JP2005123482A - Polishing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polishing method capable of reducing surface level difference by preventing the advance of dishing and erosion. <P>SOLUTION: The polishing method includes a first polishing step of polishing part of a conductor film, a second polishing step of polishing the conductor film until a barrier film is exposed, and a third polishing step of polishing the barrier film. In the second polishing step or in the first and second polishing steps, (a) a surfactant, (b) silicon oxide, (c) carbonic acid, (d) an anticorrosive, (e) an oxidant, and (f) a first polishing composition containing water are used. Alternately, (A) α-amino acid, (B) benzotriazole derivative, (C) silicon oxide, (D) a surfactant, (E) an oxidant, and (F) the first polishing composition containing water are used. On the other hand, in the third polishing step, (g) colloidal silica, (h) an acid, (i) an anticorrosive, (j) completely saponified polyvinyl alcohol, and (k) a second polishing composition containing water are used. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a polishing method for forming a wiring structure of a semiconductor device.

  In recent years, along with the high integration and high speed of ULSI used in computers, the design rules of semiconductor devices have been miniaturized. Therefore, in order to cope with an increase in wiring resistance due to miniaturization of the wiring structure of a semiconductor device, it has been studied to use a metal material containing copper as a wiring material.

  When a metal material containing copper is used as a wiring material, it is difficult to form a wiring structure by anisotropic etching because of the nature of the metal material. For this reason, the wiring structure is formed by a method using a CMP (Chemical Mechanical Polishing) method or the like. In the method of forming a wiring structure using the CMP method, a barrier film formed of a tantalum-containing compound such as tantalum or tantalum nitride is formed on an insulating film having a wiring groove formed on the surface thereof. Next, a conductor film formed of a metal material containing copper is formed on the barrier film so that at least the inside of the wiring trench is completely filled. Then, the conductor film and the barrier film are polished to form a wiring portion in the wiring groove.

  In the conventional polishing method, a part of the conductor film is polished in the first polishing step. Next, in the second polishing step, the conductor film is polished until the barrier film in portions other than the wiring grooves is exposed. Subsequently, in the third polishing step, the barrier film is polished until the insulating film in portions other than the wiring trench is exposed. The polishing composition used for polishing the conductor film contains an abrasive such as silicon dioxide, α-alanine, hydrogen peroxide, and water (see, for example, Patent Document 1). In addition, some contain an abrasive such as alumina, an oxidizing agent such as peracetic acid, a complexing agent such as citric acid, and a film forming agent such as imidazole (see, for example, Patent Document 2). These polishing compositions mechanically polish the surface to be polished with an abrasive and promote polishing of a metal material containing copper with α-alanine, a complexing agent or the like.

On the other hand, the polishing composition used for polishing the barrier film contains an abrasive, an oxidizing agent, a reducing agent and water (see, for example, Patent Document 3). This polishing composition promotes polishing of the barrier film with an oxidizing agent and a reducing agent. In addition, some contain a triazole derivative to suppress corrosion of the conductor film (see, for example, Patent Document 4). Furthermore, there is a material containing silica having a primary particle diameter of 20 nm or less as an abrasive material to improve the polishing power for a conductor film and a barrier film (see, for example, Patent Document 5).
JP 2000-160141 A Japanese Patent Laid-Open No. 11-21546 JP 2000-160139 A JP 2001-89747 A JP 2001-247853 A

  However, in the conventional polishing method, the conductor film is excessively polished in the second polishing step. For this reason, on the surface to be polished after the second polishing step, a phenomenon that the surface of the conductor film corresponding to the wiring groove retreats inward as compared with the surface of the barrier film, that is, dishing occurs. Further, the conventional polishing method polishes the insulating film in the region where the wiring grooves are densely formed in the third polishing step. For this reason, the surface to be polished after the third polishing process has a phenomenon that the surface of the region where the wiring grooves are densely formed is retreated inward compared to the surface of the insulating film in the other region, that is, erosion occurs. To do. In addition, the conductor film is excessively polished and dishing occurs. In addition, there is a problem that a step is generated on the surface of the semiconductor substrate after polishing by erosion and dishing.

  The present invention has been made paying attention to such problems existing in the prior art. An object of the present invention is to provide a polishing method capable of suppressing the surface step by suppressing the progress of dishing and the progress of erosion.

In order to achieve the above object, a polishing method according to a first aspect of the present invention is a method for polishing a semiconductor substrate, wherein the conductor film is first polished so that the polishing is finished before the barrier film is exposed. A polishing step, a second polishing step for polishing the conductor film until the barrier film is exposed, and a third polishing step for polishing the barrier film until the insulating film is exposed, the second polishing step, or The first polishing composition containing the following components (a) to (f) is used for the first and second polishing steps, and the following components (g) to (k) are used for the third polishing step. The 2nd polishing composition containing this is used.
(First polishing composition)
(A): a surfactant containing at least one compound selected from the compounds represented by any one of the following general formulas (1) to (7) and salts thereof

（式中、Ｒ¹は炭素数が８〜１６のアルキル基を示し、Ｒ²は水素原子、メチル基又はエチル基を示し、Ｒ³は炭素数が１〜８のアルキレン基、−（ＣＨ₂ＣＨ₂Ｏ）_l−及び−（ＣＨ₂ＣＨ（ＣＨ₃）Ｏ）_m−から選ばれる少なくとも一種からなる繰返し単位を示し、Ｘ¹はカルボキシル基又はスルホン基を示す。ここで、ｌ及びｍの合計は１〜８の整数である。）

(Wherein R ¹ represents an alkyl group having 8 to 16 carbon atoms, R ² represents a hydrogen atom, a methyl group or an ethyl group, R ³ represents an alkylene group having 1 to 8 carbon atoms, — (CH ₂ CH ₂ O) _1-and- (CH ₂ CH (CH ₃ ) O) _m- represent at least one repeating unit, and X ¹ represents a carboxyl group or a sulfone group, where l and m The total is an integer from 1 to 8.)

（式中、Ｒ⁴は炭素数が８〜１６のアルキル基を示し、Ｚは下記式（ｉ）又は（ｉｉ）で示される官能基を示し、Ｙ¹は−（ＣＨ₂ＣＨ₂Ｏ）_n−及び−（ＣＨ₂ＣＨ（ＣＨ₃）Ｏ）_p−から選ばれる少なくとも一種からなる繰返し単位を示し、Ｘ²はリン酸基又はスルホン基を示す。ここで、ｎ及びｐの合計は１〜６の整数である。）

(In the formula, R ⁴ represents an alkyl group having 8 to 16 carbon atoms, Z represents a functional group represented by the following formula (i) or (ii), and Y ¹ represents — (CH ₂ CH ₂ O) _n. - and _{- (CH 2 CH (CH 3} ) O) p -. shows a repeating unit composed of at least one member selected from, X ² represents a phosphoric acid group or a sulfonic group wherein the sum of n and p is 1 (It is an integer of 6.)

（式中、Ｒ⁵及びＲ⁶はそれぞれ水素原子、ヒドロキシル基又は炭素数が８〜１６のアルキル基を示し、Ｙ²及びＹ³はそれぞれ−（ＣＨ₂ＣＨ₂Ｏ）_q−及び−（ＣＨ₂ＣＨ（ＣＨ₃）Ｏ）_r−から選ばれる少なくとも一種からなる繰返し単位を示す。ここで、ｑ及びｒの合計は１〜６の整数である。）
（ｂ）：酸化ケイ素
（ｃ）：カルボン酸
（ｄ）：防食剤
（ｅ）：酸化剤
（ｆ）：水
（第２研磨用組成物）
（ｇ）：コロイダルシリカ
（ｈ）：酸
（ｉ）：防食剤
（ｊ）：完全けん化型ポリビニルアルコール
（ｋ）：水
請求項２に記載の発明の研磨方法は、請求項１に記載の発明において、前記成分（ｃ）がα−アミノ酸である。

(In the formula, R ⁵ and R ⁶ each represent a hydrogen atom, a hydroxyl group, or an alkyl group having 8 to 16 carbon atoms, and Y ² and Y ³ represent — (CH ₂ CH ₂ O) _q — and — (CH ₂ represents a repeating unit consisting of at least one selected from CH (CH ₃ ) O) _r —, wherein the sum of q and r is an integer of 1 to 6.
(B): Silicon oxide (c): Carboxylic acid (d): Anticorrosive agent (e): Oxidizing agent (f): Water (second polishing composition)
(G): Colloidal silica (h): Acid (i): Anticorrosive agent (j): Completely saponified polyvinyl alcohol (k): Water The polishing method according to claim 2 is the invention according to claim 1. In the above, the component (c) is an α-amino acid.

  A polishing method according to a third aspect of the present invention is the method according to the first or second aspect, wherein the component (d) is a benzotriazole derivative represented by the following general formula (8).

（式中、Ｒ⁷はカルボキシル基を含有するアルキル基、ヒドロキシル基と３級アミノ基とを含有するアルキル基、ヒドロキシル基を含有するアルキル基又はアルキル基を示す。）
請求項４に記載の発明の研磨方法は、半導体基板の研磨方法であって、バリア膜が露出する前に研磨を終了するように導体膜を研磨する第１の研磨工程と、バリア膜が露出するまで導体膜を研磨する第２の研磨工程と、絶縁膜が露出するまでバリア膜を研磨する第３の研磨工程とを備え、第２の研磨工程、又は第１及び第２の研磨工程に下記（Ａ）〜（Ｆ）の各成分を含有する第１研磨用組成物を用いるとともに、第３の研磨工程に下記（ｇ）〜（ｋ）の各成分を含有する第２研磨用組成物を用いるものである。
（第１研磨用組成物）
（Ａ）：α−アミノ酸
（Ｂ）：下記一般式（８）で示されるベンゾトリアゾール誘導体

(In the formula, R ⁷ represents an alkyl group containing a carboxyl group, an alkyl group containing a hydroxyl group and a tertiary amino group, an alkyl group containing an hydroxyl group, or an alkyl group.)
A polishing method according to a fourth aspect of the present invention is a method for polishing a semiconductor substrate, wherein a first polishing step for polishing the conductor film so that the polishing is finished before the barrier film is exposed, and the barrier film is exposed. A second polishing step for polishing the conductive film until the insulating film is exposed, and a third polishing step for polishing the barrier film until the insulating film is exposed. The second polishing step, or the first and second polishing steps. While using the 1st polishing composition containing each component of following (A)-(F), the 2nd polishing composition containing each component of following (g)-(k) in a 3rd grinding | polishing process. Is used.
(First polishing composition)
(A): α-amino acid (B): benzotriazole derivative represented by the following general formula (8)

（式中、Ｒ⁷はカルボキシル基を含有するアルキル基、ヒドロキシル基と３級アミノ基とを含有するアルキル基、ヒドロキシル基を含有するアルキル基又はアルキル基を示す。）
（Ｃ）：酸化ケイ素
（Ｄ）：界面活性剤
（Ｅ）：酸化剤
（Ｆ）：水
（第２研磨用組成物）
（ｇ）：コロイダルシリカ
（ｈ）：酸
（ｉ）：防食剤
（ｊ）：完全けん化型ポリビニルアルコール
（ｋ）：水

(In the formula, R ⁷ represents an alkyl group containing a carboxyl group, an alkyl group containing a hydroxyl group and a tertiary amino group, an alkyl group containing an hydroxyl group, or an alkyl group.)
(C): Silicon oxide (D): Surfactant (E): Oxidizing agent (F): Water (second polishing composition)
(G): Colloidal silica (h): Acid (i): Anticorrosive agent (j): Completely saponified polyvinyl alcohol (k): Water

  According to the polishing method of the present invention, it is possible to suppress the surface step by suppressing the progress of dishing and the progress of erosion.

(First embodiment)
Hereinafter, a first embodiment of the present invention will be described in detail.
As shown in FIG. 1A, a wiring groove 13 having a predetermined pattern based on circuit design is formed on the surface of an insulating film 12 on a semiconductor substrate 11 constituting a semiconductor device by a known lithography technique or pattern etching technique. Has been. Examples of the insulating film 12 include a SiOF film, a SiOC film, and the like in addition to a SiO ₂ film formed by a method such as a CVD (Chemical Vapor Deposition) method using TEOS (tetraethoxysilane).

  A barrier film 14 having a predetermined thickness is formed on the insulating film 12 by sputtering or the like. The barrier film 14 is formed of a tantalum-containing compound such as tantalum or tantalum nitride. A portion corresponding to the wiring groove 13 on the surface of the barrier film 14 is formed in a concave shape. A conductor film 15 is formed on the barrier film 14 so that at least the inside of the wiring trench 13 is completely filled. The conductor film 15 is formed of a metal material containing copper (hereinafter referred to as a copper-containing metal) such as copper, a copper-aluminum alloy, or a copper-titanium alloy. In a portion corresponding to the wiring groove 13 on the surface of the conductor film 15, an initial concave groove 16 derived from the wiring groove 13 generally called an initial step is formed.

  The wiring structure of the semiconductor device is formed by polishing the semiconductor substrate 11 by a CMP method. Specifically, as shown in FIG. 1B, the conductor film 15 is polished in the first polishing step. The polishing of the conductor film 15 by the first polishing process is finished before the barrier film 14 is exposed. After the first polishing process, as shown in FIG. 1C, the conductor film 15 is polished in the second polishing process until the barrier film 14 at portions other than the wiring grooves 13 is exposed. Subsequently, as shown in FIG. 1D, the barrier film 14 is polished in the third polishing process until the insulating film 12 other than the wiring groove 13 is exposed, whereby the wiring portion is formed in the wiring groove 13. 17 is formed.

  The polishing composition used in the first polishing step is configured to polish the conductor film 15 with high polishing efficiency. For example, at least one selected from silicon oxide and aluminum oxide, at least one selected from glycine and α-alanine. , Hydrogen peroxide and water.

The first polishing composition used in the second polishing step includes (a) a surfactant, (b) silicon oxide, (c) carboxylic acid, (d) an anticorrosive, (e) an oxidant and (f ) Contains water.
The surfactant of the component (a) contains (a1) at least one selected from the compounds represented by any one of the following general formulas (1) to (7) and salts thereof, and the component (a1 And (a2) at least one selected from the compounds represented by the following general formula (9) or (10) and salts thereof.

（式中、Ｒ¹は炭素数が８〜１６のアルキル基を示し、Ｒ²は水素原子、メチル基又はエチル基を示し、Ｒ³は炭素数が１〜８のアルキレン基、−（ＣＨ₂ＣＨ₂Ｏ）_l−及び−（ＣＨ₂ＣＨ（ＣＨ₃）Ｏ）_m−から選ばれる少なくとも一種からなる繰返し単位を示し、Ｘ¹はカルボキシル基又はスルホン基を示す。ここで、ｌ及びｍの合計は１〜８の整数である。）

(Wherein R ¹ represents an alkyl group having 8 to 16 carbon atoms, R ² represents a hydrogen atom, a methyl group or an ethyl group, R ³ represents an alkylene group having 1 to 8 carbon atoms, — (CH ₂ CH ₂ O) _1-and- (CH ₂ CH (CH ₃ ) O) _m- represent at least one repeating unit, and X ¹ represents a carboxyl group or a sulfone group, where l and m The total is an integer from 1 to 8.)

（式中、Ｒ⁴は炭素数が８〜１６のアルキル基を示し、Ｚは下記式（ｉ）又は（ｉｉ）で示される官能基を示し、Ｙ¹は−（ＣＨ₂ＣＨ₂Ｏ）_n−及び−（ＣＨ₂ＣＨ（ＣＨ₃）Ｏ）_p−から選ばれる少なくとも一種からなる繰返し単位を示し、Ｘ²はリン酸基又はスルホン基を示す。ここで、ｎ及びｐの合計は１〜６の整数である。）

(In the formula, R ⁴ represents an alkyl group having 8 to 16 carbon atoms, Z represents a functional group represented by the following formula (i) or (ii), and Y ¹ represents — (CH ₂ CH ₂ O) _n. - and _{- (CH 2 CH (CH 3} ) O) p -. shows a repeating unit composed of at least one member selected from, X ² represents a phosphoric acid group or a sulfonic group wherein the sum of n and p is 1 (It is an integer of 6.)

（式中、Ｒ⁵及びＲ⁶はそれぞれ水素原子、ヒドロキシル基又は炭素数が８〜１６のアルキル基を示し、Ｙ²及びＹ³はそれぞれ−（ＣＨ₂ＣＨ₂Ｏ）_q−及び−（ＣＨ₂ＣＨ（ＣＨ₃）Ｏ）_r−から選ばれる少なくとも一種からなる繰返し単位を示す。ここで、ｑ及びｒの合計は１〜６の整数である。）

(In the formula, R ⁵ and R ⁶ each represent a hydrogen atom, a hydroxyl group, or an alkyl group having 8 to 16 carbon atoms, and Y ² and Y ³ represent — (CH ₂ CH ₂ O) _q — and — (CH ₂ represents a repeating unit consisting of at least one selected from CH (CH ₃ ) O) _r —, wherein the sum of q and r is an integer of 1 to 6.

（式中、Ｒ⁸は炭素数が８〜１６のアルキル基を示し、Ｙ⁴は−（ＣＨ₂ＣＨ₂Ｏ）_s−及び−（ＣＨ₂ＣＨ（ＣＨ₃）Ｏ）_t−から選ばれる少なくとも一種からなる繰返し単位を示す。ここで、ｓ及びｔの合計は２〜３０の整数である。）

Wherein R ⁸ represents an alkyl group having 8 to 16 carbon atoms, and Y ⁴ is at least selected from — (CH ₂ CH ₂ O) _s — and — (CH ₂ CH (CH ₃ ) O) _t —. A repeating unit consisting of one kind is shown, where the sum of s and t is an integer of 2 to 30.)

（式中、Ｒ⁹〜Ｒ¹⁴はそれぞれ水素原子又は炭素数が１〜１０のアルキル基を示し、Ｙ⁵及びＹ⁶はそれぞれ−（ＣＨ₂ＣＨ₂Ｏ）_u−又は−（ＣＨ₂ＣＨ（ＣＨ₃）Ｏ）_v−を示す。ここで、ｕ及びｖはそれぞれ１〜２０の整数を示す。）
前記一般式（１）〜（７）並びに（９）及び（１０）のいずれか一つで示される化合物の塩としては、アンモニウム塩、ナトリウム塩等のアルカリ金属塩、トリエタノールアミン塩等が挙げられる。一般式（１）〜（７）並びに（９）のいずれか一つで示される化合物及びその塩はアニオン系界面活性剤である。一方、一般式（１０）で示される化合物及びその塩はノニオン系界面活性剤である。

(In the formula, R ^{9 to} R ¹⁴ each represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and Y ⁵ and Y ⁶ represent — (CH ₂ CH ₂ O) _u — or — (CH ₂ CH ( CH ₃ ) O) _v —, where u and v each represent an integer of 1-20.
Examples of the salt of the compound represented by any one of the general formulas (1) to (7) and (9) and (10) include alkali metal salts such as ammonium salts and sodium salts, and triethanolamine salts. It is done. The compound represented by any one of the general formulas (1) to (7) and (9) and a salt thereof are anionic surfactants. On the other hand, the compound represented by the general formula (10) and a salt thereof are nonionic surfactants.

  Examples of the compound represented by the general formula (1) and the salt thereof include coconut oil fatty acid sarcosine triethanolamine represented by the following formula (11), coconut oil fatty acid methyl taurine sodium represented by the following formula (12), And polyoxyethylene coconut oil fatty acid monoethanolamide sodium sulfate shown in 13).

前記一般式（２）若しくは（３）で示される化合物及びその塩としては、下記式（１４）で示されるポリオキシエチレンアルキルフェニルエーテルリン酸、下記式（１５）で示されるドデシルベンゼンスルホン酸トリエタノールアミン等が挙げられる。

Examples of the compound represented by the general formula (2) or (3) and a salt thereof include polyoxyethylene alkylphenyl ether phosphoric acid represented by the following formula (14) and dodecylbenzenesulfonic acid triglyceride represented by the following formula (15). Examples include ethanolamine.

前記一般式（４）〜（７）のいずれか一つで示される化合物及びその塩としては、下記式（１６）で示されるポリオキシエチレンアルキル（１２〜１４）スルホコハク酸二ナトリウム、下記式（１７）で示されるスルホコハク酸塩（ジオクチル系）等が挙げられる。

Examples of the compound represented by any one of the general formulas (4) to (7) and a salt thereof include polyoxyethylene alkyl (12 to 14) disodium sulfosuccinate represented by the following formula (16), the following formula ( And the sulfosuccinate (dioctyl type) represented by 17).

前記一般式（９）及びその塩としては、下記式（１８）で示されるポリオキシエチレンラウリルエーテル硫酸トリエタノールアミン等が挙げられる。前記一般式（１０）及びその塩としては、下記式（１９）で示されるジイソブチルジメチルブチンジオールポリオキシエチレングリコールエーテル等が挙げられる。

Examples of the general formula (9) and salts thereof include polyoxyethylene lauryl ether sulfate triethanolamine represented by the following formula (18). Examples of the general formula (10) and salts thereof include diisobutyldimethylbutynediol polyoxyethylene glycol ether represented by the following formula (19).

成分（ａ１）は強いディッシング量低減作用を有している。このため、成分（ａ）は、第２の研磨工程において成分（ａ１）によりディッシング量を低減する。図２（ａ）に示すように、第２の研磨工程でのディッシング量ｄ１とは、バリア膜１４の配線溝１３以外の箇所の表面と導体膜１５表面との間の深さ方向の距離（高さの差）のことである。成分（ａ１）は、前記作用の他に銅含有金属に対する研磨抑制作用を有している。

The component (a1) has a strong dishing amount reducing effect. For this reason, the component (a) reduces the dishing amount by the component (a1) in the second polishing step. As shown in FIG. 2A, the dishing amount d1 in the second polishing step is the distance in the depth direction between the surface of the barrier film 14 other than the wiring groove 13 and the surface of the conductor film 15 ( Height difference). The component (a1) has a polishing suppressing action on the copper-containing metal in addition to the above action.

  The component (a2) has the effect of reducing the dishing amount and the effect of suppressing the polishing of the copper-containing metal, like the component (a1). However, each action of the component (a2) is weaker than that of the component (a1). For this reason, it is preferable that the component (a) is composed of the component (a1) and the component (a2) because the effect of reducing the dishing amount can be exhibited and the polishing suppressing effect on the copper-containing metal can be weakened.

  The content of the component (a) in the first polishing composition is preferably 0.025 to 0.2% by mass, and more preferably 0.03 to 0.1% by mass. If the content of the component (a) is less than 0.025% by mass, the dishing amount d1 cannot be sufficiently reduced. On the other hand, if it exceeds 0.2% by mass, polishing of the copper-containing metal is suppressed by the component (a), and the polishing rate for the copper-containing metal, that is, the polishing rate for the conductor film 15 is decreased. Further, the conductor film 15 remains on the polished surface after polishing because the conductor film 15 is not sufficiently polished and removed. Therefore, there is an increased risk that the clearness of the surface to be polished will deteriorate.

  When the component (a) is composed of the component (a1) and the component (a2), the mass ratio of the component (a1) and the component (a2) is preferably (a1) :( a2) = 10: 1 to 1: 1. If the mass ratio of the component (a1) to the component (a2) is less than the above range, the dishing amount d1 cannot be sufficiently reduced. On the other hand, when the mass ratio of the component (a1) to the component (a2) exceeds the above range, the polishing rate for the conductive film 15 decreases and the clearness of the surface to be polished is likely to deteriorate.

The component (b) silicon oxide has a mechanical polishing action on the surface to be polished. Examples of the silicon oxide include various types having different production methods and properties. Specific examples of silicon oxide include colloidal silica (Colloidal SiO ₂ ), fumed silica (Fumed SiO ₂ ), and precipitated silica (Precipitated SiO ₂ ). These may be contained alone or in combination of two or more. Among these, colloidal silica or fumed silica is preferable, and colloidal silica is more preferable because the polishing rate for the conductor film 15 is high.

The particle diameter of the component (b) is preferably 0.01 to 0.5 [mu] m, more preferably 0.03 to 0.3 [mu] m in terms of an average particle diameter (D _N4 ) determined by a laser diffraction scattering method. When the average particle size is less than 0.01 μm, the mechanical polishing action of the component (b) is weak, and the polishing rate for the conductor film 15 is decreased and the clearness of the surface to be polished is likely to be deteriorated. On the other hand, if it exceeds 0.5 μm, the polishing rate for the conductor film 15 becomes excessively high, and the dishing amount d1 increases. Furthermore, not only the conductor film 15 but also the barrier film 14 and the insulating film 12 are polished, which increases the possibility that the amount of erosion in the second polishing process increases. In addition, since the sedimentation property of the component (b) becomes high, it is difficult for the first polishing composition to maintain the dispersed state of the component (b), and the possibility that the stability is lowered increases. As shown in FIG. 2B, the erosion amount e1 in the second polishing step is a barrier between the surface of the region where the wiring grooves 13 are densely formed and the region where the wiring grooves 13 are sparsely formed. This is the distance (height difference) in the depth direction from the surface of the film 14.

  The content of the component (b) in the first polishing composition is preferably 0.01 to 10% by mass, and more preferably 0.1 to 3% by mass. When the content of the component (b) is less than 0.01% by mass, a sufficient polishing rate for the surface to be polished cannot be obtained and the clearness of the surface to be polished is likely to deteriorate. On the other hand, if it exceeds 10% by mass, the polishing rate for the conductor film 15 and the like becomes excessively high, and the risk of increasing the dishing amount d1 and the erosion amount e1 increases.

  The carboxylic acid of component (c) increases the polishing rate for the conductor film 15 by chelate bonding with copper during polishing. The carboxylic acid may have an amino group, a hydroxyl group, or the like, and specific examples include α-amino acids such as glycine, alanine, and valine, citric acid, oxalic acid, oxalic acid, maleic acid, and tartaric acid. These may be contained alone or in combination of two or more. The component (c) is preferably a mono- or dicarboxylic acid or α-amino acid having 10 or less carbon atoms because the polishing rate for the conductor film 15 can be further increased. Furthermore, since the component (c) has a dishing amount reducing action, an α-amino acid is more preferable, and alanine is most preferable.

  The content of the component (c) in the first polishing composition is preferably 0.01 to 2% by mass, and more preferably 0.4 to 1.5% by mass. When the content of the component (c) is less than 0.01% by mass, the effect of improving the polishing rate for the conductor film 15 is low, and the possibility that the polishing rate for the conductor film 15 is lowered increases. On the other hand, even if it exceeds 2% by mass, the polishing rate for the conductor film 15 is lowered and the dishing amount d1 is increased.

  The anticorrosive agent of component (d) prevents corrosion of the surface of the conductor film 15 by protecting the copper-containing metal from corrosion by the component (e). Furthermore, the component (d) suppresses excessive polishing of the conductor film 15 by the protective action on the surface of the conductor film 15, thereby reducing the dishing amount d1. Examples of the component (d) include benzotriazoles (benzotriazole and derivatives thereof) represented by the following general formula (20). In the following general formula (20), the carbon atom at the 4-position, 5-position, 6-position or 7-position may be substituted with a nitrogen atom, or the nitrogen atom at the 1-position may be substituted with a carbon atom.

（式中、Ｒ⁷は水素原子、カルボキシル基を含有するアルキル基、ヒドロキシル基と３級アミノ基とを含有するアルキル基、ヒドロキシル基を含有するアルキル基又はアルキル基を示し、Ｒ¹⁵〜Ｒ¹⁸はそれぞれ水素原子又はアルキル基を示す。）
成分（ｄ）は、下記一般式（８）で示されるベンゾトリアゾール誘導体が、導体膜１５表面の保護作用が強いために好ましい。

Wherein R ⁷ represents a hydrogen atom, an alkyl group containing a carboxyl group, an alkyl group containing a hydroxyl group and a tertiary amino group, an alkyl group containing a hydroxyl group or an alkyl group, and R ^{15 to} R ¹⁸ Each represents a hydrogen atom or an alkyl group.)
As the component (d), a benzotriazole derivative represented by the following general formula (8) is preferable because the protective action on the surface of the conductor film 15 is strong.

（式中、Ｒ⁷はカルボキシル基を含有するアルキル基、ヒドロキシル基と３級アミノ基とを含有するアルキル基、ヒドロキシル基を含有するアルキル基又はアルキル基を示す。）
前記一般式（８）で示されるベンゾトリアゾール誘導体において、Ｒ⁷がカルボキシル基を含有するアルキル基を示すものとしては下記一般式（２１）で示されるものが挙げられ、具体例としては下記式（２２）で示される１−（１，２−ジカルボキシエチル）ベンゾトリアゾールが挙げられる。

(In the formula, R ⁷ represents an alkyl group containing a carboxyl group, an alkyl group containing a hydroxyl group and a tertiary amino group, an alkyl group containing an hydroxyl group, or an alkyl group.)
In the benzotriazole derivative represented by the general formula (8), examples of the alkyl group containing a carboxyl group as R ⁷ include those represented by the following general formula (21). Specific examples thereof include the following formula ( 22-) 1- (1,2-dicarboxyethyl) benzotriazole.

また、Ｒ⁷がヒドロキシル基と３級アミノ基とを含有するアルキル基を示すものとしては下記一般式（２３）で示されるものが挙げられ、具体例としては下記式（２４）で示される１−［Ｎ，Ｎ−ビス（ヒドロキシエチル）アミノメチル］ベンゾトリアゾールが挙げられる。

Examples of the alkyl group containing R ⁷ and a tertiary amino group as R ⁷ include those represented by the following general formula (23), and specific examples thereof include 1 represented by the following formula (24). -[N, N-bis (hydroxyethyl) aminomethyl] benzotriazole.

Ｒ⁷がヒドロキシル基を含有するアルキル基を示すものとしては下記一般式（２５）又は下記一般式（２６）で示されるものが挙げられる。これらの具体例としては、下記式（２７）で示される１−（２，３−ジヒドロキシプロピル）ベンゾトリアゾール又は下記式（２８）で示される１−（ヒドロキシメチル）ベンゾトリアゾールが挙げられる。

Examples of R ⁷ representing an alkyl group containing a hydroxyl group include those represented by the following general formula (25) or the following general formula (26). Specific examples thereof include 1- (2,3-dihydroxypropyl) benzotriazole represented by the following formula (27) or 1- (hydroxymethyl) benzotriazole represented by the following formula (28).

前記一般式（２１）、（２３）、（２５）及び（２６）において、Ｙ⁷はアルキレン基を示す。これらは単独で含有されてもよいし、二種以上が組み合わされて含有されてもよい。成分（ｄ）は、導体膜１５表面の保護作用がより強いために、前記式（２４）で示される１−［Ｎ，Ｎ−ビス（ヒドロキシエチル）アミノメチル］ベンゾトリアゾールがより好ましい。

In the general formulas (21), (23), (25), and (26), Y ⁷ represents an alkylene group. These may be contained alone or in combination of two or more. The component (d) is more preferably 1- [N, N-bis (hydroxyethyl) aminomethyl] benzotriazole represented by the formula (24) because the protective action on the surface of the conductor film 15 is stronger.

  The content of the component (d) in the first polishing composition is preferably 0.1% by mass or less. Furthermore, when the component (d) is benzotriazole, the content of the component (d) in the first polishing composition is more preferably 0.000001 to 0.001% by mass, and 0.00003 to 0.0005% by mass. Is most preferred. Further, when the component (d) is 1- [N, N-bis (hydroxyethyl) aminomethyl] benzotriazole, 0.00005 to 0.005 mass% is more preferable, and 0.0001 to 0.001 mass is most preferable. . On the other hand, when the component (d) is 1- (2,3-dihydroxypropyl) benzotriazole, 0.001 to 0.1% by mass is more preferable, and 0.003 to 0.05% by mass is most preferable. When the component (d) is 1- (1,2-dicarboxyethyl) benzotriazole, 0.0005 to 0.01% by mass is more preferable, and 0.002 to 0.008% by mass is most preferable.

  When the content of the component (d) is less than the above range, the effect of protecting the surface of the conductor film 15 and the effect of reducing the dishing amount are low, and the surface of the conductor film 15 after polishing may be roughened and the dishing amount d1 may increase. Rise. On the other hand, if the content of the component (d) exceeds the above range, polishing of the conductor film 15 is suppressed by the component (d), and the polishing rate for the conductor film 15 is decreased and the clearness of the surface to be polished may be deteriorated. Will increase.

  The oxidizing agent of component (e) generates an oxide film that is easily peeled off by oxidizing the copper-containing metal, and promotes mechanical polishing by component (b). The oxidizing agent generally has an oxidizing power sufficient to oxidize copper. Specific examples thereof include persulfates such as ammonium persulfate, potassium persulfate, and sodium persulfate, periodic acid, and peracetic acid. , Perchloric acid, ammonium percarbonate, hydrogen peroxide and the like. Among these, persulfate is preferable because of its strong oxidizing power against copper, and ammonium persulfate is more preferable.

  The content of the component (e) in the first polishing composition is preferably 0.5 to 10% by mass, and more preferably 1 to 5% by mass. When the content of the component (e) is less than 0.5% by mass, the polishing accelerating effect is low, and the possibility that the polishing rate for the conductor film 15 is lowered increases. On the other hand, if it exceeds 10% by mass, the polishing rate for the conductor film 15 becomes excessively high, and the risk of increasing the dishing amount d1 increases.

  The water of component (f) dissolves or disperses other components. The component (f) preferably contains as little impurities as possible in order to prevent the action of other components from being inhibited. Specifically, component (f) is preferably pure water, ultrapure water, or distilled water from which foreign ions are removed through a filter after removing impurity ions with an ion exchange resin. The content of the component (f) in the first polishing composition is the remaining amount with respect to the content of other components in the first polishing composition.

  The first polishing composition may contain a thickener, an antifoaming agent, a preservative, and the like as other additive components in addition to the above-described components, depending on the necessity for stabilization and polishing processing. The first polishing composition is prepared by mixing other components with the component (f) and dispersing or dissolving each component by, for example, stirring with a blade-type stirrer or ultrasonic dispersion. Here, the mixing order of the other components with respect to the component (f) is not limited.

  The pH of the first polishing composition is preferably 7 or more, more preferably 7 to 12, and most preferably 8 to 10. When the pH of the first polishing composition is less than 7, polishing removal of the conductor film 15 does not proceed sufficiently and the polishing rate decreases. On the other hand, if it exceeds 12, the polishing rate for the conductor film 15 becomes excessively high, and the risk of increasing the dishing amount d1 increases. The pH of the first polishing composition is adjusted by adding ammonia or the like to the first polishing composition.

  The second polishing composition used in the third polishing step contains (g) colloidal silica, (h) acid, (i) anticorrosive, (j) fully saponified polyvinyl alcohol, and (k) water. ing.

  The colloidal silica of component (g) has a mechanical polishing action on the surface to be polished. Colloidal silica is synthesized by various methods, but since it contains very few impurity elements, those synthesized by a sol-gel method are preferred. The sol-gel method is generally performed by dropping methyl silicate into a solvent composed of methanol, ammonia and water and hydrolyzing it. However, in the case where the presence of the impurity element does not matter so much, so-called ion exchange method colloidal silica that uses colloidal silica by ion exchange using sodium silicate as a starting material may be used.

The average particle diameter of the component (g) is preferably from 0.01 to 0.5 μm, more preferably from 0.03 to 0.3 μm, as DN ₄ . When the average particle size is less than 0.01 μm, a sufficient polishing rate cannot be obtained. On the other hand, if it exceeds 0.5 μm, the risk of an increase in the amount of erosion in the third polishing step increases. As shown in FIG. 3B, the erosion amount e2 in the third polishing step is the surface of the region where the wiring grooves 13 are densely formed and the region where the wiring grooves 13 are sparsely formed. This is the distance in the depth direction (height difference) from the surface of the insulating film 12.

  Further, it is preferable to contain a combination of colloidal silica having a large average particle diameter (first silica, average particle diameter D1) and colloidal silica having a smaller particle diameter than the first silica (second silica, average particle diameter D2). . The average particle diameter D1 is preferably 0.05 μm or more and 0.3 μm or less, and more preferably 0.05 μm or more and 0.1 μm or less. If the average particle diameter D1 is less than 0.05 μm, it is difficult to increase the polishing rate for the insulating film 12. On the other hand, if the thickness exceeds 0.3 μm, the polishing rate for the insulating film 12 is too high, so that the erosion amount e2 is likely to increase. The average particle diameter D2 is preferably 0.01 μm or more and less than 0.05 μm, and more preferably 0.02 μm or more and 0.04 μm or less. When the average particle diameter D2 is less than 0.01 μm and exceeds 0.05 μm, there is a high possibility that a polishing rate for the tantalum-containing compound, that is, a sufficient polishing rate for the barrier film 14 cannot be obtained.

  The content of the component (g) in the second polishing composition is preferably from 0.01 to 20 mass%, more preferably from 0.1 to 10 mass%. When the content of the component (g) is less than 0.01% by mass, a sufficient polishing speed for the barrier film 14 cannot be obtained. On the other hand, if it exceeds 20% by mass, the possibility that the surface level difference is not sufficiently suppressed increases.

  The acid of component (h) increases the polishing rate for the barrier film 14. Component (h) is preferably at least one selected from nitric acid, hydrochloric acid, sulfuric acid, lactic acid, acetic acid, oxalic acid, citric acid, malic acid, succinic acid, butyric acid, and malonic acid, because it is excellent in the above-mentioned effects. At least one selected from oxalic acid and lactic acid is more preferable, and nitric acid is most preferable. In addition, when the component (h) contains nitric acid, the storage stability of the second polishing composition can be improved, and a decrease in polishing rate over time can be suppressed.

  The content of the component (h) in the second polishing composition is preferably 0.01 to 3% by mass, and more preferably 0.01 to 0.3% by mass. When the content of the component (h) is less than 0.01% by mass, a sufficient polishing rate for the barrier film 14 cannot be obtained. On the other hand, if it exceeds 3% by mass, the pH of the second polishing composition is lowered, and the handleability thereof is likely to deteriorate. When the content of the component (h) is 0.03 to 0.1% by mass, the surface step can be further suppressed.

  The effects and specific examples of the anticorrosive agent of component (i) are the same as those of component (d) of the first polishing composition. The content of component (i) in the second polishing composition is preferably 0.001 to 3 mass%, more preferably 0.01 to 0.3 mass%. When the content of the component (i) is less than 0.001% by mass, the effect of protecting the surface of the conductor film 15 and the effect of reducing the dishing amount are low, and surface roughness occurs on the surface of the conductor film 15 after polishing and the third polishing step. There is an increased risk of increasing the amount of dishing. On the other hand, when the content exceeds 3% by mass, polishing of the conductor film 15 is suppressed by the component (i), and the possibility that the polishing rate of the conductor film 15 is reduced increases. As shown in FIG. 2A, the dishing amount d2 in the third polishing step is the distance in the depth direction between the surface of the insulating film 12 other than the wiring groove 13 and the surface of the conductor film 15 ( Height difference).

  The fully saponified polyvinyl alcohol of component (j) suppresses the surface step of the surface to be polished. This component (j) is saponified (hydrolyzed) of polyvinyl acetate. Here, the complete saponification type means that the degree of saponification is 98.0 mol% or more. The molecular weight of component (j) is generally about 10,000 to 500,000, but is preferably 100,000 or less because of good solubility in component (k).

  The content of the component (j) in the second polishing composition is preferably 0.001 to 1.0% by mass, and more preferably 0.005 to 0.5% by mass. When the content of the component (j) is less than 0.001% by mass and exceeds 1.0% by mass, the dishing amount d2 is likely to increase. Further, the polishing rate for the conductive film 15 can be increased as the content of the component (j) is increased.

  The action effect and specific examples of the water of the component (k) are the same as those of the component (f) of the first polishing composition. When it is necessary to polish the conductor film 15 in the third polishing step, the second polishing composition preferably contains (l) an oxidizing agent. The effect of the component (l) is the same as the component (e) of the first polishing composition. Examples of the component (l) include hydrogen peroxide, nitric acid, potassium permanganate, persulfate and the like, and these may be contained alone or in combination of two or more. Among these, hydrogen peroxide is preferable because it is relatively inexpensive and has a sufficient oxidizing power for copper, and further has a low content of metal impurities.

  The content of the component (l) in the second polishing composition is preferably 0.1 to 20% by mass, and more preferably 0.1 to 5% by mass. When the content of the component (l) is less than 0.1% by mass, the oxidizing power is low, and the possibility that a sufficient polishing rate cannot be obtained increases. On the other hand, if it exceeds 20% by mass, the risk of increasing the dishing amount d2 increases.

  Similar to the first polishing composition, the second polishing composition may contain the other additive components. The second polishing composition is prepared by mixing other components with the component (k) and dispersing or dissolving each component in the same manner as the first polishing composition. Here, the mixing order of the other components with respect to the component (k) is not limited.

  The pH of the second polishing composition is mainly adjusted by the amount of component (h) added, and the pH of the second polishing composition is preferably 1.5 to 4, and more preferably 2-3. If pH is less than 1.5, the 2nd constituent for polish becomes a strong acid, and there is a possibility that the handleability may deteriorate. On the other hand, if it exceeds 4, the content of the component (h) is low, so that a sufficient polishing rate for the barrier film 14 cannot be obtained.

  When the semiconductor substrate 11 is polished, as shown in FIG. 1B, as the first polishing step, the conductive film 15 is used by using a polishing composition capable of polishing the conductive film 15 with high polishing efficiency. To polish. The polishing of the conductor film 15 in the first polishing step is finished before the barrier film 14 is exposed. When the polishing is completed, it is preferable that the initial grooves on the surface of the conductor film 15 are almost completely eliminated.

  After the first polishing step, as shown in FIG. 1C, the conductor film 15 is polished using the first polishing composition as the second polishing step. Specifically, while supplying the first polishing composition to the surface to be polished, the polishing pad is pressed against the surface to be polished and rotated. At this time, the first polishing composition can polish the conductor film 15 by mechanically polishing the surface to be polished with the component (b). In the second polishing step, it is preferable to adjust the polishing rate so that the exposed barrier film 14 is not polished. After the second polishing step, as shown in FIG. 1D, the barrier film 14 is polished using the second polishing composition as the third polishing step. Specifically, the polishing pad is pressed against the surface to be polished and rotated while supplying the second polishing composition to the surface to be polished. At this time, the second polishing composition can polish the barrier film 14 by mechanically polishing the surface to be polished with the component (g).

The effects exhibited by the above embodiment will be described below.
In the second polishing step in the polishing method of the first embodiment, the dishing amount d1 can be reduced by each component of (a) and (d) by using the first polishing composition, The polishing rate for the conductor film 15 can be increased by the components (c) and (e). In addition, the amount of erosion e1 can be reduced by using the first polishing composition in the second polishing step. On the other hand, in the third polishing step, the dishing amount d2 and the erosion amount e2 can be reduced by the component (j) by using the second polishing composition. This is presumed to be because component (j) has a protective effect on the surface of the portion where dishing and erosion are formed, and suppresses the promotion of polishing in that portion. The protective action of component (j) is not exhibited by partially saponified polyvinyl alcohol, and is a specific action of component (j). In addition, in the third polishing step, by using the second polishing composition, the polishing rate for the barrier film 14 can be increased by the components (g) and (h).

  Here, when each dishing amount d1, d2 and each erosion amount e1, e2 increase, dishing and erosion occur on the surface to be polished. For this reason, a step is generated on the surface of the semiconductor substrate 11 after polishing due to dishing and erosion. The semiconductor substrate 11 has problems such as difficulty in multilayering the wiring structure due to the step and an increase in wiring resistance due to a reduction in the cross-sectional area of the wiring portion 17. Therefore, the polishing method of the first embodiment reduces the dishing amount d1 and the erosion amount e1 in the second polishing step and reduces the dishing amount d2 and the erosion amount e2 in the third polishing step. Can be suppressed, and the surface step of the semiconductor substrate 11 can be suppressed.

  Further, on the surface to be polished after the second polishing step, the conductor film 15 may remain on the barrier film 14 other than the inside of the wiring groove 13 depending on the progress of the second polishing. In this case, it is necessary to remove not only the barrier film 14 but also the remaining conductor film 15 in the third polishing step. At this time, the second polishing composition can change the polishing rate for the conductor film 15 by changing the content of the component (j). For this reason, the polishing method of the first embodiment uses the second polishing composition suitable for the state of the surface to be polished when the second polishing step is completed, that is, the residual amount of the conductor film 15 to be removed. 3 polishing steps can be performed.

  The third polishing step includes a first silica having an average particle diameter D1 of 0.05 μm or more and 0.3 μm or less, and a second silica having an average particle diameter D2 of 0.01 μm or more and less than 0.05 μm as the component (g). It is preferable to use together. In this case, the polishing rate for the insulating film 12 can be increased by the first silica, and the polishing rate for the barrier film 14 can be increased by the second silica, so that the polishing efficiency in the third polishing step can be improved. Here, when the smoothness of the surface to be polished after the second polishing step is poor, it is necessary to polish the insulating film 12 in addition to the barrier film 14, and therefore the combined use of the first silica and the second silica is It is particularly useful.

(Second Embodiment)
Next, a second embodiment of the present invention will be described. Note that the second embodiment will be described focusing on differences from the first embodiment.

  The first polishing composition used in the second polishing step includes (A) an α-amino acid, (B) a benzotriazole derivative, (C) silicon oxide, (D) a surfactant, (E) an oxidizing agent, and (F) Water is contained. Here, the effects of the components (C), (E), and (F), the specific examples, and the content in the first polishing composition are the same as those in the first embodiment (b), (e), and It is the same as each component of (f).

  The α-amino acid of component (A) has a dishing amount reducing action. Furthermore, the component (A) increases the polishing rate for the conductor film 15 in the same manner as the component (c). Examples of the α-amino acid include alanine, glycine, and valine. These may be contained alone or in combination of two or more. Among these, alanine is preferable because it has a strong dishing amount reducing effect and high solubility in the component (F).

  The content of the component (A) in the first polishing composition is the same as the component (c). When the content of the component (A) is less than 0.01% by mass, the dishing amount reducing action is weak, and the dishing amount d1 cannot be sufficiently reduced. On the other hand, when it exceeds 2 mass%, the grinding | polishing with respect to a copper containing metal will be suppressed by a component (A), and the grinding | polishing rate with respect to a copper containing metal will fall. Furthermore, there is an increased risk that the clearness of the surface to be polished will deteriorate.

  The benzotriazole derivative of component (B) is represented by the general formula (8) and has the same action as component (d). Specific examples of the component (B) are the same as those of the component (d). The content of the component (B) in the first polishing composition is preferably 0.1% by mass or less. Furthermore, 0.0005-0.01 mass% is more preferable when a component (B) is shown by the said General formula (21), and 0.002-0.008 mass% is the most preferable. On the other hand, when the component (B) is represented by the general formula (23), 0.00005 to 0.005 mass% is more preferable, and 0.0001 to 0.001 mass% is most preferable. When the component (b) is represented by the general formula (25) or the general formula (26), 0.001 to 0.1 mass% is more preferable, and 0.003 to 0.005 mass% is most preferable.

  When the content of the component (B) is less than the above range, the effect of protecting the surface of the conductor film 15 and the effect of reducing the dishing amount are low, and the surface of the conductor film 15 after polishing may be roughened and the dishing amount d1 may increase. Rise. On the other hand, when content of a component (B) exceeds the said range, grinding | polishing with respect to a copper containing metal will be suppressed, and while the polishing rate with respect to a copper containing metal falls, there exists a possibility that the clearness of a to-be-polished surface may deteriorate.

  The surfactant of the component (D) reduces the dishing amount d1 similarly to the component (a). As the component (D), coconut oil fatty acid sarcosine triethanolamine represented by the above formula (11), coconut oil fatty acid methyl taurine sodium represented by the above formula (12), and polyoxyethylene coconut represented by the above formula (13) Oil fatty acid sodium monoethanolamide sulfate, polyoxyethylene alkylphenyl ether phosphoric acid represented by the above formula (14), dodecylbenzenesulfonic acid triethanolamine represented by the above formula (15), and polyoxyethylene represented by the above formula (16) Oxyethylene alkyl (12-14) disodium sulfosuccinate, sulfosuccinate (dioctyl type) represented by formula (17), polyoxyethylene lauryl ether sulfate triethanolamine represented by formula (18), 19) Diisobutyldimethylbutane Emissions diol polyoxyethylene glycol ether. The content of the component (D) in the first polishing composition is the same as the component (a).

  Accordingly, when the conductor film 15 is polished using the first polishing composition of the second embodiment as the second polishing step, the conductor film 15 is mechanically polished by the component (C). Can be polished. Furthermore, in the second polishing step, by using the first polishing composition, the dishing amount d1 can be reduced by the components (A), (B), and (D), and (A) and The polishing rate for the conductive film 15 can be increased by the components (E). In addition, the amount of erosion e1 can be reduced by using the first polishing composition in the second polishing step.

Next, the first embodiment will be described more specifically with reference to test examples and comparative examples in Example 1.
<Second polishing step>
(Test Examples 1-31 and Comparative Examples 1-11)
In Test Example 1, coconut oil fatty acid sarcosine triethanolamine as component (a1), polyoxyethylene lauryl ether triethanolamine as component (a2), colloidal silica as component (b), as component (c) A first polishing composition was prepared by mixing 1- (2,3-dihydroxypropyl) benzotriazole as component (d), ammonium persulfate as component (e) and water as component (f). . Table 1 shows the content of each component other than the component (f). Here, colloidal silica, N4 Plus Submicron Particle Sizer (Beckman Coulter, product name Inc.) was 0.05μm at D _N4 measured at iron in the 20 wt% aqueous solution of nickel, copper, chromium, zinc And the total content of calcium was 20 ppb or less.

  In Test Examples 2-31 and Comparative Examples 1-11, a first polishing composition was prepared in the same manner as in Test Example 1 except that the type or content of each component was changed as shown in Table 1. And while measuring the pH of each 1st polishing composition, it evaluated about each following item. The results are shown in Table 2. In Table 1, the content (% by mass) is indicated by “amount”.

<Polishing speed>
The thickness of the copper blanket wafer was measured using a sheet resistance machine (VR-120; manufactured by Kokusai Electric System Service Co., Ltd.). Next, the surface of the copper blanket wafer was polished for 1 minute under the following polishing conditions 1 while using the first polishing composition of each example. And after measuring the thickness of the copper blanket wafer after grinding | polishing similarly to the above, the grinding | polishing speed | rate was calculated | required based on the following formula.

Polishing rate [nm / min] = (wafer thickness before polishing [nm] −wafer thickness after polishing [nm]) ÷ polishing time [min]
<Polishing condition 1>
Polishing machine: Polishing machine for single-sided CMP (Mirra; manufactured by Applied Materials), object to be polished: copper blanket wafer (8-inch silicon wafer in which copper is formed by electrolytic plating), polishing pad: laminated polishing pad made of polyurethane (IC-1000 / Suba400; manufactured by Rodel), polishing pressure: 2 psi (= about 13.8 kPa), platen rotation speed: 60 rpm, first polishing composition supply speed: 200 ml / min, carrier rotation speed: 60 rpm
<Dishing amount: d1 and clearness of polished surface: C>
The copper pattern wafer surface was polished under the following polishing condition 2 while using a polishing composition for the first polishing step (PLANERELITE-7102; manufactured by Fujimi Incorporated). The polishing amount was 70% (700 nm) of the initial film thickness. After the polishing, the first polishing composition of each example was used on the surface of the copper pattern wafer and the polishing amount of the copper film was polished by 200 nm over the polishing condition 1 after the end point signal appeared. . Next, in the 100 μm-wide isolated wiring portion on the surface of the copper pattern wafer after the second polishing, the dishing amount d1 was measured using a profila (HRP340; manufactured by KLA Tencor) which is a contact type surface measuring device. In the table, “−” indicates that the dishing amount d1 could not be measured because the polishing rate was low and polishing itself did not proceed.

Further, the amount of the conductor film 15 remaining on the barrier film 14 other than the wiring portion 17 was visually observed using a differential interference microscope (OPTIPHOTO300; manufactured by NIKON). As for the clearness of the surface to be polished, the one in which the conductor film 15 does not remain at all is excellent (斑), and the one in which the spotted conductor film 15 remains slightly is good (◯). Spot-like conductor film 15 remains but is slightly defective (Δ) within the range that can be removed by polishing in the third polishing process, and the conductor film 15 remains and the wiring portion is not visible in the third polishing process. Those that were difficult to polish and remove were evaluated in four grades: poor (x).
<Polishing condition 2>
Polishing machine: single-side CMP polishing machine (Mirra; manufactured by Applied Materials), polishing target: copper pattern wafer (manufactured by SEMATECH, 854 mask pattern, film thickness 1000 nm, initial concave groove 800 nm), polishing pad: polyurethane Laminated polishing pad (IC-1400; manufactured by Rodel), polishing processing pressure: 2.0 psi (= about 13.8 kPa), platen rotation speed: 100 rpm, supply speed of the first polishing composition: 200 ml / min Carrier rotation speed: 100rpm
<Pot life: P>
Immediately after the preparation of the first polishing composition, the polishing rate was determined in the same manner as in the above item <Polishing rate>. Next, the first polishing composition was stored in a hermetically sealed container, and the polishing rate was determined in the same manner as described above every time a fixed period elapsed after the start of storage. Subsequently, the elapsed time when the polishing rate decreased by 90% with respect to the polishing rate immediately after preparation was defined as the pot life. The pot life is 4 (excellent (◎), 1 week or more but less than 2 weeks is good (○), 3 days or more but less than 1 week is slightly bad (△), and 3 days or less is bad (x). Rated by stage.

＜成分（ａ）＞Ａ１：ヤシ油脂肪酸サルコシントリエタノールアミン、Ａ２：ヤシ油脂肪酸メチルタウリンナトリウム、Ａ３：ポリオキシエチレンヤシ油脂肪酸モノエタノールアミド硫酸ナトリウム、Ｂ１：ポリオキシエチレンアルキルフェニルエーテルリン酸、Ｂ２：ドデシルベンゼンスルホン酸トリエタノールアミン、Ｃ１：ポリオキシエチレンアルキル（１２〜１４）スルホコハク酸二ナトリウム、Ｃ２：スルホコハク酸塩、Ｄ：ポリオキシエチレンラウリルエーテル硫酸トリエタノールアミン、Ｅ：ジイソブチルジメチルブチンジオールポリオキシエチレングリコールエーテル、Ｆ：下記式（２９）で示されるポリオキシエチレンポリオキシプロピレンアルキルエーテル

<Component (a)> A1: Palm oil fatty acid sarcosine triethanolamine, A2: Palm oil fatty acid methyl taurine sodium, A3: Polyoxyethylene coconut oil fatty acid sodium monoethanolamide sulfate, B1: Polyoxyethylene alkylphenyl ether phosphoric acid, B2: triethanolamine dodecylbenzenesulfonate, C1: polyoxyethylene alkyl (12-14) disodium sulfosuccinate, C2: sulfosuccinate, D: polyoxyethylene lauryl ether sulfate triethanolamine, E: diisobutyldimethylbutynediol Polyoxyethylene glycol ether, F: polyoxyethylene polyoxypropylene alkyl ether represented by the following formula (29)

（式中、ｗ及びｙの合計は１６４であり、ｘは３１である。）
＜成分（ｂ）＞ＣＳ１：Ｄ_N4が０．０３μｍのコロイダルシリカ、ＣＳ２：Ｄ_N4が０．０５μｍのコロイダルシリカ、ＣＳ３：Ｄ_N4が０．０７μｍのコロイダルシリカ、ＦＳ３：Ｄ_N4が０．０７μｍのフュームドシリカ
＜成分（ｃ）＞Ａｌａ：アラニン、Ｇｌｙ：グリシン、Ｖａｌ：バリン、Ｃｉｔ：クエン酸、Ｏｘａ：シュウ酸
＜成分（ｄ）＞Ｇ：１−（２，３ジヒドロキシプロピル）ベンゾトリアゾール、Ｈ：１−［Ｎ，Ｎ−ビス（ヒドロキシジメチル）アミノメチル］−ベンゾトリアゾール、Ｉ：１−（１，２−ジカルボキシエチル）ベンゾトリアゾール
＜成分（ｅ）＞ＡＰＳ：過硫酸アンモニウム、ＨＰＯ：過酸化水素

(In the formula, the sum of w and y is 164 and x is 31.)
<Component (b)> CS1: D _N4 is 0.03μm colloidal silica, CS2: D _N4 is 0.05μm colloidal silica, CS3: D _N4 is 0.07μm colloidal silica, FS3: D _N4 is 0.07μm Fumed silica <component (c)> Ala: alanine, Gly: glycine, Val: valine, Cit: citric acid, Oxa: oxalic acid <component (d)> G: 1- (2,3 dihydroxypropyl) benzotriazole , H: 1- [N, N-bis (hydroxydimethyl) aminomethyl] -benzotriazole, I: 1- (1,2-dicarboxyethyl) benzotriazole <component (e)> APS: ammonium persulfate, HPO: hydrogen peroxide

表２に示すように、試験例１〜３１においては、ディッシング量ｄ１を低減するとともに、銅含有金属に対する研磨速度を高めることができた。試験例１〜７に示すように、（ａ１）及び（ａ２）の各成分は、それぞれ含有量を０．０５質量％以上、特に０．０５〜０．１質量％にすることにより、研磨速度を維持しつつディッシング量ｄ１を特に低減することができた。

As shown in Table 2, in Test Examples 1 to 31, the dishing amount d1 was reduced and the polishing rate for the copper-containing metal could be increased. As shown in Test Examples 1 to 7, each component of (a1) and (a2) has a polishing rate of 0.05 mass% or more, particularly 0.05 to 0.1 mass%, respectively. The dishing amount d1 could be particularly reduced while maintaining the above.

<Third polishing step>
(Test Examples 32-72 and Comparative Examples 12-26)
In Test Example 32, colloidal silica as component (g), nitric acid as component (h), 1- [N, N-bis (hydroxydimethyl) aminomethyl] -benzotriazole as component (i), component ( A fully saponified polyvinyl alcohol (molecular weight: 100,000) of j), water of component (k) and hydrogen peroxide as component (l) were mixed to prepare a second polishing composition. Table 3 shows the content (% by mass) of each component other than the component (k). Here, colloidal silica is 0.07 μm in DN ₄ measured by N4 Plus Submicron Particle Sizer (product name of Beckman Coulter, Inc.), and is iron, nickel, copper, chromium, zinc in 20% by mass aqueous solution. And the total content of calcium was 20 ppb or less. In Test Examples 33 to 72 and Comparative Examples 12 to 26, a second polishing composition was prepared in the same manner as in Test Example 32 except that the type or content of each component was changed as shown in Table 3. And while measuring the pH of each 2nd polishing composition, the following polishing performance evaluation was performed. The results are shown in Table 4.
(Polishing performance evaluation)
The second polishing composition of each example was used and the object to be polished was polished for 1 minute under the following polishing condition 3.
<Polishing condition 3>
Polishing machine: Polishing machine for single-side CMP (Mirra, manufactured by Applied Materials), polishing pad: polyurethane laminated polishing pad (IC-1000 / Suba400: manufactured by Rodel), polishing processing pressure: 2 psi (= about 13.8 kPa) , Platen rotation speed: 80 rpm, second polishing composition supply speed: 200 ml / min, carrier rotation speed: 80 rpm
<Polished object>
(I) Copper pattern wafer (hereinafter referred to as wafer P)
As the first polishing step, the PLANERELITE-7102 was used and polishing was performed under the polishing condition 2. Here, the polishing amount was 70% of the initial film thickness. Next, as the second polishing step, the first polishing composition of Test Example 2 was used, and the polishing condition 1 was used to polish the copper film by 200 nm over after the end point signal appeared. .

(Ii) Copper blanket wafer (hereinafter referred to as wafer A)
An 8-inch silicon wafer on which copper is deposited by electrolytic plating.
(Iii) Tantalum blanket wafer (hereinafter referred to as wafer B)
An 8-inch silicon wafer on which tantalum is deposited by sputtering.

(Iv) Tantalum nitride blanket wafer (hereinafter referred to as wafer C)
An 8-inch silicon wafer on which tantalum nitride is deposited by sputtering.
(V) Silicon dioxide blanket wafer (hereinafter referred to as wafer D)
An 8-inch silicon wafer on which silicon dioxide is deposited by CVD using TEOS as a starting material.

(Vi) Black Diamond (R) blanket wafer (hereinafter referred to as wafer E)
An 8-inch silicon wafer on which a Low-K material film manufactured by Applied Materials is formed.
<Step shape>
In the isolated wiring portion having a width of 100 μm on the surface of the wafer P after the third polishing step, the dishing amount d2 (nm) was measured in the same manner as the item <Dishing amount: d1>. Then, the amount of progress of the step (step difference amount [nm] = d1 [nm] −dishing amount d2 [nm]) was calculated. Here, d1 is 20 nm from the result of Test Example 2 in Table 2. The amount of progress of the step is excellent (◎) when it is 0 nm or more, good (◯) when it is -10 nm or more and less than 0 nm, slightly bad (△) when it is -20 nm or more and less than -10 nm, and bad (x) when it is less than -20 nm. evaluated.

<Cleanability>
After the polished objects (wafer P, wafer A and wafer D) are immersed in an ultrasonic cleaning tank (40 kHz) filled with pure water for 1 minute, a cleaning agent SD3000 (manufactured by Mitsubishi Chemical Corporation) Scrub-cleaning was performed with pure water added. Further, the substrate was washed with pure water and spin-dried. For the wafer P after cleaning, the number of particles having a particle value (0.25 μm or more) was counted by a wafer defect inspection apparatus with a dark field pattern (AITIII, manufactured by KLA Tencor). Further, for wafer A and wafer D after cleaning, the number of particles having a particle value (0.25 μm or more) was counted by a non-patterned wafer surface foreign matter inspection apparatus (SP1-TBI: manufactured by KLA Tencor). For the number of particles, the wafer P is 600 or less, the wafer A is 250 or less, and the wafer D is 100 or less (◎), the wafer P is 601 to 1000, the wafer A is 251 to 500, A wafer having a wafer D of 101 to 200 was evaluated as good (◯). In addition, the wafer P is 1000 or more and 2000 or less, the wafer A is 501 or more and 1000 or less, and the wafer D is 201 or more and 400 or less, and the wafer P is 2001 or more, the wafer A is 1001 or more, In addition, the evaluation was made in four stages, where a wafer D of 401 or more was regarded as defective (x).

<Surface defects>
In the item <cleanability>, 100 particles were randomly extracted from the particles counted on the wafer P, the wafer A, and the wafer D, and the particles were analyzed. Next, out of 100 particles, the number corresponding to the surface defect was counted, and the ratio was calculated. And, surface defects of less than 5% are excellent (◎), 5% or more and less than 10% are good (◯), 10% or more and less than 20% are slightly bad (Δ), and 20% or more are bad (x) 4 Rated by stage.

<Stability>
Immediately after the preparation of the second polishing composition, the polishing rate for the wafer D was determined in the same manner as the item <polishing rate> in the second polishing step except that the polishing condition was changed to the polishing condition 3. Next, the second polishing composition was stored in a constant temperature bath at 43 ° C., and the wafer was prepared in the same manner as described above using the second polishing composition after one week, one month and two months after preparation. The polishing rate for D was determined. In terms of stability, the polishing rate decreases to 90% immediately after preparation, when it is 2 months or more (◎), 1 month to 2 months is good (○), 1 week to 1 month. Slightly poor (Δ) and less than 1 week were evaluated in four grades: poor (×).

<Polishing speed>
The polishing composition for copper, tantalum, tantalum nitride, silicon dioxide, and Low-K materials was determined in the same manner as in the above item <stability> while using the second polishing composition immediately after preparation in each example.

＜シリカ＞ＣＳ１：Ｄ_N4が０．０３μｍのコロイダルシリカ、ＣＳ３：Ｄ_N4が０．０７μｍのコロイダルシリカ、ＦＳ１：Ｄ_N4が０．０３μｍのフュームドシリカ、ＦＳ３：Ｄ_N4が０．０７μｍのフュームドシリカ、ＦＳ４：Ｄ_N4が０．１８μｍのフュームドシリカ
＜成分（ｈ）＞ＮＡ：硝酸、ＬＡ：乳酸、Ｃｉｔ：クエン酸、Ｏｘａ：シュウ酸
＜成分（ｉ）＞Ｇ：１−（２，３ジヒドロキシプロピル）ベンゾトリアゾール、Ｈ：１−［Ｎ，Ｎ−ビス（ヒドロキシジメチル）アミノメチル］−ベンゾトリアゾール、Ｊ：ベンゾトリアゾール
＜ＰＶＡ他＞ＰＶＡ：完全けん化型ポリビニルアルコール（けん化度：９８モル％以上）、ＰＶＡ’：部分けん化型ポリビニルアルコール（けん化度：約８８モル％）、Ａ：ポリエチレングリコール、Ｂ：ポリアクリル酸、Ｃ：ラウリル硫酸アンモニウム、Ｄ：ポリオキシエチレンポリオキシプロピレンアルキルエーテル、Ｅ：ドデシルベンゼンスルホン酸アンモニウム
＜成分（ｌ）＞過酸化水素

<Silica> CS1: D _N4 is 0.03μm colloidal silica, CS3: D _N4 is 0.07μm colloidal silica, FS1: D _N4 is 0.03μm fumed silica, FS3: D _N4 is 0.07μm fumes Dosilica, FS4: Fumed silica with DN ₄ of 0.18 μm <Component (h)> NA: Nitric acid, LA: Lactic acid, Cit: Citric acid, Oxa: Oxalic acid <Component (i)> G: 1- (2 , 3dihydroxypropyl) benzotriazole, H: 1- [N, N-bis (hydroxydimethyl) aminomethyl] -benzotriazole, J: benzotriazole <PVA and others> PVA: fully saponified polyvinyl alcohol (degree of saponification: 98 mol) % Or more), PVA ′: partially saponified polyvinyl alcohol (saponification degree: about 88 mol%), A: polyethylene glycol, B: Riakuriru acid, C: ammonium lauryl sulfate, D: polyoxyethylene polyoxypropylene alkyl ether, E: ammonium dodecylbenzenesulfonate <Component (l)> hydrogen peroxide

表４に示すように、試験例３２〜７２においては、段差形状について優れた評価となった。試験例５４〜５７に示すように、成分（ｉ）は、その含有量を０．１質量％以上、特に０．１〜０．５質量％にすることにより、表面段差を特に抑制することができた。試験例６０〜６３に示すように、成分（ｊ）は、その含有量を０．０５質量％以上、特に０．０５〜０．５質量％にすることにより、銅含有金属に対する研磨速度を特に高めることができた。試験例６８〜７２に示すように、成分（ｌ）は、その含有量を２質量％以上、特に２〜５質量％にすることにより、銅含有金属に対する研磨速度を特に高めることができた。

As shown in Table 4, in Test Examples 32-72, the step shape was excellent. As shown in Test Examples 54 to 57, the component (i) can suppress the surface step particularly by setting its content to 0.1% by mass or more, particularly 0.1 to 0.5% by mass. did it. As shown in Test Examples 60 to 63, the component (j) has a content rate of 0.05% by mass or more, particularly 0.05 to 0.5% by mass, thereby particularly increasing the polishing rate for the copper-containing metal. I was able to increase it. As shown in Test Examples 68 to 72, the component (l) was able to particularly increase the polishing rate for copper-containing metals by setting its content to 2% by mass or more, particularly 2 to 5% by mass.

Next, the second embodiment will be described more specifically with reference to test examples and comparative examples in Example 2.
<Second polishing step>
(Test Examples 73 to 105 and Comparative Examples 27 to 42)
In Test Example 73, alanine (0.01% by mass) as component (A), 1- (2,3dihydroxypropyl) benzotriazole (0.01% by mass), component (C) as component (B) Colloidal silica (0.5% by mass) as a coconut oil fatty acid sarcosine triethanolamine (0.02% by mass) and polyoxyethylene lauryl ether sulfate triethanolamine (0.015% by mass) as component (D), A first polishing composition was prepared by mixing ammonium persulfate (1% by mass) as component (E) and water of component (F). Here, colloidal silica, N4 Plus Submicron Particle Sizer (Beckman Coulter, Inc. product name) was measured at but 0.05μm at D _N4, iron in the 20 wt% aqueous solution of nickel, copper, chromium, zinc And the total content of calcium was 20 ppb or less.

  In Test Examples 74 to 105 and Comparative Examples 27 to 42, the first polishing composition was prepared in the same manner as in Test Example 73 except that the type or content of each component was changed as shown in Table 5 or Table 6. Prepared. And while measuring pH of each 1st polishing composition, it evaluated about each said item of Example 1. FIG. The results are shown in Tables 5 and 6. In Tables 5 and 6, the content (mass%) is indicated by “amount”, and the content of the components whose content is omitted is the same as in Test Example 73. In component (D), the content of the compound located on the left side of “+” is 0.02% by mass and the content of the compound located on the right side of “+” is 0.015% by mass. Furthermore, in Test Example 99, the content of A1 was set to 0.035% by mass.

＜成分（Ａ）及び研磨促進剤＞Ａｌａ：アラニン、Ｇｌｙ：グリシン、Ｖａｌ：バリン、Ｃｉｔ：クエン酸、ＬＡ：乳酸、Ｏｘａ：シュウ酸、ＮＡ：硝酸、ＳＡ：硫酸
＜成分（Ｂ）及び防食剤＞Ｇ：１−（２，３ジヒドロキシプロピル）ベンゾトリアゾール、Ｈ：１−［Ｎ，Ｎ−ビス（ヒドロキシジメチル）アミノメチル］−ベンゾトリアゾール、Ｉ：１−（１，２−ジカルボキシエチル）ベンゾトリアゾール、Ｊ：ベンゾトリアゾール
＜成分（Ｃ）＞ＣＳ１：Ｄ_N4が０．０３μｍのコロイダルシリカ、ＣＳ２：Ｄ_N4が０．０５μｍのコロイダルシリカ、ＣＳ３：Ｄ_N4が０．０７μｍのコロイダルシリカ、ＦＳ３：Ｄ_N4が０．０７μｍのフュームドシリカ
＜成分（Ｄ）＞Ａ１：ヤシ油脂肪酸サルコシントリエタノールアミン、Ａ２：ヤシ油脂肪酸メチルタウリンナトリウム、Ａ３：ポリオキシエチレンヤシ油脂肪酸モノエタノールアミド硫酸ナトリウム、Ｂ１：ポリオキシエチレンアルキルフェニルエーテルリン酸、Ｂ２：ドデシルベンゼンスルホン酸トリエタノールアミン、Ｃ１：ポリオキシエチレンアルキル（１２〜１４）スルホコハク酸二ナトリウム、Ｃ２：スルホコハク酸塩、Ｄ：ポリオキシエチレンラウリルエーテル硫酸トリエタノールアミン、Ｅ：ジイソブチルジメチルブチンジオールポリオキシエチレングリコールエーテル
＜成分（Ｅ）＞ＡＰＳ：過硫酸アンモニウム、ＨＰＯ：過酸化水素
表５に示すように、試験例７３〜１０５においては、ディッシング量ｄ１を低減するとともに、銅含有金属に対する研磨速度を高めることができた。試験例７３〜７７に示すように、成分（Ａ）は、その含有量を０．５質量％以上、特に０．５〜１．５質量％にすることにより、研磨速度を維持しつつディッシング量ｄ１を特に低減することができた。一方、試験例７８〜８０に示すように、成分（Ｂ）は、その含有量を０．００５質量％以上、特に０．００５〜０．０２質量％にすることにより、研磨速度を維持しつつディッシング量ｄ１を特に低減することができた。

<Component (A) and polishing accelerator> Ala: alanine, Gly: glycine, Val: valine, Cit: citric acid, LA: lactic acid, Oxa: oxalic acid, NA: nitric acid, SA: sulfuric acid <component (B) and anticorrosion Agent> G: 1- (2,3-dihydroxypropyl) benzotriazole, H: 1- [N, N-bis (hydroxydimethyl) aminomethyl] -benzotriazole, I: 1- (1,2-dicarboxyethyl) Benzotriazole, J: Benzotriazole <Component (C)> CS1: Colloidal silica with D _N4 of 0.03 μm, CS2: Colloidal silica with D _N4 of 0.05 μm, CS3: Colloidal silica with D _N4 of 0.07 μm, FS3 : D _N4 is fumed silica 0.07 .mu.m <component (D)> A1: coconut oil fatty acid sarcosine triethanolamine, A2: coconut oil fatty Methyl taurine sodium, A3: sodium polyoxyethylene coconut oil fatty acid monoethanolamide sulfate, B1: polyoxyethylene alkylphenyl ether phosphate, B2: triethanolamine dodecylbenzenesulfonate, C1: polyoxyethylene alkyl (12-14) Disodium sulfosuccinate, C2: sulfosuccinate, D: polyoxyethylene lauryl ether triethanolamine sulfate, E: diisobutyldimethylbutynediol polyoxyethylene glycol ether <component (E)> APS: ammonium persulfate, HPO: hydrogen peroxide As shown in Table 5, in Test Examples 73 to 105, it was possible to reduce the dishing amount d1 and increase the polishing rate for the copper-containing metal. As shown in Test Examples 73 to 77, the component (A) has a dishing amount while maintaining the polishing rate by setting its content to 0.5% by mass or more, particularly 0.5 to 1.5% by mass. In particular, d1 could be reduced. On the other hand, as shown in Test Examples 78 to 80, the content of the component (B) is 0.005% by mass or more, particularly 0.005 to 0.02% by mass while maintaining the polishing rate. The dishing amount d1 could be particularly reduced.

<Third polishing step>
Except that the first polishing composition of Test Example 2 was changed to the first polishing composition of Test Example 75 on the wafer P, the first polishing process and the first polishing process were performed in the same manner as the third polishing process of Example 1 described above. Two polishing steps were performed. Here, d1 when the first polishing composition of Test Example 75 was used was 20 nm. And when the said polishing performance evaluation of Example 1 was performed about each 2nd polishing composition which consists of the same composition as Test Examples 32-72 and Comparative Examples 12-26, respectively, the result is the result shown in Table 4. It was the same.

  In each of the above embodiments, the first and second polishing steps may be performed using the first polishing composition. At this time, the first and second polishing steps may be continuously performed as one polishing step.

Further, the technical idea that can be grasped from the embodiment will be described below.
(1) A method for polishing a semiconductor substrate, comprising: a first polishing step for polishing a conductor film so as to finish polishing before the barrier film is exposed; and a second polishing method for polishing the conductor film until the barrier film is exposed. And a third polishing step of polishing the barrier film until the insulating film is exposed,
The first polishing composition containing the following components (a) to (f) is used in the second polishing step, and the following components (g) to (k) are included in the third polishing step. A polishing method using the second polishing composition. According to this configuration, the surface step can be suppressed by suppressing the progress of dishing and the progress of erosion.
(First polishing composition)
(A): a surfactant containing at least one selected from the compound represented by any one of the general formulas (1) to (7) and a salt thereof (b): silicon oxide (c): carboxylic acid (d ): Anticorrosive (e): Oxidizing agent (f): Water (second polishing composition)
(G): Colloidal silica (h): Acid (i): Anticorrosive agent (j): Completely saponified polyvinyl alcohol (k): Water

(2) A method for polishing a semiconductor substrate, comprising: a first polishing step for polishing the conductor film until the barrier film is exposed; and a second polishing step for polishing the barrier film until the insulating film is exposed,
While using the 1st polishing composition containing each component of following (a)-(f) for a 1st grinding | polishing process, each component of the following (g)-(k) is contained in a 2nd grinding | polishing process. A polishing method using the second polishing composition. According to this configuration, the surface step can be suppressed by suppressing the progress of dishing and the progress of erosion.
(First polishing composition)
(A): a surfactant containing at least one selected from the compound represented by any one of the general formulas (1) to (7) and a salt thereof (b): silicon oxide (c): carboxylic acid (d ): Anticorrosive (e): Oxidizing agent (f): Water (second polishing composition)
(G): Colloidal silica (h): Acid (i): Anticorrosive agent (j): Completely saponified polyvinyl alcohol (k): Water

(3) A method for polishing a semiconductor substrate, the first polishing step for polishing the conductor film so that the polishing is finished before the barrier film is exposed, and the second polishing method for polishing the conductor film until the barrier film is exposed. And a third polishing step of polishing the barrier film until the insulating film is exposed,
The first polishing composition containing the following components (A) to (F) is used in the second polishing step, and the following components (g) to (k) are included in the third polishing step. A polishing method using the second polishing composition. According to this configuration, the surface step can be suppressed by suppressing the progress of dishing and the progress of erosion.
(First polishing composition)
(A): α-amino acid (B): benzotriazole derivative represented by the general formula (8) (C): silicon oxide (D): surfactant (E): oxidizing agent (F): water (second Polishing composition)
(G): Colloidal silica (h): Acid (i): Anticorrosive agent (j): Completely saponified polyvinyl alcohol (k): Water

(4) A method for polishing a semiconductor substrate, comprising: a first polishing step for polishing the conductor film until the barrier film is exposed; and a second polishing step for polishing the barrier film until the insulating film is exposed,
The first polishing composition containing the following components (A) to (F) is used in the first polishing step, and the following components (g) to (k) are included in the second polishing step. A polishing method using the second polishing composition. According to this configuration, the surface step can be suppressed by suppressing the progress of dishing and the progress of erosion.
(First polishing composition)
(A): α-amino acid (B): benzotriazole derivative represented by the general formula (8) (C): silicon oxide (D): surfactant (E): oxidizing agent (F): water (second Polishing composition)
(G): Colloidal silica (h): Acid (i): Anticorrosive agent (j): Completely saponified polyvinyl alcohol (k): Water

(5) a first polishing step for polishing the conductor film so as to finish polishing before the barrier film of the semiconductor substrate is exposed, and a second polishing step for polishing the conductor film until the barrier film is exposed; Used for the polishing process of No. 2, used for the first polishing composition containing the following components (a) to (f), and the third polishing process for polishing the barrier film until the insulating film is exposed, A polishing composition comprising: a second polishing composition containing the following components (g) to (k): According to this configuration, the surface step can be suppressed by suppressing the progress of dishing and the progress of erosion.
(First polishing composition)
(A): a surfactant containing at least one selected from the compound represented by any one of the general formulas (1) to (7) and a salt thereof (b): silicon oxide (c): carboxylic acid (d ): Anticorrosive (e): Oxidizing agent (f): Water (second polishing composition)
(G): Colloidal silica (h): Acid (i): Anticorrosive agent (j): Completely saponified polyvinyl alcohol (k): Water

(6) a first polishing step for polishing the conductor film so as to finish polishing before the barrier film of the semiconductor substrate is exposed; a second polishing step for polishing the conductor film until the barrier film is exposed; Used for the polishing process of No. 2, used for the first polishing composition containing the following components (A) to (F), and the third polishing process for polishing the barrier film until the insulating film is exposed, A polishing composition comprising: a second polishing composition containing the following components (g) to (k): According to this configuration, the surface step can be suppressed by suppressing the progress of dishing and the progress of erosion.
(First polishing composition)
(A): α-amino acid (B): benzotriazole derivative represented by the general formula (8) (C): silicon oxide (D): surfactant (E): oxidizing agent (F): water (second Polishing composition)
(G): Colloidal silica (h): Acid (i): Anticorrosive agent (j): Completely saponified polyvinyl alcohol (k): Water

(A)-(d) is the partial expanded end view which shows the grinding | polishing method of 1st Embodiment typically. (A) is a partial enlarged end view schematically showing dishing after the second polishing step, and (b) is a partially enlarged end view schematically showing erosion after the second polishing step. (A) is a partial enlarged end view schematically showing dishing after the third polishing step, and (b) is a partially enlarged end view schematically showing erosion after the third polishing step.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 11 ... Semiconductor substrate, 12 ... Insulating film, 14 ... Barrier film, 15 ... Conductor film.

Claims (4)

A method for polishing a semiconductor substrate, the first polishing step for polishing the conductor film so that the polishing is finished before the barrier film is exposed, and the second polishing step for polishing the conductor film until the barrier film is exposed. And a third polishing step for polishing the barrier film until the insulating film is exposed,
The first polishing composition containing the following components (a) to (f) is used for the second polishing step or the first and second polishing steps, and the following (g) is used for the third polishing step. Polishing method using the 2nd polishing composition containing each component of (k).
(First polishing composition)
(A): a surfactant containing at least one compound selected from the compounds represented by any one of the following general formulas (1) to (7) and salts thereof

(Wherein R ¹ represents an alkyl group having 8 to 16 carbon atoms, R ² represents a hydrogen atom, a methyl group or an ethyl group, R ³ represents an alkylene group having 1 to 8 carbon atoms, — (CH ₂ CH ₂ O) _1-and- (CH ₂ CH (CH ₃ ) O) _m- represent at least one repeating unit, and X ¹ represents a carboxyl group or a sulfone group, where l and m The total is an integer from 1 to 8.)

(In the formula, R ⁴ represents an alkyl group having 8 to 16 carbon atoms, Z represents a functional group represented by the following formula (i) or (ii), and Y ¹ represents — (CH ₂ CH ₂ O) _n. - and _{- (CH 2 CH (CH 3} ) O) p -. shows a repeating unit composed of at least one member selected from, X ² represents a phosphoric acid group or a sulfonic group wherein the sum of n and p is 1 (It is an integer of 6.)

(In the formula, R ⁵ and R ⁶ each represent a hydrogen atom, a hydroxyl group, or an alkyl group having 8 to 16 carbon atoms, and Y ² and Y ³ represent — (CH ₂ CH ₂ O) _q — and — (CH ₂ represents a repeating unit consisting of at least one selected from CH (CH ₃ ) O) _r —, wherein the sum of q and r is an integer of 1 to 6.
(B): Silicon oxide (c): Carboxylic acid (d): Anticorrosive agent (e): Oxidizing agent (f): Water (second polishing composition)
(G): Colloidal silica (h): Acid (i): Anticorrosive agent (j): Completely saponified polyvinyl alcohol (k): Water The polishing method according to claim 1, wherein the component (c) is an α-amino acid. The polishing method according to claim 1, wherein the component (d) is a benzotriazole derivative represented by the following general formula (8).

(In the formula, R ⁷ represents an alkyl group containing a carboxyl group, an alkyl group containing a hydroxyl group and a tertiary amino group, an alkyl group containing an hydroxyl group, or an alkyl group.) A method for polishing a semiconductor substrate, the first polishing step for polishing the conductor film so that the polishing is finished before the barrier film is exposed, and the second polishing step for polishing the conductor film until the barrier film is exposed. And a third polishing step for polishing the barrier film until the insulating film is exposed,
The first polishing composition containing the following components (A) to (F) is used for the second polishing step or the first and second polishing steps, and the following (g) is used for the third polishing step. Polishing method using the 2nd polishing composition containing each component of (k).
(First polishing composition)
(A): α-amino acid (B): benzotriazole derivative represented by the following general formula (8)

(In the formula, R ⁷ represents an alkyl group containing a carboxyl group, an alkyl group containing a hydroxyl group and a tertiary amino group, an alkyl group containing an hydroxyl group, or an alkyl group.)
(C): Silicon oxide (D): Surfactant (E): Oxidizing agent (F): Water (second polishing composition)
(G): Colloidal silica (h): Acid (i): Anticorrosive agent (j): Completely saponified polyvinyl alcohol (k): Water

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