JP2007180568A - Polishing compound for chemimechanical polishing and polishing method - Google Patents
Polishing compound for chemimechanical polishing and polishing method Download PDFInfo
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- JP2007180568A JP2007180568A JP2007032437A JP2007032437A JP2007180568A JP 2007180568 A JP2007180568 A JP 2007180568A JP 2007032437 A JP2007032437 A JP 2007032437A JP 2007032437 A JP2007032437 A JP 2007032437A JP 2007180568 A JP2007180568 A JP 2007180568A
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- Prior art keywords
- acid
- polishing
- water
- chemical mechanical
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Abstract
Description
本発明は、特に半導体デバイスの配線工程における研磨に好適な、化学機械研磨用の研磨剤と、それを用いた研磨方法とに関する。 The present invention relates to an abrasive for chemical mechanical polishing particularly suitable for polishing in a wiring process of a semiconductor device, and a polishing method using the same.
近年、半導体集積回路（以下ＬＳＩと記す）の高集積化、高性能化に伴って、新たな微細加工技術が開発されており、化学機械研磨（以下ＣＭＰと記す）法もその一つである。ＣＭＰは、ＬＳＩ製造工程、特に多層配線形成工程における層間絶縁膜の平坦化、金属プラグ形成、埋め込み配線形成において頻繁に利用される。この技術については、例えば米国特許第４，９４４，８３６号に開示されている。 In recent years, along with higher integration and higher performance of semiconductor integrated circuits (hereinafter referred to as LSI), new microfabrication techniques have been developed, and chemical mechanical polishing (hereinafter referred to as CMP) is one of them. . CMP is frequently used in planarization of an interlayer insulating film, formation of a metal plug, and formation of a buried wiring in an LSI manufacturing process, particularly in a multilayer wiring forming process. This technique is disclosed, for example, in US Pat. No. 4,944,836.
また、最近はＬＳＩを高性能化するために、配線材料として銅合金の利用が試みられている。しかし、銅合金は従来のアルミニウム合金配線の形成で頻繁に用いられたドライエッチング法による微細加工が困難である。そこで、あらかじめ溝を形成してある絶縁膜上に銅合金薄膜を堆積して埋め込み、溝部以外の銅合金薄膜をＣＭＰにより除去して埋め込み配線を形成する、いわゆるダマシン法が主に採用されている。この技術は、例えば特開平２−２７８８２２号公報に開示されている。 Recently, in order to improve the performance of LSIs, the use of copper alloys as wiring materials has been attempted. However, it is difficult to finely process the copper alloy by the dry etching method frequently used in the formation of the conventional aluminum alloy wiring. Therefore, a so-called damascene method is mainly employed in which a copper alloy thin film is deposited and embedded on an insulating film in which grooves have been formed in advance, and the copper alloy thin film other than the grooves is removed by CMP to form embedded wiring. . This technique is disclosed, for example, in JP-A-2-278822.
金属をＣＭＰにより研磨する一般的な方法は、円形の研磨定盤（プラテン）上に研磨パッドを貼り付け、研磨パッド表面を化学機械研磨用研磨剤で浸し、基体の金属膜を形成した面を押し付けて、その裏面から所定の圧力（以下、研磨圧力と記す）を加えた状態で研磨定盤を回し、研磨剤と金属膜の凸部との機械的摩擦によって凸部の金属膜を除去するものである。 A general method for polishing metal by CMP is to apply a polishing pad on a circular polishing platen (platen), immerse the polishing pad surface with a chemical mechanical polishing abrasive, and form a surface on which the metal film of the substrate is formed. Pressing and turning the polishing platen while applying a predetermined pressure (hereinafter referred to as polishing pressure) from the back surface, and removing the metal film on the convex part by mechanical friction between the abrasive and the convex part of the metal film Is.
ＣＭＰに用いられる研磨剤は、一般には酸化剤及び固体砥粒からなっており、必要に応じてさらに酸化金属溶解剤及び／又は保護膜形成剤が添加される。このＣＭＰ用研磨剤によるＣＭＰの基本的なメカニズムは、まず酸化によって金属膜表面を酸化し、その酸化層を固体砥粒によって削り取るというものであると考えられている。凹部の金属表面の酸化層は研磨パッドにあまり触れず、固体砥粒による削り取りの効果が及ばないので、ＣＭＰの進行とともに凸部の金属層が除去されて、基体表面が平坦化される。この詳細についてはジャ−ナル・オブ・エレクトロケミカルソサエティ誌の第１３８巻１１号（１９９１年発行）の３４６０〜３４６４頁に開示されている。 The abrasive used for CMP is generally composed of an oxidizing agent and solid abrasive grains, and a metal oxide dissolving agent and / or a protective film forming agent is further added as necessary. It is believed that the basic mechanism of CMP by this CMP abrasive is that the surface of the metal film is first oxidized by oxidation and the oxidized layer is scraped off by solid abrasive grains. Since the oxide layer on the metal surface of the recess does not touch the polishing pad so much and the effect of scraping off by the solid abrasive grains does not reach, the metal layer of the protrusion is removed with the progress of CMP, and the substrate surface is flattened. The details are disclosed in Journal of Electrochemical Society, Vol. 138, No. 11 (published in 1991), pages 3460-3464.
ＣＭＰによる研磨速度を高めるには、酸化金属溶解剤を添加することが有効とされている。これは、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により、固体砥粒による削り取りの効果を増すことができるためであると解釈できる。しかし、酸化金属溶解剤を添加すると、凹部の金属膜表面の酸化層も溶解（以下、エッチングと記す）されてしまい、これによって金属膜表面が露出すると、酸化剤により金属膜表面がさらに酸化される。これが繰り返されると、凹部の金属膜のエッチングが進行してしまい、平坦化効果が損なわれることが懸念される。 In order to increase the polishing rate by CMP, it is effective to add a metal oxide solubilizer. This can be interpreted to be because the effect of scraping with the solid abrasive grains can be increased by dissolving the metal oxide grains scraped with the solid abrasive grains into the abrasive. However, when a metal oxide solubilizer is added, the oxide layer on the surface of the metal film in the recess is also dissolved (hereinafter referred to as etching), and when the metal film surface is exposed, the metal film surface is further oxidized by the oxidant. The If this is repeated, there is a concern that the etching of the metal film in the recesses proceeds and the planarization effect is impaired.
これを防ぐため、ＣＭＰ用研磨剤には、さらに保護膜形成剤が添加される。このように酸化金属溶解剤と保護膜形成剤とを添加することにより化学反応の効果を加えることで、ＣＭＰ速度（ＣＭＰによる研磨速度）が向上するとともに、ＣＭＰされる金属層表面の損傷（ダメージ）も低減されるという効果が得られる。 In order to prevent this, a protective film forming agent is further added to the CMP abrasive. Thus, by adding the effect of chemical reaction by adding the metal oxide solubilizer and the protective film forming agent, the CMP rate (polishing rate by CMP) is improved and the damage (damage to the surface of the metal layer to be CMPed) ) Is also reduced.
なお、平坦な被研磨面を得るためには、ＣＭＰ用研磨剤における酸化金属溶解剤と保護膜形成剤との効果のバランスを取ることが重要である。ＣＭＰでは、凹部の金属膜表面の酸化層はあまりエッチングされず、削り取られた酸化層の粒が効率よく溶解される、研磨速度が大きい研磨剤を用いることが望ましい。 In order to obtain a flat surface to be polished, it is important to balance the effects of the metal oxide dissolving agent and the protective film forming agent in the CMP polishing slurry. In CMP, it is desirable to use an abrasive having a high polishing rate, in which the oxide layer on the surface of the metal film in the recess is not etched so much, and the particles of the oxide layer removed are efficiently dissolved.
しかし、従来の固体砥粒を含む化学機械研磨用研磨剤を用いてＣＭＰによる埋め込み配線形成には、
（１）埋め込まれた金属配線の表面中央部分が等方的に腐食されて皿のように窪む現象（以下ディッシングと記す）の発生、
（２）固体砥粒に由来する研磨傷（スクラッチ）の発生、
（３）研磨後の基体表面に残留する固体砥粒を除去するための洗浄プロセスの複雑さ、
（４）固体砥粒そのものの原価や廃液処理によるコストの上昇
等の問題がある。
However, in embedded wiring formation by CMP using a chemical mechanical polishing abrasive containing conventional solid abrasive grains,
(1) Occurrence of a phenomenon in which the central part of the surface of the embedded metal wiring is isotropically corroded and becomes depressed like a dish (hereinafter referred to as dishing),
(2) Generation of polishing scratches (scratches) derived from solid abrasive grains,
(3) Complexity of a cleaning process for removing solid abrasive grains remaining on the substrate surface after polishing,
(4) There are problems such as the cost of the solid abrasive grains themselves and the cost increase due to waste liquid treatment.
そこで、ディッシングや研磨中の銅合金の腐食を抑制し、信頼性の高いＬＳＩ配線を形成するために、グリシン等のアミノ酢酸又はアミド硫酸からなる酸化金属溶解剤及びＢＴＡ（ベンゾトリアゾール）を含有するＣＭＰ用研磨剤を用いる方法が提唱されている。この技術は例えば特開平８−８３７８０号公報に記載されている。 Therefore, in order to suppress the corrosion of the copper alloy during dishing and polishing and to form a highly reliable LSI wiring, it contains a metal oxide solubilizer made of aminoacetic acid or amide sulfuric acid such as glycine and BTA (benzotriazole). A method using an abrasive for CMP has been proposed. This technique is described, for example, in JP-A-8-83780.
しかし、ＢＴＡの保護膜形成効果は非常に高いため、エッチング速度のみならず研磨速度をも顕著に低下させてしまう。従って、エッチング速度は十分に低下させるものの、ＣＭＰ速度は低下させないＣＭＰ用研磨剤が望まれている。 However, since the protective film formation effect of BTA is very high, not only the etching rate but also the polishing rate is significantly reduced. Therefore, there is a demand for an abrasive for CMP that can sufficiently reduce the etching rate but does not decrease the CMP rate.
本発明は、高いＣＭＰ速度を維持しつつ、エッチング速度を十分に低下させることにより、信頼性の高い金属膜の埋め込みパターンを効率よく形成することができる、ＣＭＰ用研磨剤及び研磨方法を提供することを目的とする。 The present invention provides an abrasive for CMP and a polishing method capable of efficiently forming a highly reliable embedded pattern of a metal film by sufficiently reducing an etching rate while maintaining a high CMP rate. For the purpose.
なお、保護膜形成剤には、銅とキレート錯体を生じやすいもの、例えばエチレンジアミンテトラ酢酸、ベンゾトリアゾール等が用いられる。これらの被研磨面に保護膜を形成する効果は極めて強く、例えばＣＭＰ用研磨剤中に０．５重量％以上を含ませると銅合金膜はエッチングはおろかＣＭＰすらされなくなる。 In addition, as the protective film forming agent, one that easily forms a chelate complex with copper, such as ethylenediaminetetraacetic acid, benzotriazole, or the like is used. The effect of forming a protective film on these surfaces to be polished is extremely strong. For example, if 0.5 wt% or more is contained in the CMP abrasive, the copper alloy film is not etched or even CMPed.
これに対して本発明者らは、保護膜形成剤と水溶性ポリマを併用することにより、十分に低いエッチング速度を維持したまま高いＣＭＰ速度が得られることを見出した。しかもこのような研磨剤を用いることにより、研磨剤に固体砥粒を含ませなくとも実用的なＣＭＰ速度での研磨が可能になることを見出した。 On the other hand, the present inventors have found that a high CMP rate can be obtained while maintaining a sufficiently low etching rate by using a protective film forming agent and a water-soluble polymer in combination. Moreover, it has been found that by using such an abrasive, polishing at a practical CMP rate can be performed without including solid abrasive grains in the abrasive.
これは従来の固体砥粒の摩擦による削り取りの効果に代わって、研磨パッドの摩擦による削り取りが起こるためと考えられる。本発明によれば、被研磨物の酸化剤、酸化金属溶解剤、保護膜形成剤及び水を含有する金属研磨剤に水溶性ポリマを添加することによりエッチング速度を維持したままＣＭＰ速度を上昇させることができる。 This is presumably because the polishing by the friction of the polishing pad occurs instead of the effect of the conventional solid abrasive by the friction. According to the present invention, a CMP rate is increased while maintaining an etching rate by adding a water-soluble polymer to a metal abrasive containing an oxidizer, a metal oxide solubilizer, a protective film forming agent, and water. be able to.
なお、エッチング速度の値としては、１０ｎｍ／分以下に抑制できれば好ましい平坦化効果が得られることが分かった。ＣＭＰ速度の低下が許容できる範囲であれば、エッチング速度はさらに低い方が望ましく、５ｎｍ／分以下に抑制できれば、例えば５０％程度の過剰ＣＭＰ（被研磨物をＣＭＰ除去するに必要な時間の１．５倍のＣＭＰを行うこと）を行ってもディッシングは問題とならない程度に留まる。さらにエッチング速度を１ｎｍ／分以下に抑制できれば、１００％以上の過剰ＣＭＰを行ってもディッシングは問題とならない。 It was found that a preferable planarization effect can be obtained if the etching rate can be suppressed to 10 nm / min or less. If the decrease in the CMP rate can be tolerated, the lower etching rate is desirable, and if it can be suppressed to 5 nm / min or less, for example, about 50% excess CMP (one of the time required for removing the polishing target by CMP) (5. CMP is performed), dishing does not become a problem. Further, if the etching rate can be suppressed to 1 nm / min or less, dishing does not cause a problem even if 100% or more of excess CMP is performed.
そこで、本発明では、酸化剤と、酸化金属溶解剤と、保護膜形成剤と、水溶性ポリマと、水とを含有するＣＭＰ用研磨剤と、これを用いる研磨方法とが提供される。 Therefore, the present invention provides an abrasive for CMP containing an oxidizing agent, a metal oxide dissolving agent, a protective film forming agent, a water-soluble polymer, and water, and a polishing method using the same.
なお、さらなるＣＭＰ速度の高速化、高平坦化、ディッシング量の低減、エロージョン量の低減を図るためには、ＣＭＰ用研磨剤がつぎの（１）〜（４）の少なくともいずれかを満たすことが望ましく、全てを満たしていることが特に好ましい。 Note that in order to further increase the CMP speed, increase the flatness, reduce the dishing amount, and reduce the erosion amount, the CMP abrasive must satisfy at least one of the following (1) to (4). Desirably, it is particularly preferred that all are satisfied.
（１）水溶性ポリマの重量平均分子量が５００以上であること。 (1) The weight average molecular weight of the water-soluble polymer is 500 or more.
これにより、エッチング速度を維持したままＣＭＰ速度を上昇させることができる。水溶性ポリマの重量平均分子量は５００以上とすることが好ましく、１５００以上とすることがより好ましく、５０００以上とすることが特に好ましい。重量平均分子量の上限は特に規定するものではないが、溶解性の観点から５００万以下であることが好ましい。 As a result, the CMP rate can be increased while maintaining the etching rate. The weight average molecular weight of the water-soluble polymer is preferably 500 or more, more preferably 1500 or more, and particularly preferably 5000 or more. The upper limit of the weight average molecular weight is not particularly specified, but is preferably 5 million or less from the viewpoint of solubility.
水溶性ポリマーは、同種の水溶性ポリマであっても、異種の水溶性ポリマであってもよいが、重量平均分子量が５００以上の、互いに重量平均分子量が異なる２種以上のポリマーを併用することが好ましい。 The water-soluble polymer may be the same type of water-soluble polymer or a different type of water-soluble polymer, but two or more types of polymers having a weight average molecular weight of 500 or more and different in weight average molecular weight should be used in combination. Is preferred.
なお、重量平均分子量は、ＧＰＣ（ゲルパーミエーション）カラムに水溶性ポリマ水溶液を流すことにより測定して得られる。 The weight average molecular weight is obtained by measuring by flowing a water-soluble polymer aqueous solution through a GPC (gel permeation) column.
（２）研磨剤の動摩擦係数が０．２５以上であること。 (2) The dynamic friction coefficient of the abrasive is 0.25 or more.
保護膜形成剤に水溶性ポリマを併用し、動摩擦係数を０．２５以上とすることによりエッチング速度を維持したままＣＭＰ速度をさらに高速にすることができる。研磨時の圧力を一定にして比較すると、動摩擦係数がより高い金属研磨剤を用いる程、より高いＣＭＰ速度が得られる。 By using a water-soluble polymer in combination with the protective film forming agent and setting the dynamic friction coefficient to 0.25 or more, the CMP rate can be further increased while maintaining the etching rate. When compared with a constant pressure during polishing, a higher CMP rate is obtained as a metal abrasive having a higher coefficient of dynamic friction is used.
なお、ＣＭＰ用研磨剤を介した金属膜と金属研磨布との間の動摩擦係数は、水溶性ポリマを含まない金属用研磨剤１００ｇ中の保護膜形成剤の含有量が０．０００１ｍｏｌ以上の範囲では０．２５未満となることが本発明者らの実験結果から分かっている。 Note that the coefficient of dynamic friction between the metal film and the metal polishing cloth through the CMP polishing slurry is such that the content of the protective film forming agent in 100 g of the metal polishing slurry not containing the water-soluble polymer is 0.0001 mol or more. Then, it is known from the experimental results of the present inventors that it is less than 0.25.
ここで、動摩擦係数は、ウエハ表面の金属膜を研磨する際に、ウエハキャリア部に掛かる力すなわち動摩擦力を、研磨圧力で割ったものである。具体的には、引っ張り応力等の測定値から換算して求める。 Here, the dynamic friction coefficient is obtained by dividing the force applied to the wafer carrier portion when the metal film on the wafer surface is polished, that is, the dynamic friction force, by the polishing pressure. Specifically, it is obtained by converting from measured values such as tensile stress.
なお、本発明のＣＭＰ用研磨剤の動摩擦係数は、０．３５以上とすることがさらに好ましく、０．４５以上とすることが特に好ましい。 The dynamic friction coefficient of the CMP polishing slurry of the present invention is more preferably 0.35 or more, and particularly preferably 0.45 or more.
（３）研磨剤のウベローデ粘度が０．９５ｍＰａ・ｓ（０．９５ｃＰ）以上、１．５ｍＰａ・ｓ（１．５ｃＰ）以下であること。 (3) The Ubbelohde viscosity of the abrasive is 0.95 mPa · s (0.95 cP) or more and 1.5 mPa · s (1.5 cP) or less.
ウベローデ粘度を０．９５〜１．５ｍＰａ・ｓ（０．９５〜１．５ｃＰ）とすることにより、エッチング速度を維持したままＣＭＰ速度をさらに高速化することができる。研磨時の圧力を一定にして比較すると、ウベローデ粘度がより高い研磨剤を用いる程、より高いＣＭＰ速度が得られる。 By setting the Ubbelohde viscosity to 0.95 to 1.5 mPa · s (0.95 to 1.5 cP), the CMP rate can be further increased while maintaining the etching rate. When compared with a constant pressure during polishing, a higher CMP rate can be obtained by using an abrasive having a higher Ubbelohde viscosity.
なお、ウベローデ粘度は、ウベローデ粘度測定用ガラス管中で液温２５℃に保ったＣＭＰ用研磨剤が規定の距離を移動する時間を測定し、移動時間に定数を掛けたものである（ＪＩＳ Ｋ ２２８３）。ウベローデ粘度は、０．９６〜１．３ｍＰａ・ｓ（０．９６〜１．３ｃＰ）とすることがより好ましく、０．９７〜１．０ｍＰａ・ｓ（０．９７〜１．０ｃＰ）とすることが特に好ましい。ウベローデ粘度が０．９５ｍＰａ・ｓ（０．９５ｃＰ）未満ではＣＭＰ速度が低くなってしまう傾向があり、１．５ｍＰａ・ｓ（１．５ｃＰ）を超えるとＣＭＰ速度のウエハ面内均一性が悪くなる傾向がある。 The Ubbelohde viscosity is a value obtained by measuring the time required for the CMP abrasive kept at a liquid temperature of 25 ° C. in a glass tube for measuring the Ubbelohde viscosity to move a specified distance and multiplying the moving time by a constant (JIS K). 2283). The Ubbelohde viscosity is more preferably 0.96 to 1.3 mPa · s (0.96 to 1.3 cP), and 0.97 to 1.0 mPa · s (0.97 to 1.0 cP). Is particularly preferred. When the Ubbelohde viscosity is less than 0.95 mPa · s (0.95 cP), the CMP rate tends to be low. When the Ubbelohde viscosity exceeds 1.5 mPa · s (1.5 cP), the uniformity of the CMP rate within the wafer surface is deteriorated. Tend.
（４）研磨剤の変曲点圧力が５ｋＰａ（５０ｇｆ／ｃｍ２）以上であること。 (4) The inflection point pressure of the abrasive is 5 kPa (50 gf / cm 2 ) or more.
変曲点圧力を５ｋＰａ（５０ｇｆ／ｃｍ２）以上とすることにより、高平坦化、ディッシング量低減及びエロージョン量低減の効果をさらに効果的に発現することができる。なお、変曲点圧力とは、ＣＭＰ速度が急激に立ち上がる研磨圧力のことである。具体的には、ＣＭＰ速度が１０ｎｍ／分以下から５０ｎｍ／分以上に上昇する領域の研磨圧力（中間値）であり、種々の研磨圧力による研磨速度（ＣＭＰ速度）を測定することにより求められる。 By setting the inflection point pressure to 5 kPa (50 gf / cm 2 ) or more, the effects of high planarization, dishing amount reduction, and erosion amount reduction can be more effectively exhibited. The inflection point pressure is a polishing pressure at which the CMP rate suddenly rises. Specifically, it is the polishing pressure (intermediate value) in a region where the CMP rate increases from 10 nm / min or less to 50 nm / min or more, and is obtained by measuring the polishing rate (CMP rate) by various polishing pressures.
変曲点圧力は、５ｋＰａ（５０ｇｆ／ｃｍ２）以上とすることが望ましく、１０ｋＰａ（１００ｇｆ／ｃｍ２）以上とすることがより望ましい。変曲点圧力が５ｋＰａ（５０ｇｆ／ｃｍ２）未満では高平坦化効果が劣る傾向がある。 The inflection point pressure is preferably 5 kPa (50 gf / cm 2 ) or more, and more preferably 10 kPa (100 gf / cm 2 ) or more. When the inflection point pressure is less than 5 kPa (50 gf / cm 2 ), the high planarization effect tends to be inferior.
（図面の簡単な説明）
図１は、実施例における基板研磨工程を示す説明図である。
(Brief description of the drawings)
FIG. 1 is an explanatory view showing a substrate polishing step in the embodiment.
Ａ．研磨剤の組成
本発明のＣＭＰ用研磨剤は、酸化剤と、酸化金属溶解剤と、保護膜形成剤と、水溶性ポリマと、水とを含む。以下、各成分について説明する。
A. Composition of abrasive | polishing agent The abrasive | polishing agent for CMP of this invention contains an oxidizing agent, a metal oxide dissolving agent, a protective film formation agent, a water-soluble polymer, and water. Hereinafter, each component will be described.
（１）酸化剤
本発明のＣＭＰ用研磨剤に含まれる酸化剤は、被研磨物に対して酸化力を有する化合物であり、具体的には、過酸化水素、硝酸、過ヨウ素酸カリウム、次亜塩素酸、オゾン水等が挙げられる。これらのうち、過酸化水素が特に好ましい。これらは単一の化合物を用いてもよく、二以上の化合物を併用してもよい。
(1) Oxidizing agent The oxidizing agent contained in the polishing slurry for CMP of the present invention is a compound having an oxidizing power with respect to an object to be polished. Specifically, hydrogen peroxide, nitric acid, potassium periodate, Examples include chlorous acid and ozone water. Of these, hydrogen peroxide is particularly preferred. These may use a single compound or may use two or more compounds in combination.
基体が集積回路用素子を含むシリコン基板である場合、アルカリ金属、アルカリ土類金属、ハロゲン化物などによる汚染は望ましくないため、酸化剤は不揮発成分を含まないことが望ましいが、オゾン水は組成の時間変化が激しい。このため、本発明には過酸化水素が最も適している。ただし、適用対象の基体が半導体素子を含まないガラス基板などである場合は不揮発成分を含む酸化剤であっても差し支えない。 When the substrate is a silicon substrate including an integrated circuit element, contamination by alkali metal, alkaline earth metal, halide, etc. is not desirable. Therefore, it is desirable that the oxidizing agent does not contain a nonvolatile component, but ozone water has a composition. The time change is intense. For this reason, hydrogen peroxide is most suitable for the present invention. However, when the substrate to be applied is a glass substrate or the like that does not include a semiconductor element, an oxidizing agent that includes a nonvolatile component may be used.
酸化剤成分の配合量は、酸化剤、酸化金属溶解剤、保護膜形成剤、水溶性ポリマ及び水の総量１００ｇに対して、０．００３ｍｏｌ〜０．７ｍｏｌとすることが好ましく、０．０３ｍｏｌ〜０．５ｍｏｌとすることがより好ましく、０．２ｍｏｌ〜０．３ｍｏｌとすることが特に好ましい。この配合量が ０．００３ｍｏｌ未満では、金属の酸化が不十分でＣＭＰ速度が低く、０．７ｍｏｌを超えると、研磨面に荒れが生じる傾向がある。 The blending amount of the oxidant component is preferably 0.003 mol to 0.7 mol with respect to 100 g of the total amount of the oxidant, the metal oxide solubilizer, the protective film forming agent, the water-soluble polymer, and water, It is more preferable to set it as 0.5 mol, and it is especially preferable to set it as 0.2 mol-0.3 mol. If the blending amount is less than 0.003 mol, metal oxidation is insufficient and the CMP rate is low, and if it exceeds 0.7 mol, the polished surface tends to be rough.
（２）酸化金属溶解剤
本発明のＣＭＰ用研磨剤に含まれる酸化金属溶解剤としては、有機酸、有機酸エステル、有機酸のアンモニウム塩及び硫酸のうちの少なくともいずれかが好ましい。
(2) Metal Oxide Solvent As the metal oxide solubilizer contained in the CMP polishing slurry of the present invention, at least one of an organic acid, an organic acid ester, an ammonium salt of an organic acid, and sulfuric acid is preferable.
酸化金属溶解剤は、水溶性のものが望ましく、水溶液の状態で配合してもよい。本発明に好適な酸化金属溶解剤の具体例としては、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、アジピン酸、ピメリン酸、マレイン酸、フタル酸、リンゴ酸、酒石酸、クエン酸等の有機酸、これらの有機酸のエステル、これらの有機酸の塩（アンモニウム塩等）、硫酸、硝酸、アンモニア、アンモニウム塩類（例えば過硫酸アンモニウム、硝酸アンモニウム、塩化アンモニウム等）、クロム酸などが挙げられる。これらは単一の化合物を用いてもよく、二以上の化合物を併用してもよい。 The metal oxide solubilizer is preferably water-soluble and may be blended in the form of an aqueous solution. Specific examples of the metal oxide solubilizer suitable for the present invention 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, salicylic acid, glyceric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, Organic acids such as adipic acid, pimelic acid, maleic acid, phthalic acid, malic acid, tartaric acid, citric acid, esters of these organic acids, salts of these organic acids (such as ammonium salts), sulfuric acid, nitric acid, ammonia, ammonium Examples thereof include salts (for example, ammonium persulfate, ammonium nitrate, ammonium chloride, etc.), chromic acid, and the like. These may use a single compound or may use two or more compounds in combination.
これらのうち、ギ酸、マロン酸、リンゴ酸、酒石酸、クエン酸は、保護膜形成剤とのバランスが得やすい点で好ましく、これらを用いたＣＭＰ用研磨剤は、銅、銅合金、銅酸化物及び／又は銅合金酸化物（以下、これらを総称して銅合金と呼ぶ場合がある）からなる導体（半導体でもよい）層を含む積層膜に対して好適である。特に、リンゴ酸、酒石酸、クエン酸については、実用的なＣＭＰ速度を維持しつつ、エッチング速度を効果的に抑制できるという点で好ましい。 Among these, formic acid, malonic acid, malic acid, tartaric acid, and citric acid are preferable in that they can easily be balanced with a protective film forming agent, and polishing agents for CMP using these are copper, copper alloys, copper oxides And / or a laminated film including a conductor (may be a semiconductor) layer made of a copper alloy oxide (hereinafter may be collectively referred to as a copper alloy). In particular, malic acid, tartaric acid, and citric acid are preferable in that the etching rate can be effectively suppressed while maintaining a practical CMP rate.
本発明における酸化金属溶解剤成分の配合量は、酸化剤、酸化金属溶解剤、保護膜形成剤、水溶性ポリマ及び水の総量１００ｇに対して０〜０．００５ｍｏｌとすることが好ましく、０．００００５ｍｏｌ〜０．００２５ｍｏｌとすることがより好ましく、０．０００５ｍｏｌ〜０．００１５ｍｏｌとすることが特に好ましい。この配合量が０．００５ｍｏｌを超えると、エッチングの抑制が困難となる傾向がある。 The compounding amount of the metal oxide solubilizer component in the present invention is preferably 0 to 0.005 mol with respect to 100 g of the total amount of the oxidizing agent, metal oxide solubilizer, protective film forming agent, water-soluble polymer and water. More preferably, it is 0.0005 mol to 0.0025 mol, and particularly preferably 0.0005 mol to 0.0015 mol. If this amount exceeds 0.005 mol, it tends to be difficult to suppress etching.
（３）保護膜形成剤
保護膜形成剤は、被研磨対象の表面に保護膜を形成するものであり、含窒素化合物（例えば、アンモニア、アルキルアミン、アミノ酸、イミン、アゾール及びこれらの塩）、メルカプタン、グルコース及びセルロースなどが好ましい。
(3) Protective film forming agent The protective film forming agent forms a protective film on the surface of the object to be polished, and contains a nitrogen-containing compound (for example, ammonia, alkylamine, amino acid, imine, azole and salts thereof), Mercaptans, glucose and cellulose are preferred.
本発明に好適な保護膜形成剤の具体例としては、アンモニア；ジメチルアミン、トリメチルアミン、トリエチルアミン、プロピレンジアミン、エチレンジアミンテトラ酢酸（ＥＤＴＡ）、ジエチルジチオカルバミン酸ナトリウム及びキトサン等のアルキルアミン；グリシン、Ｌ−アラニン、β−アラニン、Ｌ−２−アミノ酪酸、Ｌ−ノルバリン、Ｌ−バリン、Ｌ−ロイシン、Ｌ−ノルロイシン、Ｌ−イソロイシン、Ｌ−アロイソロイシン、Ｌ−フェニルアラニン、Ｌ−プロリン、サルコシン、Ｌ−オルニチン、Ｌ−リシン、タウリン、Ｌ−セリン、Ｌ−トレオニン、Ｌ−アロトレオニン、Ｌ−ホモセリン、Ｌ−チロシン、３，５−ジヨ−ド−Ｌ−チロシン、β−（３，４−ジヒドロキシフェニル）−Ｌ−アラニン、Ｌ−チロキシン、４−ヒドロキシ−Ｌ−プロリン、Ｌ−システイン、Ｌ−メチオニン、Ｌ−エチオニン、Ｌ−ランチオニン、Ｌ−シスタチオニン、Ｌ−システイン、Ｌ−システイン酸、Ｌ−アスパラギン酸、Ｌ−グルタミン酸、Ｓ−（カルボキシメチル）−Ｌ−システイン、４−アミノ酪酸、Ｌ−アスパラギン、Ｌ−グルタミン、アザセリン、Ｌ−アルギニン、Ｌ−カナバニン、Ｌ−シトルリン、δ−ヒドロキシ−Ｌ−リシン、クレアチン、Ｌ−キヌレニン、Ｌ−ヒスチジン、１−メチル−Ｌ−ヒスチジン、３−メチル−Ｌ−ヒスチジン、エルゴチオネイン、Ｌ−トリプトファン、アクチノマイシンＣ１、アパミン、アンギオテンシンＩ、アンギオテンシンＩＩ及びアンチパイン等のアミノ酸；ジチゾン、クプロイン（２，２’−ビキノリン）、ネオクプロイン（２，９−ジメチル−１，１０−フェナントロリン）、バソクプロイン（２，９−ジメチル−４，７−ジフェニル−１，１０−フェナントロリン）及びキュペラゾン（ビスシクロヘキサノンオキサリルヒドラゾン）等のイミン；ベンズイミダゾール−２−チオ−ル、トリアジンジチオ−ル、トリアジントリチオ−ル、２−［２−（ベンゾチアゾリル）］チオプロピオン酸、２−［２−（ベンゾチアゾリル）］チオブチル酸、２−メルカプトベンゾチアゾール、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、ベンゾトリアゾール、１−ヒドロキシベンゾトリアゾール、１−ジヒドロキシプロピルベンゾトリアゾール、２，３−ジカルボキシプロピルベンゾトリアゾール、４−ヒドロキシベンゾトリアゾール、４−カルボキシル−１Ｈ−ベンゾトリアゾール、４−カルボキシル−１Ｈ−ベンゾトリアゾールメチルエステル、４−カルボキシル−１Ｈ−ベンゾトリアゾールブチルエステル、４−カルボキシル−１Ｈ−ベンゾトリアゾールオクチルエステル、５−ヘキシルベンゾトリアゾール、［１，２，３−ベンゾトリアゾリル−１−メチル］［１，２，４−トリアゾリル−１−メチル］［２−エチルヘキシル］アミン、トリルトリアゾール、ナフトトリアゾール、ビス［（１−ベンゾトリアゾリル）メチル］ホスホン酸等のアゾール；ノニルメルカプタン及びドデシルメルカプタン等のメルカプタン；並びに、グルコース、セルロース等の糖類が挙げられる。これらは単一の化合物を用いてもよく、二以上の化合物を併用してもよい。 Specific examples of protective film forming agents suitable for the present invention include ammonia; dimethylamine, trimethylamine, triethylamine, propylenediamine, ethylenediaminetetraacetic acid (EDTA), alkyldiamines such as sodium diethyldithiocarbamate and chitosan; glycine, L-alanine , Β-alanine, L-2-aminobutyric acid, L-norvaline, L-valine, L-leucine, L-norleucine, L-isoleucine, L-alloisoleucine, L-phenylalanine, L-proline, sarcosine, L-ornithine , L-lysine, taurine, L-serine, L-threonine, L-allothreonine, L-homoserine, L-tyrosine, 3,5-diiodo-L-tyrosine, β- (3,4-dihydroxyphenyl) -L-alanine, L-thyroxine, 4-hydro X-L-proline, L-cysteine, L-methionine, L-ethionine, L-lanthionine, L-cystathionine, L-cysteine, L-cysteic acid, L-aspartic acid, L-glutamic acid, S- (carboxymethyl) -L-cysteine, 4-aminobutyric acid, L-asparagine, L-glutamine, azaserine, L-arginine, L-canavanine, L-citrulline, δ-hydroxy-L-lysine, creatine, L-quinurenin, L-histidine, Amino acids such as 1-methyl-L-histidine, 3-methyl-L-histidine, ergothioneine, L-tryptophan, actinomycin C1, apamin, angiotensin I, angiotensin II and antipine; dithizone, cuproin (2,2′-biquinoline) ), Neocuproin (2,9 Imines such as dimethyl-1,10-phenanthroline), bathocuproine (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline) and cuperazone (biscyclohexanone oxalyl hydrazone); benzimidazol-2-thiol; Triazine dithiol, triazine trithiol, 2- [2- (benzothiazolyl)] thiopropionic acid, 2- [2- (benzothiazolyl)] thiobutyric acid, 2-mercaptobenzothiazole, 1,2,3-triazole, 1,2,4-triazole, 3-amino-1H-1,2,4-triazole, benzotriazole, 1-hydroxybenzotriazole, 1-dihydroxypropylbenzotriazole, 2,3-dicarboxypropylbenzotriazole, 4- Hydroxybenzoto Riazole, 4-carboxyl-1H-benzotriazole, 4-carboxyl-1H-benzotriazole methyl ester, 4-carboxyl-1H-benzotriazole butyl ester, 4-carboxyl-1H-benzotriazole octyl ester, 5-hexylbenzotriazole, [1,2,3-benzotriazolyl-1-methyl] [1,2,4-triazolyl-1-methyl] [2-ethylhexyl] amine, tolyltriazole, naphthotriazole, bis [(1-benzotriazolyl A) azoles such as methyl) phosphonic acid; mercaptans such as nonyl mercaptan and dodecyl mercaptan; and sugars such as glucose and cellulose. These may use a single compound or may use two or more compounds in combination.
これらの中でも、キトサン、エチレンジアミンテトラ酢酸、Ｌ−トリプトファン、キュペラゾン、トリアジンジチオ−ル、ベンゾトリアゾール、４−ヒドロキシベンゾトリアゾール、４−カルボキシル−１Ｈ−ベンゾトリアゾールブチルエステル、トリルトリアゾール、ナフトトリアゾールは、高いＣＭＰ速度と低いエッチング速度を両立する上で好ましい。 Among these, chitosan, ethylenediaminetetraacetic acid, L-tryptophan, cuperazone, triazinedithiol, benzotriazole, 4-hydroxybenzotriazole, 4-carboxyl-1H-benzotriazole butyl ester, tolyltriazole, and naphthotriazole are high CMP. This is preferable for achieving both a high speed and a low etching speed.
保護膜形成剤の配合量は、酸化剤、酸化金属溶解剤、保護膜形成剤、水溶性ポリマ及び水の総量１００ｇに対して０．０００１ｍｏｌ〜０．０５ｍｏｌとすることが好ましく０．０００３ｍｏｌ〜０．００５ｍｏｌとすることがより好ましく、０．０００５ｍｏｌ〜０．００３５ｍｏｌとすることが特に好ましい。この配合量が０．０００１ｍｏｌ未満では、エッチングの抑制が困難となる傾向があり、０．０５ｍｏｌを超えるとＣＭＰ速度が低くなってしまう傾向がある。 The blending amount of the protective film forming agent is preferably 0.0001 mol to 0.05 mol with respect to 100 g of the total amount of the oxidizing agent, metal oxide solubilizer, protective film forming agent, water-soluble polymer and water. The amount is more preferably 0.005 mol, and particularly preferably 0.0005 mol to 0.0035 mol. If this amount is less than 0.0001 mol, it tends to be difficult to suppress etching, and if it exceeds 0.05 mol, the CMP rate tends to be low.
（４）水溶性ポリマ
本発明に好適な水溶性ポリマとしては、アルギン酸、ペクチン酸、カルボキシメチルセルロース、寒天、カードラン及びプルラン等の多糖類；ポリアスパラギン酸、ポリグルタミン酸、ポリリシン、ポリリンゴ酸、ポリメタクリル酸、ポリメタクリル酸アンモニウム塩、ポリメタクリル酸ナトリウム塩、ポリマレイン酸、ポリイタコン酸、ポリフマル酸、ポリ（ｐ−スチレンカルボン酸）、ポリアクリル酸、ポリアクリルアミド、アミノポリアクリルアミド、ポリアクリル酸メチル、ポリアクリル酸エチル、ポリアクリル酸アンモニウム塩、ポリアクリル酸ナトリウム塩、ポリアミド酸、ポリアミド酸アンモニウム塩、ポリアミド酸ナトリウム塩及びポリグリオキシル酸等のポリカルボン酸、ポリカルボン酸エステル及びその塩；ポリビニルアルコ−ル、ポリビニルピロリドン及びポリアクロレイン等のビニル系ポリマ等が挙げられる。これらは単一の化合物を用いてもよく、二以上の化合物を併用してもよい。
(4) Water-soluble polymer Water-soluble polymers suitable for the present invention include polysaccharides such as alginic acid, pectic acid, carboxymethylcellulose, agar, curdlan and pullulan; polyaspartic acid, polyglutamic acid, polylysine, polymalic acid, polymethacrylic acid Acid, polymethacrylic acid ammonium salt, polymethacrylic acid sodium salt, polymaleic acid, polyitaconic acid, polyfumaric acid, poly (p-styrene carboxylic acid), polyacrylic acid, polyacrylamide, aminopolyacrylamide, polymethyl acrylate, polyacrylic Polycarboxylic acids such as ethyl acrylate, polyacrylic acid ammonium salt, polyacrylic acid sodium salt, polyamic acid, polyamic acid ammonium salt, polyamic acid sodium salt and polyglyoxylic acid, polycarboxylic acid esters and Examples thereof include vinyl polymers such as polyvinyl alcohol, polyvinyl pyrrolidone and polyacrolein. These may use a single compound or may use two or more compounds in combination.
ただし、適用する基体が半導体集積回路用シリコン基板などの場合は、アルカリ金属、アルカリ土類金属、ハロゲン化物等による汚染は望ましくないため、酸又はそのアンモニウム塩が望ましい。基体がガラス基板等である場合はその限りではない。 However, when the substrate to be applied is a silicon substrate for a semiconductor integrated circuit or the like, contamination with an alkali metal, an alkaline earth metal, a halide or the like is not desirable, and thus an acid or an ammonium salt thereof is desirable. This is not the case when the substrate is a glass substrate or the like.
これらの化合物のうち、ペクチン酸、寒天、ポリリンゴ酸、ポリメタクリル酸、ポリアクリル酸、ポリアクリルアミド、ポリビニルアルコール及びポリビニルピロリドン、それらのエステル及びそれらのアンモニウム塩が特に好ましい。 Of these compounds, pectinic acid, agar, polymalic acid, polymethacrylic acid, polyacrylic acid, polyacrylamide, polyvinyl alcohol and polyvinylpyrrolidone, esters thereof and ammonium salts thereof are particularly preferable.
水溶性ポリマの配合量は、酸化剤、酸化金属溶解剤、保護膜形成剤、水溶性ポリマ及び水の総量１００ｇに対して０．００１〜０．３重量％とすることが好ましく０．００３重量％〜０．１重量％とすることがより好ましく０．０１重量％〜０．０８重量％とすることが特に好ましい。この配合量が０．００１重量％未満では、エッチング抑制において保護膜形成剤との併用効果が現れない傾向があり０．３重量％を超えるとＣＭＰ速度が低下してしまう傾向がある。 The blending amount of the water-soluble polymer is preferably 0.001 to 0.3% by weight with respect to 100 g of the total amount of the oxidizing agent, metal oxide solubilizer, protective film forming agent, water-soluble polymer and water. % To 0.1% by weight is more preferable, and 0.01% to 0.08% by weight is particularly preferable. If the blending amount is less than 0.001% by weight, the combined effect with the protective film forming agent tends not to appear in etching suppression, and if it exceeds 0.3% by weight, the CMP rate tends to decrease.
（５）その他
本発明のＣＭＰ研磨剤は、必要に応じて適宜添加剤を含んでいてもよい。固体砥粒は実質的に含まれなくともよいが、含んでいてもよい。なお、砥粒を含まない本発明のＣＭＰ用研磨剤では、固体砥粒よりもはるかに機械的に柔らかい研磨パッドとの摩擦によってＣＭＰが進むため、研磨傷は劇的に低減される。
(5) Others The CMP abrasive | polishing agent of this invention may contain the additive suitably as needed. The solid abrasive grains need not be substantially contained, but may be contained. In the CMP abrasive | polishing agent of this invention which does not contain an abrasive grain, CMP advances by friction with a polishing pad much mechanically softer than a solid abrasive grain, Therefore Abrasion flaw is reduced dramatically.
Ｂ．研磨剤の特徴
本発明の研磨剤は、従来の保護膜形成剤のみを用いた研磨剤とは異なり、固体砥粒による強い機械的摩擦に頼らなくとも、それよりもはるかに柔らかい研磨パッドとの摩擦によってＣＭＰによる平坦化が可能である。
B. Characteristics of the Abrasive The abrasive of the present invention is different from an abrasive using only a protective film forming agent in the past, and does not rely on strong mechanical friction due to solid abrasive grains, but with a much softer polishing pad. Flattening by CMP is possible by friction.
本発明のＣＭＰ用研磨剤では、保護膜形成剤と水溶性ポリマとを併用したことにより、エッチングは抑制されるのに対して、研磨パッドによる摩擦では金属表面保護膜が機能せずにＣＭＰが進行すると推定される。 In the polishing slurry for CMP of the present invention, the etching is suppressed by using the protective film forming agent and the water-soluble polymer in combination, whereas the metal surface protective film does not function by the friction with the polishing pad and the CMP is performed. Presumed to progress.
一般に、ＣＭＰにおいては研磨傷の発生の度合いは固体砥粒の粒径や粒径分布や形状に依存する。また、絶縁膜の削れによる膜厚減少（以下エロージョンと記す）や平坦化効果の劣化も、やはり固体砥粒の粒径や研磨パッドの物理的性質に依存する。 In general, in CMP, the degree of occurrence of polishing flaws depends on the particle size, particle size distribution, and shape of solid abrasive grains. Further, the reduction in film thickness (hereinafter referred to as erosion) and the deterioration of the flattening effect due to the abrasion of the insulating film also depend on the grain size of the solid abrasive grains and the physical properties of the polishing pad.
金属膜、特に銅膜の表面をＢＴＡで処理した場合、金属膜のディッシングは研磨パッドの硬さや研磨剤の化学的性質に依存すると考えられる。すなわち、硬い固体砥粒はＣＭＰの進行には必要ではあるが、ＣＭＰにおける平坦化効果やＣＭＰ面の完全性（研磨傷等の損傷がないこと）を向上させるためには望ましくない。このことから、平坦化効果は実際には固体砥粒よりも柔らかい研磨パッドの特性に依存していることが分かる。 When the surface of a metal film, particularly a copper film, is treated with BTA, the dishing of the metal film is considered to depend on the hardness of the polishing pad and the chemical properties of the polishing agent. That is, hard solid abrasive grains are necessary for the progress of CMP, but are not desirable for improving the planarization effect in CMP and the integrity of the CMP surface (there is no damage such as polishing scratches). From this, it can be seen that the planarization effect actually depends on the characteristics of the polishing pad softer than the solid abrasive grains.
これについて、保護膜形成剤のうちＢＴＡを例として説明する。ＢＴＡを含む液に銅合金膜表面をさらすと、銅又はその酸化物とＢＴＡとの反応により、Ｃｕ（Ｉ）ＢＴＡ又はＣｕ（ＩＩ）ＢＴＡの構造を主骨格とするポリマ状錯化合物皮膜を形成すると考えられる。この皮膜はかなり強固で、ＢＴＡ１重量％を含むＣＭＰ用研磨剤を用いた場合、この研磨剤に固体砥粒が含まれていたとしても、一般にはほとんど研磨されない。また、水溶性ポリマのみをＣＭＰ用研磨剤中に配合し、保護膜形成剤を配合しない場合、特にエッチング速度の抑制が困難となり、保護効果は十分でない。このように保護膜形成剤の種類に応じて異なる種類の保護膜が形成されることは従来から知られていたが、本発明で示した保護膜形成剤と水溶性ポリマの組み合わせであれば高いＣＭＰ速度と低いエッチング速度を両立でき、しかも固体砥粒による強い摩擦をも不要になる。 This will be described using BTA as an example of the protective film forming agent. When the surface of a copper alloy film is exposed to a liquid containing BTA, a polymer complex film having a Cu (I) BTA or Cu (II) BTA structure as a main skeleton is formed by a reaction between copper or an oxide thereof and BTA. I think that. This film is quite strong, and when a CMP abrasive containing 1% by weight of BTA is used, even if solid abrasive is contained in this abrasive, it is generally hardly polished. Further, when only a water-soluble polymer is blended in the CMP abrasive and no protective film forming agent is blended, it becomes difficult to suppress the etching rate, and the protective effect is not sufficient. Thus, it has been conventionally known that different types of protective films are formed depending on the type of protective film forming agent, but the combination of the protective film forming agent and the water-soluble polymer shown in the present invention is high. A CMP rate and a low etching rate can be achieved at the same time, and strong friction due to solid abrasive grains is not required.
従って、本発明のＣＭＰ用研磨剤は、固体砥粒がなくともＣＭＰの進行を実現させたという点で、銅合金のＣＭＰ、延いてはそれを用いた埋め込みパターンの形成に対して、極めて望ましい。 Therefore, the CMP abrasive | polishing agent of this invention is very desirable with respect to CMP of a copper alloy, and also formation of the embedding pattern using the same in the point that progress of CMP was implement | achieved even if there was no solid abrasive grain. .
Ｃ．研磨方法
本発明では、上述の本発明のＣＭＰ用研磨剤を用いて、金属又は金属酸化物の被研磨膜を研磨することにより、被研磨膜の少なくとも一部を除去する研磨方法が提供される。本発明のＣＭＰ用研磨剤は、被研磨膜が銅、銅合金、銅酸化物及び／又は銅合金酸化物を含む積層膜であっても、高速に高平坦化を実現することができる。
C. Polishing Method The present invention provides a polishing method for removing at least a part of a film to be polished by polishing the metal or metal oxide film to be polished using the above-described CMP polishing slurry of the present invention. . The CMP abrasive | polishing agent of this invention can implement | achieve high planarization at high speed, even if a to-be-polished film is a laminated film containing copper, a copper alloy, a copper oxide, and / or a copper alloy oxide.
本発明の研磨方法は、研磨定盤の研磨布上に本発明のＣＭＰ用研磨剤を供給しながら、被研磨膜を有する基板を研磨布に押圧した状態で研磨定盤と基板を相対的に動かすことによって被研磨膜を研磨することができる。 In the polishing method of the present invention, the polishing surface plate and the substrate are relatively moved while the substrate having the film to be polished is pressed against the polishing cloth while supplying the polishing slurry for CMP of the present invention onto the polishing cloth of the polishing surface plate. The film to be polished can be polished by moving the film.
本発明においては、表面に凹部を有する基体上に銅、銅合金（銅／クロム等）を含む金属膜を形成・充填する。この基体を本発明による研磨剤を用いてＣＭＰすると、基体の凸部の金属膜が選択的にＣＭＰされて凹部に金属膜が残され、所望の導体パターンが得られる。 In the present invention, a metal film containing copper or a copper alloy (copper / chromium or the like) is formed and filled on a substrate having a recess on the surface. When this substrate is subjected to CMP using the abrasive according to the present invention, the metal film on the convex portion of the substrate is selectively CMPed to leave the metal film in the concave portion, thereby obtaining a desired conductor pattern.
本発明の研磨方法には、半導体基板などの被研磨物を保持するホルダーと研磨布（パッド）を貼り付けた（回転数が変更可能なモータ等を取り付けてある）定盤とを有する一般的な研磨装置が使用できる。研磨布としては、一般的な不織布、発泡ポリウレタン、多孔質フッ素樹脂などが使用でき、特に制限がない。 The polishing method of the present invention generally includes a holder for holding an object to be polished such as a semiconductor substrate and a surface plate to which a polishing cloth (pad) is attached (a motor or the like whose rotation speed can be changed is attached). A simple polishing apparatus can be used. As an abrasive cloth, a general nonwoven fabric, a polyurethane foam, a porous fluororesin, etc. can be used, and there is no restriction | limiting in particular.
研磨条件には制限はないが、定盤の回転速度は基板が飛び出さないように２００ｒｐｍ以下の低回転が好ましい。被研磨膜を有する半導体基板の研磨布への押しつけ圧力が１０〜１００ｋＰａ（１００〜１０００ｇｆ／ｃｍ２）であることが好ましく、研磨速度のウエハ面内均一性及びパターンの平坦性を満足するためには、１０〜５０ｋＰａ（１００〜５００ｇｆ／ｃｍ２）であることがより好ましい。 The polishing conditions are not limited, but the rotation speed of the surface plate is preferably a low rotation of 200 rpm or less so that the substrate does not jump out. The pressure applied to the polishing cloth of the semiconductor substrate having the film to be polished is preferably 10 to 100 kPa (100 to 1000 gf / cm 2 ). Is more preferably 10 to 50 kPa (100 to 500 gf / cm 2 ).
研磨している間、研磨布にはＣＭＰ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研磨剤で覆われていることが好ましい。 During polishing, a polishing slurry for CMP 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.
研磨終了後の半導体基板は、流水中でよく洗浄後、スピンドライヤ等を用いて半導体基板上に付着した水滴を払い落としてから乾燥させることが好ましい。 The semiconductor substrate after polishing is preferably washed in running water and then dried after removing water droplets adhering to the semiconductor substrate using a spin dryer or the like.
なお、本発明の研磨方法は、半導体デバイスにおける銅合金配線の研磨に好適である。例えば、図１に示すようにシリコンウエハ１０（図１（ａ））の表面に二酸化シリコン膜１１を形成し（図１（ｂ））、この表面に所定のパターンのレジスト層１２を形成して（図１（ｃ））、ドライエッチングにより二酸化シリコン膜１１に凹部１３を形成してレジスト層１２を除去し（図１（ｄ））、二酸化シリコン膜１１表面とシリコンウエハ１０の露出箇所とを覆うように、銅などの金属を蒸着、めっき又はＣＶＤにより成膜して配線層１５（図１（ｅ））とした後、この表面をＣＭＰにより研磨することで、図１（ｆ）に示すように、銅の埋め込み配線１５を有する半導体基板１４が得られる。
（実施例）
The polishing method of the present invention is suitable for polishing copper alloy wiring in a semiconductor device. For example, as shown in FIG. 1, a
(Example)
以下、実施例により本発明を具体的に説明するが、本発明はこれらの実施例により限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited by these Examples.
（１）ＣＭＰ用研磨剤の調製
ＤＬ−リンゴ酸（試薬特級）０．１５重量部に水７０重量部を加えて溶解させ、これにベンゾトリアゾール０．２重量部をメタノール０．８重量部に溶解させた溶液を加えた。さらに、水溶性ポリマ０．０５重量部（固形分量）を加えた（ただし、比較例３のみ、水溶性ポリマーの配合量を１．５重量部とした）。最後に、過酸化水素水（試薬特級、３０重量％水溶液）３３．２重量部を加え、ＣＭＰ用研磨剤を得た。各実施例及び比較例で用いた表面保護剤及び水溶性ポリマを、表１〜３に示す。
(1) Preparation of polishing agent for CMP 70 parts by weight of water was dissolved in 0.15 part by weight of DL-malic acid (special grade reagent), and 0.2 parts by weight of benzotriazole was added to 0.8 parts by weight of methanol. The dissolved solution was added. Furthermore, 0.05 part by weight of water-soluble polymer (solid content) was added (however, only in Comparative Example 3, the blending amount of the water-soluble polymer was 1.5 parts by weight). Finally, 33.2 parts by weight of hydrogen peroxide solution (special grade reagent, 30% by weight aqueous solution) was added to obtain an abrasive for CMP. Tables 1 to 3 show the surface protective agent and the water-soluble polymer used in each Example and Comparative Example.
（２）研磨
得られた研磨剤を用い、つぎの条件でＣＭＰを実施した。
被研磨基体：厚さ１μｍの銅膜を形成したシリコン基板
研磨パッド：ＩＣ１０００（ロデ−ル社製）
研磨圧力：２１ｋＰａ（２１０ｇｆ／ｃｍ２）（変曲点圧力：（０〜５０ｋＰａ（０〜５００ｇｆ／ｃｍ２））
基体と研磨定盤との相対速度：３６ｍ／分
(2) Polishing CMP was carried out using the obtained abrasive under the following conditions.
Substrate to be polished: Silicon substrate polishing pad on which a 1 μm thick copper film is formed: IC1000 (Rodel)
Polishing pressure: 21 kPa (210 gf / cm 2 ) (Inflection point pressure: (0-50 kPa (0-500 gf / cm 2 ))
Relative speed between substrate and polishing surface plate: 36 m / min
（３）研磨品評価項目
ＣＭＰ速度：銅膜のＣＭＰ前後での膜厚差を電気抵抗値から換算して求めた。
エッチング速度：攪拌した研磨剤への浸漬前後の銅層膜厚差を電気抵抗値から換算して求めた。
(3) Polished product evaluation item CMP rate: The film thickness difference of the copper film before and after CMP was calculated from the electrical resistance value.
Etching rate: The difference in thickness of the copper layer before and after immersion in the stirred abrasive was calculated from the electrical resistance value.
（４）評価結果
各実施例及び比較例における、上述の項目についての評価結果を表１〜３に示す。
(4) Evaluation result The evaluation result about the above-mentioned item in each Example and a comparative example is shown to Tables 1-3.
なお、実際のＣＭＰ特性を評価するため、絶縁層中に深さ０．５μｍの溝を形成して公知のスパッタ法によって銅膜を形成して公知の熱処理によって埋め込んだシリコン基板についてＣＭＰを行い、ＣＭＰ後の基体の目視、光学顕微鏡観察、及び電子顕微鏡観察によりエロージョン及び研磨傷発生の有無を確認した。その結果、いずれの実施例でもエロージョン及び研磨傷の発生は見られなかった。 In order to evaluate actual CMP characteristics, CMP is performed on a silicon substrate in which a groove having a depth of 0.5 μm is formed in an insulating layer, a copper film is formed by a known sputtering method, and embedded by a known heat treatment, The presence or absence of erosion and polishing scratches was confirmed by visual inspection of the substrate after CMP, observation with an optical microscope, and observation with an electron microscope. As a result, no erosion or polishing flaw was observed in any of the examples.
研磨剤に保護膜形成剤のみ配合し、水溶性ポリマを配合しなかった比較例１では、ＣＭＰ速度が遅かった。また、水溶性ポリマーのみ配合し、保護膜形成剤を配合しなかった比較例２及び３、並びに、保護膜形成剤と水溶性ポリマーとをいずれも配合しない比較例４では、エッチング速度が速く、その結果、ディッシング量が大きかった。 In Comparative Example 1 in which only the protective film forming agent was blended in the abrasive and no water-soluble polymer was blended, the CMP rate was slow. Also, in Comparative Examples 2 and 3 in which only the water-soluble polymer was blended and no protective film forming agent was blended, and in Comparative Example 4 in which neither the protective film forming agent and the water-soluble polymer were blended, the etching rate was fast, As a result, the dishing amount was large.
これらに対し、保護膜形成剤と水溶性ポリマーとを併用した実施例１〜１４では、エッチング速度が遅いにもかかわらず、ＣＭＰ速度が速く、研磨時間を短縮できた。しかも、ディッシング量が小さく、高平坦化できた。なお、水溶性ポリマの分子量が５００以下である実施例３に比べて、５００以上である実施例４〜６はＣＭＰ速度が速く、水溶性ポリマの分子量は５００以上であることが好ましいことがわかった。 On the other hand, in Examples 1 to 14 in which the protective film forming agent and the water-soluble polymer were used in combination, the CMP rate was high and the polishing time could be shortened despite the low etching rate. In addition, the dishing amount was small and high flatness was achieved. In addition, it turns out that it is preferable that Example 4-6 which is 500 or more has a high CMP rate, and the molecular weight of water-soluble polymer is 500 or more compared with Example 3 whose molecular weight of water-soluble polymer is 500 or less. It was.
また、動摩擦係数が０．１６と０．２５より低い比較例１では、ＣＭＰ速度が遅かった。さらに、動摩擦係数が０．２３と低い比較例４の研磨剤でも、ＣＭＰ速度に比べてエッチング速度が速いためディッシング量が大きかった。ウベローデ粘度が０．９４ｍＰａ・ｓ（０．９４ｃＰ）と０．９５より低い比較例１及び４では、ＣＭＰ速度が遅かった。また、変曲点圧力が５ｋＰａ（５０ｇｆ／ｃｍ２）より低い２ｋＰａ（２０ｇｆ／ｃｍ２）の比較例１では、ＣＭＰ速度が遅かった。また、変曲点圧力が存在しなかった比較例２〜４では、エッチング速度が速く、その結果ディッシング量が大きかった。 In Comparative Example 1 in which the dynamic friction coefficient was lower than 0.16 and 0.25, the CMP rate was slow. Furthermore, even with the abrasive of Comparative Example 4 having a low dynamic friction coefficient of 0.23, the dishing amount was large because the etching rate was faster than the CMP rate. In Comparative Examples 1 and 4 in which the Ubbelohde viscosity is 0.94 mPa · s (0.94 cP), which is lower than 0.95, the CMP rate was slow. Further, in Comparative Example 1 where the inflection point pressure was 2 kPa (20 gf / cm 2 ) lower than 5 kPa (50 gf / cm 2 ), the CMP rate was slow. Further, in Comparative Examples 2 to 4 where the inflection point pressure did not exist, the etching rate was high, and as a result, the dishing amount was large.
上述のように、本発明のＣＭＰ用研磨剤によれば、信頼性の高い金属膜の埋め込みパターンを効率よく形成することができる。 As described above, according to the polishing slurry for CMP of the present invention, a highly reliable embedded pattern of a metal film can be efficiently formed.
Claims (10)
前記酸化剤と、前記酸化金属溶解剤と、前記保護膜形成剤と、前記水溶性ポリマとは、互いに異なり、
前記酸化金属溶解剤は、有機酸、有機酸エステル、有機酸のアンモニウム塩及び硫酸のうちの少なくとも１種から選択され、
前記保護膜形成剤は、含窒素化合物、メルカプタン、グルコース及びセルロースのうちの少なくとも１種から選択され、
前記水溶性ポリマは、多糖類、ポリカルボン酸、ポリカルボン酸エステル、ポリカルボン酸塩及びビニル系ポリマのうちの少なくとも１種から選択され、
前記水溶性ポリマの重量平均分子量は、１５００以上９００００以下である、
金属又は金属酸化物の被研磨膜を研磨する化学機械研磨用研磨剤。 Contains an oxidizing agent, a metal oxide solubilizer, a protective film forming agent, a water-soluble polymer, and water,
The oxidizing agent, the metal oxide solubilizer, the protective film forming agent, and the water-soluble polymer are different from each other,
The metal oxide solubilizer is selected from at least one of organic acids, organic acid esters, ammonium salts of organic acids and sulfuric acid,
The protective film forming agent is selected from at least one of nitrogen-containing compounds, mercaptans, glucose and cellulose,
The water-soluble polymer is selected from at least one of polysaccharides, polycarboxylic acids, polycarboxylic acid esters, polycarboxylates, and vinyl polymers,
The water-soluble polymer has a weight average molecular weight of 1500 or more and 90000 or less.
A chemical mechanical polishing abrasive for polishing a metal or metal oxide film to be polished.
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