保護膜形成剤としてＢＴＡ０．１０ｍｏｌ／ｋｇ、酸化剤として過酸化水素９質量％、有機酸としてシュウ酸０．２０ｍｏｌ／ｋｇ、砥粒としてコロイダルシリカ１．００質量％を含み、ｐＨを２．５０（少量のＮＨ３で調整）としたスラリー状の銅用研磨剤を用いてＣＭＰを実施した。本研磨剤は、上記実施例３における無機酸を硫酸及びリン酸から硫酸及び硝酸に変更した場合に相当する。無機酸の合計添加量は０．３０ｍｏｌ／ｋｇであり、実施例３と同一とした。表２に示すように、研磨速度は２６０００Å／分に低下した。無機酸と保護膜形成剤の添加量（ｍｏｌ／ｋｇ）の比は３．００であり、２．００より大きい値を示すが、研磨速度が低下したのは硝酸の影響である。
(Comparative Example 5)
0.15 mol / kg sulfuric acid as inorganic acid, 0.15 mol / kg nitric acid (total addition amount of inorganic acid 0.30 mol / kg), 0.95 mol / kg as amino acid, 0.10 mol / kg as BTA as protective film forming agent, Slurry containing 9% by mass of hydrogen peroxide as an oxidizing agent, 0.20 mol / kg of oxalic acid as an organic acid, 1.00% by mass of colloidal silica as abrasive grains, and having a pH of 2.50 (adjusted with a small amount of NH 3 ). CMP was performed using a copper abrasive. This abrasive corresponds to the case where the inorganic acid in Example 3 is changed from sulfuric acid and phosphoric acid to sulfuric acid and nitric acid. The total amount of inorganic acid added was 0.30 mol / kg, which was the same as in Example 3. As shown in Table 2, the polishing rate was reduced to 26000 kg / min. The ratio of the addition amount (mol / kg) of the inorganic acid to the protective film forming agent is 3.00 and shows a value larger than 2.00, but the polishing rate was lowered due to the influence of nitric acid.
（比較例６）
アミノ酸としてグリシン０．９５ｍｏｌ／ｋｇ、保護膜形成剤としてＢＴＡ０．１０ｍｏｌ／ｋｇ、酸化剤として過酸化水素９質量％、有機酸としてシュウ酸０．２０ｍｏｌ／ｋｇ、砥粒としてコロイダルシリカ１．００質量％を含み、ｐＨを２．５０（少量のＮＨ３で調整）としたスラリー状の銅用研磨剤を用いてＣＭＰを実施した。本研磨剤は、上記実施例３の組成から無機酸を全て取り除いた組成に相当する。表２に示すように、研磨速度は５０００Å／分に低下した。
(Comparative Example 6)
Glycine 0.95 mol / kg as an amino acid, BTA 0.10 mol / kg as a protective film forming agent, hydrogen peroxide 9 mass% as an oxidizing agent, oxalic acid 0.20 mol / kg as an organic acid, colloidal silica 1.00 mass as an abrasive CMP was carried out using a slurry-like copper polishing slurry containing 1% and having a pH of 2.50 (adjusted with a small amount of NH 3 ). This abrasive corresponds to a composition obtained by removing all inorganic acids from the composition of Example 3 above. As shown in Table 2, the polishing rate was reduced to 5000 kg / min.
（比較例７）
無機酸として硫酸０．１５ｍｏｌ／ｋｇ、リン酸０．１５ｍｏｌ／ｋｇ（無機酸の合計添加量０．３０ｍｏｌ／ｋｇ）、アミノ酸としてグリシン０．９５ｍｏｌ／ｋｇ、保護膜形成剤としてＢＴＡ０．１０ｍｏｌ／ｋｇ、酸化剤として過酸化水素９質量％、有機酸としてシュウ酸０．２０ｍｏｌ／ｋｇ、砥粒としてコロイダルシリカ１．００質量％を含み、ｐＨを２．２０（少量のＨ２ＳＯ４で調整）としたスラリー状の銅用研磨剤を用いてＣＭＰを実施した。本研磨剤は、上記実施例３における研磨剤のｐＨを２．５０から２．２０に変更した場合に相当する。無機酸の合計添加量は０．３０ｍｏｌ／ｋｇであり、実施例３と同一とした。表２に示すように、研磨速度は３００００Å／分に低下した。無機酸と保護膜形成剤の添加量（ｍｏｌ／ｋｇ）の比は３．００であり、２．００より大きい値を示すが、研磨剤のｐＨがグリシンのｐＫａより小さく、ｐＨ＞グリシンのｐＫａの関係を満たしていない。
(Comparative Example 7)
Sulfuric acid 0.15 mol / kg, phosphoric acid 0.15 mol / kg (total addition amount of inorganic acid 0.30 mol / kg) as amino acid, glycine 0.95 mol / kg as amino acid, BTA 0.10 mol / kg as protective film forming agent In addition, it contains 9% by mass of hydrogen peroxide as an oxidizing agent, 0.20 mol / kg of oxalic acid as an organic acid, and 1.00% by mass of colloidal silica as abrasive grains, and has a pH of 2.20 (adjusted with a small amount of H 2 SO 4 ) CMP was performed using the slurry-like copper polishing agent. This abrasive corresponds to the case where the pH of the abrasive in Example 3 is changed from 2.50 to 2.20. The total amount of inorganic acid added was 0.30 mol / kg, which was the same as in Example 3. As shown in Table 2, the polishing rate was reduced to 30000 mm / min. The ratio of the addition amount of the inorganic acid to the protective film forming agent (mol / kg) is 3.00 and shows a value larger than 2.00, but the pH of the abrasive is smaller than pKa of glycine, and pH> pKa of glycine Does not meet the relationship.
（比較例８）
無機酸として硫酸０．１５ｍｏｌ／ｋｇ、リン酸０．１５ｍｏｌ／ｋｇ（無機酸の合計添加量０．３０ｍｏｌ／ｋｇ）、アミノ酸としてグリシン０．９５ｍｏｌ／ｋｇ、保護膜形成剤としてＢＴＡ０．１０ｍｏｌ／ｋｇ、酸化剤として過酸化水素９質量％、有機酸としてキナルジン酸０．２０ｍｏｌ／ｋｇ、砥粒としてコロイダルシリカ１．００質量％を含み、ｐＨを２．５０（少量のＮＨ３で調整）としたスラリー状の銅用研磨剤を用いてＣＭＰを実施した。本研磨剤は、上記実施例３におけるシュウ酸をキナルジン酸に変更した場合に相当する。無機酸の合計添加量は０．３０ｍｏｌ／ｋｇであり、実施例３と同一とした。表２に示すように、研磨速度は１５０００Å／分に低下した。無機酸と保護膜形成剤の添加量（ｍｏｌ／ｋｇ）の比は３．００であり、２．００より大きい値を示すが、研磨剤のｐＨがキナルジン酸のｐＫａより小さく、ｐＨ＞キナルジン酸のｐＫａの関係を満たしていない。
(Comparative Example 8)
Sulfuric acid 0.15 mol / kg, phosphoric acid 0.15 mol / kg (total addition amount of inorganic acid 0.30 mol / kg) as amino acid, glycine 0.95 mol / kg as amino acid, BTA 0.10 mol / kg as protective film forming agent In addition, 9% by mass of hydrogen peroxide as an oxidizing agent, 0.20 mol / kg of quinaldic acid as an organic acid, 1.00% by mass of colloidal silica as abrasive grains, and a pH of 2.50 (adjusted with a small amount of NH 3 ). CMP was performed using a slurry-like abrasive for copper. This abrasive corresponds to the case where oxalic acid in Example 3 is changed to quinaldic acid. The total amount of inorganic acid added was 0.30 mol / kg, which was the same as in Example 3. As shown in Table 2, the polishing rate was reduced to 15000 Å / min. The ratio of the addition amount (mol / kg) of the inorganic acid to the protective film forming agent is 3.00, which is larger than 2.00, but the pH of the abrasive is smaller than the pKa of quinaldic acid, and pH> quinaldic acid PKa relationship is not satisfied.
（比較例９）
無機酸として硫酸０．１５ｍｏｌ／ｋｇ、リン酸０．１５ｍｏｌ／ｋｇ（無機酸の合計添加量０．３０ｍｏｌ／ｋｇ）、アミノ酸としてグリシン０．９５ｍｏｌ／ｋｇ、保護膜形成剤としてＢＴＡ０．１０ｍｏｌ／ｋｇ、酸化剤として過酸化水素９質量％、有機酸として酢酸０．２０ｍｏｌ／ｋｇ、砥粒としてコロイダルシリカ１．００質量％を含み、ｐＨを３．００（少量のＮＨ３で調整）としたスラリー状の銅用研磨剤を用いてＣＭＰを実施した。本研磨剤は、上記実施例３におけるシュウ酸を酢酸に変更した場合に相当する。無機酸の合計添加量は０．３０ｍｏｌ／ｋｇであり、実施例３と同一とした。表２に示すように、研磨速度は２８０００Å／分に低下した。無機酸と保護膜形成剤の添加量（ｍｏｌ／ｋｇ）の比は３．００であり、２．００より大きい値を示すが、研磨剤のｐＨが酢酸のｐＫａより小さく、ｐＨ＞酢酸のｐＫａの関係を満たしていない。
(Comparative Example 9)
Sulfuric acid 0.15 mol / kg, phosphoric acid 0.15 mol / kg (total addition amount of inorganic acid 0.30 mol / kg) as amino acid, glycine 0.95 mol / kg as amino acid, BTA 0.10 mol / kg as protective film forming agent And a slurry containing 9% by mass of hydrogen peroxide as an oxidizing agent, 0.20 mol / kg of acetic acid as an organic acid, 1.00% by mass of colloidal silica as an abrasive, and a pH of 3.00 (adjusted with a small amount of NH 3 ). CMP was performed using a copper abrasive. This abrasive corresponds to the case where oxalic acid in Example 3 is changed to acetic acid. The total amount of inorganic acid added was 0.30 mol / kg, which was the same as in Example 3. As shown in Table 2, the polishing rate was reduced to 28000 kg / min. The ratio of the addition amount (mol / kg) of the inorganic acid to the protective film forming agent is 3.00, which is larger than 2.00, but the pH of the polishing agent is smaller than the pKa of acetic acid, and pH> pKa of acetic acid. Does not meet the relationship.
（比較例１０）
無機酸として硫酸０．１５ｍｏｌ／ｋｇ、リン酸０．１５ｍｏｌ／ｋｇ（無機酸の合計添加量０．３０ｍｏｌ／ｋｇ）、アミノ酸としてグリシン０．９５ｍｏｌ／ｋｇ、保護膜形成剤としてＢＴＡ０．１０ｍｏｌ／ｋｇ、酸化剤として過酸化水素９質量％、有機酸としてシュウ酸０．２０ｍｏｌ／ｋｇ、砥粒としてコロイダルシリカ１．００質量％を含み、ｐＨを５．５０（少量のＮＨ３で調整）としたスラリー状の銅用研磨剤を用いてＣＭＰを実施した。本研磨剤は、上記実施例３の研磨剤のｐＨを２．５０から５．５０に変更した場合に相当する。無機酸の合計添加量は０．３０ｍｏｌ／ｋｇであり、実施例３と同一とした。表２に示すように、研磨速度は１５０００Å／分に低下した。無機酸と保護膜形成剤の添加量（ｍｏｌ／ｋｇ）の比は３．００であり、２．００より大きい値を示すが、研磨剤のｐＨが５．５０であり、４．０以上になっている。この場合、保護膜形成剤の作用が強く出て、強固な保護膜が形成されるために研磨速度が低下する。
(Comparative Example 10)
Sulfuric acid 0.15 mol / kg, phosphoric acid 0.15 mol / kg (total addition amount of inorganic acid 0.30 mol / kg) as amino acid, glycine 0.95 mol / kg as amino acid, BTA 0.10 mol / kg as protective film forming agent In addition, 9% by mass of hydrogen peroxide as an oxidizing agent, 0.20 mol / kg of oxalic acid as an organic acid, 1.00% by mass of colloidal silica as abrasive grains, and a pH of 5.50 (adjusted with a small amount of NH 3 ). CMP was performed using a slurry-like abrasive for copper. This abrasive corresponds to the case where the pH of the abrasive of Example 3 is changed from 2.50 to 5.50. The total amount of inorganic acid added was 0.30 mol / kg, which was the same as in Example 3. As shown in Table 2, the polishing rate was reduced to 15000 Å / min. The ratio of the addition amount (mol / kg) of the inorganic acid to the protective film forming agent is 3.00, showing a value larger than 2.00, but the pH of the polishing agent is 5.50, which is 4.0 or more. It has become. In this case, the action of the protective film forming agent is strong, and a strong protective film is formed, so that the polishing rate is reduced.
（比較例１１）
無機酸として硫酸０．１５ｍｏｌ／ｋｇ、リン酸０．１５ｍｏｌ／ｋｇ（無機酸の合計添加量０．３０ｍｏｌ／ｋｇ）、保護膜形成剤としてＢＴＡ０．１０ｍｏｌ／ｋｇ、酸化剤として過酸化水素９質量％、有機酸としてシュウ酸０．２０ｍｏｌ／ｋｇ、砥粒としてコロイダルシリカ１．００質量％を含み、ｐＨを２．５０（少量のＮＨ３で調整）としたスラリー状の銅用研磨剤を用いてＣＭＰを実施した。本研磨剤は、上記実施例３の研磨剤からアミノ酸であるグリシンを取り除いた場合に相当する。無機酸の合計添加量は０．３０ｍｏｌ／ｋｇであり、実施例３と同一とした。表２に示すように、研磨速度は２５０００Å／分に低下した。無機酸と保護膜形成剤の添加量（ｍｏｌ／ｋｇ）の比は３．００であり、２．００より大きい値を示す。
(Comparative Example 11)
Sulfuric acid 0.15 mol / kg, phosphoric acid 0.15 mol / kg (total addition amount of inorganic acid 0.30 mol / kg) as inorganic acid, BTA 0.10 mol / kg as protective film forming agent, hydrogen peroxide 9 mass as oxidizing agent %, An oxalic acid 0.20 mol / kg as an organic acid, a colloidal silica 1.00% by mass as an abrasive grain, and a slurry-like copper abrasive with a pH of 2.50 (adjusted with a small amount of NH 3 ) Then, CMP was performed. This abrasive corresponds to the case where the amino acid glycine is removed from the abrasive of Example 3 above. The total amount of inorganic acid added was 0.30 mol / kg, which was the same as in Example 3. As shown in Table 2, the polishing rate decreased to 25000 Å / min. The ratio of the addition amount (mol / kg) of the inorganic acid to the protective film forming agent is 3.00, which is larger than 2.00.
（比較例１２）
無機酸として硫酸０．１５ｍｏｌ／ｋｇ、リン酸０．１５ｍｏｌ／ｋｇ（無機酸の合計添加量０．３０ｍｏｌ／ｋｇ）、アミノ酸としてグリシン０．９５ｍｏｌ／ｋｇ、酸化剤として過酸化水素９質量％、有機酸としてシュウ酸０．２０ｍｏｌ／ｋｇ、砥粒としてコロイダルシリカ１．００質量％を含み、ｐＨを２．５０（少量のＮＨ３で調整）としたスラリー状の銅用研磨剤を用いてＣＭＰを実施した。本研磨剤は、上記実施例３の研磨剤から保護膜形成剤であるＢＴＡを取り除いた場合に相当する。無機酸の合計添加量は０．３０ｍｏｌ／ｋｇであり、実施例３と同一とした。表２に示すように、研磨速度は３００００Å／分に低下した。これは前述したように、保護膜形成剤は銅表面に対して保護膜を形成する作用を有する物質であり、研磨進行時には研磨によって除去されるいわゆる反応層を形成しているものと推察されるためである。
(Comparative Example 12)
0.15 mol / kg sulfuric acid as inorganic acid, 0.15 mol / kg phosphoric acid (total addition amount of inorganic acid 0.30 mol / kg), 0.95 mol / kg as glycine as amino acid, 9% by mass of hydrogen peroxide as oxidant, CMP using a slurry of copper abrasive containing 0.20 mol / kg of oxalic acid as an organic acid, 1.00% by mass of colloidal silica as an abrasive, and having a pH of 2.50 (adjusted with a small amount of NH 3 ). Carried out. This abrasive corresponds to the case where BTA, which is a protective film forming agent, is removed from the abrasive of Example 3 above. The total amount of inorganic acid added was 0.30 mol / kg, which was the same as in Example 3. As shown in Table 2, the polishing rate was reduced to 30000 mm / min. As described above, the protective film forming agent is a substance having a function of forming a protective film on the copper surface, and is presumed to form a so-called reaction layer that is removed by polishing when the polishing progresses. Because.
（比較例１３）
無機酸として硫酸０．１５ｍｏｌ／ｋｇ、リン酸０．１５ｍｏｌ／ｋｇ（無機酸の合計添加量０．３０ｍｏｌ／ｋｇ）、アミノ酸としてＡＤＡ（Ｎ−（２−アセトアミド）イミノ二酢酸）０．５０ｍｏｌ／ｋｇ、保護膜形成剤としてＢＴＡ０．１０ｍｏｌ／ｋｇ、酸化剤として過酸化水素９質量％、有機酸としてシュウ酸０．２０ｍｏｌ／ｋｇ、砥粒としてコロイダルシリカ１．００質量％を含み、ｐＨを２．５０（少量のＮＨ３で調整）としたスラリー状の銅用研磨剤を用いてＣＭＰを実施した。本研磨剤は、上記実施例３におけるアミノ酸をグリシンから高ｐＫａのＡＤＡに変更した場合に相当する。無機酸の合計添加量は０．３０ｍｏｌ／ｋｇであり、実施例３と同一とした。表２に示すように、研磨速度は１２０００Å／分に低下した。無機酸と保護膜形成剤の添加量（ｍｏｌ／ｋｇ）の比は３．００であり、２．００より大きい値を示すが、研磨剤のｐＨがＡＤＡのｐＫａより小さく、ｐＨ＞ＡＤＡのｐＫａの関係を満たしていない。
(Comparative Example 13)
Sulfuric acid 0.15 mol / kg, phosphoric acid 0.15 mol / kg (total addition amount of inorganic acid 0.30 mol / kg) as inorganic acid, ADA (N- (2-acetamido) iminodiacetic acid) 0.50 mol / as amino acid kg, BTA 0.10 mol / kg as a protective film forming agent, hydrogen peroxide 9 mass% as an oxidizing agent, oxalic acid 0.20 mol / kg as an organic acid, colloidal silica 1.00 mass% as an abrasive, pH 2 CMP was performed using a slurry-like copper abrasive that was .50 (adjusted with a small amount of NH 3 ). This abrasive corresponds to the case where the amino acid in Example 3 is changed from glycine to ADA with high pKa. The total amount of inorganic acid added was 0.30 mol / kg, which was the same as in Example 3. As shown in Table 2, the polishing rate was reduced to 12000 kg / min. The ratio of the addition amount (mol / kg) of the inorganic acid to the protective film forming agent is 3.00, which is larger than 2.00, but the pH of the abrasive is smaller than the pKa of ADA, and the pKa of pH> ADA Does not meet the relationship.
以上の結果から、無機酸として少なくとも硫酸及びリン酸の両方を含み、アミノ酸、保護膜形成剤、酸化剤、及び有機酸の添加量を最適化するとともに、使用するアミノ酸及び有機酸の種類等によりｐＨを適切に制御することで、通常の研磨剤に比べて格段に高速な研磨が可能である銅用研磨剤が得られることが分かった。銅に対する研磨速度が４μｍ／分を超える本発明の銅用研磨剤は、特に、短時間で大量の銅を研磨しなければならない用途、例えば化学的機械的研磨によるＴＳＶ等の作製において使用することが可能である。 From the above results, the inorganic acid contains at least both sulfuric acid and phosphoric acid, and the addition amount of amino acid, protective film forming agent, oxidizing agent and organic acid is optimized, and depending on the type of amino acid and organic acid used, etc. It was found that by properly controlling the pH, an abrasive for copper that can be polished much faster than a normal abrasive can be obtained. The copper polishing agent of the present invention having a polishing rate for copper exceeding 4 μm / min is particularly used in applications where a large amount of copper must be polished in a short period of time, for example, TSV by chemical mechanical polishing. Is possible.
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| WO2019030865A1 (en) * | 2017-08-09 | 2019-02-14 | 日立化成株式会社 | Polishing solution and polishing method |
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| JP2008118099A (en) * | 2006-10-11 | 2008-05-22 | Hitachi Chem Co Ltd | Polishing fluid for metal, and method of polishing film to be polished using the polishing fluid |
| WO2009031389A1 (en) * | 2007-09-03 | 2009-03-12 | Jsr Corporation | Aqueous dispersion for chemical mechanical polishing and method for preparing the same, kit for preparing aqueous dispersion for chemical mechanical polishing, and chemical mechanical polishing method for semiconductor device |
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| JP2007150264A (en) * | 2005-10-27 | 2007-06-14 | Hitachi Chem Co Ltd | Organic insulating material, polishing material for copper film compound material, and polishing method |
| JP2008118099A (en) * | 2006-10-11 | 2008-05-22 | Hitachi Chem Co Ltd | Polishing fluid for metal, and method of polishing film to be polished using the polishing fluid |
| WO2009031389A1 (en) * | 2007-09-03 | 2009-03-12 | Jsr Corporation | Aqueous dispersion for chemical mechanical polishing and method for preparing the same, kit for preparing aqueous dispersion for chemical mechanical polishing, and chemical mechanical polishing method for semiconductor device |
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| KR20140119096A (en) * | 2012-02-01 | 2014-10-08 | 히타치가세이가부시끼가이샤 | Polishing fluid for metal and polishing method |
| KR102033495B1 (en) | 2012-02-01 | 2019-10-17 | 히타치가세이가부시끼가이샤 | Polishing liquid for metal and polishing method |
| WO2019030865A1 (en) * | 2017-08-09 | 2019-02-14 | 日立化成株式会社 | Polishing solution and polishing method |
| JPWO2019030865A1 (en) * | 2017-08-09 | 2020-04-16 | 日立化成株式会社 | Polishing liquid and polishing method |
| TWI773803B (en) * | 2017-08-09 | 2022-08-11 | 日商昭和電工材料股份有限公司 | Grinding liquid and grinding method |
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