JP2017122134A - Polishing liquid for metal film and polishing method using the same - Google Patents
Polishing liquid for metal film and polishing method using the same Download PDFInfo
- Publication number
- JP2017122134A JP2017122134A JP2014106113A JP2014106113A JP2017122134A JP 2017122134 A JP2017122134 A JP 2017122134A JP 2014106113 A JP2014106113 A JP 2014106113A JP 2014106113 A JP2014106113 A JP 2014106113A JP 2017122134 A JP2017122134 A JP 2017122134A
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- Prior art keywords
- polishing
- metal
- polishing liquid
- acid
- film
- Prior art date
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- 238000005498 polishing Methods 0.000 title claims abstract description 336
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 214
- 239000002184 metal Substances 0.000 title claims abstract description 214
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- 238000000034 method Methods 0.000 title claims abstract description 59
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- 239000002253 acid Substances 0.000 claims abstract description 17
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- 230000004888 barrier function Effects 0.000 claims description 63
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 32
- 239000007800 oxidant agent Substances 0.000 claims description 28
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 239000003945 anionic surfactant Substances 0.000 description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
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- 238000007517 polishing process Methods 0.000 description 4
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- 150000003918 triazines Chemical class 0.000 description 1
- POFDSYGXHVPQNX-UHFFFAOYSA-N triazolo[1,5-a]pyrimidine Chemical compound C1=CC=NC2=CN=NN21 POFDSYGXHVPQNX-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- HUZZQXYTKNNCOU-UHFFFAOYSA-N triethyl(methoxy)silane Chemical compound CC[Si](CC)(CC)OC HUZZQXYTKNNCOU-UHFFFAOYSA-N 0.000 description 1
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 description 1
- PQDJYEQOELDLCP-UHFFFAOYSA-N trimethylsilane Chemical compound C[SiH](C)C PQDJYEQOELDLCP-UHFFFAOYSA-N 0.000 description 1
- 150000003658 tungsten compounds Chemical class 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000004260 weight control Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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- C23F3/00—Brightening metals by chemical means
- C23F3/04—Heavy metals
- C23F3/06—Heavy metals with acidic solutions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
- B24B37/00—Lapping machines or devices; Accessories
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09G—POLISHING COMPOSITIONS; SKI WAXES
- C09G1/00—Polishing compositions
- C09G1/02—Polishing compositions containing abrasives or grinding agents
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting
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Abstract
Description
本発明は、金属膜用研磨液と、それを用いた研磨方法に関する。具体的には、本発明は、半導体デバイスの配線形成工程等における研磨に使用される金属膜用研磨液及びその金属膜用研磨液を用いた研磨方法に関する。 The present invention relates to a metal film polishing liquid and a polishing method using the same. Specifically, the present invention relates to a metal film polishing liquid used for polishing in a wiring formation process or the like of a semiconductor device and a polishing method using the metal film polishing liquid.
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いる。化学機械研磨(以下、CMPと記す。)法もその一つであり、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技術である。この技術は、例えば米国特許第4944836号明細書(特許文献1)に開示されている。 In recent years, new microfabrication techniques have been developed along with higher integration and higher performance of semiconductor integrated circuits (hereinafter referred to as LSIs). A chemical mechanical polishing (hereinafter referred to as CMP) method is one of them, and a technique frequently used in the planarization of an interlayer insulating film, the formation of a metal plug, and the formation of a buried wiring in an LSI manufacturing process, particularly a multilayer wiring forming process. It is. This technique is disclosed in, for example, US Pat. No. 4,944,836 (Patent Document 1).
また、最近はLSIを高性能化するために、配線材料となる導電性物質として銅及び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。 Recently, in order to improve the performance of LSIs, attempts have been made to use copper and copper alloys as conductive materials serving as wiring materials. 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.
そこで、あらかじめ溝を形成してある絶縁膜上に銅又は銅合金の薄膜を堆積して埋め込み、溝部以外の上記薄膜を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(特許文献2)に開示されている。 Therefore, a so-called damascene method is mainly employed in which a thin film of copper or copper alloy is deposited and embedded on an insulating film in which a groove is formed in advance, and the above-mentioned thin film other than the groove is removed by CMP to form a buried wiring. ing. This technique is disclosed, for example, in JP-A-2-278822 (Patent Document 2).
銅又は銅合金等の金属配線を研磨する金属CMPの一般的な方法は、円形の研磨定盤(プラテン)上に研磨布(パッド)を貼り付け、研磨布表面を金属膜用研磨液で浸しながら、基板の金属膜を形成した面を研磨布表面に押し付けて、研磨布の裏面から所定の圧力(以下、研磨圧力と記す。)を金属膜に加えた状態で研磨定盤を回し、研磨液と金属膜の凸部との相対的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 of metal CMP for polishing metal wiring such as copper or copper alloy is to apply a polishing cloth (pad) on a circular polishing platen (platen) and immerse the surface of the polishing cloth with a polishing solution for metal film. While pressing the surface of the substrate on which the metal film was formed against the surface of the polishing cloth, rotating the polishing platen while applying a predetermined pressure (hereinafter referred to as polishing pressure) from the back surface of the polishing cloth to the metal film, polishing The metal film on the convex portion is removed by relative mechanical friction between the liquid and the convex portion of the metal film.
CMPに用いられる金属膜用研磨液は、一般には酸化剤、研磨粒子及び水からなっており、必要に応じてさらに酸化金属溶解剤、保護膜形成剤などが添加される。まず酸化剤によって金属膜表面を酸化して酸化層を形成し、その酸化層を研磨粒子によって削り取るのが基本的なメカニズムであると考えられている。凹部の金属膜表面の酸化層は研磨パッドにあまり触れず、研磨粒子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膜の酸化層が除去されて基板表面は平坦化される。この詳細についてはジャーナル・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)、3460〜3464頁(非特許文献1)に開示されている。 The metal film polishing liquid used in CMP is generally composed of an oxidant, abrasive particles, and water, and a metal oxide solubilizer, a protective film forming agent, and the like are further added as necessary. It is considered that the basic mechanism is to first oxidize the surface of the metal film with an oxidizing agent to form an oxide layer, and then scrape the oxide layer with abrasive particles. The oxide layer on the surface of the metal film in the recess does not touch the polishing pad so much, and the effect of scraping off by the abrasive particles does not reach, so the oxide layer on the metal film in the convex portion is removed and the substrate surface is flattened with the progress of CMP. . The details are disclosed in Journal of Electrochemical Society, Vol. 138, No. 11 (issued in 1991), pages 3460 to 3464 (Non-patent Document 1).
CMPによる研磨速度を高める方法として金属膜用研磨液に酸化金属溶解剤を添加することが有効とされている。研磨粒子によって削り取られた金属酸化物の粒を研磨液に溶解(以下、エッチングと記す。)させてしまうと研磨粒子による削り取りの効果が増すためであると解釈される。酸化金属溶解剤の添加によりCMPによる研磨速度は向上するが、一方、凹部の金属膜表面の酸化層もエッチングされて金属膜表面が露出すると、酸化剤によって金属膜表面がさらに酸化され、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う。このため研磨後に埋め込まれた金属配線の表面中央部分が皿のように窪む現象(以下、ディッシングと記す。)が発生し、平坦化効果が損なわれる。 As a method for increasing the polishing rate by CMP, it is effective to add a metal oxide dissolving agent to the metal film polishing liquid. It is interpreted that if the metal oxide particles scraped by the abrasive particles are dissolved in the polishing liquid (hereinafter referred to as etching), the effect of scraping by the abrasive particles is increased. Although the polishing rate by CMP is improved by adding a metal oxide solubilizer, on the other hand, when the oxide layer on the metal film surface in the recess is also etched to expose the metal film surface, the metal film surface is further oxidized by the oxidant and this is repeated. As a result, the etching of the metal film in the recesses proceeds. For this reason, a phenomenon occurs in which the central portion of the surface of the metal wiring embedded after polishing is depressed like a dish (hereinafter referred to as dishing), and the planarization effect is impaired.
これを防ぐために、金属膜用研磨液にさらに保護膜形成剤が添加される。保護膜形成剤は金属膜表面の酸化層上に保護膜を形成し、酸化層がエッチングされるのを防止するものである。この保護膜は研磨粒子により容易に削り取ることが可能で、CMPによる研磨速度を低下させないことが望まれる。 In order to prevent this, a protective film forming agent is further added to the metal film polishing liquid. The protective film forming agent forms a protective film on the oxide layer on the surface of the metal film and prevents the oxide layer from being etched. This protective film can be easily scraped off by abrasive particles, and it is desirable not to decrease the polishing rate by CMP.
金属膜のディッシングやエッチングを抑制し、信頼性の高いLSI配線を形成するために、酸化金属溶解剤としてグリシン等のアミノ酢酸又はアミド硫酸を、保護膜形成剤としてベンゾトリアゾールを含有する金属膜用研磨液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(特許文献3)に記載されている。 For metal films containing aminoacetic acid or amide sulfuric acid such as glycine as a metal oxide solubilizing agent and benzotriazole as a protective film forming agent to suppress dishing and etching of the metal film and form highly reliable LSI wiring A method using a polishing liquid has been proposed. This technique is described, for example, in JP-A-8-83780 (Patent Document 3).
銅又は銅合金等のダマシン配線形成やタングステン等のプラグ配線形成等の金属埋め込み形成においては、埋め込み部分以外に形成される層間絶縁膜の研磨速度も大きい場合には、配線の間にある層間絶縁膜の厚みが薄くなる現象(以下、配線間エロージョンと記す。)が発生し、平坦性が悪化する。その結果、配線抵抗の増加等の問題が生じてしまうので、配線間エロージョンは可能な限り小さくすることが要求される。 In metal buried formation such as damascene wiring formation such as copper or copper alloy or plug wiring formation such as tungsten, if the polishing rate of the interlayer insulating film formed other than the embedded portion is high, the interlayer insulation between the wirings A phenomenon that the thickness of the film becomes thin (hereinafter referred to as inter-wiring erosion) occurs and flatness deteriorates. As a result, problems such as an increase in wiring resistance occur, so that erosion between wirings is required to be as small as possible.
一方、銅又は銅合金等の金属配線の下層には、層間絶縁膜中への金属の拡散防止や密着性向上のためのバリア導体層(以下、バリア層という。)として、タンタル、タンタル合金、窒化タンタル等の導体からなる層が形成される。したがって、銅又は銅合金等の金属配線を埋め込む配線部以外では、露出したバリア層をCMPにより取り除く必要がある。しかし、これらのバリア層の導体は、銅又は銅合金に比べ硬度が高いために、銅又は銅合金用の研磨材料を組み合わせても十分な研磨速度が得られず、かつ被研磨面の平坦性が悪くなる場合が多い。そこで、金属配線を研磨する第1の研磨工程と、バリア層を研磨する第2の研磨工程からなる2段研磨方法が検討されている。 On the other hand, under the metal wiring such as copper or copper alloy, tantalum, tantalum alloy, as a barrier conductor layer (hereinafter referred to as a barrier layer) for preventing metal diffusion into the interlayer insulating film and improving adhesion. A layer made of a conductor such as tantalum nitride is formed. Therefore, it is necessary to remove the exposed barrier layer by CMP except for the wiring portion in which metal wiring such as copper or copper alloy is embedded. However, since the conductors of these barrier layers are higher in hardness than copper or copper alloys, a sufficient polishing rate cannot be obtained even when a polishing material for copper or copper alloys is combined, and the surface to be polished is flat. Is often worse. In view of this, a two-stage polishing method comprising a first polishing step for polishing a metal wiring and a second polishing step for polishing a barrier layer has been studied.
図1に一般的なダマシンプロセスによる配線形成を断面模式図で示す。図1の(a)は研磨前の状態を示し、表面に溝を形成した層間絶縁膜1、層間絶縁膜1の表面凹凸に追従するように形成されたバリア層2、凹凸を埋めるように堆積された銅又は銅合金の金属配線層3を有する。 FIG. 1 is a schematic cross-sectional view showing wiring formation by a general damascene process. FIG. 1A shows a state before polishing, an interlayer insulating film 1 having grooves formed on the surface, a barrier layer 2 formed so as to follow the surface irregularities of the interlayer insulating film 1, and deposited so as to fill the irregularities. The copper or copper alloy metal wiring layer 3 is provided.
まず、図1の(b)に示すように、金属配線研磨用の研磨液で、バリア層2が露出するまで金属配線層3を研磨する。次に、図1の(c)に示すように、バリア層研磨用の研磨液で層間絶縁膜1の凸部が露出するまで研磨する。 First, as shown in FIG. 1B, the metal wiring layer 3 is polished with a polishing liquid for polishing metal wiring until the barrier layer 2 is exposed. Next, as shown in FIG. 1C, polishing is performed with a polishing liquid for polishing the barrier layer until the convex portions of the interlayer insulating film 1 are exposed.
このようなバリア層研磨用の研磨液として、酸化剤と、金属表面に対する保護膜形成剤と、酸と、水とを含み、pHが3以下であり、上記酸化剤の濃度が0.01〜3質量%である化学機械研磨用研磨剤が提案されている(例えば再公表特許第01/13417号参照(特許文献4)。)。 As such a polishing liquid for polishing the barrier layer, it contains an oxidizing agent, a protective film forming agent for the metal surface, an acid, and water, has a pH of 3 or less, and a concentration of the oxidizing agent of 0.01 to An abrasive for chemical mechanical polishing of 3% by mass has been proposed (see, for example, Republished Patent No. 01/13417 (Patent Document 4)).
上記2段研磨方法において、金属配線層3を金属配線研磨用の研磨液で研磨する第1の研磨工程の後、金属配線の周辺部に導電性物質の残渣が発生する場合がある。例えば、酸化剤に過硫酸アンモニウム(ペルオキソ二硫酸アンモニウム)を含む研磨液を第一の研磨工程で用いた場合、この導電性物質の残渣は顕著に現れる(例えば特開2007−335531号公報参照(特許文献5))。
この導電性物質の残渣は金属配線と金属配線の間の部分の上部(例えば図2の(b)の導電性物質と導電性物質の間の部分)には発生せず、周辺に金属配線が無いフィールドの部分には導電性物質の残渣が発生する状態となる。
また、上記2段研磨方法において、バリア層を研磨する第2の研磨工程において、被研磨面の平坦化のため、層間絶縁膜を余分に研磨する、オーバー研磨工程を要求される場合がある。上記層間絶縁膜としては、例えば、二酸化珪素、またLow−k(低誘電率)膜であるオルガノシリケートグラスや全芳香環系Low−k膜が挙げられる。
In the above-described two-stage polishing method, after the first polishing step of polishing the metal wiring layer 3 with a polishing liquid for metal wiring polishing, a residue of a conductive substance may be generated in the peripheral portion of the metal wiring. For example, when a polishing liquid containing ammonium persulfate (ammonium peroxodisulfate) as an oxidizing agent is used in the first polishing step, the residue of the conductive material appears remarkably (see, for example, JP-A-2007-335531 (Patent Document) 5)).
This conductive material residue does not occur in the upper part of the portion between the metal wiring (for example, the portion between the conductive material and the conductive material in FIG. 2B), and there is no metal wiring around. There is a state in which a residue of the conductive material is generated in the portion of the field that does not exist.
In the above-described two-stage polishing method, in the second polishing step for polishing the barrier layer, an over-polishing step of polishing the interlayer insulating film excessively may be required in order to flatten the surface to be polished. Examples of the interlayer insulating film include silicon dioxide, organosilicate glass which is a low-k (low dielectric constant) film, and a wholly aromatic ring-based low-k film.
図2(a)に示すように金属配線層3を研磨する第1の研磨工程の行った後、図2(b)で示すように、金属配線の周辺部に導電性物質の残渣が発生し、金属配線と金属配線の間の部分には残渣が発生していない基板を用いて、第2の研磨工程である、バリア層の研磨を行う場合、周辺に金属配線が無いフィールドの部分は導電性物質の残渣が存在するためにバリア層の研磨の進行が遅れるが、金属配線と金属配線の間の部分は研磨開始と同時にバリア層が研磨されるため、図2(c)で示すように金属配線と金属配線の間の部分が過剰に研磨される配線間エロージョンが発生する。
そこで、バリア層を研磨する第2の研磨工程で用いる研磨液に、多量の酸化剤を用いることで、フィールド部分の導電性物質の残渣を速やかに除去し、配線間エロージョンを低減することが可能である。しかし、その研磨液を用いた場合、金属配線の研磨速度も上昇するため、ディッシングが更に大きくなる問題がある。
本発明は、上記の課題に鑑み、層間絶縁膜に対し良好な研磨速度を維持しながら配線間エロージョンの発生を抑制しつつ、ディッシングも抑制した被研磨面の平坦性が高い金属膜用研磨液及びそれを用いた研磨方法を提供する。
After the first polishing step for polishing the metal wiring layer 3 as shown in FIG. 2A, a conductive material residue is generated in the periphery of the metal wiring as shown in FIG. 2B. When the barrier layer is polished in the second polishing step using a substrate in which no residue is generated between the metal wiring and the metal wiring, the portion of the field where there is no metal wiring in the periphery is conductive. As shown in FIG. 2C, the progress of the polishing of the barrier layer is delayed because of the residue of the active substance, but the barrier layer is polished at the same time as the polishing starts at the portion between the metal wiring and the metal wiring. Inter-wiring erosion occurs in which the portion between the metal wiring and the metal wiring is excessively polished.
Therefore, by using a large amount of oxidizing agent in the polishing liquid used in the second polishing process for polishing the barrier layer, it is possible to quickly remove the residue of the conductive material in the field portion and reduce erosion between the wirings. It is. However, when the polishing liquid is used, the polishing rate of the metal wiring also increases, and there is a problem that dishing is further increased.
In view of the above problems, the present invention provides a metal film polishing liquid with high flatness of a surface to be polished that suppresses the occurrence of erosion between wirings while maintaining a good polishing rate for an interlayer insulating film and also suppresses dishing. And a polishing method using the same.
本発明者らは、上記の配線間エロージョンを低減しつつ、ディッシングを抑制するためには、フィールド部分にある導電性物質の残渣に対する研磨速度が高いが、金属配線部分の様な、凹みのある金属配線部分に対する研磨速度は小さい添加剤を用いることが有効であると着想し、特定のポリマを添加剤として使用した場合に、これを達成できることを見いだした。
すなわち、本発明は、(1)研磨粒子、重量平均分子量が20,000以上のメタクリル酸系ポリマ及び水系溶媒を含有することを特徴とする金属膜用研磨液に関する。
In order to suppress dishing while reducing the above-mentioned erosion between the wirings, the present inventors have a high polishing rate with respect to the residue of the conductive material in the field part, but there are dents like the metal wiring part. The inventors have conceived that it is effective to use an additive having a low polishing rate for a metal wiring portion, and found that this can be achieved when a specific polymer is used as an additive.
That is, the present invention relates to (1) a polishing slurry for metal films, comprising abrasive particles, a methacrylic acid polymer having a weight average molecular weight of 20,000 or more, and an aqueous solvent.
また、本発明は、(2)前記水系溶媒が水、又は、水及び酸からなる、上記(1)記載の金属膜用研磨液に関する。
また、本発明は、(3)前記金属膜用研磨液が、金属配線の周辺部に導電性物質の残渣が発生し、金属配線と金属配線の間の部分には残渣が発生していない基体を化学機械研磨するための研磨液である、上記(1)又は(2)記載の金属膜用研磨液に関する。
また、本発明は、(4)上記メタクリル酸系ポリマが、メタクリル酸のホモポリマ、及び、メタクリル酸と該メタクリル酸と共重合可能なモノマとのコポリマから選ばれる少なくとも1種である上記(1)〜(3)のいずれか一項に記載の金属膜用研磨液に関する。
The present invention also relates to (2) the metal film polishing liquid according to (1) above, wherein the aqueous solvent comprises water or water and an acid.
Further, the present invention provides: (3) A substrate in which the metal film polishing liquid generates a residue of a conductive material in a peripheral portion of the metal wiring and does not generate a residue in a portion between the metal wiring and the metal wiring. The metal film polishing liquid according to (1) or (2) above, which is a polishing liquid for chemical mechanical polishing.
Further, the present invention provides (4) wherein the methacrylic acid polymer is at least one selected from a homopolymer of methacrylic acid and a copolymer of methacrylic acid and a monomer copolymerizable with the methacrylic acid. It is related with the polishing liquid for metal films as described in any one of-(3).
また、本発明は、(5)上記研磨粒子が、シリカ、アルミナ、セリア、チタニア、ジルコニア、ゲルマニア及びこれらの変性物からなる群より選択される少なくとも1種を含有する上記(1)〜(4)のいずれか一項に記載の金属膜用研磨液に関する。
また、本発明は、(6)さらに、金属防食剤としてトリアゾール骨格を有する化合物を含有する、上記(1)〜(5)のいずれか一項に記載の金属膜用研磨液に関する。
The present invention also provides (5) the above (1) to (4), wherein the abrasive particles contain at least one selected from the group consisting of silica, alumina, ceria, titania, zirconia, germania, and modified products thereof. The polishing liquid for metal films as described in any one of 1).
The present invention also relates to (6) the metal film polishing liquid according to any one of (1) to (5) above, further comprising a compound having a triazole skeleton as a metal anticorrosive.
また、本発明は、(7)さらに有機溶媒を含有する上記(1)〜(6)のいずれか一項に記載の金属膜用研磨液に関する。 Moreover, this invention relates to the polishing liquid for metal films as described in any one of said (1)-(6) which further contains (7) organic solvent.
また、本発明は、(8)さらに、金属の酸化剤を含有する上記(1)〜(7)のいずれか一項に記載の金属膜用研磨液に関する。 The present invention also relates to (8) the metal film polishing liquid according to any one of (1) to (7), further comprising a metal oxidant.
また、本発明は、(9)上記金属膜用研磨液のpHを2.0以上、3.5以下とした上記(1)〜(8)のいずれか一項に記載の金属膜用研磨液に関する。 Moreover, this invention is (9) Polishing liquid for metal films as described in any one of said (1)-(8) which set pH of the said polishing liquid for metal films to 2.0-3.5. About.
また、本発明は、(10)前記研磨粒子、前記メタクリル酸系ポリマ、前記水系溶媒及び前記金属防食剤を含む第一の液と、前記酸化剤を含む第二の液と、を混合して前記金属膜用研磨液を得る、上記(8)又は(9)に記載の金属膜用研磨液に関する。 Moreover, this invention mixes the 1st liquid containing the said abrasive particle, the said methacrylic acid type polymer, the said aqueous solvent, and the said metal anticorrosive agent, and the 2nd liquid containing the said oxidizing agent. The metal film polishing liquid according to (8) or (9), wherein the metal film polishing liquid is obtained.
また、本発明は、(11)表面が凹部及び凸部からなる層間絶縁膜と、上記層間絶縁膜を表面に沿って被覆するバリア層と、上記凹部を充填してバリア層を被覆する導電性物質層とを有する基板の導電性物質層を研磨して上記凸部のバリア層を露出させる第1の研磨工程と、
上記第1の研磨工程で露出した上記基板のバリア層を上記(1)〜(10)のいずれか一項に記載の金属膜用研磨液を用いて研磨して上記凸部の層間絶縁膜を露出させる第2の研磨工程を含むことを特徴とする研磨方法に関する。
In addition, the present invention provides (11) an interlayer insulating film having a concave portion and a convex surface, a barrier layer that covers the interlayer insulating film along the surface, and a conductive layer that fills the concave portion and covers the barrier layer. A first polishing step of polishing a conductive material layer of a substrate having a material layer to expose the barrier layer of the convex portion;
The barrier layer of the substrate exposed in the first polishing step is polished using the metal film polishing liquid according to any one of (1) to (10) to form an interlayer insulating film of the convex portion. It is related with the grinding | polishing method characterized by including the 2nd grinding | polishing process to expose.
また、本発明の研磨方法は、バリア層を被覆する導電性物質層を研磨して形成される配線の配線密度が50%以上である配線形成部を有する基板であると好ましい。
また、本発明の研磨方法は、上記層間絶縁膜がシリコン系被膜又は有機ポリマ膜であると好ましい。
Further, the polishing method of the present invention is preferably a substrate having a wiring forming portion in which the wiring density of wiring formed by polishing the conductive material layer covering the barrier layer is 50% or more.
In the polishing method of the present invention, the interlayer insulating film is preferably a silicon-based film or an organic polymer film.
また、本発明の研磨方法は、上記導電性物質が銅を主成分とすると好ましい。 In the polishing method of the present invention, it is preferable that the conductive material contains copper as a main component.
また、本発明の研磨方法は、上記バリア層がタンタル、タンタル化合物、チタン、チタン化合物、タングステン、タングステン化合物、ルテニウム、ルテニウム化合物コバルト及びコバルト化合物から選ばれる少なくとも1種を含むと好ましい。 In the polishing method of the present invention, it is preferable that the barrier layer contains at least one selected from tantalum, a tantalum compound, titanium, a titanium compound, tungsten, a tungsten compound, ruthenium, a ruthenium compound cobalt, and a cobalt compound.
本発明によれば、重量平均分子量が20,000以上のメタクリル酸系ポリマを含有することによって、層間絶縁膜に対する良好な研磨速度を維持しながら、導電性物質の残渣が発生し、金属配線と金属配線の間の部分には残渣が発生していない基板のバリア層を研磨する場合に、配線間エロージョンの発生を抑制し、ディッシングも抑制した被研磨面の平坦性が高い金属膜用研磨液及びそれを用いた研磨方法を提供することができる。 According to the present invention, by containing a methacrylic acid polymer having a weight average molecular weight of 20,000 or more, a conductive material residue is generated while maintaining a good polishing rate for the interlayer insulating film, and metal wiring and When polishing the barrier layer of the substrate where no residue is generated between the metal wirings, the metal film polishing liquid with high flatness of the surface to be polished that suppresses the occurrence of erosion between the wirings and suppresses dishing. And a polishing method using the same.
また、本発明によれば、研磨粒子、金属の酸化剤、金属の防食剤等を含ませることにより、上記の効果に加えて、金属配線及びバリア金属に対する良好な研磨速度を得ることができ、これにより上記第2の研磨工程に適した金属膜用研磨液を得ることができる。 Further, according to the present invention, by including abrasive particles, metal oxidizer, metal anticorrosive, etc., in addition to the above effects, a good polishing rate for metal wiring and barrier metal can be obtained, Thus, a metal film polishing liquid suitable for the second polishing step can be obtained.
本発明の金属膜用研磨液は、重量平均分子量が20,000以上のメタクリル酸系ポリマを含有することを特徴とする。重量平均分子量が20,000以上のメタクリル酸系ポリマは、重量平均分子量20,000未満のポリマと比較して脆弱な銅反応層を形成するため、研磨速度が速く、かつ酸化剤を多量に含んだ研磨液と比較してディッシングを抑制するため、配線間のエロージョンを抑制しつつ、ディッシングも低減することが可能となると推定される。上記メタクリル酸系ポリマとしては、メタクリル酸のホモポリマ及び、メタクリル酸と該メタクリル酸と共重合可能なモノマとのコポリマから選ばれる少なくとも1種であることが好ましい。 The metal film polishing liquid of the present invention contains a methacrylic acid polymer having a weight average molecular weight of 20,000 or more. A methacrylic acid polymer having a weight average molecular weight of 20,000 or more forms a fragile copper reaction layer as compared with a polymer having a weight average molecular weight of less than 20,000, and therefore has a high polishing rate and contains a large amount of an oxidizing agent. Since the dishing is suppressed as compared with the polishing liquid, it is estimated that the dishing can be reduced while suppressing the erosion between the wirings. The methacrylic acid polymer is preferably at least one selected from a homopolymer of methacrylic acid and a copolymer of methacrylic acid and a monomer copolymerizable with the methacrylic acid.
本明細書において「工程」との用語には、独立した工程が含まれるだけではなく、他の工程と明確に区別できない工程であってその工程において所期の目的が達成されうる工程も含まれる。また「〜」を用いて示された数値範囲は、「〜」の前後に記載される数値をそれぞれ最小値及び最大値として含む範囲を示す。さらに研磨液中の各成分の含有量は、研磨液中に各成分に該当する物質が複数存在する場合、特に断らない限り、研磨液中に存在する当該複数の物質の合計量を意味する。 In this specification, the term “process” includes not only an independent process but also a process that cannot be clearly distinguished from other processes and in which the intended purpose can be achieved. . Moreover, the numerical range shown using "to" shows the range which includes the numerical value described before and behind "to" as a minimum value and a maximum value, respectively. Further, the content of each component in the polishing liquid means the total amount of the plurality of substances present in the polishing liquid unless there is a specific notice when there are a plurality of substances corresponding to each component in the polishing liquid.
以下、本発明の金属膜用研磨液(以下、単に「研磨液」ともいう。)、及び金属膜用研磨液を用いた基板の研磨方法の好適な実施形態について詳細に説明する。 Hereinafter, preferred embodiments of the metal film polishing liquid of the present invention (hereinafter also simply referred to as “polishing liquid”) and a method for polishing a substrate using the metal film polishing liquid will be described in detail.
[金属膜用研磨液]
本実施形態の金属膜用研磨液は、重量平均分子量が20,000以上のメタクリル酸系ポリマ及び水系溶媒を含有することを特徴とする。その製造方法は、溶液中で少なくともメタクリル酸を含むモノマ成分を重合させて重量平均分子量が20,000以上のメタクリル酸系ポリマを得る工程と、重量平均分子量が20,000以上のメタクリル酸系ポリマ、水系溶媒、研磨粒子を混合して研磨液を得る工程と、を備える。
[Metal film polishing liquid]
The metal film polishing liquid of this embodiment is characterized by containing a methacrylic acid polymer having a weight average molecular weight of 20,000 or more and an aqueous solvent. The production method includes a step of polymerizing a monomer component containing at least methacrylic acid in a solution to obtain a methacrylic acid polymer having a weight average molecular weight of 20,000 or more, and a methacrylic acid polymer having a weight average molecular weight of 20,000 or more. And a step of mixing an aqueous solvent and abrasive particles to obtain a polishing liquid.
それぞれの工程における「重合」及び「混合」の操作については当業者であれば適宜実施することができる。したがって、各工程で規定される化合物等について、次の「研磨液」の項で詳述する。 The operations of “polymerization” and “mixing” in each step can be appropriately performed by those skilled in the art. Therefore, the compounds defined in each step will be described in detail in the next section “Polishing liquid”.
[研磨液]
本実施形態の研磨液は、重量平均分子量が20,000以上のメタクリル酸系ポリマと、研磨粒子と、水系溶媒とを含有する。このような研磨液は導電性物質の残渣を含む基体を化学機械研磨するために好適に用いることができる。
[Polishing liquid]
The polishing liquid of this embodiment contains a methacrylic acid polymer having a weight average molecular weight of 20,000 or more, abrasive particles, and an aqueous solvent. Such a polishing liquid can be suitably used for chemical mechanical polishing a substrate containing a residue of a conductive substance.
<メタクリル酸系ポリマ>
本実施形態のメタクリル酸系ポリマは、水溶性の重合開始剤を用いる場合と、メタクリル酸を含むモノマ成分に溶解する重合開始剤を用いる場合の2種類の方法がある。後者の、メタクリル酸を含むモノマ成分に溶解する重合開始剤を用いる場合は、まずメタクリル酸を含むモノマ成分に前記の重合開始剤を一旦溶解させ、その後水系溶媒中に前記重合開始剤を溶解させたメタクリル酸を含むモノマ成分を滴下することで重合開始剤を水系溶媒に溶解させつつポリマを得ることができる。
<Methacrylic acid polymer>
The methacrylic acid polymer of this embodiment has two methods, a case where a water-soluble polymerization initiator is used and a case where a polymerization initiator dissolved in a monomer component containing methacrylic acid is used. When using the latter polymerization initiator that dissolves in the monomer component containing methacrylic acid, first dissolve the polymerization initiator in the monomer component containing methacrylic acid, and then dissolve the polymerization initiator in an aqueous solvent. By adding dropwise a monomer component containing methacrylic acid, a polymer can be obtained while dissolving the polymerization initiator in an aqueous solvent.
また、上記メタクリル酸系ポリマとしては、メタクリル酸のホモポリマ及び、メタクリル酸と該メタクリル酸と共重合可能なモノマとのコポリマから選ばれる少なくとも1種であることが好ましい。 The methacrylic acid polymer is preferably at least one selected from a homopolymer of methacrylic acid and a copolymer of methacrylic acid and a monomer copolymerizable with the methacrylic acid.
メタクリル酸系ポリマがメタクリル酸と該メタクリル酸と共重合可能なモノマとのコポリマである場合、モノマ全量に対するメタクリル酸の割合は、好ましくは40モル%以上、100モル%未満、より好ましくは50モル%以上、100モル%未満、さらに好ましくは60モル%以上、100モル%未満、特に好ましくは70モル%以上、100モル%未満である。上記メタクリル酸の割合を40モル%以上にすることにより、配線間エロージョンの発生を効果的に抑制し、被研磨面の平坦性を高めやすくなる。 When the methacrylic acid polymer is a copolymer of methacrylic acid and a monomer copolymerizable with the methacrylic acid, the ratio of methacrylic acid to the total amount of the monomer is preferably 40 mol% or more and less than 100 mol%, more preferably 50 mol. % Or more and less than 100 mol%, more preferably 60 mol% or more and less than 100 mol%, particularly preferably 70 mol% or more and less than 100 mol%. By setting the ratio of the methacrylic acid to 40 mol% or more, generation of erosion between wirings can be effectively suppressed, and the flatness of the surface to be polished can be easily improved.
メタクリル酸系ポリマの重量平均分子量は、20,000以上、好ましくは50,000以上である。上記メタクリル酸系ポリマの重量平均分子量が20,000以上のポリマを含んでなる研磨液を用いて、導電性物質の残渣が発生しつつ、金属配線と金属配線の間の部分には残渣が発生していない基板のバリア層を研磨する場合に、配線間エロージョンの発生を効果的に抑制し、被研磨面の平坦性を高めやすくなる。また、上記重量平均分子量の上限は特に規定されるものではないが、溶解性の観点から500万以下であることが好ましい。また、合成のしやすさ、分子量制御の容易さ等の観点より、上重量平均分子量は100万以下であることが好ましく、水への溶解性に優れ、添加量の自由度が上がる観点では100,000以下であることがより好ましい。 The weight average molecular weight of the methacrylic acid polymer is 20,000 or more, preferably 50,000 or more. Using a polishing liquid containing a polymer having a weight average molecular weight of 20,000 or more of the methacrylic acid polymer, a residue of the conductive material is generated, and a residue is generated between the metal wiring and the metal wiring. When polishing a barrier layer of a substrate that has not been processed, generation of erosion between wirings can be effectively suppressed, and the flatness of the surface to be polished can be easily improved. The upper limit of the weight average molecular weight is not particularly defined, but is preferably 5 million or less from the viewpoint of solubility. Further, from the viewpoint of ease of synthesis, ease of molecular weight control, etc., the upper weight average molecular weight is preferably 1,000,000 or less, from the viewpoint of excellent solubility in water and increasing the degree of freedom of addition. More preferably, it is 1,000 or less.
メタクリル酸系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る。具体的には、例えば、下記のような測定条件にて、ポリマーラボラトリー社製のポリアクリル酸ナトリウム標準物質で作成した検量線を用い、サイズ排除クロマトグラフ法で測定することができる。
カラム:昭和電工株式会社製 Shodex Asahipak GS−520HQ+620HQ
ポンプ:株式会社日立製作所製 L−71000
溶離液:50mM−Na2HPO4 aq./CH3CN=90/10
流速:0.6mL/min
検出器:株式会社日立製作所製 L−3300型示差屈折計
データ処理:株式会社日立製作所製 D−2520型GPCインデグレーター
試料濃度:10mg/mL
注入量:5μL
The weight average molecular weight of the methacrylic acid polymer can be measured by gel permeation chromatography using a standard polystyrene calibration curve. Specifically, for example, measurement can be performed by size exclusion chromatography using a calibration curve prepared with a sodium polyacrylate standard substance manufactured by Polymer Laboratories under the following measurement conditions.
Column: Shodex Asahipak GS-520HQ + 620HQ manufactured by Showa Denko KK
Pump: Hitachi Ltd. L-71000
Eluent: 50mM-Na 2 HPO 4 aq . / CH 3 CN = 90/10
Flow rate: 0.6 mL / min
Detector: L-3300 type differential refractometer manufactured by Hitachi, Ltd. Data processing: D-2520 type GPC indexer manufactured by Hitachi, Ltd. Sample concentration: 10 mg / mL
Injection volume: 5 μL
上記メタクリル酸と共重合可能なモノマとしては、アクリル酸、クロトン酸、ビニル酢酸、チグリック酸、2−トリフルオロメチルアクリル酸、イタコン酸、フマル酸、マレイン酸、シトラコン酸、メサコン酸、グルコン酸等のカルボン酸類;2−アクリルアミド−2−メチルプロパンスルホン酸等のスルホン酸類;アクリル酸メチル、アクリル酸エチル、アクリル酸プロピル、アクリル酸ブチル、アクリル酸2−エチルヘキシル、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸プロピル、メタクリル酸ブチル、メタクリル酸2−エチルヘキシル等のアクリル酸系エステル類;及びこれらのアンモニウム塩、アルカリ金属塩、アルキルアミン塩等の塩などが挙げられる。適用する基板が半導体集積回路用シリコン基板などの場合は、アルカリ金属による汚染は望ましくないため、酸もしくはそのアンモニウム塩が好ましい。基板がガラス基板等である場合はその限りではない。 Monomers copolymerizable with methacrylic acid include acrylic acid, crotonic acid, vinyl acetic acid, tiglic acid, 2-trifluoromethyl acrylic acid, itaconic acid, fumaric acid, maleic acid, citraconic acid, mesaconic acid, gluconic acid, etc. Carboxylic acids such as 2-acrylamido-2-methylpropane sulfonic acid; methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, methacrylic acid And acrylic acid esters such as propyl acid, butyl methacrylate and 2-ethylhexyl methacrylate; and salts such as ammonium salts, alkali metal salts and alkylamine salts thereof. In the case where the substrate to be applied is a silicon substrate for a semiconductor integrated circuit or the like, acid or its ammonium salt is preferable because contamination with an alkali metal is not desirable. This is not the case when the substrate is a glass substrate or the like.
上記の通り、メタクリル酸系ポリマにおいてメタクリル酸の含有量が多い方が配線間エロージョンの発生の低減には有効である。 As described above, a higher content of methacrylic acid in the methacrylic acid polymer is effective in reducing the occurrence of erosion between wirings.
メタクリル酸系ポリマの配合量は、研磨液の全成分の総量を100gとしたとき、好ましくは0.001〜15g、より好ましくは0.01〜5gである。上記メタクリル酸系ポリマの配合量を0.001g以上にすることにより、配線間エロージョンの発生を効果的に抑制し、被研磨面の平坦性を高めやすくなり、15g以下にすることにより、配線間エロージョンの発生を抑制しつつ、研磨液に含まれる研磨粒子の安定性を維持し、研磨粒子の分散性を良好にしやすくなる。 The blending amount of the methacrylic acid polymer is preferably 0.001 to 15 g, more preferably 0.01 to 5 g, when the total amount of all components of the polishing liquid is 100 g. By making the blending amount of the methacrylic acid-based polymer 0.001 g or more, the occurrence of erosion between wirings can be effectively suppressed, and the flatness of the surface to be polished can be easily improved. While suppressing the occurrence of erosion, the stability of the abrasive particles contained in the polishing liquid is maintained, and the dispersibility of the abrasive particles is easily improved.
<研磨粒子>
本実施形態の金属膜用研磨液は、バリア層及び層間絶縁膜に対する良好な研磨速度を得る点で、研磨粒子を含有することが好ましい。用いることのできる研磨粒子としては、シリカ、アルミナ、ジルコニア、セリア、チタニア、ゲルマニア及びこれらの変性物から選ばれる少なくとも一種である。上記変性物は、シリカ、アルミナ、ジルコニア、セリア、チタニア、ゲルマニアなどの研磨粒子の表面をアルキル基で変性したものである。
<Abrasive particles>
The metal film polishing liquid of the present embodiment preferably contains abrasive particles from the viewpoint of obtaining a good polishing rate for the barrier layer and the interlayer insulating film. The abrasive particles that can be used are at least one selected from silica, alumina, zirconia, ceria, titania, germania, and modified products thereof. The modified product is obtained by modifying the surface of abrasive particles such as silica, alumina, zirconia, ceria, titania and germania with an alkyl group.
研磨粒子の表面をアルキル基で変性する方法には、特に制限はないが、研磨粒子の表面に存在する水酸基とアルキル基を有するアルコキシシランとを反応させる方法が挙げられる。アルキル基を有するアルコキシシランとしては、特に制限はないが、モノメチルトリメトキシシラン、ジメチルジメトキシシラン、トリメチルモノメトキシシラン、モノエチルトリメトキシシラン、ジエチルジメトキシシラン、トリエチルモノメトキシシラン、モノメチルトリエトキシシラン、ジメチルジエトキシシラン、トリメチルモノエトキシシラン等が挙げられる。反応方法としては、特に制限はなく、例えば研磨粒子とアルコキシシランとを含む研磨液を室温に置いても反応するが、反応を加速するために加熱してもよい。 The method for modifying the surface of the abrasive particles with an alkyl group is not particularly limited, and examples thereof include a method of reacting a hydroxyl group present on the surface of the abrasive particle with an alkoxysilane having an alkyl group. The alkoxysilane having an alkyl group is not particularly limited, but monomethyltrimethoxysilane, dimethyldimethoxysilane, trimethylmonomethoxysilane, monoethyltrimethoxysilane, diethyldimethoxysilane, triethylmonomethoxysilane, monomethyltriethoxysilane, dimethyl Examples include diethoxysilane and trimethylmonoethoxysilane. The reaction method is not particularly limited. For example, the reaction is performed even when a polishing liquid containing abrasive particles and alkoxysilane is placed at room temperature, but the reaction may be heated to accelerate the reaction.
上記研磨粒子のなかでも、研磨液中での分散安定性が良く、CMPにより発生する研磨傷(スクラッチ)の発生数の少ない、平均粒径が200nm以下のコロイダルシリカ、コロイダルアルミナが好ましく、平均粒径が120nm以下のコロイダルシリカ、コロイダルアルミナがより好ましい。 Among the above-mentioned abrasive particles, colloidal silica and colloidal alumina having a good dispersion stability in the polishing liquid, a small number of polishing scratches (scratches) generated by CMP, and an average particle diameter of 200 nm or less are preferable. Colloidal silica and colloidal alumina having a diameter of 120 nm or less are more preferable.
研磨粒子の「平均粒径」とは、研磨粒子の平均二次粒子径を意味する。前記平均粒径は、研磨液を動的光散乱式粒度分布計(例えば、COULTER Electronics社製の商品名:COULTER N4 SD)で測定したD50の値(体積分布のメジアン径、累積中央値)をいう。 The “average particle diameter” of the abrasive particles means the average secondary particle diameter of the abrasive particles. The average particle diameter is a value of D50 (median diameter of volume distribution, cumulative median value) obtained by measuring the polishing liquid with a dynamic light scattering particle size distribution meter (for example, product name: COULTER Electronics 4 manufactured by COULTER Electronics). Say.
具体的には、平均粒径は下記の手順により測定できる。まず、研磨液を100μL(Lはリットルを表す。以下同じ。)程度量り取り、研磨粒子の含有量が0.05質量%前後(測定時透過率(H)が60〜70%である含有量)になるようにイオン交換水で希釈して希釈液を得る。そして、希釈液を動的光散乱式粒度分布計の試料槽に投入し、D50として表示される値を読み取ることにより、平均粒径を測ることができる。 Specifically, the average particle diameter can be measured by the following procedure. First, 100 μL of polishing liquid (L represents liter; the same applies hereinafter) is weighed, and the content of abrasive particles is around 0.05% by mass (the transmittance (H) during measurement is 60 to 70%). ) To obtain a diluted solution. And an average particle diameter can be measured by throwing a dilution liquid into the sample tank of a dynamic light scattering type particle size distribution analyzer, and reading the value displayed as D50.
また、金属配線膜、バリアメタル膜及び層間絶縁膜の研磨速度の観点より、上記研磨粒子は一次粒子が平均2粒子未満しか凝集していない粒子が好ましく、一次粒子が平均1.2粒子未満しか凝集していない粒子がより好ましい。会合度の上限は、使用する研磨粒子の一次粒子径によって異なり、二次粒子径が上記で説明した範囲に入っていればよいと考えられる。なお、上記の会合度は、二次粒子径と一次粒子径を求め、その比(二次粒子径/一次粒子径)として得ることができる。 In addition, from the viewpoint of the polishing rate of the metal wiring film, barrier metal film, and interlayer insulating film, the abrasive particles are preferably particles in which primary particles are aggregated less than an average of less than 2 particles, and primary particles are less than an average of less than 1.2 particles. More preferred are non-aggregated particles. The upper limit of the degree of association differs depending on the primary particle size of the abrasive particles used, and it is considered that the secondary particle size only needs to be in the range described above. The degree of association can be obtained as the ratio (secondary particle diameter / primary particle diameter) by determining the secondary particle diameter and the primary particle diameter.
上記一次粒子径の測定方法としては、公知の透過型電子顕微鏡(例えば株式会社日立製作所製のH−7100FA)により測定することができる。例えば、上記電子顕微鏡を用いて、粒子の画像を撮影し、所定数の任意の粒子について二軸平均一次粒子径を算出し、これらの平均値を求める。粒度分布が広い場合、上記所定数は、平均値が安定する数量とするべきである。研磨粒子として、コロイダルシリカ又はコロイダルアルミナを用いる場合、一般に粒径がそろっているため、測定する粒子数は例えば20粒子程度でよい。 As a measuring method of the said primary particle diameter, it can measure with a well-known transmission electron microscope (for example, H-7100FA by Hitachi, Ltd.). For example, using the electron microscope, an image of particles is taken, a biaxial average primary particle diameter is calculated for a predetermined number of arbitrary particles, and an average value thereof is obtained. When the particle size distribution is wide, the predetermined number should be a quantity whose average value is stable. When colloidal silica or colloidal alumina is used as the abrasive particles, since the particle diameter is generally uniform, the number of particles to be measured may be about 20 particles, for example.
具体的には、選択した粒子に外接し、その長径が最も長くなるように配置した長方形(外接長方形)を導く。そしてその外接長方形の長径をL、短径をBとして、(L+B)/2として一粒子の二軸平均一次粒子径を算出する。この作業を任意の20粒子に対して実施し、得られた値の平均値を、本実施形態における二軸平均一次粒子径(R1)という。この操作はコンピュータプログラムで自動化することも可能である。 Specifically, a rectangle (circumscribed rectangle) that circumscribes the selected particle and is arranged so that its major axis is the longest is derived. Then, assuming that the major axis of the circumscribed rectangle is L and the minor axis is B, the biaxial average primary particle diameter of one particle is calculated as (L + B) / 2. This operation is performed on 20 arbitrary particles, and the average value obtained is referred to as a biaxial average primary particle diameter (R1) in the present embodiment. This operation can also be automated by a computer program.
同時に、平均粒度分布の標準偏差が10nm以下であることが好ましく、平均粒度分布の標準偏差が5nm以下であることがより好ましい。粒度分布の標準偏差の測定方法としては、研磨液中の研磨粒子をCOULTER Electronics社製のCOULTER N4SDに投入し、粒度分布のチャートにより標準偏差の値を得ることができる。 At the same time, the standard deviation of the average particle size distribution is preferably 10 nm or less, and the standard deviation of the average particle size distribution is more preferably 5 nm or less. As a method for measuring the standard deviation of the particle size distribution, the abrasive particles in the polishing liquid can be put into COULTER N4SD manufactured by COULTER Electronics, and the standard deviation value can be obtained from the particle size distribution chart.
研磨粒子の配合量は、研磨液の全成分の総量100gに対して、好ましくは0.01〜50g、より好ましくは0.02〜30g、特に好ましくは0.05〜20gである。上記研磨粒子の配合量を0.01g以上にすることにより研磨速度を良好にし、50g以下にすることによりスクラッチの発生を抑制しやすくなる。 The blending amount of the abrasive particles is preferably 0.01 to 50 g, more preferably 0.02 to 30 g, and particularly preferably 0.05 to 20 g with respect to 100 g of the total amount of all components of the polishing liquid. By making the blending amount of the abrasive particles 0.01 g or more, the polishing rate is improved, and by making it 50 g or less, it becomes easy to suppress the generation of scratches.
研磨粒子は研磨粒子の表面にアニオン基やカチオン基を修飾した研磨粒子を用いても良い。アニオン基やカチオン基を修飾することで、研磨粒子の表面電位がマイナス又はプラスチャージとなるため、研磨液のpH変化による研磨粒子の凝集を抑制することが出来る。 As the abrasive particles, abrasive particles obtained by modifying the surface of the abrasive particles with an anionic group or a cationic group may be used. By modifying the anion group or the cation group, the surface potential of the abrasive particles becomes negative or positive charge, so that aggregation of the abrasive particles due to pH change of the polishing liquid can be suppressed.
修飾するアニオン基の種類としては、スルホン酸修飾やアルミン酸修飾等が挙げられる。また、修飾するカチオン基の種類としては、アミン系化合物等が挙げられる。 Examples of the anionic group to be modified include sulfonic acid modification and aluminate modification. Examples of the cationic group to be modified include amine compounds.
<水系溶媒の酸>
本発明の金属膜用研磨液は、酸化剤により酸化された金属配線及びバリア金属の溶解を促進し、研磨速度を向上させることができる点で、酸を含むことが好ましい。本発明で用いられる酸は、酸化されたバリア金属又は金属配線を水に溶解させることができれば特に制限はないが、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、3−メチルフタル酸、4−メチルフタル酸、3−アミノフタル酸、4−アミノフタル酸、3−ニトロフタル酸、4−ニトロフタル酸、グルタル酸、アジピン酸、ピメリン酸、マレイン酸、フタル酸、イソフタル酸、リンゴ酸、酒石酸、クエン酸、p−トルエンスルホン酸、p−フェノールスルホン酸、メチルスルホン酸、乳酸、イタコン酸、安息香酸、マレイン酸、キナルジン酸、アジピン酸、ピメリン酸等の有機酸、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、アルカリ金属、アルカリ土類金属、ハロゲン化物等との塩が挙げられる。また塩酸、硫酸、硝酸等の無機酸、これら無機酸のアンモニウム塩類、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、クロム酸等が挙げられる。ただし、例えば研磨する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ため、上記酸の塩としてはアルカリ金属、アルカリ土類金属又はハロゲン化物との塩以外が好ましい。これらの中では、実用的な研磨速度を維持しつつ、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、フタル酸、グリコール酸、コハク酸から選ばれる少なくとも1種であることが好ましい。また、これらは1種類を単独で、もしくは2種類以上を混合して用いることができる。
<Aqueous solvent acid>
The metal film polishing liquid of the present invention preferably contains an acid in that the metal wiring oxidized by the oxidizing agent and the barrier metal can be accelerated and the polishing rate can be improved. The acid used in the present invention is not particularly limited as long as the oxidized barrier metal or metal wiring can be dissolved in water. For example, 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, 3-methylphthalic acid, 4-methylphthalic acid, 3-aminophthalic acid, 4-aminophthalic acid, 3-nitrophthalic acid, 4-nitrophthalic acid, glutaric acid, adipic acid, Pimelic acid, maleic acid, phthalic acid, isophthalic acid, malic acid, tartaric acid, citric acid, p-toluenesulfonic acid, p-phenolsulfone , Methylsulfonic acid, lactic acid, itaconic acid, benzoic acid, maleic acid, quinaldic acid, adipic acid, pimelic acid, and other organic acids, organic acid esters thereof and ammonium salts of these organic acids, alkali metals, alkaline earth metals, And salts with halides and the like. Further, inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid, ammonium salts of these inorganic acids, ammonium persulfate, ammonium nitrate, ammonium chloride, chromic acid and the like can be mentioned. However, for example, when the substrate to be polished is a silicon substrate including an integrated circuit element, contamination by alkali metal, alkaline earth metal, halide, etc. is not desirable. Or a salt other than a salt with a halide is preferred. Among these, malonic acid, malic acid, tartaric acid, citric acid, salicylic acid, adipic acid, phthalic acid, glycolic acid, succinic acid in that the etching rate can be effectively suppressed while maintaining a practical polishing rate. It is preferably at least one selected from Moreover, these can be used individually by 1 type or in mixture of 2 or more types.
酸の配合量は、金属膜用研磨液の全成分の総量100gに対して、好ましくは0.001〜20g、より好ましくは0.002〜10g、さらに好ましくは0.005〜5gである。上記酸の配合量を0.001g以上にすることにより、金属配線及びバリア金属の研磨速度を良好にし、20g以下にすることによりエッチングを抑制し被研磨面の荒れを低減しやすくなる。 The compounding amount of the acid is preferably 0.001 to 20 g, more preferably 0.002 to 10 g, and still more preferably 0.005 to 5 g with respect to 100 g of the total amount of all components of the metal film polishing liquid. When the amount of the acid is 0.001 g or more, the polishing rate of the metal wiring and the barrier metal is improved, and when the amount is 20 g or less, etching is suppressed and the roughness of the surface to be polished is easily reduced.
本実施形態の研磨液は、少なくとも研磨粒子を含むスラリと、少なくともメタクリル酸系ポリマを含む添加液とに分けられた二液を混合することにより得ることもできる。このようにすることによって、メタクリル酸系ポリマを大量に添加したときに生じる研磨粒子の安定性の問題を回避することができる。二液に分ける場合、スラリ側にメタクリル酸系ポリマが含まれていてもかまわない。この場合、スラリ中のメタクリル酸系ポリマの含有量は研磨粒子の分散性を損なわない範囲とする。 The polishing liquid of this embodiment can also be obtained by mixing two liquids divided into a slurry containing at least abrasive particles and an additive liquid containing at least a methacrylic acid polymer. By doing so, it is possible to avoid the problem of stability of the abrasive particles which occurs when a large amount of methacrylic acid polymer is added. When dividing into two liquids, a methacrylic acid polymer may be contained on the slurry side. In this case, the content of the methacrylic acid polymer in the slurry is in a range that does not impair the dispersibility of the abrasive particles.
<金属防食剤>
本実施形態の金属膜用研磨液には、さらに金属防食剤を含有することができる。金属防食剤としては特に制限はなく、金属に対する防食作用を有する化合物として従来公知のものがいずれも使用可能である。具体的には、トリアゾール化合物、ピリジン化合物、ピラゾール化合物、ピリミジン化合物、イミダゾール化合物、グアニジン化合物、チアゾール化合物、テトラゾール化合物、トリアジン化合物、ヘキサメチレンテトラミンから選択される少なくとも1種を用いることができる。ここで「化合物」とは、その骨格を有する化合物の総称であり、例えばトリアゾール化合物とはトリアゾール骨格を有する化合物を意味する。本発明の金属膜用研磨液に用いる金属防食剤として、トリアゾール骨格を有するトリアゾール化合物が好ましい。
<Metal anticorrosive>
The metal film polishing liquid of the present embodiment may further contain a metal anticorrosive. There is no restriction | limiting in particular as a metal anticorrosive agent, Any conventionally well-known thing can be used as a compound which has the anticorrosion action with respect to a metal. Specifically, at least one selected from triazole compounds, pyridine compounds, pyrazole compounds, pyrimidine compounds, imidazole compounds, guanidine compounds, thiazole compounds, tetrazole compounds, triazine compounds, and hexamethylenetetramine can be used. Here, “compound” is a general term for compounds having the skeleton, and for example, a triazole compound means a compound having a triazole skeleton. A triazole compound having a triazole skeleton is preferable as the metal anticorrosive used in the metal film polishing liquid of the present invention.
トリアゾール化合物としては、例えば、1,2,3−トリアゾ−ル、1,2,4−トリアゾ−ル、3−アミノ−1H−1,2,4−トリアゾ−ル、ベンゾトリアゾ−ル、1−ヒドロキシベンゾトリアゾ−ル、1−ジヒドロキシプロピルベンゾトリアゾ−ル、2,3−ジカルボキシプロピルベンゾトリアゾ−ル、4−ヒドロキシベンゾトリアゾ−ル、4−カルボキシ−1H−ベンゾトリアゾ−ル、4−カルボキシ−1H−ベンゾトリアゾ−ルメチルエステル(1H−ベンゾトリアゾール−4−カルボン酸メチル)、4−カルボキシ−1H−ベンゾトリアゾ−ルブチルエステル(1H−ベンゾトリアゾール−4−カルボン酸ブチル)、4−カルボキシ−1H−ベンゾトリアゾ−ルオクチルエステル(1Hベンゾトリアゾール−4−カルボン酸オクチル)、5−ヘキシルベンゾトリアゾ−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−エチルヘキル)アミン、トリルトリアゾ−ル、ナフトトリアゾ−ル、ビス[(1−ベンゾトリアゾリル)メチル]ホスホン酸、3H−1,2,3−トリアゾロ[4,5−b]ピリジン−3−オール、1H−1,2,3−トリアゾロ[4,5−b]ピリジン、1−アセチル−1H−1,2,3−トリアゾロ[4,5−b]ピリジン、3−ヒドロキシピリジン、1,2,4−トリアゾロ[1,5−a]ピリミジン、1,3,4,6,7,8−ヘキサヒドロ−2H−ピリミド[1,2−a]ピリミジン、2−メチル−5,7−ジフェニル−[1,2,4]トリアゾロ[1,5−a]ピリミジン、2−メチルサルファニル−5,7−ジフェニル−[1,2,4]トリアゾロ[1,5−a]ピリミジン、2−メチルサルファニル−5,7−ジフェニル−4,7−ジヒドロ−[1,2,4]トリアゾロ[1,5−a]ピリミジンが挙げられる。なお、一分子中にトリアゾール骨格と、それ以外の骨格を有する場合には、トリアゾール化合物と分類するものとする。 Examples of the triazole compound include 1,2,3-triazole, 1,2,4-triazole, 3-amino-1H-1,2,4-triazole, benzotriazole, 1-hydroxy. Benzotriazole, 1-dihydroxypropylbenzotriazole, 2,3-dicarboxypropylbenzotriazole, 4-hydroxybenzotriazole, 4-carboxy-1H-benzotriazole, 4- Carboxy-1H-benzotriazole-methyl ester (methyl 1H-benzotriazole-4-carboxylate), 4-carboxy-1H-benzotriazole-butyl ester (butyl 1H-benzotriazole-4-carboxylate), 4-carboxy- 1H-benzotriazol-octyl ester (1H-benzotriazole-4-carboxylic acid oct ), 5-hexylbenzotriazol, (1,2,3-benzotriazolyl-1-methyl) (1,2,4-triazolyl-1-methyl) (2-ethylhexyl) amine, tolyltriazo- , Naphthotriazole, bis [(1-benzotriazolyl) methyl] phosphonic acid, 3H-1,2,3-triazolo [4,5-b] pyridin-3-ol, 1H-1,2,3 -Triazolo [4,5-b] pyridine, 1-acetyl-1H-1,2,3-triazolo [4,5-b] pyridine, 3-hydroxypyridine, 1,2,4-triazolo [1,5- a] pyrimidine, 1,3,4,6,7,8-hexahydro-2H-pyrimido [1,2-a] pyrimidine, 2-methyl-5,7-diphenyl- [1,2,4] triazolo [1 , 5-a] pyrimidine, 2-me Rusulfanyl-5,7-diphenyl- [1,2,4] triazolo [1,5-a] pyrimidine, 2-methylsulfanyl-5,7-diphenyl-4,7-dihydro- [1,2,4] And triazolo [1,5-a] pyrimidine. In addition, when it has a triazole skeleton and other skeletons in one molecule, it shall be classified as a triazole compound.
ピリジン化合物としては、例えば、8−ヒドロキシキノリン、プロチオナミド、2−ニトロピリン−3−オール、ピリドキサミン、ニコチンアミド、イプロニアジド、イソニコチン酸、ベンソ[f]キノリン、2,5−ピリジンジカルボン酸、4−スチリルピリジン、アナバシン、4−ニトロピリジン−1−オキシド、ピリジン−3−酢酸エチル、キノリン、2−エチルピリジン、キノリン酸、アレコリン、シトラジン酸、ピリジン−3−メタノール、2−メチル−5−エチルピリジン、2−フルオロピリジン、ペンタフルオロピリジン、6−メチルピリジン−3−オール、ピリジン−2−酢酸エチルが挙げられる。 Examples of the pyridine compound include 8-hydroxyquinoline, prothionamide, 2-nitropyrin-3-ol, pyridoxamine, nicotinamide, iproniazide, isonicotinic acid, benzo [f] quinoline, 2,5-pyridinedicarboxylic acid, 4-styryl. Pyridine, anabasine, 4-nitropyridine-1-oxide, pyridine-3-ethyl acetate, quinoline, 2-ethylpyridine, quinolinic acid, arecoline, citrazic acid, pyridine-3-methanol, 2-methyl-5-ethylpyridine, Examples include 2-fluoropyridine, pentafluoropyridine, 6-methylpyridin-3-ol, and pyridine-2-ethyl acetate.
ピラゾール化合物としては、例えば、ピラゾール、1−アリル−3,5−ジメチルピラゾール、3,5−ジ(2−ピリジル)ピラゾール、3,5−ジイソプロピルピラゾール、3,5−ジメチル−1−ヒドロキシメチルピラゾール、3,5−ジメチル−1−フェニルピラゾール、3,5−ジメチルピラゾール、3−アミノ−5−ヒドロキシピラゾール、4−メチルピラゾール、N−メチルピラゾール、3−アミノピラゾール、3−アミノピラゾールが挙げられる。 Examples of the pyrazole compound include pyrazole, 1-allyl-3,5-dimethylpyrazole, 3,5-di (2-pyridyl) pyrazole, 3,5-diisopropylpyrazole, 3,5-dimethyl-1-hydroxymethylpyrazole. 3,5-dimethyl-1-phenylpyrazole, 3,5-dimethylpyrazole, 3-amino-5-hydroxypyrazole, 4-methylpyrazole, N-methylpyrazole, 3-aminopyrazole, 3-aminopyrazole .
ピリミジン化合物としては、ピリミジン、1,3−ジフェニル−ピリミジン−2,4,6−トリオン、1,4,5,6−テトラヒドロピリミジン、2,4,5,6−テトラアミノピリミジンサルフェイト、2,4,5−トリヒドロキシピリミジン、2,4,6−トリアミノピリミジン、2,4,6−トリクロロピリミジン、2,4,6−トリメトキシピリミジン、2,4,6−トリフェニルピリミジン、2,4−ジアミノ−6−ヒドロキシルピリミジン、2,4−ジアミノピリミジン、2−アセトアミドピリミジン、2−アミノピリミジン、4−アミノピラゾロ[3,4−d]ピリミジン等が挙げられる。 Pyrimidine compounds include pyrimidine, 1,3-diphenyl-pyrimidine-2,4,6-trione, 1,4,5,6-tetrahydropyrimidine, 2,4,5,6-tetraaminopyrimidine sulfate, 2, 4,5-trihydroxypyrimidine, 2,4,6-triaminopyrimidine, 2,4,6-trichloropyrimidine, 2,4,6-trimethoxypyrimidine, 2,4,6-triphenylpyrimidine, 2,4 -Diamino-6-hydroxylpyrimidine, 2,4-diaminopyrimidine, 2-acetamidopyrimidine, 2-aminopyrimidine, 4-aminopyrazolo [3,4-d] pyrimidine and the like.
イミダゾール化合物としては、例えば、1,1´−カルボニルビス−1H−イミダゾール、1,1´−オキサリルジイミダゾール、1,2,4,5−テトラメチルイミダゾール、1,2−ジメチル−5−ニトロイミダゾール、1,2−ジメチルイミダゾール、1−(3−アミノプロピル)イミダゾール、1−ブチルイミダゾール、1−エチルイミダゾール、1−メチルイミダゾール、ベンズイミダゾールが挙げられる。 Examples of the imidazole compound include 1,1′-carbonylbis-1H-imidazole, 1,1′-oxalyldiimidazole, 1,2,4,5-tetramethylimidazole, and 1,2-dimethyl-5-nitroimidazole. 1,2-dimethylimidazole, 1- (3-aminopropyl) imidazole, 1-butylimidazole, 1-ethylimidazole, 1-methylimidazole and benzimidazole.
グアニジン化合物としては、例えば、1,1,3,3−テトラメチルグアニジン、1,2,3−トリフェニルグアニジン、1,3−ジ−o−トリルグアニジン、1,3−ジフェニルグアニジンが挙げられる。 Examples of the guanidine compound include 1,1,3,3-tetramethylguanidine, 1,2,3-triphenylguanidine, 1,3-di-o-tolylguanidine, and 1,3-diphenylguanidine.
チアゾール化合物としては、例えば、2−メルカプトベンゾチアゾール、2,4−ジメチルチアゾールが挙げられる。 Examples of the thiazole compound include 2-mercaptobenzothiazole and 2,4-dimethylthiazole.
テトラゾール化合物としては、例えば、テトラゾール、5−メチルテトラゾール、5−アミノ−1H−テトラゾール、1−(2−ジメチルアミノエチル)−5−メルカプトテトラゾールが挙げられる。 Examples of the tetrazole compound include tetrazole, 5-methyltetrazole, 5-amino-1H-tetrazole, and 1- (2-dimethylaminoethyl) -5-mercaptotetrazole.
トリアジン化合物としては、例えば、3,4−ジヒドロ−3−ヒドロキシ−4−オキソ−1,2,4−トリアジンが挙げられる。 Examples of the triazine compound include 3,4-dihydro-3-hydroxy-4-oxo-1,2,4-triazine.
前記金属防食剤は1種類を単独で、又は2種類以上を混合して用いることができる。前記金属防食剤の含有量は、被研磨膜に対して良好な研磨速度を得ることができる点で、研磨液の総質量に対し、0.001質量%〜10質量%であることが好ましい。同様の観点で、前記金属防食剤の含有量は、0.01質量%以上であることがより好ましく、0.02質量%以上であることが更に好ましい。また、同様の観点で、前記金属防食剤の含有量は、5.0質量%以下であることがより好ましく、0.5質量%であることが更に好ましい。 The said metal anticorrosive can be used individually by 1 type or in mixture of 2 or more types. The content of the metal anticorrosive is preferably 0.001% by mass to 10% by mass with respect to the total mass of the polishing liquid in that a good polishing rate can be obtained for the film to be polished. From the same viewpoint, the content of the metal anticorrosive is more preferably 0.01% by mass or more, and further preferably 0.02% by mass or more. Further, from the same viewpoint, the content of the metal anticorrosive is more preferably 5.0% by mass or less, and further preferably 0.5% by mass.
前記金属防食剤は銅系金属等の金属配線に対して保護膜を形成することで、金属配線のエッチングを抑制し被研磨面の荒れを低減しやすくなる。 The metal anticorrosive agent forms a protective film on a metal wiring such as a copper-based metal, thereby suppressing the etching of the metal wiring and easily reducing the roughness of the surface to be polished.
このような観点で、前記金属防食剤の中でも、トリアゾール化合物、ピリジン化合物、イミダゾール化合物、テトラゾール化合物、トリアジン化合物及びヘキサメチレンテトラミンからなる群より選択される少なくとも1種が好ましく、3H−1,2,3−トリアゾロ[4,5−b]ピリジン−3−オール、1−ヒドロキシベンゾトリアゾール、1H−1,2,3−トリアゾロ[4,5−b]ピリジン、ベンゾトリアゾール等のトリアゾール化合物、3−ヒドロキシピリジン、ベンズイミダゾール、5−アミノ−1H−テトラゾール、3,4−ジヒドロ−3−ヒドロキシ−4−オキソ−1,2,4−トリアジン及びヘキサメチレンテトラミンからなる群より選ばれる少なくとも1種がより好ましい。 From such a viewpoint, at least one selected from the group consisting of a triazole compound, a pyridine compound, an imidazole compound, a tetrazole compound, a triazine compound, and hexamethylenetetramine is preferable among the metal anticorrosive agents. Triazole compounds such as 3-triazolo [4,5-b] pyridin-3-ol, 1-hydroxybenzotriazole, 1H-1,2,3-triazolo [4,5-b] pyridine, benzotriazole, 3-hydroxy More preferred is at least one selected from the group consisting of pyridine, benzimidazole, 5-amino-1H-tetrazole, 3,4-dihydro-3-hydroxy-4-oxo-1,2,4-triazine and hexamethylenetetramine. .
前記研磨液における酸と金属防食剤との比率(酸/金属防食剤)は、エッチング速度と研磨速度を良好に制御する観点から、質量比で10/1〜1/5の範囲であることが好ましく、7/1〜1/5の範囲であることがより好ましく、5/1〜1/5の範囲であることが更に好ましく、5/1〜1/1の範囲であることが特に好ましい。 The ratio of the acid and the metal anticorrosive agent (acid / metal anticorrosive agent) in the polishing liquid is in the range of 10/1 to 1/5 in terms of mass ratio from the viewpoint of favorably controlling the etching rate and the polishing rate. The range of 7/1 to 1/5 is more preferable, the range of 5/1 to 1/5 is more preferable, and the range of 5/1 to 1/1 is particularly preferable.
更に前記金属膜用研磨液は、エッチング速度と研磨速度を良好に制御する観点から、カルボン酸化合物と、トリアゾール化合物、ピリジン化合物、イミダゾール化合物、テトラゾール化合物、トリアジン化合物及びヘキサメチレンテトラミンからなる群より選択される少なくとも1種の金属防食剤との比率(カルボン酸化合物/金属防食剤)が10/1〜1/5であることが好ましく、前記カルボン酸化合物と、トリアゾール化合物、ピリジン化合物、イミダゾール化合物、テトラゾール化合物、トリアジン化合物及びヘキサメチレンテトラミンからなる群より選択される少なくとも1種の金属防食剤との比率(カルボン酸化合物/金属防食剤)が5/1〜1/5であることがより好ましく、前記カルボン酸化合物と、3H−1,2,3−トリアゾロ[4,5−b]ピリジン−3−オール、1−ヒドロキシベンゾトリアゾール、1H−1,2,3−トリアゾロ[4,5−b]ピリジン、ベンゾトリアゾール等のトリアゾール化合物、3−ヒドロキシピリジン、ベンズイミダゾール、5−アミノ−1H−テトラゾール、3,4−ジヒドロ−3−ヒドロキシ−4−オキソ−1,2,4−トリアジン及びヘキサメチレンテトラミンからなる群より選ばれる少なくとも1種の金属防食剤との比率(カルボン酸化合物/金属防食剤)が5/1〜1/1であることが更に好ましい。 Further, the metal film polishing liquid is selected from the group consisting of a carboxylic acid compound, a triazole compound, a pyridine compound, an imidazole compound, a tetrazole compound, a triazine compound, and hexamethylenetetramine from the viewpoint of favorably controlling the etching rate and the polishing rate. It is preferable that the ratio (carboxylic acid compound / metal anticorrosive) to at least one metal anticorrosive to be 10/1 to 1/5, the carboxylic acid compound, triazole compound, pyridine compound, imidazole compound, It is more preferable that the ratio (carboxylic acid compound / metal anticorrosive) to at least one metal anticorrosive selected from the group consisting of a tetrazole compound, a triazine compound and hexamethylenetetramine is 5/1 to 1/5, The carboxylic acid compound and 3H-1,2,3-to Triazol compounds such as azolo [4,5-b] pyridin-3-ol, 1-hydroxybenzotriazole, 1H-1,2,3-triazolo [4,5-b] pyridine, benzotriazole, 3-hydroxypyridine, At least one metal corrosion inhibitor selected from the group consisting of benzimidazole, 5-amino-1H-tetrazole, 3,4-dihydro-3-hydroxy-4-oxo-1,2,4-triazine and hexamethylenetetramine; The ratio (carboxylic acid compound / metal anticorrosive) is more preferably 5/1 to 1/1.
<酸化剤>
前記金属膜用研磨液は、少なくとも1種の酸化剤(金属酸化剤)を更に含むことが好ましい。酸化剤を更に含むことで金属層の研磨速度をより向上させることができる。前記酸化剤は、特に制限はなく、通常用いられる酸化剤から適宜選択することができる。具体的には、過酸化水素、ペルオキソ硫酸塩、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、これらの中でも過酸化水素が好ましい。これら酸化剤は、1種類単独で又は2種類以上を混合して用いることができる。
<Oxidizing agent>
The metal film polishing liquid preferably further includes at least one oxidizing agent (metal oxidizing agent). By further containing an oxidizing agent, the polishing rate of the metal layer can be further improved. There is no restriction | limiting in particular in the said oxidizing agent, It can select suitably from the oxidizing agent used normally. Specific examples include hydrogen peroxide, peroxosulfate, nitric acid, potassium periodate, hypochlorous acid, ozone water, etc. Among these, hydrogen peroxide is preferable. These oxidizing agents can be used individually by 1 type or in mixture of 2 or more types.
研磨液が酸化剤を含む場合、酸化剤の含有量は、研磨液の総質量に対し、0.01質量%〜5質量%とすることが好ましい。前記含有量は、金属の酸化が不充分となり、研磨速度が低下することを防ぐ観点から、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、被研磨面に荒れが生じることと、ディッシングを小さく抑えることができる点で、5質量%以下がより好ましく、3質量%以下が更に好ましい。なお、過酸化水素水のように、一般に水溶液として入手できる酸化剤は、当該水溶液中に含まれる酸化剤の含有量が研磨液において前記範囲になるように調製できる。 When the polishing liquid contains an oxidizing agent, the content of the oxidizing agent is preferably 0.01% by mass to 5% by mass with respect to the total mass of the polishing liquid. The content is more preferably 0.02% by mass or more, and still more preferably 0.05% by mass or more from the viewpoint of preventing metal oxidation from becoming insufficient and reducing the polishing rate. Moreover, 5 mass% or less is more preferable, and 3 mass% or less is still more preferable at the point which can produce roughness on a to-be-polished surface and can suppress dishing small. Note that an oxidizing agent that is generally available as an aqueous solution, such as aqueous hydrogen peroxide, can be prepared so that the content of the oxidizing agent contained in the aqueous solution falls within the above range in the polishing liquid.
<有機溶媒>
前記研磨液は、さらに有機溶媒を含んでいてもよい。有機溶媒の添加により、バリア層の近傍に設けられたバリア層以外の層の濡れ性を向上させることができ、研磨速度をより向上させることができる。前記有機溶媒としては、特に制限はないが、水溶性のものが好ましい。ここで水溶性とは、水100gに対して25℃において0.1g以上溶解するものとして定義される。
<Organic solvent>
The polishing liquid may further contain an organic solvent. By adding the organic solvent, the wettability of layers other than the barrier layer provided in the vicinity of the barrier layer can be improved, and the polishing rate can be further improved. Although there is no restriction | limiting in particular as said organic solvent, A water-soluble thing is preferable. Here, water-soluble is defined as one that dissolves at least 0.1 g at 25 ° C. with respect to 100 g of water.
前記有機溶媒としては、エチレンカーボネート、プロピレンカーボネート、ジメチルカーボネート、ジエチルカーボネート、メチルエチルカーボネート等の炭酸エステル溶剤;ブチルラクトン、プロピルラクトン等のラクトン溶剤;エチレングリコール、プロピレングリコール、ジエチレングリコール、ジプロピレングリコール、トリエチレングリコール、トリプロピレングリコール等のグリコール溶剤;テトラヒドロフラン、ジオキサン、ジメトキシエタン、ポリエチレンオキサイド、エチレングリコールモノメチルアセテート、ジエチレングリコールモノエチルエーテルアセテート、プロピレングリコールモノメチルエーテルアセテート等のエーテル溶剤;メタノール、エタノール、プロパノール、n−ブタノール、n−ペンタノール、n−ヘキサノール、イソプロパノール、3−メトキシ−3−メチル−1−ブタノール等のアルコール溶剤;アセトン、メチルエチルケトン等のケトン溶剤;ジメチルホルムアミド、N−メチルピロリドン、酢酸エチル、乳酸エチル、スルホラン等のその他の有機溶媒などが挙げられる。 Examples of the organic solvent include carbonate solvents such as ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, and methyl ethyl carbonate; lactone solvents such as butyl lactone and propyl lactone; ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, Glycol solvents such as ethylene glycol and tripropylene glycol; ether solvents such as tetrahydrofuran, dioxane, dimethoxyethane, polyethylene oxide, ethylene glycol monomethyl acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate; methanol, ethanol, propanol, n- Butanol, n-pentanol, -Alcohol solvents such as hexanol, isopropanol and 3-methoxy-3-methyl-1-butanol; ketone solvents such as acetone and methyl ethyl ketone; other organic solvents such as dimethylformamide, N-methylpyrrolidone, ethyl acetate, ethyl lactate and sulfolane Etc.
また、有機溶媒はグリコール溶剤の誘導体であってもよい。エチレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテル、ジエチレングリコールモノメチルエーテル、ジプロピレングリコールモノメチルエーテル、トリエチレングリコールモノメチルエーテル、トリプロピレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、プロピレングリコールモノエチルエーテル、ジエチレングリコールモノエチルエーテル、ジプロピレングリコールモノエチルエーテル、トリエチレングリコールモノエチルエーテル、トリプロピレングリコールモノエチルエーテル、エチレングリコールモノプロピルエーテル、プロピレングリコールモノプロピルエーテル、ジエチレングリコールモノプロピルエーテル、トリエチレングリコールモノプロピルエーテル、トリプロピレングリコールモノプロピルエーテル、エチレングリコールモノブチルエーテル、プロピレングリコールモノブチルエーテル、ジエチレングリコールモノブチルエーテル、トリプロピレングリコールモノブチルエーテル、トリエチレングリコールモノブチルエーテル、トリプロピレングリコールモノブチルエーテル等のグリコールモノエーテル溶剤;エチレングリコールジメチルエーテル、プロピレングリコールジメチルエーテル、ジエチレングリコールジメチルエーテル、ジプロピレングリコールジメチルエーテル、トリエチレングリコールジメチルエチルエーテル、トリプロピレングリコールジメチルエーテル、エチレングリコールジエチルエーテル、プロピレングリコールジエチルエーテル、ジエチレングリコールジエチルエーテル、ジプロピレングリコールジエチルエーテル、トリエチレングリコールジエチルエーテル、トリプロピレングリコールジエチルエーテル、エチレングリコールジプロピルエーテル、プロピレングリコールジプロピルエーテル、ジエチレングリコールジプロピルエーテル、ジプロピレングリコールジプロピルエーテル、トリエチレングリコールジプロピルエーテル、トリプロピレングリコールジプロピルエーテル、エチレングリコールジブチルエーテル、プロピレングリコールジブチルエーテル、ジエチレングリコールジブチルエーテル、ジプロピレングリコールジブチルエーテル、トリエチレングリコールジブチルエーテル、トリプロピレングリコールジブチルエーテル等のグリコールエーテル溶剤などが挙げられる。 The organic solvent may be a glycol solvent derivative. Ethylene glycol monomethyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, triethylene glycol monomethyl ether, tripropylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monoethyl ether, di Propylene glycol monoethyl ether, triethylene glycol monoethyl ether, tripropylene glycol monoethyl ether, ethylene glycol monopropyl ether, propylene glycol monopropyl ether, diethylene glycol monopropyl ether, triethylene glycol monopropyl ether, triplicate Glycol monoether solvents such as pyrene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monobutyl ether, diethylene glycol monobutyl ether, tripropylene glycol monobutyl ether, triethylene glycol monobutyl ether, tripropylene glycol monobutyl ether; ethylene glycol dimethyl ether, propylene glycol Dimethyl ether, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, triethylene glycol dimethyl ethyl ether, tripropylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol diethyl ether, diethylene glycol diethyl ether , Dipropylene glycol diethyl ether, triethylene glycol diethyl ether, tripropylene glycol diethyl ether, ethylene glycol dipropyl ether, propylene glycol dipropyl ether, diethylene glycol dipropyl ether, dipropylene glycol dipropyl ether, triethylene glycol dipropyl ether, Examples thereof include glycol ether solvents such as tripropylene glycol dipropyl ether, ethylene glycol dibutyl ether, propylene glycol dibutyl ether, diethylene glycol dibutyl ether, dipropylene glycol dibutyl ether, triethylene glycol dibutyl ether, and tripropylene glycol dibutyl ether.
これらの中でも、グリコール溶剤、グリコール溶剤の誘導体、アルコール溶剤及び炭酸エステル溶剤から選ばれる少なくとも1種であることが好ましく、アルコール溶剤から選ばれる少なくとも1種であることがより好ましい。これら有機溶媒は、1種類単独で又は2種類以上を混合して用いることができる。 Among these, at least one selected from a glycol solvent, a derivative of a glycol solvent, an alcohol solvent, and a carbonate ester solvent is preferable, and at least one selected from an alcohol solvent is more preferable. These organic solvents can be used individually by 1 type or in mixture of 2 or more types.
研磨液が有機溶媒を含む場合、有機溶媒の含有量は、研磨液の総質量に対し、0.1質量%〜95質量%であることが好ましい。前記有機溶媒の含有量は、研磨液の基板に対する濡れ性が低くなるのを防ぐ点で、0.2質量%以上がより好ましく、0.5質量%以上が更に好ましい。また、研磨液の調製、使用、廃液処理等が容易になる点で、同含有量は50質量%以下がより好ましく、10質量%以下が更に好ましい。 When the polishing liquid contains an organic solvent, the content of the organic solvent is preferably 0.1% by mass to 95% by mass with respect to the total mass of the polishing liquid. The content of the organic solvent is more preferably 0.2% by mass or more, and still more preferably 0.5% by mass or more in terms of preventing the wettability of the polishing liquid to the substrate from being lowered. Further, the content is more preferably 50% by mass or less, and further preferably 10% by mass or less, in terms of facilitating preparation, use, waste liquid treatment, and the like of the polishing liquid.
<界面活性剤>
本実施形態に係る金属膜用研磨液は、界面活性剤を更に含有できる。界面活性剤としては、ラウリル硫酸アンモニウム、ポリオキシエチレンラウリルエーテル硫酸アンモニウム、アルキルリン酸エステル塩、ポリオキシエチレンアルキルエーテルリン酸塩等の水溶性陰イオン性界面活性剤;ポリオキシエチレンラウリルエーテル、ポリエチレングリコールモノステアレート等の水溶性非イオン性界面活性剤などが挙げられる。これらの中でも、界面活性剤としては、水溶性陰イオン性界面活性剤が好ましい。特に、共重合成分としてアンモニウム塩を用いて得られた高分子分散剤等の水溶性陰イオン性界面活性剤の少なくとも一種を使用することがより好ましい。水溶性非イオン性界面活性剤、水溶性陰イオン性界面活性剤、水溶性陽イオン性界面活性剤等を併用してもよい。界面活性剤の含有量は、研磨液の全質量基準で例えば0.0001〜0.1質量%である。
<Surfactant>
The metal film polishing liquid according to this embodiment may further contain a surfactant. Examples of the surfactant include water-soluble anionic surfactants such as ammonium lauryl sulfate, polyoxyethylene lauryl ether ammonium sulfate, alkyl phosphate ester salt, and polyoxyethylene alkyl ether phosphate; polyoxyethylene lauryl ether, polyethylene glycol mono Examples thereof include water-soluble nonionic surfactants such as stearate. Among these, as the surfactant, a water-soluble anionic surfactant is preferable. In particular, it is more preferable to use at least one water-soluble anionic surfactant such as a polymer dispersant obtained using an ammonium salt as a copolymerization component. A water-soluble nonionic surfactant, a water-soluble anionic surfactant, a water-soluble cationic surfactant and the like may be used in combination. The content of the surfactant is, for example, 0.0001 to 0.1% by mass based on the total mass of the polishing liquid.
<水系溶媒の水>
本実施形態に係る金属膜用研磨液は、水を含有している。研磨液における水の含有量は、他の構成成分の含有量を除いた研磨液の残部でよい。水としては、特に制限されないが、脱イオン水、イオン交換水及び超純水等が好ましい。
<Water of aqueous solvent>
The metal film polishing liquid according to this embodiment contains water. The content of water in the polishing liquid may be the remainder of the polishing liquid excluding the content of other components. Although it does not restrict | limit especially as water, Deionized water, ion-exchange water, ultrapure water, etc. are preferable.
<研磨液のpH>
本実施形態に係る金属膜用研磨液のpHは、配線金属の腐食を抑制する観点から2.0以上であることが好ましく、2.5以上であることが更に好ましい。pHが2.0未満の場合、研磨液中の水素イオンが金属配線に作用し、金属配線の腐食を促す。一方、バリア層、酸化珪素膜を良好な研磨速度で除去することが出来る観点からpHは3.5以下が好ましく、3.0以下がより好ましい。かかる効果が奏される要因は、pHが3.5を超えると、研磨粒子のゼータ電位が小さくなることでバリア層や酸化珪素膜と反発しやすくなり、これらの膜の研磨速度が低下すると考えられる。なお、pHを調整するために、酸及び塩基等の公知のpH調整剤(例えばアンモニア水や水酸化カリウム、硝酸、硫酸、塩酸、リン酸、ホウ酸及び酢酸の酸)を使用できる。pHは液温25℃におけるpHと定義する。
<PH of polishing liquid>
The pH of the metal film polishing liquid according to this embodiment is preferably 2.0 or more, and more preferably 2.5 or more, from the viewpoint of suppressing corrosion of the wiring metal. When the pH is less than 2.0, hydrogen ions in the polishing liquid act on the metal wiring and promote corrosion of the metal wiring. On the other hand, the pH is preferably 3.5 or less, more preferably 3.0 or less, from the viewpoint that the barrier layer and the silicon oxide film can be removed at a good polishing rate. The reason for this effect is that when the pH exceeds 3.5, the zeta potential of the abrasive particles becomes small, which tends to repel the barrier layer and the silicon oxide film, and the polishing rate of these films decreases. It is done. In addition, in order to adjust pH, well-known pH adjusters (for example, ammonia water, potassium hydroxide, nitric acid, a sulfuric acid, hydrochloric acid, phosphoric acid, boric acid, and an acetic acid) can be used in order to adjust pH. The pH is defined as the pH at a liquid temperature of 25 ° C.
研磨液のpHは、pHメータ(例えば、電気化学計器株式会社製、型番:PHL−40)で測定できる。例えば、標準緩衝液(フタル酸塩pH緩衝剤、pH:4.01(25℃);中性リン酸塩pH緩衝剤、pH:6.86(25℃))を用いて2点校正した後、電極を研磨液に入れて、25℃で2分以上経過して安定した後の値を測定することで、研磨液のpHを測定できる。 The pH of the polishing liquid can be measured with a pH meter (for example, model number: PHL-40, manufactured by Electrochemical Instrument Co., Ltd.). For example, after two-point calibration using a standard buffer (phthalate pH buffer, pH: 4.01 (25 ° C.); neutral phosphate pH buffer, pH: 6.86 (25 ° C.)) The pH of the polishing liquid can be measured by putting the electrode in the polishing liquid and measuring the value after 2 minutes or more have passed and stabilized at 25 ° C.
本実施形態に係る研磨液の構成成分は、複数の液に分けて貯蔵、運搬及び使用できる。したがって、例えば、本実施形態に係る研磨液は、分けて保管されていた酸化剤を含む成分と、酸化剤以外の構成成分とを混合して得てもよく、分けて保管されていた第一の液と第二の液(すなわち、前記研磨粒子と、前記重量平均分子量が20,000以上のメタクリル酸系ポリマと、前記酸、これらの塩と、前記金属防食剤とを含む第一の液と、前記酸化剤を含む第二の液)と、を混合して得てもよい。第一の液は、有機溶媒、界面活性剤等を更に含んでいてもよい。 The constituents of the polishing liquid according to this embodiment can be stored, transported and used in a plurality of liquids. Therefore, for example, the polishing liquid according to the present embodiment may be obtained by mixing a component containing an oxidizing agent that has been stored separately and a component other than the oxidizing agent, and the first stored separately. And a second liquid (that is, a first liquid containing the abrasive particles, the methacrylic acid polymer having a weight average molecular weight of 20,000 or more, the acid, a salt thereof, and the metal corrosion inhibitor). And a second liquid containing the oxidizing agent). The first liquid may further contain an organic solvent, a surfactant and the like.
本実施形態の金属膜用研磨液は、配線密度が50%以上である配線形成部を有する被研磨膜を研磨する場合に好適に使用できる。ここで配線密度とは、配線が形成されている部位において、層間絶縁膜部と金属配線部(バリア金属を含む)のそれぞれの幅から計算される値であり、例えばラインアンドスペースが100μm/100μmである場合は、その部分の配線密度は50%である。 The metal film polishing liquid of this embodiment can be suitably used for polishing a film to be polished having a wiring forming portion having a wiring density of 50% or more. Here, the wiring density is a value calculated from the respective widths of the interlayer insulating film portion and the metal wiring portion (including the barrier metal) at the portion where the wiring is formed. For example, the line and space is 100 μm / 100 μm. In this case, the wiring density in that portion is 50%.
配線密度が50%以上であると、金属配線部の占める面積が大きくなるため、その部分における配線間エロージョンの問題が顕著になる傾向があるが、本実施形態の研磨液を用いて研磨を行うことで、これらの問題を低減することができる。本実施形態の研磨液は、上記配線密度が80%以上である配線形成部を有する被研磨膜を研磨する場合にも好適に使用できる。 When the wiring density is 50% or more, the area occupied by the metal wiring portion becomes large, and thus the problem of erosion between wirings in the portion tends to become remarkable. However, polishing is performed using the polishing liquid of this embodiment. Thus, these problems can be reduced. The polishing liquid of this embodiment can also be suitably used for polishing a film to be polished having a wiring forming portion having a wiring density of 80% or more.
[研磨方法]
本実施形態の研磨方法は、導電性物質の残渣が発生し、金属配線と金属配線の間の部分には残渣が発生していない基板を、前述した金属膜用研磨液を用いて研磨して、導電性物質の残渣とバリア層を除去する研磨方法である。すなわち、研磨粒子、重量平均分子量が20,000以上のメタクリル酸系ポリマ及び水系溶媒を含有する研磨液を用いて、導電性物質の残渣が発生し、金属配線と金属配線の間の部分には残渣が発生していない基板を研磨する方法である。なお、基体を化学機械研磨する工程は、より具体的には、導電性物質の残渣が発生し、金属配線と金属配線の間の部分には残渣が発生していない基板の表面に形成された被研磨膜と研磨定盤上の研磨布との間に、前述した研磨液を供給しながら、前記被研磨膜が設けられた面側の前記基板表面を研磨布に押圧した状態で、該基板と研磨定盤とを相対的に動かすことによって被研磨膜の少なくとも一部を除去する工程である。
[Polishing method]
In the polishing method of this embodiment, a residue of a conductive material is generated, and a substrate in which no residue is generated between the metal wiring and the metal wiring is polished using the metal film polishing liquid described above. The polishing method removes the residue of the conductive material and the barrier layer. That is, using a polishing liquid containing abrasive particles, a methacrylic acid polymer having a weight average molecular weight of 20,000 or more, and an aqueous solvent, a residue of a conductive material is generated, and a portion between the metal wiring and the metal wiring is formed. This is a method of polishing a substrate on which no residue is generated. More specifically, the chemical mechanical polishing step of the substrate is formed on the surface of the substrate where the residue of the conductive material is generated and no residue is generated between the metal wiring and the metal wiring. While supplying the above-described polishing liquid between the film to be polished and the polishing cloth on the polishing surface plate, the substrate surface in a state where the surface of the substrate on which the film to be polished is provided is pressed against the polishing cloth. And removing at least a part of the film to be polished by relatively moving the polishing surface plate and the polishing surface plate.
以下、本実施形態の基板の研磨方法を用いる、半導体デバイスにおける配線層形成の一連の工程を、図2を参照しながら説明する。但し、本実施形態の金属膜用研磨液の用途は、下記工程に限定されない。なお、金属膜用研磨液については既に述べたとおりであるためここでの詳述は割愛する。 Hereinafter, a series of steps for forming a wiring layer in a semiconductor device using the substrate polishing method of this embodiment will be described with reference to FIG. However, the use of the metal film polishing liquid of the present embodiment is not limited to the following steps. Since the metal film polishing liquid has already been described, detailed description thereof will be omitted.
バリア層研磨前の基板は、図2(a)に示すように、シリコン基板の上に、所定パターンの凹部を有する絶縁体の層間絶縁膜1と、この絶縁体の層間絶縁膜1の表面の凸凹に沿って層間絶縁膜1を被覆するバリア(金属)層2を有し、所定パターンの凹部中のバリア(金属)層2上に導電性物質層4が形成される。本実施形態において「基体」とは、例えばこのようにシリコン基板上に所定の層が順次形成されたものを指す。 As shown in FIG. 2 (a), the substrate before polishing the barrier layer is an insulating interlayer insulating film 1 having a predetermined pattern of recesses on the silicon substrate, and the surface of the insulating interlayer insulating film 1 on the surface. A barrier (metal) layer 2 covering the interlayer insulating film 1 is provided along the unevenness, and a conductive material layer 4 is formed on the barrier (metal) layer 2 in the recess of a predetermined pattern. In this embodiment, the “base” refers to a substrate in which predetermined layers are sequentially formed on a silicon substrate, for example.
絶縁体の層間絶縁膜1としては、シリコン系絶縁体、有機ポリマ系絶縁体等が挙げられる。シリコン系絶縁体としては、二酸化珪素;フルオロシリケートグラス;トリメチルシラン又はジメトキシジメチルシランを出発原料として得られるオルガノシリケートグラス;シリコンオキシナイトライド、水素化シルセスキオキサン等のシリカ系絶縁体;シリコンカーバイド;シリコンナイトライドなどが挙げられる。また、有機ポリマ系絶縁体としては、全芳香族系低誘電率絶縁体が挙げられる。これらの中でも特に、二酸化珪素、オルガノシリケートグラスが好ましい。 Examples of the insulating interlayer insulating film 1 include a silicon-based insulator and an organic polymer-based insulator. Examples of silicon-based insulators include silicon dioxide; fluorosilicate glass; organosilicate glass obtained using trimethylsilane or dimethoxydimethylsilane as a starting material; silica-based insulators such as silicon oxynitride and silsesquioxane hydride; silicon carbide A silicon nitride may be used. Examples of the organic polymer insulator include wholly aromatic low dielectric constant insulators. Among these, silicon dioxide and organosilicate glass are particularly preferable.
絶縁体の層間絶縁膜1は、CVD(化学気相成長)法、スピンコート法、ディップコート法、又はスプレー法によって成膜される。絶縁体2の具体例としては、LSI製造工程、特に多層配線形成工程における絶縁体等が挙げられる。 The insulating interlayer insulating film 1 is formed by a CVD (chemical vapor deposition) method, a spin coat method, a dip coat method, or a spray method. Specific examples of the insulator 2 include an insulator in an LSI manufacturing process, particularly a multilayer wiring forming process.
バリア(金属)層2は、層間絶縁膜1中への導電性物質が拡散するのを防止するため、及び層間絶縁膜1と導電性物質層4との密着性向上のために形成される。バリア(金属)層2に用いられるバリア(金属)としては、タンタル、窒化タンタル、タンタル合金等のタンタル化合物、チタン、窒化チタン、チタン合金等のチタン化合物、タングステン、窒化タングステン、タングステン合金等のタングステン化合物、ルテニウム等のルテニウム化合物、コバルト等のコバルト化合物などが挙げられる。バリア(金属)層2は、これらの1種からなる単層構造であっても、2種以上からなる積層構造であってもよい。バリア(金属)層2は、蒸着、CVD(化学気相成長)、ALD(原子層堆積法)等によって成膜される。 The barrier (metal) layer 2 is formed to prevent the conductive material from diffusing into the interlayer insulating film 1 and to improve the adhesion between the interlayer insulating film 1 and the conductive material layer 4. Examples of the barrier (metal) used in the barrier (metal) layer 2 include tantalum compounds such as tantalum, tantalum nitride, and tantalum alloys, titanium compounds such as titanium, titanium nitride, and titanium alloys, and tungsten such as tungsten, tungsten nitride, and tungsten alloys. Examples thereof include a compound, a ruthenium compound such as ruthenium, and a cobalt compound such as cobalt. The barrier (metal) layer 2 may have a single layer structure composed of one kind of these or a laminated structure composed of two or more kinds. The barrier (metal) layer 2 is formed by vapor deposition, CVD (chemical vapor deposition), ALD (atomic layer deposition), or the like.
導電性物質層4に用いられる導電性物質としては、銅、銅合金、銅の酸化物、銅合金の酸化物等の銅を主成分とする金属、タングステン、タングステン合金等のタングステン金属、銀、金等の貴金属などが挙げられる。これらの中でも、銅、銅合金、銅の酸化物、銅合金の酸化物等の銅を主成分とする金属が好ましい。導電性物質層4は、公知のスパッタ法、メッキ法等によって成膜される。 Examples of the conductive material used for the conductive material layer 4 include copper, copper alloys, copper oxides, copper-based metals such as copper alloys, tungsten metals such as tungsten and tungsten alloys, silver, Examples include noble metals such as gold. Among these, metals having copper as a main component such as copper, copper alloys, copper oxides, and copper alloy oxides are preferable. The conductive material layer 4 is formed by a known sputtering method, plating method or the like.
絶縁体の層間絶縁膜1の厚さは、0.01μm〜2.0μm程度、バリア(金属)層2の厚さは、0.01μm〜2.5μm程度、導電性物質層4の厚さは、0.01μm〜2.5μm程度が好ましい。 The insulating interlayer insulating film 1 has a thickness of about 0.01 μm to 2.0 μm, the barrier (metal) layer 2 has a thickness of about 0.01 μm to 2.5 μm, and the conductive material layer 4 has a thickness of About 0.01 μm to 2.5 μm is preferable.
金属膜用研磨液を用いて、バリア層2を化学機械研磨する工程は、例えば次の第1の研磨工程と第2の研磨工程とを含むことができる。図2(a)に示される状態から図2(b)に示される状態まで導電性物質層4を研磨する第1の研磨工程では、研磨前の基板の表面の導電性物質層4を、例えば、導電性物質層4/バリア層2の研磨速度比が充分大きい導電性物質用の研磨液を用いて、CMPにより研磨する。これにより、基板上の凸部のバリア層2が表面に露出し、凹部に導電性物質層4が残された導体パターンを有する基板が得られる。第1の研磨工程では、導電性物質層4とともに凸部のバリア層2の一部が研磨されてもよい。 The step of chemically mechanically polishing the barrier layer 2 using the metal film polishing liquid can include, for example, the following first polishing step and second polishing step. In the first polishing step of polishing the conductive material layer 4 from the state shown in FIG. 2A to the state shown in FIG. 2B, the conductive material layer 4 on the surface of the substrate before polishing is, for example, Then, polishing is performed by CMP using a polishing liquid for conductive material having a sufficiently high polishing rate ratio of conductive material layer 4 / barrier layer 2. Thereby, the board | substrate which has the conductor pattern in which the barrier layer 2 of the convex part on a board | substrate is exposed to the surface, and the electroconductive substance layer 4 was left in the recessed part is obtained. In the first polishing step, a part of the convex barrier layer 2 may be polished together with the conductive material layer 4.
この第1の研磨工程によっては、図2(b)に示される導電性物質の残渣が発生する。 Depending on the first polishing process, a residue of the conductive material shown in FIG. 2B is generated.
引き続く第2の研磨工程では、第1の研磨工程により得られた導体パターンを、第2の研磨工程用の被研磨膜として、本実施形態の金属膜用研磨液を用いて研磨する。 In the subsequent second polishing step, the conductor pattern obtained in the first polishing step is polished using the metal film polishing liquid of this embodiment as a film to be polished for the second polishing step.
第2の研磨工程では、研磨定盤の研磨布上に基板を押圧した状態で、研磨布と基板との間に、本実施形態の金属膜用研磨液を供給しながら、研磨定盤と基板とを相対的に動かすことにより、導電性物質の残渣と、第1の研磨工程により露出したバリア層2を研磨する。 In the second polishing step, while the substrate is pressed onto the polishing cloth of the polishing surface plate, while supplying the metal film polishing liquid of the present embodiment between the polishing cloth and the substrate, the polishing surface plate and the substrate Are relatively moved to polish the residue of the conductive material and the barrier layer 2 exposed by the first polishing step.
研磨する装置としては、研磨される基板を保持するホルダと、回転数が変更可能なモータ等と接続し、研磨布を貼り付けた研磨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、多孔質フッ素樹脂等が使用でき、特に制限はない。 As a polishing apparatus, a general polishing apparatus having a holder for holding a substrate to be polished and a polishing platen connected to a motor or the like whose rotation speed can be changed and a polishing cloth attached thereto 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.
研磨条件は、特に制限がないが、研磨定盤の回転速度は基板が飛び出さないように、200回転/分(200min−1)以下の低回転が好ましい。被研磨膜を有する基板の研磨布への押し付け圧力は、1kPa〜100kPaであることが好ましく、研磨速度の被研磨面内均一性及びパターンの平坦性を満足するためには、5kPa〜50kPaであることがより好ましい。 The polishing conditions are not particularly limited, but the rotation speed of the polishing platen is preferably a low rotation of 200 rotations / minute (200 min −1 ) or less so that the substrate does not pop out. The pressure for pressing the substrate having the film to be polished onto the polishing cloth is preferably 1 kPa to 100 kPa, and 5 kPa to 50 kPa in order to satisfy the uniformity of the polishing speed within the surface and the flatness of the pattern. It is more preferable.
研磨している間、研磨布と被研磨膜との間には、本実施形態の金属膜用研磨液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液で覆われていることが好ましい。研磨終了後の基板は、流水中でよく洗浄後、スピンドライ等を用いて基板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。 During polishing, the metal film polishing liquid of this embodiment is continuously supplied by a pump or the like between the polishing cloth and the film to be polished. 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 substrate after polishing is preferably washed in running water and then dried after removing water droplets adhering to the substrate using spin drying or the like.
研磨布の表面状態を常に同一にして化学機械研磨を行うために、研磨の前に研磨布のコンディショニング工程を入れるのが好ましい。例えば、ダイヤモンド粒子のついたドレッサを用いて少なくとも水を含む液で研磨布のコンディショニングを行う。続いて本実施形態の研磨方法を実施し、さらに、基板洗浄工程を加えるのが好ましい。 In order to perform chemical mechanical polishing with the surface state of the polishing cloth always the same, it is preferable to perform a conditioning process of the polishing cloth before polishing. For example, the polishing cloth is conditioned with a liquid containing at least water using a dresser with diamond particles. Subsequently, it is preferable to perform the polishing method of the present embodiment and further add a substrate cleaning step.
第2の研磨工程では、少なくとも、露出しているバリア層2を研磨し、余分のバリア部分を除去する。更に、凹部に埋め込まれた導電性物質層4がバリア層2とともに研磨されてもよい。 In the second polishing step, at least the exposed barrier layer 2 is polished to remove excess barrier portions. Further, the conductive material layer 4 embedded in the recess may be polished together with the barrier layer 2.
凸部のバリア(金属)層2の下の絶縁体の層間絶縁膜1が全て露出し、凹部に配線層となる導電性物質層4が残され、凸部と凹部との境界にバリア(金属)層2の断面が露出した所望のパターンを有する基板が得られた時点で研磨を終了する。 The insulating interlayer insulating film 1 under the barrier (metal) layer 2 of the convex portion is completely exposed, the conductive material layer 4 serving as a wiring layer is left in the concave portion, and the barrier (metal) is formed at the boundary between the convex portion and the concave portion. The polishing is finished when a substrate having a desired pattern in which the cross section of the layer 2 is exposed is obtained.
研磨終了時のより優れた平坦性を確保するために、更に、オーバー研磨(例えば、第2の研磨工程で所望のパターンを得られるまでの時間が100秒の場合、この100秒の研磨に加えて50秒追加して研磨することをオーバー研磨50%という。)してもよい。オーバー研磨する場合には、絶縁体の層間絶縁膜1の一部も研磨で除去される。 In order to ensure better flatness at the end of polishing, in addition to over polishing (for example, if the time until a desired pattern is obtained in the second polishing step is 100 seconds, in addition to this 100 second polishing, Polishing for an additional 50 seconds may be referred to as over-polishing 50%). In the case of overpolishing, a part of the insulating interlayer insulating film 1 is also removed by polishing.
このようにして形成された金属配線の上に、更に、第2層目の絶縁体及び金属配線を形成した後、研磨して半導体基板全面に渡って平滑な面とする。この工程を所定数繰り返すことにより、所望の配線層数を有する半導体デバイスを製造することができる。 A second-layer insulator and metal wiring are further formed on the metal wiring thus formed, and then polished to obtain a smooth surface over the entire surface of the semiconductor substrate. By repeating this step a predetermined number of times, a semiconductor device having a desired number of wiring layers can be manufactured.
本実施形態の研磨液は、上記のような半導体基板に形成された金属膜の研磨だけでなく、磁気ヘッド等の基板を研磨するためにも使用することができる。 The polishing liquid of the present embodiment can be used not only for polishing a metal film formed on a semiconductor substrate as described above but also for polishing a substrate such as a magnetic head.
以下に、実施例により本発明をさらに詳しく説明するが、本発明の技術思想を逸脱しない限り、本発明はこれらの実施例に限定されるものではない。例えば、研磨液の材料の種類やその配合比率は、本実施例記載の種類や比率以外でも構わないし、研磨対象の組成や構造も、本実施例記載以外の組成や構造でも構わない。 Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples without departing from the technical idea of the present invention. For example, the type of polishing liquid material and the blending ratio thereof may be other than those described in this embodiment, and the composition and structure of the polishing target may be other than those described in this embodiment.
<実施例及び比較例>
(金属膜用研磨液調製方法)
表1にメタクリル酸系ポリマにおける各モノマのモル比率(モル%)と、ポリマの重量平均分子量を示す。表1に示すモノマ成分を重合させてメタクリル酸系ポリマを得た。
<Examples and Comparative Examples>
(Metal film polishing liquid preparation method)
Table 1 shows the molar ratio (mol%) of each monomer in the methacrylic acid polymer and the weight average molecular weight of the polymer. The monomer components shown in Table 1 were polymerized to obtain methacrylic acid polymers.
さらに、表2〜表3に従って、研磨粒子、メタクリル酸系ポリマ、酸化合物(水系溶媒の酸)、金属防食剤等を所定量混合して、各実施例及び各比較例の各金属膜用研磨液を調製した。なお、研磨粒子としては平均粒径70nmのコロイダルシリカを使用した。pHは、pHメータ(電気化学計器株式会社製、型番:PHL−40)で測定した。 Further, according to Tables 2 to 3, a predetermined amount of abrasive particles, methacrylic acid polymer, acid compound (aqueous solvent acid), metal anticorrosive agent, etc. are mixed to polish each metal film of each example and each comparative example. A liquid was prepared. Incidentally, colloidal silica having an average particle diameter of 70 nm was used as the abrasive particles. The pH was measured with a pH meter (manufactured by Electrochemical Instrument Co., Ltd., model number: PHL-40).
(銅パターン基板の研磨)
銅配線付きパターン基板(ATDF(Advanced Technology Development Facility )製854CMPパターン:二酸化珪素からなる厚さ500nmの層間絶縁膜)の溝部以外の銅膜を、銅膜研磨用研磨液(日立化成株式会社製、HS−H635)を用いて、公知のCMP法により研磨して、凸部のバリア層を被研磨面に露出させかつ、フィールド部分のバリア層上部に銅残渣のある図2の(b)に示すような状態の基板を得た。この基板を各実施例及び比較例の研磨液の研磨特性評価に使用した。なお、上記パターン基板のバリア層は厚さ250Åの窒化タンタル膜からなっていた。
(Polishing copper pattern substrate)
A copper film other than the groove of the pattern substrate with copper wiring (ATDF (Advanced Technology Development Facility) 854 CMP pattern: 500 nm thick interlayer insulating film made of silicon dioxide) is used as a polishing liquid for copper film polishing (manufactured by Hitachi Chemical Co., Ltd., HS-H635) is polished by a known CMP method so that the convex barrier layer is exposed on the surface to be polished and copper residue is present on the upper portion of the barrier layer in the field portion as shown in FIG. A substrate in such a state was obtained. This board | substrate was used for the grinding | polishing characteristic evaluation of the polishing liquid of each Example and a comparative example. The barrier layer of the pattern substrate was made of a tantalum nitride film having a thickness of 250 mm.
上記パターン基板を上記研磨液調製方法で調製した各金属膜用研磨液で、下記研磨条件にて50秒間化学機械研磨した。これは、第2の研磨工程に相当し、約20秒で凸部の層間絶縁膜が被研磨面に露出し、残りの30秒は、凸部ではこの露出した層間絶縁膜を研磨した。 The pattern substrate was subjected to chemical mechanical polishing for 50 seconds under the following polishing conditions with each metal film polishing liquid prepared by the polishing liquid preparation method. This corresponds to the second polishing step, and the convex interlayer insulating film was exposed to the surface to be polished in about 20 seconds, and the exposed interlayer insulating film was polished in the convex portion for the remaining 30 seconds.
[基板研磨条件]
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、MIRRA)
研磨布:スウェード状ポリウレタン樹脂製研磨布(富士紡ホールディングス株式会社製)
定盤回転数:93回転/min(93min−1)
ヘッド回転数:87回転/min(87min−1)
研磨圧力:21kPa
研磨液の供給量:200ml/min
[Substrate polishing conditions]
Polishing device: Single-sided metal film polishing machine (MIRRA, Applied Materials)
Abrasive cloth: Abrasive cloth made of suede polyurethane resin (Fujibo Holdings Co., Ltd.)
Surface plate rotation speed: 93 rotations / min (93 min −1 )
Head rotation speed: 87 rotations / min (87 min −1 )
Polishing pressure: 21 kPa
Supply amount of polishing liquid: 200 ml / min
次に、上記基板の研磨工程で研磨したパターン基板の被研磨面にスポンジブラシ(ポリビニルアルコール系樹脂製)を押し付け、蒸留水を基板に供給しながら基板とスポンジブラシを回転させ、60秒間洗浄した。次にスポンジブラシを取り除き、基板の被研磨面に蒸留水を60秒間供給した。最後に基板を高速で回転させることで蒸留水を弾き飛ばして基板を乾燥し、以下の評価で用いるパターン基板を得た。 Next, a sponge brush (made of polyvinyl alcohol resin) was pressed against the surface to be polished of the patterned substrate polished in the substrate polishing step, and the substrate and the sponge brush were rotated while supplying distilled water to the substrate, and washed for 60 seconds. . Next, the sponge brush was removed, and distilled water was supplied to the polished surface of the substrate for 60 seconds. Finally, the substrate was rotated at high speed to blow off distilled water and dried to obtain a pattern substrate to be used in the following evaluation.
(平坦性評価)
上記基板の洗浄工程で得たパターン基板について、下記(1)〜(3)に示す評価を行った。
(Flatness evaluation)
The following evaluations (1) to (3) were performed on the pattern substrate obtained in the substrate cleaning step.
(1)層間絶縁膜研磨量:層間絶縁膜部の膜厚の測定は、銅配線付きパターン基板を用いて研磨を行い、幅100μmの金属配線部、幅100μmの層間絶縁膜部が交互に並んだ総幅2900μmのストライプ状パターン部の層間絶縁膜の膜厚を光学式膜厚計により求め、層間絶縁膜研磨量とした。 (1) Amount of polishing of interlayer insulating film: The film thickness of the interlayer insulating film portion is measured using a patterned substrate with copper wiring, and a metal wiring portion having a width of 100 μm and an interlayer insulating film portion having a width of 100 μm are alternately arranged. The thickness of the interlayer insulating film in the stripe-shaped pattern portion having a total width of 2900 μm was obtained by an optical film thickness meter, and was defined as the amount of interlayer insulating film polishing.
(2)配線間エロージョン量:上記基板の洗浄工程で得たパターン基板において、図3の(a)に示すように、幅70μmの金属配線部、幅30μmの層間絶縁膜部が交互に並んだ総幅2990μmのストライプ状パターン部の表面形状を触針式段差計により測定した。次いで、図2の(b)に示すように、ストライプ状パターン部の層間絶縁膜の研磨量の最大値(B)と、ストライプ状パターン部外縁の層間絶縁膜部の(A)との差(B)−(A)、すなわち配線間エロージョン量を求め、平坦性の指標とした。
(3)ディッシング量:上記基板の洗浄工程で得たパターン基板において、図3の(a)に示すように、幅70μmの金属配線部、幅30μmの層間絶縁膜部が交互に並んだ総幅2990μmのストライプ状パターン部の表面形状を触針式段差計により測定した。次いで、図2の(b)に示すように、ストライプ状パターン部の金属配線層の研磨量の最大値(C)と、ストライプ状パターン部外縁の層間絶縁膜部の(A)との差(C)−(A)、すなわちディッシング量を求め、平坦性の指標とした。
(2) Inter-wiring erosion amount: In the pattern substrate obtained in the above-described substrate cleaning process, as shown in FIG. 3A, a metal wiring portion having a width of 70 μm and an interlayer insulating film portion having a width of 30 μm are alternately arranged. The surface shape of the stripe-shaped pattern portion having a total width of 2990 μm was measured with a stylus type step meter. Next, as shown in FIG. 2B, the difference between the maximum polishing amount (B) of the interlayer insulating film in the stripe pattern portion and (A) of the interlayer insulating film portion on the outer edge of the stripe pattern portion ( B)-(A), that is, the amount of erosion between wirings was obtained and used as an index of flatness.
(3) Dishing amount: In the patterned substrate obtained in the above substrate cleaning process, as shown in FIG. 3A, the total width in which metal wiring portions having a width of 70 μm and interlayer insulating film portions having a width of 30 μm are alternately arranged. The surface shape of the 2990 μm stripe pattern portion was measured with a stylus type step gauge. Next, as shown in FIG. 2B, the difference between the maximum polishing amount (C) of the metal wiring layer of the stripe pattern portion and (A) of the interlayer insulating film portion at the outer edge of the stripe pattern portion ( C)-(A), that is, the dishing amount was obtained and used as an index of flatness.
なお、図3は、上記銅配線付きパターン基板の、幅70μmの金属配線部、幅30μmの層間絶縁膜部が交互に並んだストライプ状パターン部の断面模式図であり、11は層間絶縁膜、13はバリア層、15は金属配線層、Aはストライプ状パターン部外縁の層間絶縁膜部の研磨量、Bはストライプ状パターン部の層間絶縁膜部の研磨量の最大値、Cはストライプ状パターン部の金属配線層の研磨量の最大値をそれぞれ示す。 FIG. 3 is a schematic cross-sectional view of a stripe pattern portion in which a metal wiring portion having a width of 70 μm and an interlayer insulating film portion having a width of 30 μm are alternately arranged on the patterned substrate with copper wiring, and 11 is an interlayer insulating film, 13 is a barrier layer, 15 is a metal wiring layer, A is the polishing amount of the interlayer insulating film portion at the outer edge of the stripe pattern portion, B is the maximum polishing amount of the interlayer insulating film portion of the stripe pattern portion, and C is the stripe pattern The maximum value of the polishing amount of the metal wiring layer of the part is shown.
以上の評価結果を表2及び表3に示した。 The above evaluation results are shown in Tables 2 and 3.
(研磨速度の評価)
ブランケット基板の研磨速度の評価には、以下の基板(a)〜(e)をそれぞれ使用した。
ブランケット基板(a):めっき法で銅(厚さ:1000nm)を形成したシリコン基板。
ブランケット基板(b):スパッタ法で窒化タンタル(厚さ:200nm)を形成したシリコン基板。
ブランケット基板(c):CVD法で二酸化珪素(厚さ:1000nm)を形成したシリコン基板。
ブランケット基板(d):オルガノシリケートグラス(厚さ:1000nm)を形成したシリコン基板。
上記ブランケット基板(a)〜(d)を用い、実施例1〜6の研磨液により、上記基板研磨条件で60秒間化学機械研磨を行った。
(Evaluation of polishing rate)
The following substrates (a) to (e) were used for evaluation of the polishing rate of the blanket substrate.
Blanket substrate (a): A silicon substrate on which copper (thickness: 1000 nm) is formed by a plating method.
Blanket substrate (b): A silicon substrate on which tantalum nitride (thickness: 200 nm) is formed by sputtering.
Blanket substrate (c): A silicon substrate on which silicon dioxide (thickness: 1000 nm) is formed by CVD.
Blanket substrate (d): A silicon substrate on which an organosilicate glass (thickness: 1000 nm) is formed.
Using the blanket substrates (a) to (d), chemical mechanical polishing was performed for 60 seconds under the substrate polishing conditions with the polishing liquids of Examples 1 to 6.
[研磨速度の算出]
上記ブランケット基板(a)〜(d)を用いて下記の方法で研磨速度を算出した。
銅膜、窒化タンタル膜:ブランケット基板(a)及び(b)について、金属膜厚測定装置(日立国際電気株式会社製、製品名“VR−120/08S”)を用いて研磨前後での膜厚差を測定し、得られた結果から銅膜を研磨したときの研磨速度(Cu研磨速度)[Å/min]と窒化タンタル膜を研磨したときの研磨速度(TaN研磨速度)[Å/min]を評価した。
二酸化珪素膜、オルガノシリケートグラス膜:膜厚測定装置(大日本スクリーン製造株式会社製、製品名“ラムダエース、VL−M8000LS”)を用いて研磨前後での膜厚差を測定し、得られた結果から二酸化珪素膜を研磨したときの研磨速度(SiO2研磨速度)[Å/min]とオルガノシリケートグラス膜を研磨したときの研磨速度(SiOC研磨速度)[Å/min]を評価した。
これらの結果を表4に示した。
[Calculation of polishing speed]
The polishing rate was calculated by the following method using the blanket substrates (a) to (d).
Copper film, tantalum nitride film: About blanket substrates (a) and (b), film thickness before and after polishing using a metal film thickness measuring device (product name “VR-120 / 08S” manufactured by Hitachi Kokusai Electric Co., Ltd.) The difference was measured, and from the obtained results, the polishing rate when polishing the copper film (Cu polishing rate) [Å / min] and the polishing rate when polishing the tantalum nitride film (TaN polishing rate) [Å / min] Evaluated.
Silicon dioxide film, organosilicate glass film: obtained by measuring the film thickness difference before and after polishing using a film thickness measuring device (manufactured by Dainippon Screen Mfg. Co., Ltd., product name “Lambda Ace, VL-M8000LS”) From the results, the polishing rate when polishing the silicon dioxide film (SiO 2 polishing rate) [Å / min] and the polishing rate when polishing the organosilicate glass film (SiOC polishing rate) [Å / min] were evaluated.
These results are shown in Table 4.
表2から明らかなように、実施例1〜6では、特定の重量平均分子量のメタクリル酸系ポリマを含むことで、配線間エロージョンが効果的に抑制され、被研磨面の高い平坦性が得られる。 As is apparent from Table 2, in Examples 1 to 6, by including a methacrylic acid polymer having a specific weight average molecular weight, erosion between wirings is effectively suppressed, and high flatness of the surface to be polished is obtained. .
一方、表3の比較例1〜5では、配線間エロージョンが実施例と比較して大きく発生しており、被研磨面の平坦性が低かった。
また、比較例6では配線間エロージョンは小さいが、ディッシングが大きく発生しており、被研磨面の平坦性が低かった。
On the other hand, in Comparative Examples 1 to 5 in Table 3, erosion between wirings was larger than that in Examples, and the flatness of the polished surface was low.
In Comparative Example 6, erosion between the wirings was small, but dishing occurred greatly, and the flatness of the surface to be polished was low.
表4から、実施例1〜6は、銅、窒化タンタル、二酸化珪素及びオルガノシリケートグラスに対して良好な研磨速度が得られていることがわかった。このことから、前記メタクリル酸系ポリマを含有する本発明の金属膜用研磨液においては、前記重量平均分子量が20,000以上のメタクリル酸系ポリマを用いることで配線間エロージョンとディッシングを効果的に抑えていることが示唆される。すなわち、上記の結果から、本発明の金属膜用研磨液によれば配線間エロージョン及びディッシングが抑制されることを効果的に抑制して研磨できることが示唆される。 From Table 4, it was found that in Examples 1 to 6, good polishing rates were obtained for copper, tantalum nitride, silicon dioxide, and organosilicate glass. Therefore, in the metal film polishing liquid of the present invention containing the methacrylic acid polymer, erosion and dishing between wirings can be effectively performed by using the methacrylic acid polymer having a weight average molecular weight of 20,000 or more. It is suggested that it is suppressed. That is, from the above results, it is suggested that the metal film polishing liquid of the present invention can be effectively polished while suppressing erosion and dishing between wirings.
1…層間絶縁膜
2…バリア(金属)層
3…金属配線層
4…導電性物質層
11…層間絶縁膜
13…バリア(金属)層
15…金属配線層
DESCRIPTION OF SYMBOLS 1 ... Interlayer insulating film 2 ... Barrier (metal) layer 3 ... Metal wiring layer 4 ...
Claims (11)
上記第1の研磨工程で露出した上記基板のバリア層を請求項1〜10のいずれか一項に記載の金属膜用研磨液を用いて研磨して上記凸部の層間絶縁膜を露出させる第2の研磨工程を含むことを特徴とする研磨方法。 Conductivity of a substrate having an interlayer insulating film having a concave portion and a convex surface, a barrier layer covering the surface of the interlayer insulating film, and a conductive material layer filling the concave portion and covering the barrier layer A first polishing step of polishing the material layer to expose the barrier layer of the convex portion;
The barrier layer of the substrate exposed in the first polishing step is polished with the metal film polishing liquid according to claim 1 to expose the convex interlayer insulating film. A polishing method comprising two polishing steps.
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