JP5493528B2 - CMP polishing liquid and polishing method using this CMP polishing liquid - Google Patents
CMP polishing liquid and polishing method using this CMP polishing liquid Download PDFInfo
- Publication number
- JP5493528B2 JP5493528B2 JP2009166967A JP2009166967A JP5493528B2 JP 5493528 B2 JP5493528 B2 JP 5493528B2 JP 2009166967 A JP2009166967 A JP 2009166967A JP 2009166967 A JP2009166967 A JP 2009166967A JP 5493528 B2 JP5493528 B2 JP 5493528B2
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- JP
- Japan
- Prior art keywords
- polishing
- polishing liquid
- abrasive grains
- copper
- cmp
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 238000005498 polishing Methods 0.000 title claims description 217
- 239000007788 liquid Substances 0.000 title claims description 122
- 238000000034 method Methods 0.000 title claims description 46
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- 239000010949 copper Substances 0.000 claims description 48
- 239000000758 substrate Substances 0.000 claims description 46
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- 229910052802 copper Inorganic materials 0.000 claims description 43
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Images
Description
本発明は、ＣＭＰ研磨液及びこのＣＭＰ研磨液を用いた研磨方法に関する。 The present invention relates to a CMP polishing liquid and a polishing method using the CMP polishing liquid.
半導体集積回路（以下、「ＬＳＩ」という。）で代表される半導体デバイスの開発において、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（Ｃｈｅｍｉｃａｌ Ｍｅｃｈａｎｉｃａｌ Ｐｏｌｉｓｈｉｎｇ）」という。）等の種々の技術が用いられてきている。主に、ＣＭＰは、シリコン、ガリウム砒素等からなるウエハ表面に形成された、酸化膜、金属膜、セラミックス膜等の多層配線形成用の薄膜を平坦化するために利用されている（例えば、特許文献１参照）。このように、ウエハ表面に配線の高密度化及び微細化が更に進んだ多層配線が形成された超ＬＳＩを製造する上で、ＣＭＰは必要不可欠な技術になっている。 In the development of semiconductor devices represented by semiconductor integrated circuits (hereinafter referred to as “LSI”), new microfabrication techniques have been developed along with higher integration and higher performance, and chemical mechanical polishing (hereinafter referred to as “ Various techniques such as CMP (Chemical Mechanical Polishing) have been used. CMP is mainly used to planarize a thin film for forming a multilayer wiring such as an oxide film, a metal film, and a ceramic film formed on a wafer surface made of silicon, gallium arsenide, or the like (for example, patents). Reference 1). As described above, CMP is an indispensable technique for manufacturing a VLSI having multilayer wiring on which the wiring density is further increased and miniaturized on the wafer surface.
従来、配線用の金属として、タングステン、アルミニウム、アルミニウム合金等がインタコネクト構造体に汎用されてきたが、近年では、ＬＳＩの更なる高性能化のために、これらの金属より配線抵抗の低い銅又は銅合金の利用が試みられている。しかし、銅又は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、あらかじめ溝部（凹部）及び隆起部（凸部）が形成された絶縁膜上に銅又は銅合金の薄膜を堆積して溝部に銅又は銅合金を埋め込み、次いで、隆起部上に堆積した銅又は銅合金薄膜（溝部以外の薄膜）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（例えば、特許文献２参照）。 Conventionally, tungsten, aluminum, aluminum alloys, etc. have been widely used for interconnect structures as wiring metals, but in recent years, copper with lower wiring resistance than these metals has been used to further enhance the performance of LSIs. Or the utilization of a copper alloy is tried. However, it is difficult to finely process copper or a copper alloy by a dry etching method frequently used in forming a conventional aluminum alloy wiring. Therefore, a copper or copper alloy thin film is deposited on an insulating film in which grooves (concave portions) and ridges (convex portions) are formed in advance, and copper or copper alloy is embedded in the grooves, and then the copper deposited on the ridges. Alternatively, a so-called damascene method is mainly employed in which a copper alloy thin film (thin film other than the groove) is removed by CMP to form a buried wiring (see, for example, Patent Document 2).
銅又は銅合金を研磨するために、これまで様々なＣＭＰ研磨液の開発が試みられてきた。銅又は銅合金を研磨するためのＣＭＰ研磨液は、一般に、酸化金属溶解剤、酸化剤、砥粒を含む。このような研磨液では、砥粒の機械的作用により、研磨後の被研磨体の表面（以下、「研磨面」という。）の平坦性が低下する可能性がある。平坦性が低下する要因としては、研磨面に傷が生じる現象（スクラッチ）、研磨面全体が必要以上に研磨される現象（シニング）、金属配線部分の中央が深く研磨されて皿状のくぼみが生じ、研磨面の金属配線部分が平坦でなくなる現象（ディッシング）、金属配線間の隆起部の絶縁膜が必要以上に研磨されたうえ、金属配線部分の中央に皿状のくぼみが生じる現象（エロージョン）等がある。 In order to polish copper or a copper alloy, development of various CMP polishing liquids has been attempted so far. A CMP polishing liquid for polishing copper or a copper alloy generally contains a metal oxide dissolving agent, an oxidizing agent, and abrasive grains. In such a polishing liquid, the flatness of the surface of the polished object after polishing (hereinafter referred to as “polishing surface”) may decrease due to the mechanical action of the abrasive grains. Factors that reduce flatness include a phenomenon in which the polished surface is scratched (scratch), a phenomenon in which the entire polished surface is polished more than necessary (thinning), and the center of the metal wiring portion is deeply polished, resulting in a dish-shaped dent. Phenomenon that occurs when the metal wiring part of the polished surface is not flat (dishing), the insulating film at the raised part between the metal wirings is polished more than necessary, and a dish-shaped dent occurs in the center of the metal wiring part (erosion) ) Etc.
このような平坦性の悪化を抑制するために、銅又は銅合金に対する防食剤や、水溶性ポリマ等をＣＭＰ研磨液に添加することにより、銅又は銅合金表面に保護膜を形成する方法が提唱されている（例えば、特許文献３参照。）。また、平坦性の悪化を抑制するために、砥粒の会合度が１０以下（会合度が１、すなわち単分散の場合も含む。）であり、界面活性剤や親水性ポリマを構成成分として含有する研磨液が知られている（例えば、特許文献４参照）。 In order to suppress such deterioration of flatness, a method for forming a protective film on the surface of copper or copper alloy by adding a corrosion inhibitor for copper or copper alloy, a water-soluble polymer, or the like to the CMP polishing liquid is proposed. (For example, see Patent Document 3). Further, in order to suppress deterioration in flatness, the degree of association of abrasive grains is 10 or less (including the case where the degree of association is 1, that is, monodisperse), and a surfactant or a hydrophilic polymer is contained as a constituent component. A polishing liquid is known (see, for example, Patent Document 4).
近年、半導体デバイスの薄型化や小型化、それに伴う配線の微細化がより進んでおり、良好なＣＭＰ速度と研磨後の研磨面の平坦性とを一層高水準で両立することが要求されている。例えば、上記特許文献４等ではディッシングの発生量は上限値２００ｎｍまで許容されているが、良好なＣＭＰ速度を維持しつつ、ディッシング量を更に低減してより高いレベルでの平坦性を達成することが要求されるようになってきている。
In recent years, semiconductor devices have been made thinner and smaller, and the finer wiring associated therewith, and it has been required to achieve both a good CMP rate and flatness of the polished surface after polishing at a higher level. . For example, in the
本発明の目的は、このような実情に鑑みてなされたものであり、良好なＣＭＰ速度が得られると共に、従来のＣＭＰ研磨液よりも優れた平坦性が得られるＣＭＰ研磨液及びこれを用いた研磨方法を提供するものである。 The object of the present invention has been made in view of such circumstances, and a CMP polishing liquid capable of obtaining a good CMP rate and a flatness superior to that of a conventional CMP polishing liquid, and the same are used. A polishing method is provided.
本発明者らは、上記課題を解決すべく鋭意研究を重ねた結果、砥粒、酸化金属溶解剤、酸化剤、防食剤、水溶性ポリマ及び水を含有し、ｐＨが７以下であり、砥粒がアニオン処理されており、かつ、砥粒が所定の粒子径を有するＣＭＰ研磨液を用いることで、銅に対する優れた研磨速度と平坦性とを両立できることを見いだした。なお、特に断りのない限り、本発明でいう「銅」には、純銅の他、銅合金、銅の酸化物及び銅合金の酸化物等が包含される。 As a result of intensive studies to solve the above problems, the inventors of the present invention contain abrasive grains, a metal oxide solubilizer, an oxidizer, an anticorrosive, a water-soluble polymer and water, and have a pH of 7 or less. It has been found that by using a CMP polishing liquid in which the grains are anion-treated and the abrasive grains have a predetermined particle diameter, both excellent polishing rate and flatness for copper can be achieved. Unless otherwise specified, “copper” as used in the present invention includes pure copper, copper alloy, copper oxide, copper alloy oxide, and the like.
本発明は、銅を含む金属を研磨するためのＣＭＰ研磨液であって、該ＣＭＰ研磨液は、砥粒、酸化金属溶解剤、酸化剤、防食剤、水溶性ポリマ及び水を含有し、ＣＭＰ研磨液のｐＨが７以下であり、砥粒がアニオン処理されており、砥粒の平均一次粒子径が１０〜８０ｎｍであり、砥粒の平均二次粒子径が２５〜２５０ｎｍであり、平均二次粒子径を平均一次粒子径で除して求められる会合度が２．３以上であるＣＭＰ研磨液である。 The present invention is a CMP polishing liquid for polishing a metal containing copper, and the CMP polishing liquid contains abrasive grains, a metal oxide dissolving agent, an oxidizing agent, an anticorrosive, a water-soluble polymer, and water. The pH of the polishing liquid is 7 or less, the abrasive grains are anion-treated, the average primary particle diameter of the abrasive grains is 10 to 80 nm, the average secondary particle diameter of the abrasive grains is 25 to 250 nm, The CMP polishing liquid has a degree of association determined by dividing the secondary particle diameter by the average primary particle diameter of 2.3 or more.
このようなＣＭＰ研磨液によって、良好なＣＭＰ速度が得られると共に、従来のＣＭＰ研磨液よりも優れた平坦性が得られる原因は詳細には不明であるが、本発明者らは以下のように推察している。但し、原因が以下の内容に限定されるものではない。 The reason why such a CMP polishing liquid can provide a good CMP rate and a flatness superior to that of the conventional CMP polishing liquid is unknown in detail, but the present inventors are as follows. I guess. However, the cause is not limited to the following contents.
本発明の研磨液を用いた研磨の基本的なメカニズムは、酸化金属溶解剤を添加しｐＨを７以下（好ましくは酸性側）にした上で、酸化剤で銅の表面を酸化して酸化層を形成し、その酸化層を砥粒によって削り取るものであると考えられる。そして、水溶性ポリマと防食剤との作用によって、比較的研磨されやすい反応層が銅表面に形成されると推定される。このように形成された反応層を、上記特定の条件を満たす砥粒で研磨することにより、平坦性を損なうことなく、良好な研磨速度で銅を研磨することができると考えられる。 The basic mechanism of polishing using the polishing liquid of the present invention is that an oxide layer is formed by oxidizing a copper surface with an oxidizing agent after adding a metal oxide solubilizing agent to a pH of 7 or less (preferably on the acidic side). It is considered that the oxide layer is scraped off by abrasive grains. It is estimated that a reaction layer that is relatively easily polished is formed on the copper surface by the action of the water-soluble polymer and the anticorrosive. By polishing the reaction layer thus formed with abrasive grains satisfying the above specific conditions, it is considered that copper can be polished at a good polishing rate without impairing the flatness.
本発明では、ＣＭＰ研磨液における砥粒の含有量が１質量％以下であることが好ましい。 In this invention, it is preferable that content of the abrasive grain in CMP polishing liquid is 1 mass% or less.
本発明では、酸化金属溶解剤が無機酸及び有機酸からなる群より選ばれた少なくとも１種の酸又はその塩であることが好ましい。 In the present invention, the metal oxide solubilizer is preferably at least one acid selected from the group consisting of inorganic acids and organic acids or salts thereof.
本発明では、防食剤がトリアゾール化合物であることが好ましい。 In the present invention, the anticorrosive agent is preferably a triazole compound.
本発明では、トリアゾール化合物がベンゾトリアゾール、１，２，３−トリアゾール、４−アミノ−１，２，３−トリアゾール、４，５−ジアミノ−１，２，３−トリアゾール、１，２，４−トリアゾール、３−アミノ−１，２，４−トリアゾール、及び３，５−ジアミノ−１，２，４−トリアゾールからなる群より選ばれる少なくとも１種であることが好ましい。 In the present invention, the triazole compound is benzotriazole, 1,2,3-triazole, 4-amino-1,2,3-triazole, 4,5-diamino-1,2,3-triazole, 1,2,4- It is preferably at least one selected from the group consisting of triazole, 3-amino-1,2,4-triazole, and 3,5-diamino-1,2,4-triazole.
本発明では、水溶性ポリマが、アクリル酸系化合物をモノマとして含む前駆体成分を重合して得られる水溶性ポリマであることが好ましい。 In the present invention, the water-soluble polymer is preferably a water-soluble polymer obtained by polymerizing a precursor component containing an acrylic acid compound as a monomer.
本発明では、ＣＭＰ研磨液のｐＨが２〜５であることが好ましい。 In the present invention, the CMP polishing liquid preferably has a pH of 2 to 5.
本発明では、銅を含む金属が銅、銅合金、銅の酸化物及び銅合金の酸化物からなる群より選ばれる少なくとも１種であることが好ましい。 In the present invention, the metal containing copper is preferably at least one selected from the group consisting of copper, copper alloys, copper oxides, and copper alloy oxides.
また、本発明は、銅を含む金属層を表面に有する基板と、研磨布（研磨パッド）との間に、上記ＣＭＰ研磨液を供給し、銅を含む金属層の少なくとも一部を研磨する研磨方法を提供する。 The present invention also provides polishing for supplying at least a part of a metal layer containing copper by supplying the CMP polishing liquid between a substrate having a metal layer containing copper on the surface and a polishing cloth (polishing pad). Provide a method.
本発明の研磨方法では、上記研磨液を用いていることにより、良好なＣＭＰ速度が得られると共に、従来のＣＭＰ研磨液よりも優れた平坦性が得られる。これにより、微細化、薄膜化、寸法精度に優れ、信頼性の高い、低コストの半導体デバイス等を好適に製造することができる。 In the polishing method of the present invention, by using the above polishing liquid, a good CMP rate can be obtained, and flatness superior to the conventional CMP polishing liquid can be obtained. Thereby, it is possible to suitably manufacture a semiconductor device or the like that is excellent in miniaturization, thinning, dimensional accuracy, high reliability, and low cost.
本発明によれば、銅を含む金属を、高速且つ平坦性良く研磨することができるＣＭＰ研磨液を提供することができる。また、本発明によれば、上記のＣＭＰ研磨液を用いて、微細化、薄膜化、寸法精度に優れ、信頼性の高い、低コストの半導体デバイス等の製造における研磨方法を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the CMP polishing liquid which can grind | polish the metal containing copper with high-speed and sufficient flatness can be provided. Further, according to the present invention, it is possible to provide a polishing method in the manufacture of a semiconductor device or the like that is excellent in miniaturization, thinning, dimensional accuracy, high reliability, and low cost by using the above-described CMP polishing liquid. .
本発明のＣＭＰ研磨液は、銅を含む金属を研磨するためのＣＭＰ研磨液であって、該ＣＭＰ研磨液は、砥粒、酸化金属溶解剤、酸化剤、防食剤、水溶性ポリマ及び水を含有する。以下、発明を実施するための最良の具体的態様について詳細に説明する。 The CMP polishing liquid of the present invention is a CMP polishing liquid for polishing a metal containing copper, and the CMP polishing liquid contains abrasive grains, a metal oxide dissolving agent, an oxidizing agent, an anticorrosive, a water-soluble polymer, and water. contains. Hereinafter, the best specific mode for carrying out the invention will be described in detail.
（ｐＨ）
ＣＭＰ研磨液のｐＨは、７以下であり、７未満が好ましく、１〜６がより好ましく、２〜５が更に好ましい。ＣＭＰ研磨液のｐＨは、後述する酸化金属溶解剤として用いられる化合物をｐＨ調整剤として添加することにより調整することができる。もちろん、ｐＨ調整剤を含まずにＣＭＰ研磨液のｐＨが７以下である場合には、ｐＨ調整剤を含有する必要はない。
(PH)
The pH of the CMP polishing liquid is 7 or less, preferably less than 7, more preferably 1 to 6, and still more preferably 2 to 5. The pH of the CMP polishing liquid can be adjusted by adding a compound used as a metal oxide solubilizer described later as a pH adjuster. Of course, when the pH of the CMP polishing liquid is 7 or less without including the pH adjusting agent, it is not necessary to contain the pH adjusting agent.
ＣＭＰ研磨液のｐＨは、ｐＨメータ（例えば、堀場製作所株式会社製、型番Ｆ・８０）で測定することができる。ｐＨとしては、標準緩衝液（フタル酸塩ｐＨ緩衝液ｐＨ：４．０１（２５℃）、中性りん酸塩ｐＨ緩衝液ｐＨ６．８６（２５℃））を用いて、２点校正した後、電極をＣＭＰ研磨液に入れて、２分以上経過して安定した後の値を採用することができる。 The pH of the CMP polishing liquid can be measured with a pH meter (for example, model number F · 80, manufactured by Horiba, Ltd.). The pH was calibrated at two points using a standard buffer (phthalate pH buffer pH: 4.01 (25 ° C.), neutral phosphate pH buffer pH 6.86 (25 ° C.)). The value after the electrode is put into the CMP polishing liquid and stabilized after 2 minutes or more can be adopted.
（１．砥粒）
砥粒の材質としては特に制限はなく、例えば、シリカ、アルミナ等を挙げることができる。中でも、粒子径の制御が容易であり、平坦性に優れた研磨液が得られる点で、シリカが好ましく、コロイダルシリカがより好ましい。
(1. Abrasive grains)
There is no restriction | limiting in particular as a material of an abrasive grain, For example, a silica, an alumina, etc. can be mentioned. Among these, silica is preferable and colloidal silica is more preferable in that it is easy to control the particle size and a polishing liquid having excellent flatness can be obtained.
（２．アニオン処理）
本実施形態のＣＭＰ研磨液における砥粒は、通常の砥粒と異なり、アニオン処理されている必要がある。研磨対象である銅表面に形成される反応層がアニオン性であることから、砥粒表面にアニオン処理を行うことで、砥粒と反応層とが互いに反発し合い、砥粒が過剰に銅表面と接触することが抑制され、研磨後の銅表面の平坦性を向上させることができると考えられる。ここで、「アニオン処理」とは、酸性領域においてマイナスイオンを形成しやすい構造を、砥粒表面に付与する処理を意味する。別の観点では、ｐＨが７以下であるＣＭＰ研磨液において、砥粒のゼータ電位がマイナス、好ましくは−５ｍV以下になるように、砥粒にアニオン種を付加する処理を意味する。なお、ゼータ電位は、ＺＥＴＡＳＩＺＥＲ ３０００ ＨＡＳ（マルバーンインスツルメンツ製、商品名）を用いて測定することができる。
(2. Anion treatment)
Unlike normal abrasive grains, the abrasive grains in the CMP polishing liquid of this embodiment must be anion-treated. Since the reaction layer formed on the copper surface to be polished is anionic, the anion treatment is performed on the abrasive grain surface so that the abrasive grain and the reactive layer repel each other, and the abrasive grains are excessive in the copper surface. It is considered that contact with the copper is suppressed, and the flatness of the copper surface after polishing can be improved. Here, the “anion treatment” means a treatment for imparting a structure that easily forms negative ions in the acidic region to the abrasive grain surface. In another aspect, in a CMP polishing liquid having a pH of 7 or less, it means a process of adding an anionic species to the abrasive grains so that the zeta potential of the abrasive grains is negative, preferably −5 mV or lower. The zeta potential can be measured using ZETASIZER 3000 HAS (trade name, manufactured by Malvern Instruments).
アニオン処理について、シリカを砥粒として使用する場合を例に説明する。シリカは、一般式ではＳｉＯ２であるが、その末端（表面）にはいくつかのシラノール基（Ｓｉ−ＯＨ基）が存在している。このシラノール基における水素原子は、酸性領域においてほとんど解離しないため、通常のシリカ粒子は、酸性領域において、プラス又はゼロに近いゼータ電位を示す。ここで、前記シラノール基に、アニオン種を反応させることによって、表面にシラノール基よりもマイナスイオンを生じやすい基が存在するシリカ粒子を得ることができる。 An anion treatment will be described using a case where silica is used as an abrasive. Silica is SiO 2 in general formula, but some silanol groups (Si—OH groups) are present at the terminal (surface). Since the hydrogen atom in this silanol group hardly dissociates in the acidic region, ordinary silica particles exhibit a zeta potential close to plus or zero in the acidic region. Here, by reacting the silanol group with an anionic species, silica particles having a group that is more likely to generate a negative ion than the silanol group can be obtained on the surface.
このようなアニオン種としては、例えば、アルミン酸カリウム（ＡｌＯ（ＯＨ）２Ｋ）等のアルミニウム化合物を挙げることができる。より具体的には、例えば、コロイダルシリカを含む液中に上記アルミン酸カリウムを添加し、６０℃以上で還流することで、シラノール基をよりイオン化しやすい基（Ｓｉ−Ｏ−Ａｌ（ＯＨ）２）にすることができる。 Examples of such anionic species include aluminum compounds such as potassium aluminate (AlO (OH) 2 K). More specifically, for example, by adding the potassium aluminate to a liquid containing colloidal silica and refluxing at 60 ° C. or higher, a group (Si—O—Al (OH) 2 ) that can easily ionize a silanol group. ).
アニオン処理方法としては、他にも、砥粒（研磨粒子）表面に微量金属種（例えば、チタンやジルコニウム等）を付加する方法、コロイダルシリカ等の砥粒に硫酸を添加し反応させることによって砥粒表面にスルホン酸基を導入する方法、カルボキシル基、スルホン酸基等のアニオン性基を有する水溶性ポリマで砥粒を被覆する方法等を挙げることができる。処理が簡便である点では、上記アルミン酸カリウム処理が好ましい。ＣＭＰ研磨液中に不純物が混入しづらく、また、ＣＭＰ研磨液の安定性に優れる点で、砥粒表面にスルホン酸基を導入する方法が好ましい。 Other anion treatment methods include adding trace metal species (eg, titanium, zirconium, etc.) to the surface of abrasive grains (abrasive particles), adding sulfuric acid to abrasive grains such as colloidal silica, and reacting them. Examples thereof include a method of introducing a sulfonic acid group on the surface of the grain, a method of coating abrasive grains with a water-soluble polymer having an anionic group such as a carboxyl group and a sulfonic acid group. In terms of simple treatment, the potassium aluminate treatment is preferred. A method of introducing a sulfonic acid group to the surface of the abrasive grains is preferable because impurities are not easily mixed in the CMP polishing liquid and the stability of the CMP polishing liquid is excellent.
（３．平均一次粒子径）
ＣＭＰ研磨液に使用する砥粒としては、平均一次粒子径が１０〜８０ｎｍのものを使用する。このような砥粒を使用することにより、優れた平坦性を維持しつつ、良好な研磨速度を得ることができる。平均一次粒子径は、研磨速度の観点では大きいことが好ましく、具体的には、１５ｎｍ以上がより好ましく、２５ｎｍ以上が更に好ましい。平坦性（特にディッシング）を小さくし、更に砥粒同士が過剰に凝集するのを防ぐ観点では、７０ｎｍ以下が好ましく、６０ｎｍ以下がより好ましい。しかしながら、平均一次粒子径が小さくなるほど、研磨速度は低下する傾向があるので、用途や必要とされる研磨速度及び平坦性に応じて、平均一次粒子径を前記範囲において適宜設定することが好ましい。
(3. Average primary particle size)
As an abrasive grain used for CMP polishing liquid, a thing with an average primary particle diameter of 10-80 nm is used. By using such abrasive grains, a good polishing rate can be obtained while maintaining excellent flatness. The average primary particle size is preferably large from the viewpoint of polishing rate, specifically, 15 nm or more is more preferable, and 25 nm or more is more preferable. 70 nm or less is preferable and 60 nm or less is more preferable from the viewpoint of reducing flatness (particularly dishing) and preventing the abrasive grains from aggregating excessively. However, since the polishing rate tends to decrease as the average primary particle size decreases, it is preferable to appropriately set the average primary particle size within the above range according to the application and the required polishing rate and flatness.
ここで、「平均一次粒子径」とは、ＢＥＴ比表面積から算出できる粒子の平均直径をいう。具体的には、まず砥粒を８００℃(±１０℃)で１時間乾燥し灼熱残分を得る。次に、この灼熱残分を乳鉢(磁性、１００ｍｌ)で細かく砕いて測定用試料とする。そして、ＢＥＴ比表面積測定装置（例えばユアサアイオニクス（株）製、商品名：オートソーブ６）を用いて、測定用試料のＢＥＴ比表面積Ｖ（単位：ｎｍ２／ｇ）を測定し、式：Ｄ＝６／（ρ・Ｖ）により求められる値Ｄ（ｎｍ）を平均一次粒子径とする。なお、上記式中のρは粒子の密度（単位：ｇ／ｎｍ３）を表しており、粒子がコロイダルシリカの場合には「ρ＝０．０２２」である。 Here, the “average primary particle size” refers to the average particle diameter that can be calculated from the BET specific surface area. Specifically, first, the abrasive grains are dried at 800 ° C. (± 10 ° C.) for 1 hour to obtain a burning residue. Next, this burning residue is finely crushed with a mortar (magnetic, 100 ml) to obtain a measurement sample. And the BET specific surface area V (unit: nm < 2 > / g) of the sample for a measurement is measured using the BET specific surface area measuring apparatus (For example, Yuasa Ionics Co., Ltd. make, brand name: Autosorb 6), Formula: D A value D (nm) obtained by = 6 / (ρ · V) is defined as an average primary particle diameter. In the above formula, ρ represents the density of the particles (unit: g / nm 3 ), and when the particles are colloidal silica, “ρ = 0.022”.
（４．平均二次粒子径）
ＣＭＰ研磨液に使用する砥粒としては、平均二次粒子径が２５〜２５０ｎｍのものを使用する。このような砥粒を使用することにより、優れた平坦性を維持しつつ、良好な研磨速度を得ることができる。平均二次粒子径としては、研磨速度のみに着目すると、平均二次粒子径は大きい方が良好な研磨速度が得られる傾向があり、３０ｎｍ以上が好ましく、３５ｎｍ以上がより好ましい。一方で、研磨後の平坦性（例えばディッシング量）に着目すると、平均二次粒子径は、１００ｎｍ以下であることが好ましく、２５〜１００ｎｍであることがより好ましい。また、研磨液の安定性の観点では、平均二次粒子径は、１００ｎｍ以下であることが好ましい。他の成分の添加、又は、研磨液の濃縮保存によっても優れた安定性を維持できるという観点では、平均二次粒子径は２５〜９０ｎｍであることがより好ましい。以上のような観点から、保存安定性と平坦性とを両立できるという点では、２５〜９０ｎｍが好ましい。
(4. Average secondary particle size)
As an abrasive grain used for CMP polishing liquid, that whose average secondary particle diameter is 25-250 nm is used. By using such abrasive grains, a good polishing rate can be obtained while maintaining excellent flatness. Focusing only on the polishing rate as the average secondary particle size, a larger average secondary particle size tends to provide a better polishing rate, preferably 30 nm or more, and more preferably 35 nm or more. On the other hand, when attention is paid to flatness after polishing (for example, dishing amount), the average secondary particle diameter is preferably 100 nm or less, and more preferably 25 to 100 nm. Further, from the viewpoint of the stability of the polishing liquid, the average secondary particle diameter is preferably 100 nm or less. From the viewpoint that excellent stability can be maintained even by adding other components or concentrating and storing the polishing liquid, the average secondary particle diameter is more preferably 25 to 90 nm. From the viewpoint as described above, 25 to 90 nm is preferable in that both storage stability and flatness can be achieved.
ここで、「平均二次粒子径」とは、砥粒を水に分散させたものを、動的光散乱方式の粒度分布計を用いて測定し、測定結果から得られた平均粒子径である。具体的には、まずサンプル（砥粒）４ｇに０．３％クエン酸５０ｍｌを加え、軽く振とうしたものを測定用試料とする。この測定用試料を粒径測定装置（例えば大塚電子（株）製、商品名：ＥＬＳ−８０００）を用いて測定し、得られた平均粒子径の値を平均二次粒子径とする。 Here, the “average secondary particle diameter” is an average particle diameter obtained from the measurement result obtained by measuring a dispersion of abrasive grains in water using a dynamic light scattering particle size distribution meter. . Specifically, first, 50 ml of 0.3% citric acid is added to 4 g of a sample (abrasive grain), and the sample shaken lightly is used as a measurement sample. This measurement sample is measured using a particle size measuring device (for example, trade name: ELS-8000, manufactured by Otsuka Electronics Co., Ltd.), and the obtained average particle size is defined as the average secondary particle size.
なお、ＣＭＰ研磨液に使用する砥粒は、研磨後の表面の平坦性に優れる点で、数珠状(moniliform)に結合している結合粒子(aggregate)を含むことが好ましい。ここで、「結合粒子」とは、個々の粒子が強く結びついたものであり、超音波等の分散により再度単分散（粒子一つ一つがばらばらに分散）するような弱く凝集した粒子ではない。また、２個の粒子が結合した、いわゆる「まゆ型」の結合粒子は、平坦性の向上に十分に寄与しない傾向があり、「まゆ型」の結合粒子のみを含む砥粒（すなわち、会合度が２．０）では、十分な被研磨面の平坦性を得ることはできない。そのため、砥粒としては、３〜５粒子が凝集した結合粒子を含むことが好ましい。結合粒子の存在は、例えば走査型電子顕微鏡（ＳＥＭ）で観察することにより確かめることができる。 In addition, it is preferable that the abrasive grain used for CMP polishing liquid contains the coupling | bonding particle | grain (aggregate) couple | bonded with the bead shape (moniliform) at the point which is excellent in the flatness of the surface after grinding | polishing. Here, “bonded particles” are particles in which individual particles are strongly bound, and are not weakly aggregated particles that are monodispersed again (dispersed particles one by one) by dispersion of ultrasonic waves or the like. In addition, so-called “brow-shaped” bonded particles in which two particles are bonded tend not to contribute sufficiently to the improvement of flatness, and abrasive grains containing only “brow-shaped” bonded particles (that is, the degree of association) However, in 2.0), sufficient flatness of the surface to be polished cannot be obtained. Therefore, it is preferable that the abrasive grains include binding particles in which 3 to 5 particles are aggregated. The presence of the binding particles can be confirmed by observing with a scanning electron microscope (SEM), for example.
（５．会合度）
ＣＭＰ研磨液に使用する砥粒は、良好な研磨速度と優れた平坦性を得る点で、その会合度が２．３以上であり、２．４以上であることが好ましく、２．５以上であることがより好ましい。会合度の上限は特に制限はないが、入手容易性の点から通常５以下が好ましく、３以下がより好ましい。
(5. Meeting degree)
The abrasive grains used in the CMP polishing liquid have a degree of association of 2.3 or more, preferably 2.4 or more, and preferably 2.5 or more in terms of obtaining a good polishing rate and excellent flatness. More preferably. The upper limit of the degree of association is not particularly limited, but is usually preferably 5 or less and more preferably 3 or less from the viewpoint of availability.
ここで、「会合度」とは、平均二次粒子径を平均一次粒子径で除した値である。この値が２．３以上の砥粒を使用することで、砥粒１個当たりの接触面積が小さくなり、砥粒と被研磨面との接触が抑制され、被研磨面の平坦性を向上させることができると推測される。そして、砥粒がアニオン化されると、この効果は更に高まると推測される。 Here, “degree of association” is a value obtained by dividing the average secondary particle diameter by the average primary particle diameter. By using abrasive grains having a value of 2.3 or more, the contact area per abrasive grain is reduced, the contact between the abrasive grains and the surface to be polished is suppressed, and the flatness of the surface to be polished is improved. It is speculated that it can. And if an abrasive grain is anionized, it is estimated that this effect increases further.
会合度が２．３以上の砥粒を用いることにより被研磨面の平坦性を向上させることができる理由について、本発明者らは以下のように推察している。但し、理由は図１〜４によって説明される以下の内容に限定されるものではない。図１は、会合度が１の砥粒が基板表面に供給されたときの状態を模式的に示す断面図である。図２は、会合度が１の砥粒が基板表面に供給されたときの状態を模式的に示す平面図である。図３は、会合度が１よりも高い（例えば会合度が２．３〜３）砥粒が基板表面に供給されたときの状態を模式的に示す断面図である。図４は、会合度が１よりも高い（例えば会合度が２．３〜３）砥粒が基板表面に供給されたときの状態を模式的に示す平面図である。なお、図１〜４の砥粒の状態は、例えば、砥粒の水分散液を基板表面に垂らし、乾燥させたときの基板表面の状態を観察することにより確認することができる。 The present inventors infer the reason why the flatness of the surface to be polished can be improved by using abrasive grains having an association degree of 2.3 or more. However, the reason is not limited to the following contents explained by FIGS. FIG. 1 is a cross-sectional view schematically showing a state when abrasive grains having an association degree of 1 are supplied to the substrate surface. FIG. 2 is a plan view schematically showing a state when abrasive grains having an association degree of 1 are supplied to the substrate surface. FIG. 3 is a cross-sectional view schematically showing a state when abrasive grains having an association degree higher than 1 (for example, an association degree of 2.3 to 3) are supplied to the substrate surface. FIG. 4 is a plan view schematically showing a state when abrasive grains having an association degree higher than 1 (for example, an association degree of 2.3 to 3) are supplied to the substrate surface. The state of the abrasive grains in FIGS. 1 to 4 can be confirmed by, for example, suspending the aqueous dispersion of abrasive grains on the substrate surface and observing the state of the substrate surface when dried.
図１，２に示すように、砥粒１０が会合していない場合、砥粒同士の移動が妨げられることが少なく、それぞれの砥粒１０が基板２０の被研磨面２０ａと接する確率が高くなる。一方、図３，４に示すように、砥粒１０（１０ａ，１０ｂ）が会合している場合、基板２０の被研磨面２０ａと接した砥粒１０ａと、砥粒１０ａに結合するものの被研磨面２０ａと接触しない砥粒１０ｂとが存在することとなり、砥粒１０と被研磨面２０ａとの接触が抑制される。このように、会合度が２．３以上の砥粒を用いると、砥粒１０と被研磨面２０ａとの接触が抑制され、被研磨面２０ａの平坦性を向上させることができると推察される。
As shown in FIGS. 1 and 2, when the
（６．含有量）
砥粒の含有量は、ＣＭＰ研磨液全量に対して、０．０１〜１質量％であることが好ましく、０．０２〜１質量％であることがより好ましく、０．０５〜１質量％であることが更に好ましい。砥粒の含有量が０．０１質量％以上であれば、更に良好な研磨速度が得られる傾向があり、１質量％以下であれば、平坦性を更に高く維持できる傾向がある。
(6. Content)
The content of the abrasive grains is preferably 0.01 to 1% by mass, more preferably 0.02 to 1% by mass, and 0.05 to 1% by mass with respect to the total amount of the CMP polishing liquid. More preferably it is. If the content of abrasive grains is 0.01% by mass or more, a better polishing rate tends to be obtained, and if it is 1% by mass or less, flatness tends to be maintained higher.
（酸化金属溶解剤）
本実施形態のＣＭＰ研磨液に使用できる酸化金属溶解剤としては、特に制限はないが、有機酸、有機酸エステル、無機酸、及びこれらの塩等を挙げることができる。
(Metal oxide solubilizer)
Although there is no restriction | limiting in particular as a metal oxide dissolving agent which can be used for CMP polishing liquid of this embodiment, Organic acid, organic acid ester, inorganic acid, these salts, etc. can be mentioned.
酸化金属溶解剤としては、例えば、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、ｐ−トルエンスルホン酸等の有機酸；これらの有機酸エステル及びこれら有機酸のアンモニウム塩；
塩酸、硫酸、硝酸等の無機酸；これら無機酸のアンモニウム塩類、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；クロム酸；などを挙げることができる。
これらの中では、実用的な研磨速度を維持しつつ、優れた平坦性が得られる点で、無機酸及び有機酸が好ましく、ギ酸、マロン酸、リンゴ酸、酒石酸、クエン酸、サリチル酸、アジピン酸がより好ましい。これら酸化金属溶解剤は、１種類単独で又は２種類以上混合して用いることができる。
Examples of the metal oxide solubilizer 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, adipic acid, pimelic acid, Organic acids such as maleic acid, phthalic acid, malic acid, tartaric acid, citric acid and p-toluenesulfonic acid; these organic acid esters and ammonium salts of these organic acids;
Inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid; ammonium salts of these inorganic acids such as ammonium persulfate, ammonium nitrate, ammonium chloride; chromic acid;
Among these, inorganic acids and organic acids are preferable in that excellent flatness can be obtained while maintaining a practical polishing rate. Formic acid, malonic acid, malic acid, tartaric acid, citric acid, salicylic acid, adipic acid Is more preferable. These metal oxide solubilizers can be used alone or in combination of two or more.
酸化金属溶解剤の含有量は、ＣＭＰ研磨液全量に対して、更に良好な研磨速度を得る点で０．００１質量％以上であることが好ましく、０．００２質量％以上であることがより好ましく、０．００５質量％以上であることが更に好ましい。また、研磨後の平坦性に更に優れ、研磨後の表面に荒れが生じるのを防ぐ点で、２０質量％以下であることが好ましく、１０質量％以下であることがより好ましく、５質量％以下であることが更に好ましい。 The content of the metal oxide solubilizer is preferably 0.001% by mass or more, and more preferably 0.002% by mass or more in terms of obtaining a better polishing rate with respect to the total amount of the CMP polishing liquid. More preferably, it is 0.005 mass% or more. Further, it is more preferably 20% by mass or less, more preferably 10% by mass or less, and more preferably 5% by mass or less in view of further excellent flatness after polishing and preventing the surface after polishing from being rough. More preferably.
（酸化剤）
本実施形態のＣＭＰ研磨液において、酸化剤としては、銅の表面を酸化できるものであれば特に制限はなく、例えば、過酸化水素（Ｈ２Ｏ２）、硝酸、過ヨウ素酸カリウム、過硫酸アンモニウム、次亜塩素酸、オゾン水等が挙げられ、その中でも過酸化水素が特に好ましい。基板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、ハロゲン化物等による汚染は望ましくないので、不揮発成分を含まない酸化剤が好ましい。但し、オゾン水は組成の経時的変化が激しいので、過酸化水素が最も適している。
(Oxidant)
In the CMP polishing liquid of the present embodiment, the oxidizing agent is not particularly limited as long as it can oxidize the copper surface. For example, hydrogen peroxide (H 2 O 2 ), nitric acid, potassium periodate, ammonium persulfate Hypochlorous acid, ozone water and the like can be mentioned, among which hydrogen peroxide is particularly preferable. In the case where the substrate is a silicon substrate including an integrated circuit element, contamination by alkali metal, alkaline earth metal, halide, etc. is not desirable, so an oxidizing agent that does not contain a nonvolatile component is preferable. However, hydrogen peroxide is most suitable because the composition of ozone water changes with time.
金属の酸化剤の含有量は、銅を充分に酸化でき、更に良好な研磨速度が得られる点で、ＣＭＰ用研磨液全量に対して、０．０１質量％以上が好ましく、０．０２質量％以上がより好ましく、０．０５質量％以上が更に好ましい。また、研磨後の表面に荒れが生じることを更に防ぐ点で、５０質量％以下が好ましく、３０質量％以下がより好ましく、１５質量％以下が更に好ましい。 The content of the metal oxidant is preferably 0.01% by mass or more, and 0.02% by mass with respect to the total amount of the polishing slurry for CMP in that copper can be sufficiently oxidized and a better polishing rate can be obtained. The above is more preferable, and 0.05 mass% or more is still more preferable. Moreover, 50 mass% or less is preferable, 30 mass% or less is more preferable, and 15 mass% or less is still more preferable at the point which further prevents that the surface after grinding | polishing arises.
（水溶性ポリマ）
本実施形態のＣＭＰ用研磨液は、水溶性ポリマを含有する。高い研磨速度が発現しやすい点で、水溶性ポリマの重量平均分子量の下限は、好ましくは５００以上、より好ましくは１５００以上、更に好ましくは５０００以上である。水溶性ポリマの重量平均分子量の上限は、特に制限はないが、溶解度の観点から５００万以下が好ましい。水溶性ポリマの重量平均分子量は、ゲルパーミエーションクロマトグラフィーにより標準ポリスチレンの検量線を用いて測定することができ、例えば、以下の条件で測定することができる。
(Water-soluble polymer)
The CMP polishing liquid of this embodiment contains a water-soluble polymer. The lower limit of the weight average molecular weight of the water-soluble polymer is preferably 500 or more, more preferably 1500 or more, and still more preferably 5000 or more in that a high polishing rate is easily exhibited. The upper limit of the weight average molecular weight of the water-soluble polymer is not particularly limited, but is preferably 5 million or less from the viewpoint of solubility. The weight average molecular weight of the water-soluble polymer can be measured by gel permeation chromatography using a standard polystyrene calibration curve, and can be measured, for example, under the following conditions.
（条件）
使用機器（検出器）：株式会社日立製作所製、Ｌ−３３００型液体クロマトグラフ用示差屈折率計
ポンプ：株式会社日立製作所製、Ｌ−７１００型液体クロマトグラフ用
データ処理：株式会社日立製作所製、Ｄ−２５２０型ＧＰＣインテグレーター
カラム：昭和電工製、商品名：Ｓｈｏｄｅｘ Ａｓａｈｉｐａｋ ＧＦ−７１０ＨＱ、内径７．６ｍｍ×３００ｍｍ
溶離液：５０ｍＭ―Ｎａ２ＨＰＯ４水溶液／アセトニトリル＝９０／１０（ｖ／ｖ）
流量：０．６ｍＬ／分
試料：樹脂分濃度２％になるように溶離液と同じ組成の溶液で調整し、０．４５μｍのポリテトラフルオロエチレンフィルターでろ過
注入量：０．４μＬ
校正用標準物質：Polymer Laboratories製、狭分子量ポリアクリル酸ナトリウム
(conditions)
Equipment used (detector): Hitachi, Ltd., L-3300 differential refractometer for liquid chromatograph Pump: Hitachi, Ltd., L-7100 type liquid chromatograph Data processing: Hitachi, Ltd. D-2520 type GPC integrator Column: Showa Denko, trade name: Shodex Asahipak GF-710HQ, inner diameter 7.6 mm × 300 mm
Eluent: 50mM-Na 2 HPO 4 aqueous solution / acetonitrile = 90/10 (v / v )
Flow rate: 0.6 mL / min Sample: Adjust with a solution having the same composition as the eluent so that the resin concentration is 2%, and filter with a 0.45 μm polytetrafluoroethylene filter Injection volume: 0.4 μL
Calibration standard: Polymer Laboratories, narrow molecular weight sodium polyacrylate
水溶性ポリマとしては、例えば、
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、ポリアミド酸、ポリマレイン酸、ポリイタコン酸、ポリフマル酸、ポリ（ｐ−スチレンカルボン酸）、ポリアクリル酸、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及びその塩；
アルギン酸、ペクチン酸、カルボキシメチルセルロ−ス、寒天、カ−ドラン及びプルラン等の多糖類；
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、
などが挙げられる。水溶性ポリマとしては、アクリル酸系化合物をモノマとして含む前駆体成分を重合して得られる水溶性ポリマが好ましい。上記水溶性ポリマは、ホモポリマのみならず、官能基が２種類以上含まれる共重合体でも使用することができる。
Examples of water-soluble polymers include:
Polyaspartic acid, polyglutamic acid, polylysine, polymalic acid, polymethacrylic acid, polymethacrylic acid ammonium salt, polymethacrylic acid sodium salt, polyamic acid, polymaleic acid, polyitaconic acid, polyfumaric acid, poly (p-styrenecarboxylic acid), poly Polycarboxylic acids such as acrylic acid, polyacrylamide, amino polyacrylamide, ammonium polyacrylate, sodium polyacrylate, polyamic acid, ammonium polyamic acid, sodium polyamic acid and polyglyoxylic acid and salts thereof;
Polysaccharides such as alginic acid, pectic acid, carboxymethylcellulose, agar, cardran and pullulan;
Vinyl polymers such as polyvinyl alcohol, polyvinyl pyrrolidone and polyacrolein;
Etc. As the water-soluble polymer, a water-soluble polymer obtained by polymerizing a precursor component containing an acrylic acid compound as a monomer is preferable. The water-soluble polymer can be used not only as a homopolymer but also as a copolymer containing two or more functional groups.
但し、ＣＭＰ用研磨液を適用する基板が半導体集積回路用シリコン基板等の場合は、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、水溶性ポリマとしては、アルカリ金属、アルカリ土類金属、ハロゲン化物を含まないものが好ましく、例えば、ポリリンゴ酸、ポリメタクリル酸、ポリアクリル酸、ポリアクリル酸アンモニウム塩、ポリアクリルアミド、ペクチン酸、寒天、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等が特に好ましい。 However, when the substrate to which the CMP polishing liquid is applied is a silicon substrate for a semiconductor integrated circuit or the like, contamination with alkali metal, alkaline earth metal, halide, etc. is not desirable. Preferred are those containing no earth metal or halide, such as polymalic acid, polymethacrylic acid, polyacrylic acid, polyacrylic acid ammonium salt, polyacrylamide, pectic acid, agar, polyvinyl alcohol and polyvinylpyrrolidone, their esters and Their ammonium salts are particularly preferred.
水溶性ポリマの含有量は、ＣＭＰ用研磨液全量に対して、好ましくは０．００１〜１５質量％、より好ましくは０．００５〜１０質量％、更に好ましくは０．０１〜５質量％である。水溶性ポリマの含有量が０．００１質量％以上であると、研磨速度及び平坦性が更に向上する傾向があり、１５質量％以下であると、ＣＭＰ用研磨液に含まれる砥粒の安定性を高く保持することができる傾向がある。 The content of the water-soluble polymer is preferably 0.001 to 15% by mass, more preferably 0.005 to 10% by mass, and still more preferably 0.01 to 5% by mass with respect to the total amount of the polishing slurry for CMP. . When the content of the water-soluble polymer is 0.001% by mass or more, the polishing rate and the flatness tend to be further improved, and when it is 15% by mass or less, the stability of the abrasive grains contained in the CMP polishing liquid. Tends to be kept high.
（防食剤）
ＣＭＰ研磨液に使用する防食剤は、銅に対して保護膜を形成しうるものであれば特に制限はないが、砥粒との組合せにおいては、トリアゾール化合物を使用することが好ましく、ベンゾトリアゾール、１，２，３−トリアゾール、４−アミノ−１，２，３−トリアゾール、４，５−ジアミノ−１，２，３−トリアゾール、１，２，４−トリアゾール、３−アミノ−１，２，４−トリアゾール、及び３，５−ジアミノ−１，２，４−トリアゾールからなる群より選ばれる少なくとも１種であることがより好ましい。
(Anticorrosive)
The anticorrosive used in the CMP polishing liquid is not particularly limited as long as it can form a protective film against copper, but in combination with abrasive grains, it is preferable to use a triazole compound, benzotriazole, 1,2,3-triazole, 4-amino-1,2,3-triazole, 4,5-diamino-1,2,3-triazole, 1,2,4-triazole, 3-amino-1,2, More preferably, it is at least one selected from the group consisting of 4-triazole and 3,5-diamino-1,2,4-triazole.
防食剤の含有量は、ＣＭＰ用研磨液全量に対して、好ましくは０．０１〜１０質量％、より好ましくは０．０５〜７質量％、更に好ましくは０．１０〜４質量％である。防食剤の含有量が０．０１質量％以上であると、平坦性が更に向上する傾向があり、１０質量％以下であると、研磨速度が更に向上する傾向がある。 The content of the anticorrosive is preferably 0.01 to 10% by mass, more preferably 0.05 to 7% by mass, and still more preferably 0.10 to 4% by mass with respect to the total amount of the polishing slurry for CMP. When the content of the anticorrosive agent is 0.01% by mass or more, the flatness tends to be further improved, and when it is 10% by mass or less, the polishing rate tends to be further improved.
（その他の成分）
本実施形態のＣＭＰ研磨液は、ＣＭＰ研磨液の被研磨面への濡れ性の向上、水に溶解しにくい成分の溶解補助、研磨速度の向上や平坦性の向上等の目的で、その他の公知の成分を含むことができ、例えば、界面活性剤、有機溶剤を更に含むことができる。なお、ＣＭＰ研磨液における水の含有量は、ＣＭＰ研磨液における砥粒等の上記含有成分の含有量の残部でよく、研磨液中に含有されていれば特に制限はない。
(Other ingredients)
The CMP polishing liquid of this embodiment is used for other purposes such as improving wettability of the CMP polishing liquid to the surface to be polished, assisting dissolution of components that are difficult to dissolve in water, improving polishing speed, and improving flatness. For example, a surfactant and an organic solvent can be further included. Note that the content of water in the CMP polishing liquid may be the remainder of the content of the above-described components such as abrasive grains in the CMP polishing liquid, and is not particularly limited as long as it is contained in the polishing liquid.
（研磨方法）
以上説明したＣＭＰ研磨液を用いることで、良好なＣＭＰ速度が得られると共に、従来のＣＭＰ研磨液よりも優れた平坦性が得られる基板の研磨が可能となる。本実施形態の研磨方法では、銅層を有する基板と研磨布との間に、上記ＣＭＰ研磨液を供給し、基板の銅層の少なくとも一部を研磨布で研磨する。
(Polishing method)
By using the CMP polishing liquid described above, it is possible to obtain a good CMP rate and to polish a substrate that can obtain flatness superior to that of a conventional CMP polishing liquid. In the polishing method of this embodiment, the CMP polishing liquid is supplied between a substrate having a copper layer and a polishing cloth, and at least a part of the copper layer of the substrate is polished with the polishing cloth.
図５を参照しながら、本実施形態に係る研磨方法について更に説明する。図５は、本実施形態の研磨方法を示す模式断面図である。図５（ａ）に示されるように、基板１００は、シリコン基板１と、シリコン基板１上に形成された層間絶縁膜２と、層間絶縁膜２上に形成されたバリア層３と、バリア層３上に形成された銅層４とを有している。層間絶縁膜２の表面には、相互に隣接する隆起部（凸部）と溝部（凹部）とを有する段差部が形成されており、バリア層３は、層間絶縁膜２の表面の段差部に追従して形成されている。銅層４は、バリア層３の溝部を埋めるように形成されている。
The polishing method according to this embodiment will be further described with reference to FIG. FIG. 5 is a schematic cross-sectional view showing the polishing method of the present embodiment. As shown in FIG. 5A, a
本実施形態の研磨方法を適用するにあたり、基板１００の被研磨面（銅層４の表面）を研磨定盤の研磨布に押しあて、被研磨面と研磨布との間に本実施形態のＣＭＰ研磨液を供給しながら、基板１００の裏面（被研磨面と反対の面）に所定の圧力を加えた状態で、基板１００を研磨定盤に対して相対的に動かすことによって被研磨面を研磨することが好ましい。本実施形態に係る研磨方法では、例えば、図５（ｂ）に示されるように、層間絶縁膜２の隆起部上に位置するバリア層３が露出した基板２００が得られるまで研磨が行われる。
In applying the polishing method of this embodiment, the surface to be polished (the surface of the copper layer 4) of the
本実施形態の研磨方法は、研磨液の流量（研磨液供給速度）が０．０３５〜０．２５ｍｌ／ｍｉｎとなる範囲で、研磨定盤の研磨布上に上記研磨液を供給しながら、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り研磨することが好ましい。これにより、導電性材料膜が形成されたウエハ（半導体基板）を化学的、機械的に平坦化することができる。 In the polishing method of the present embodiment, the polishing liquid is supplied onto the polishing cloth of the polishing surface plate in a range where the polishing liquid flow rate (polishing liquid supply rate) is 0.035 to 0.25 ml / min. It is preferable to perform polishing by relatively moving the polishing platen and the substrate while pressing the substrate having the polishing film against the polishing cloth. Thereby, the wafer (semiconductor substrate) on which the conductive material film is formed can be planarized chemically and mechanically.
研磨装置としては、例えば、回転数が変更可能なモータ等が取り付けてあると共に研磨布を貼り付けられる研磨定盤と、基板を保持するホルダーとを有する一般的な研磨装置が使用できる。研磨布としては、特に制限はないが、一般的な不織布、発泡ポリウレタン、多孔質フッ素樹脂等が使用できる。研磨条件には、特に制限はないが、基板が飛び出さないように研磨定盤の回転速度を２００ｍｉｎ−１以下の低回転にすることが好ましい。 As the polishing apparatus, for example, a general polishing apparatus having a polishing platen to which a motor capable of changing the number of rotations and the like and a polishing cloth is attached and a holder for holding the substrate can be used. Although there is no restriction | limiting in particular as abrasive cloth, A general nonwoven fabric, a polyurethane foam, a porous fluororesin, etc. can be used. The polishing conditions are not particularly limited, but it is preferable that the rotation speed of the polishing platen be as low as 200 min −1 or less so that the substrate does not jump out.
被研磨膜を有する基板の研磨布への研磨圧力は５〜１００ｋＰａであることが好ましく、研磨速度のウエハ面内の均一性及びパターンの平坦性の見地から１０〜５０ｋＰａであることがより好ましい。研磨している間、研磨布にはＣＭＰ研磨液をポンプ等で連続的に供給することが好ましい。この供給量に制限はないが、研磨布の表面が常に研磨液で覆われていることが好ましい。研磨終了後の被研磨体は、流水中で良く洗浄後、スピンドライヤ等を用いて被研磨体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 polishing pressure of the substrate having the film to be polished onto the polishing cloth is preferably 5 to 100 kPa, and more preferably 10 to 50 kPa from the viewpoint of the uniformity of the polishing rate within the wafer surface and the flatness of the pattern. During polishing, it is preferable to continuously supply the CMP polishing liquid 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 polishing liquid. The object to be polished after polishing is preferably washed in running water and then dried after removing water droplets adhering to the object to be polished using a spin dryer or the like.
本実施形態において、研磨時に濃縮液を希釈してＣＭＰ研磨液を得る場合には、水又は下記に示す水溶液を用いて濃縮液を希釈することができる。水溶液は、予め、酸化剤、有機酸、添加剤及び界面活性剤のうち少なくとも１つ以上を含有しており、この水溶液中に含有している成分と、希釈される濃縮液中に含有している成分とを合計した各成分の含有量が、研磨に使用する研磨液（使用液）の成分の含有量となるようにする。このように、濃縮液を水溶液で希釈して使用する場合には、研磨液に溶解しにくい成分を水溶液の形で後から配合することができることから、より濃縮した濃縮液を調製することができる。 In this embodiment, when a CMP polishing liquid is obtained by diluting the concentrated liquid during polishing, the concentrated liquid can be diluted with water or an aqueous solution shown below. The aqueous solution contains at least one of an oxidizing agent, an organic acid, an additive, and a surfactant in advance, and the components contained in the aqueous solution and the concentrated solution to be diluted. The total content of each component is adjusted to the content of the component of the polishing liquid (use liquid) used for polishing. Thus, when the concentrated solution is diluted with an aqueous solution, components that are difficult to dissolve in the polishing solution can be added later in the form of an aqueous solution, so that a more concentrated concentrated solution can be prepared. .
また、濃縮液に水又は水溶液を加え希釈する方法としては、濃縮液を供給する配管と、水又は水溶液を供給する配管とを研磨布に供給される前に合流させ、濃縮液と水又は水溶液とを混合し、希釈された研磨液（使用液）を研磨布に供給する方法がある。濃縮液と水又は水溶液との混合は、圧力を付した状態で狭い通路を通して液同士を衝突混合する方法、配管中にガラス管等の充填物を詰め液体の流れを分流分離し合流させることを繰り返し行う方法、配管中に動力で回転する羽根を設ける方法等の通常行われている方法を採用することができる。 In addition, as a method of diluting by adding water or an aqueous solution to the concentrate, the pipe for supplying the concentrate and the pipe for supplying the water or aqueous solution are joined before being supplied to the polishing cloth, and the concentrate and water or the aqueous solution are combined. And a diluted polishing liquid (use liquid) is supplied to the polishing cloth. Mixing of concentrated liquid and water or aqueous solution is a method of colliding and mixing liquids through a narrow passage with pressure applied, filling a pipe with a filling such as a glass tube, and separating and separating the liquid flow. Ordinary methods such as a method of repeatedly performing, a method of providing a blade rotating with power in the pipe, and the like can be employed.
更に、濃縮液を水又は水溶液等により希釈しながら研磨する方法としては、濃縮液を供給する配管と、水又は水溶液を供給する配管とを独立に設け、それぞれから所定量の液を研磨布に供給し、研磨布と研磨対象の被研磨面との相対運動で濃縮液と水又は水溶液とを混合しつつ研磨する方法がある。また、１つの容器に、所定量の濃縮液と水又は水溶液とを入れ混合してから、研磨布にその混合した研磨液を供給し、研磨をする方法を用いることもできる。 Furthermore, as a method of polishing while diluting the concentrate with water or an aqueous solution, etc., a pipe for supplying the concentrate and a pipe for supplying water or an aqueous solution are provided independently, and a predetermined amount of liquid is respectively applied to the polishing cloth. There is a method of supplying and polishing while mixing a concentrated solution and water or an aqueous solution by a relative motion between a polishing cloth and a surface to be polished. Alternatively, a method may be used in which a predetermined amount of concentrated liquid and water or an aqueous solution are mixed in a single container, and then the mixed polishing liquid is supplied to a polishing cloth for polishing.
また、別の研磨方法としては、研磨液の含有成分を少なくとも２つの構成成分に分けて濃縮し、使用する際にそれぞれに水又は水溶液を加え希釈して研磨定盤上の研磨布に供給し、研磨対象の被研磨面と研磨布とを相対運動させて２つの構成成分を混合しつつ研磨する方法がある。例えば、酸化剤を構成成分（Ａ）とし、有機酸、添加剤、界面活性剤、及び水を構成成分（Ｂ）とし、使用する際に水又は水溶液で構成成分（Ａ）及び構成成分（Ｂ）を希釈して使用することができる。また、溶解度の低い添加剤を２つの構成成分（Ａ）と（Ｂ）とに分けてもよい。例えば、酸化剤、添加剤、及び界面活性剤を構成成分（Ａ）とし、有機酸、添加剤、界面活性剤、及び水を構成成分（Ｂ）とし、使用する際にそれぞれに水又は水溶液を加え、構成成分（Ａ）及び構成成分（Ｂ）を希釈して使用する。 Further, as another polishing method, the components contained in the polishing liquid are divided into at least two components and concentrated, and when used, diluted with water or an aqueous solution, respectively, and supplied to the polishing cloth on the polishing surface plate. There is a method in which a surface to be polished and a polishing cloth are moved relative to each other to perform polishing while mixing two components. For example, an oxidant is used as the constituent component (A), an organic acid, an additive, a surfactant, and water are used as the constituent component (B). ) Can be used diluted. Moreover, you may divide an additive with low solubility into two structural component (A) and (B). For example, an oxidizing agent, an additive, and a surfactant are used as the constituent component (A), and an organic acid, an additive, a surfactant, and water are used as the constituent component (B). In addition, component (A) and component (B) are diluted and used.
上記のような構成成分の異なる２つの濃縮液を用いる場合、構成成分（Ａ）と、構成成分（Ｂ）と、水又は水溶液とをそれぞれ供給する３つの配管が必要である。この場合、３つの配管について、研磨布につながる１つの配管に残りの２つの配管を結合し、配管内で混合希釈する方法があり、２つの配管を結合してから他の１つの配管を結合することも可能である。具体的には、溶解しにくい添加剤を含む構成成分と他の構成成分とを混合し、混合経路を長くして溶解時間を確保してから、更に、水又は水溶液の配管を結合する方法が挙げられる。その他の混合方法は、上記したように直接に３つの配管をそれぞれ研磨布に導き、研磨布と研磨対象の被研磨面の相対運動により混合希釈する方法や、１つの容器に３つの構成成分を混合して、希釈された研磨液を研磨布に供給する方法がある。 When two concentrated liquids having different constituent components as described above are used, three pipes for supplying the constituent component (A), the constituent component (B), and water or an aqueous solution are required. In this case, for the three pipes, there is a method of joining the remaining two pipes to one pipe connected to the polishing cloth, and mixing and diluting in the pipe. After joining the two pipes, join the other pipe. It is also possible to do. Specifically, there is a method in which a constituent component containing an additive that is difficult to dissolve is mixed with other constituent components, a mixing path is lengthened to ensure a dissolution time, and then a water or aqueous solution pipe is combined. Can be mentioned. Other mixing methods include, as described above, directing three pipes directly to the polishing cloth, mixing and diluting them by relative movement of the polishing cloth and the surface to be polished, and three components in one container. There is a method of mixing and supplying the diluted polishing liquid to the polishing cloth.
上記した研磨方法において、一の構成成分の液温と他の構成成分の液温とを互いに異ならせてもよい。例えば、一の構成成分の液温を４０℃以下にし、他の構成成分の液温を室温から１００℃の範囲としてもよい。この方法によれば、温度が高いと溶解度が高くなる現象を利用することにより、室温において溶解度の低い原料を溶解度の高い温度領域で溶解させることができる。また、液温が下がると室温における溶解度の低い原料が溶液中に析出してしまうため、一の構成成分と他の構成成分とを混合するためには、溶解度の低い原料を含有する構成成分を予め加温して溶解させる必要がある。この場合、加温して原料を溶解させた後に送液する方法や、析出物を含む液を攪拌した後に配管中へ送液し、配管中で加温して原料を溶解させる方法を採用することができる。 In the above polishing method, the liquid temperature of one constituent component may be different from the liquid temperature of another constituent component. For example, the liquid temperature of one constituent component may be 40 ° C. or lower, and the liquid temperature of the other constituent component may be in the range of room temperature to 100 ° C. According to this method, a raw material having low solubility at room temperature can be dissolved in a high-solubility temperature region by utilizing the phenomenon that the solubility increases when the temperature is high. In addition, since the raw material with low solubility at room temperature is precipitated in the solution when the liquid temperature is lowered, in order to mix one constituent component with another constituent component, the constituent component containing the raw material with low solubility is used. It is necessary to preheat and dissolve. In this case, a method of heating and dissolving the raw material and feeding the solution, or a method of stirring the liquid containing the precipitate and feeding it into the pipe and heating in the pipe and dissolving the raw material are employed. be able to.
また、上記一の構成成分が酸化剤を含む場合、一の構成成分の温度が４０℃以上に高められると酸化剤が分解する恐れがある。そのため、上記加温した他の構成成分と、酸化剤を含む一の構成成分とを混合した場合、液温が４０℃以下となるようにすることが好ましい。このように、一の構成成分の液温と他の構成成分の液温とを互いに異ならせることにより、原料の溶解度や分解温度に応じて研磨液を調製することができる。 Moreover, when the said one component contains an oxidizing agent, there exists a possibility that an oxidizing agent may decompose | disassemble when the temperature of one constituent is raised to 40 degreeC or more. Therefore, it is preferable that the liquid temperature be 40 ° C. or lower when the other heated component and one component containing an oxidizing agent are mixed. In this way, by making the liquid temperature of one constituent component different from the liquid temperature of another constituent component, a polishing liquid can be prepared according to the solubility and decomposition temperature of the raw material.
このように、成分を二以上に分割した研磨液を研磨布に供給してもよい。この場合、酸化物を含む成分と、有機酸を含有する成分とに分割して供給することが好ましい。また、研磨液を濃縮液とし、希釈水を別にして研磨布に供給してもよい。 Thus, you may supply the polishing liquid which divided | segmented the component into two or more to polishing cloth. In this case, it is preferable to divide and supply a component containing an oxide and a component containing an organic acid. Alternatively, the polishing liquid may be a concentrated liquid and supplied to the polishing cloth separately from the dilution water.
成分を二以上に分割した研磨液を研磨布に供給する方法を適用する場合、その供給量は、各配管からの各研磨液の供給量の合計により表される。 When applying a method of supplying a polishing liquid in which a component is divided into two or more to a polishing cloth, the supply amount is represented by the total supply amount of each polishing liquid from each pipe.
以下、実施例により本発明を説明する。本発明はこれらの実施例に制限されるものではない。 Hereinafter, the present invention will be described by way of examples. The present invention is not limited to these examples.
（砥粒）
表１に示す砥粒Ａ〜Ｒを用意した。砥粒Ａ〜Ｒはコロイダルシリカである。また、砥粒のアニオン処理として、砥粒Ａ〜Ｄ及び砥粒Ｐ〜Ｒはアルミン酸化合物修飾を施し、Ｅはスルホン酸化合物修飾を施した。
(Abrasive grains)
Abrasive grains A to R shown in Table 1 were prepared. The abrasive grains A to R are colloidal silica. Further, as anion treatment of abrasive grains, abrasive grains AD and abrasive grains P-R were modified with aluminate compound, and E was modified with sulfonic acid compound.
（砥粒の物性測定）
砥粒Ａ〜Ｒについて、平均一次粒子径及び平均二次粒子径を以下のようにして測定し、得られた平均一次粒子径及び平均二次粒子径の値から、会合度を算出した。
(Measurement of physical properties of abrasive grains)
About abrasive grain A-R, the average primary particle diameter and the average secondary particle diameter were measured as follows, and the association degree was computed from the value of the obtained average primary particle diameter and average secondary particle diameter.
平均一次粒子径は、以下のように測定した。まず砥粒を８００℃(±１０℃)で１時間乾燥し灼熱残分を得た。次に、この灼熱残分を乳鉢(磁性、１００ｍｌ)で細かく砕いて測定用試料とした。そして、ＢＥＴ比表面積測定装置（ユアサアイオニクス（株）製、商品名：オートソーブ６）を用いて、測定用試料のＢＥＴ比表面積V（単位：ｎｍ２／ｇ）を測定し、式：Ｄ＝６／（ρ・V）により求められる値Ｄ（ｎｍ）を平均一次粒子径とした。なお、上記式中のρは粒子の密度（単位：ｇ／ｎｍ３）を表しており、粒子がコロイダルシリカの場合には「ρ＝０．０２２」である。 The average primary particle size was measured as follows. First, the abrasive grains were dried at 800 ° C. (± 10 ° C.) for 1 hour to obtain a burning residue. Next, this burning residue was finely crushed with a mortar (magnetic, 100 ml) to obtain a measurement sample. Then, using a BET specific surface area measuring device (manufactured by Yuasa Ionics Co., Ltd., trade name: Autosorb 6), the BET specific surface area V (unit: nm 2 / g) of the measurement sample is measured, and the formula: D = The value D (nm) obtained by 6 / (ρ · V) was defined as the average primary particle size. In the above formula, ρ represents the density of the particles (unit: g / nm 3 ), and when the particles are colloidal silica, “ρ = 0.022”.
平均二次粒子径は、以下のように測定した。砥粒４ｇに０．３％クエン酸５０ｍｌを加え、軽く振とうしたものを測定用試料とした。この試料を大塚電子（株）製、商品名：ＥＬＳ−８０００を用いて測定した値を平均二次粒子径とした。 The average secondary particle diameter was measured as follows. A sample for measurement was prepared by adding 50 ml of 0.3% citric acid to 4 g of abrasive grains and shaking lightly. The value measured for this sample using Otsuka Electronics Co., Ltd., brand name: ELS-8000 was taken as the average secondary particle diameter.
（ＣＭＰ研磨液作製方法：実施例１〜５）
研磨液用スラリーの総質量に対して、１，２，４-トリアゾールを０．２質量％、ベンゾトリアゾールを０．２質量％、ポリアクリル酸（重量平均分子量：８００００〜１７００００）を１．５質量％、マレイン酸を０．６質量％、表１に示す平均一次粒子径、平均二次粒子径及び会合度を有する砥粒Ａ〜Ｅを０．８質量％、及び、純水をスラリー質量全量の残部である９６．７質量％含有するようにしてスラリーを得た。次いで、このスラリーと、酸化剤としての３０質量％の過酸化水素水を質量比１:１で混合し、研磨液を作製した。
(CMP polishing liquid preparation method: Examples 1 to 5)
0.2% by mass of 1,2,4-triazole, 0.2% by mass of benzotriazole, and 1.5% of polyacrylic acid (weight average molecular weight: 80000-170000) with respect to the total mass of the slurry for polishing liquid % By weight, 0.6% by weight of maleic acid, 0.8% by weight of abrasive grains A to E having average primary particle diameter, average secondary particle diameter and degree of association shown in Table 1, and slurry weight of pure water A slurry was obtained so as to contain 96.7% by mass of the remainder of the total amount. Next, this slurry was mixed with 30% by mass of hydrogen peroxide as an oxidizing agent at a mass ratio of 1: 1 to prepare a polishing liquid.
なお、ポリアクリル酸の重量平均分子量は下記の方法により測定した。
使用機器（検出器）：株式会社日立製作所製、Ｌ−３３００型液体クロマトグラフ用示差屈折率計
ポンプ：株式会社日立製作所製、Ｌ−７１００型液体クロマトグラフ用
データ処理：株式会社日立製作所製、Ｄ−２５２０型ＧＰＣインテグレーター
カラム：昭和電工製、商品名：Ｓｈｏｄｅｘ Ａｓａｈｉｐａｋ ＧＦ−７１０ＨＱ、内径７．６ｍｍ×３００ｍｍ
溶離液：５０ｍＭ―Ｎａ２ＨＰＯ４水溶液／アセトニトリル＝９０／１０（ｖ／ｖ）
流量：０．６ｍＬ／分
試料：樹脂分濃度２％になるように溶離液と同じ組成の溶液で調整し、０．４５μｍのポリテトラフルオロエチレンフィルターでろ過
注入量：０．４μＬ
校正用標準物質：Polymer Laboratories製、狭分子量ポリアクリル酸ナトリウム
The weight average molecular weight of polyacrylic acid was measured by the following method.
Equipment used (detector): Hitachi, Ltd., L-3300 differential refractometer for liquid chromatograph Pump: Hitachi, Ltd., L-7100 type liquid chromatograph Data processing: Hitachi, Ltd. D-2520 type GPC integrator Column: Showa Denko, trade name: Shodex Asahipak GF-710HQ, inner diameter 7.6 mm × 300 mm
Eluent: 50mM-Na 2 HPO 4 aqueous solution / acetonitrile = 90/10 (v / v )
Flow rate: 0.6 mL / min Sample: Adjust with a solution having the same composition as the eluent so that the resin concentration is 2%, and filter with a 0.45 μm polytetrafluoroethylene filter Injection volume: 0.4 μL
Calibration standard: Polymer Laboratories, narrow molecular weight sodium polyacrylate
（ＣＭＰ研磨液作製方法：比較例１〜１３）
砥粒Ａ〜Ｅに替えて、砥粒Ｆ〜Ｒを用いたこと以外は実施例１〜５と同様にして比較例１〜１３で用いるＣＭＰ研磨液を得た。
(CMP polishing liquid preparation method: Comparative Examples 1 to 13)
In place of the abrasive grains A to E, CMP polishing liquids used in Comparative Examples 1 to 13 were obtained in the same manner as in Examples 1 to 5 except that the abrasive grains F to R were used.
（研磨液のｐＨ測定）
各研磨液のｐＨを堀場製作所株式会社製、型番Ｆ・８０を用いて測定した。標準緩衝液（フタル酸塩ｐＨ緩衝液ｐＨ：４．０１（２５℃）、中性りん酸塩ｐＨ緩衝液ｐＨ６．８６（２５℃））を用いて、２点校正した後、電極をＣＭＰ研磨液に入れて、２分以上経過して安定した後の値をｐＨとした。
(Measurement of pH of polishing liquid)
The pH of each polishing liquid was measured using a model number F • 80 manufactured by HORIBA, Ltd. After calibrating two points using a standard buffer solution (phthalate pH buffer solution pH: 4.01 (25 ° C), neutral phosphate pH buffer solution pH 6.86 (25 ° C)), the electrode was subjected to CMP polishing. The value after putting in the liquid and stabilizing after 2 minutes or more was defined as pH.
（銅配線が形成された被研磨用基板）
研磨速度及びディッシング量の評価には、被研磨用基板（ＳＥＭＡＴＥＣＨ社製、商品名：「ＳＥＭＡＴＥＣＨ８５４」、マスクパターンウエハ）を用いた。この基板は、シリコン基板と、シリコン基板上に形成されると共に、深さ５００ｎｍの溝部により形成されたパターンを有する絶縁膜と、絶縁膜上にスパッタ法により順に形成された２５ｎｍのＴａＮ膜と１０ｎｍの銅膜と、電解メッキ法により形成された１．２μｍの銅層とを有する。なお、溝部に埋め込まれた配線パターンの配線幅は１００μｍであり、配線スペース幅は１００μｍであった。
(Substrate for polishing with copper wiring)
For evaluation of the polishing rate and dishing amount, a substrate to be polished (manufactured by SEMATECH, trade name: “SEMATECH 854”, mask pattern wafer) was used. This substrate is formed on a silicon substrate, a silicon substrate, and has an insulating film having a pattern formed by a groove portion having a depth of 500 nm, a 25 nm TaN film and a 10 nm film formed on the insulating film by sputtering. And a 1.2 μm copper layer formed by electrolytic plating. The wiring width of the wiring pattern embedded in the groove was 100 μm and the wiring space width was 100 μm.
実施例１〜５及び比較例１〜１３では、下記研磨条件で被研磨用基板を研磨した。 In Examples 1 to 5 and Comparative Examples 1 to 13, the substrate to be polished was polished under the following polishing conditions.
（ＣＭＰ研磨条件）
研磨装置：片面金属膜用研磨機（アプライドマテリアルズ社製、商品名：ＭＩＲＲＡ）
研磨布：スウェード状発泡ポリウレタン樹脂製研磨布（ニッタ・ハース社製、商品名：ＩＣ−１０１０）
研磨圧力：１３．８ｋＰａ
研磨液供給速度：２００ｍｌ／ｍｉｎ
（ＣＭＰ後洗浄）
ＣＭＰ処理後の基板に対しては、ＰＶＡ（ポリビニルアルコール）ブラシ、超音波水による洗浄を行った後、スピンドライヤにて乾燥を行った。
(CMP polishing conditions)
Polishing device: Polishing machine for single-sided metal film (Applied Materials, trade name: MIRRA)
Abrasive cloth: Abrasive cloth made of suede-like polyurethane foam resin (Nitta Haas, trade name: IC-1010)
Polishing pressure: 13.8 kPa
Polishing liquid supply rate: 200 ml / min
(Cleaning after CMP)
The substrate after the CMP treatment was washed with a PVA (polyvinyl alcohol) brush and ultrasonic water, and then dried with a spin dryer.
（研磨評価項目）
Ｃｕ研磨速度は、上記基板の銅膜のＣＭＰ前後での膜厚差を電気抵抗値から換算して求めた。測定装置は、日立国際電気エンジニアリング社製の抵抗率測定器、商品名：ＶＲ−１２０／０８Ｓを用いた。ウエハの直径方向８１点（エッジから５ｍｍ部分除外）の平均値を抵抗値とした。
(Polishing evaluation items)
The Cu polishing rate was determined by converting the film thickness difference before and after CMP of the copper film of the substrate from the electrical resistance value. As a measuring device, a resistivity measuring instrument manufactured by Hitachi Kokusai Electric Engineering Co., Ltd., trade name: VR-120 / 08S was used. The average value of 81 points in the diameter direction of the wafer (excluding 5 mm from the edge) was taken as the resistance value.
ディッシング量は、研磨後の基板の配線幅１００μｍ、配線スペース幅１００μｍの段差を接触式段差計（Ｖｅｅｃｏ製、商品名：ＤＥＣＫＴＡＫ Ｖ２００−Ｓｉ）で走査して得られた段差量で判断した。 The dishing amount was judged by the step amount obtained by scanning a step having a wiring width of 100 μm and a wiring space width of 100 μm after polishing with a contact-type step meter (product name: DECKTAK V200-Si).
実施例１〜５及び比較例１〜１３における、Ｃｕ研磨速度、ディッシング量（段差量）の評価結果を表１に示す。 Table 1 shows the evaluation results of the Cu polishing rate and dishing amount (step amount) in Examples 1 to 5 and Comparative Examples 1 to 13.
Ｃｕ研磨速度：１５０ｎｍ／ｍｉｎ以上、平坦性（ディッシング量）：２５ｎｍ以下を良好と判断した。表１に示されるように、実施例１〜５は、Ｃｕ研磨速度及び平坦性共に良好な結果であったが、比較例１〜１３は、Ｃｕ研磨速度及び平坦性のいずれかに欠点があることが示される。 Cu polishing rate: 150 nm / min or more, flatness (dishing amount): 25 nm or less was judged good. As shown in Table 1, Examples 1 to 5 were good results in both the Cu polishing rate and flatness, but Comparative Examples 1 to 13 had defects in either the Cu polishing rate or flatness. Is shown.
１…シリコン基板、２…層間絶縁膜、３…バリア層、４…銅層、１０…砥粒、２０…基板、２０ａ…被研磨面、１００，２００…基板。
DESCRIPTION OF
Claims (6)
該ＣＭＰ研磨液は、砥粒、酸化金属溶解剤、酸化剤、防食剤、水溶性ポリマ及び水を含有し、前記ＣＭＰ研磨液のｐＨが２〜５であり、
前記水溶性ポリマが、アクリル酸系化合物をモノマとして含む前駆体成分を重合して得られるものであり、
前記酸化金属溶解剤が、有機酸、有機酸エステル及びこれらの塩からなる群より選ばれる少なくとも１種であり、
前記砥粒がアニオン処理されており、前記砥粒の平均一次粒子径が１０〜８０ｎｍであり、前記砥粒の平均二次粒子径が２５〜２５０ｎｍであり、前記平均二次粒子径を前記平均一次粒子径で除して求められる会合度が２．３以上であるＣＭＰ研磨液。 A CMP polishing liquid for polishing a metal containing copper,
The CMP polishing liquid contains abrasive grains, a metal oxide dissolving agent, an oxidizing agent, an anticorrosive, a water-soluble polymer, and water, and the pH of the CMP polishing liquid is 2 to 5 ,
The water-soluble polymer is obtained by polymerizing a precursor component containing an acrylic acid compound as a monomer,
The metal oxide solubilizer is at least one selected from the group consisting of organic acids, organic acid esters and salts thereof,
The abrasive grains are anion-treated, the average primary particle diameter of the abrasive grains is 10 to 80 nm, the average secondary particle diameter of the abrasive grains is 25 to 250 nm, and the average secondary particle diameter is the average A CMP polishing liquid whose degree of association determined by dividing by the primary particle diameter is 2.3 or more.
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| JP5695367B2 (en) | 2010-08-23 | 2015-04-01 | 株式会社フジミインコーポレーテッド | Polishing composition and polishing method using the same |
| JP2013074036A (en) * | 2011-09-27 | 2013-04-22 | Toshiba Corp | Slurry for cmp and method for manufacturing semiconductor device |
| JP2013138053A (en) * | 2011-12-28 | 2013-07-11 | Fujimi Inc | Polishing composition |
| JP6325441B2 (en) * | 2012-07-17 | 2018-05-16 | 株式会社フジミインコーポレーテッド | Composition for polishing alloy material and method for producing alloy material using the same |
| JP5897200B2 (en) * | 2013-02-13 | 2016-03-30 | 株式会社フジミインコーポレーテッド | Polishing composition, polishing composition manufacturing method and polishing product manufacturing method |
| KR101713824B1 (en) * | 2015-01-26 | 2017-03-09 | 주식회사 케이씨텍 | Slurry composition for semiconductor polishing |
| JP6145501B1 (en) * | 2015-12-24 | 2017-06-14 | 株式会社フジミインコーポレーテッド | Polishing composition and silicon substrate polishing method |
| JP2017101248A (en) * | 2017-01-13 | 2017-06-08 | 株式会社フジミインコーポレーテッド | Polishing composition, manufacturing method of polishing composition and manufacturing method of polished article |
| JP2017163148A (en) * | 2017-04-17 | 2017-09-14 | 株式会社フジミインコーポレーテッド | Scratch reducing agent and scratch reducing method |
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| JP3525824B2 (en) * | 1999-09-17 | 2004-05-10 | 日立化成工業株式会社 | CMP polishing liquid |
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| WO2009017095A1 (en) * | 2007-07-30 | 2009-02-05 | Hitachi Chemical Co., Ltd. | Polishing liquid for metal and method of polishing |
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