TWI769219B

TWI769219B - Polishing agent, method for manufacturing polishing agent, undiluted solution of polishing agent, container filled with undiluted solution of polishing agent, method for chemical mechanical polishing

Info

Publication number: TWI769219B
Application number: TW107106553A
Authority: TW
Inventors: 上村哲也
Original assignee: 日商富士軟片股份有限公司
Priority date: 2017-02-28
Filing date: 2018-02-27
Publication date: 2022-07-01
Also published as: CN110325614B; KR20190109450A; KR20210104162A; WO2018159530A1; JP6890656B2; KR102405560B1; TW201835287A; JPWO2018159530A1; CN110325614A

Abstract

本發明的課題在於提供一種適用於包含含鈷的層之被研磨體的CMP時，在被研磨面難以產生凹陷及缺陷之研磨液。又，本發明的另一課題在於提供一種研磨液之製造方法、研磨液原液、研磨液原液收容體及化學機械研磨方法。本發明的研磨液係化學機械研磨用研磨液，其含有：締合度1～3的膠體二氧化矽；有機酸；唑系化合物；及過氧化氫，在使上述研磨液與鈷基板接觸24小時時，在上述鈷基板上形成含有鈷原子之厚度0.5～20nm的反應層。An object of the present invention is to provide a polishing liquid that is less likely to generate dents and defects on a surface to be polished when applied to CMP of an object to be polished including a cobalt-containing layer. Moreover, another subject of this invention is to provide the manufacturing method of a polishing liquid, a polishing liquid stock solution, a polishing liquid stock liquid container, and a chemical mechanical polishing method. The polishing liquid of the present invention is a polishing liquid for chemical mechanical polishing, which contains: colloidal silica with an association degree of 1 to 3; an organic acid; an azole compound; and hydrogen peroxide, and the polishing liquid is brought into contact with a cobalt substrate for 24 hours At the time, a reaction layer having a thickness of 0.5 to 20 nm containing cobalt atoms is formed on the cobalt substrate.

Description

研磨液、研磨液的製造方法、研磨液原液、研磨液原液收容體、化學機械研磨方法Polishing liquid, polishing liquid manufacturing method, polishing liquid stock liquid, polishing liquid stock liquid container, chemical mechanical polishing method

本發明係有關一種研磨液、研磨液之製造方法、研磨液原液、研磨液原液收容體及化學機械研磨方法。The present invention relates to a polishing liquid, a manufacturing method of the polishing liquid, a polishing liquid stock solution, a polishing liquid stock liquid container and a chemical mechanical polishing method.

半導體積體電路（LSI：large-scale integrated circuit）的製造中，在裸晶圓的平坦化、層間絕緣膜的平坦化、金屬栓塞的形成及埋入配線的形成等時使用化學機械研磨（CMP：chemical mechanical polishing）法。作為使用於CMP之研磨液，例如在專利文獻1中記載有「一種研磨液，其特徵係，在與研磨液接觸24小時之被研磨面上形成厚度為100nm以上的反應層。」。 [先前技術文獻] [專利文獻]In the manufacture of semiconductor integrated circuits (LSI: large-scale integrated circuits), chemical mechanical polishing (CMP) is used for the planarization of bare wafers, the planarization of interlayer insulating films, the formation of metal plugs, and the formation of buried wirings. : chemical mechanical polishing) method. As a polishing liquid used in CMP, for example, Patent Document 1 describes "a polishing liquid characterized by forming a reaction layer having a thickness of 100 nm or more on a surface to be polished that is in contact with the polishing liquid for 24 hours." [Prior Art Literature] [Patent Literature]

[專利文獻1]日本特開2004-123931號公報[Patent Document 1] Japanese Patent Laid-Open No. 2004-123931

但是，近年來，隨著配線的微細化的要求，鈷作為取代銅之配線金屬元素而備受關注。本發明人參閱專利文獻1，製備摻合作為研磨粒膠體二氧化矽之研磨液並對其特性進行研究，其結果發現，在將包含鈷或其合金之含鈷的層設為被研磨體之CMP中適用該研磨液時，在被研磨體的被研磨面容易產生凹陷。又，發現了在被研磨體的被研磨面上產生了很多因劃痕等表面粗糙及部分腐蝕等而引起之缺陷。However, in recent years, cobalt has been attracting attention as a wiring metal element to replace copper with the demand for miniaturization of wiring. Referring to Patent Document 1, the present inventors prepared a polishing liquid blended with colloidal silica as abrasive grains, and studied the characteristics thereof. As a result, they found that when a cobalt-containing layer containing cobalt or an alloy thereof is used as the object to be polished When this polishing liquid is applied to CMP, pits tend to be generated on the polished surface of the polished body. In addition, it was found that many defects caused by surface roughness such as scratches, partial corrosion, etc. occurred on the polished surface of the polished body.

因此，本發明的課題在於提供一種適用於包含含鈷的層之被研磨體的CMP時，在被研磨面難以產生凹陷及缺陷之研磨液。又，本發明的課題還在於提供一種研磨液之製造方法、研磨液原液、研磨液原液收容體及化學機械研磨方法。Therefore, an object of the present invention is to provide a polishing liquid that is less likely to generate dents and defects on a surface to be polished when applied to CMP of an object to be polished including a cobalt-containing layer. Moreover, the subject of this invention is to provide the manufacturing method of a polishing liquid, a polishing liquid undiluted liquid, a polishing liquid undiluted liquid container, and a chemical-mechanical polishing method.

本發明人等為了實現上述課題而進行深入研究之結果，得知如下研磨液能夠解決上述課題，並完成了本發明，該研磨液含有規定的成分，在與鈷基板接觸時，可以形成規定厚度的反應層。亦即，得知藉由以下結構而能夠實現上述課題。The inventors of the present invention, as a result of intensive studies in order to achieve the above-mentioned problems, have found that the following polishing liquid can solve the above-mentioned problems, and completed the present invention, and completed the present invention. reaction layer. That is, it turned out that the said subject can be achieved by the following structure.

[1]一種研磨液，其含有：締合度1～3的膠體二氧化矽；有機酸；唑系化合物；以及過氧化氫；並且用於對含鈷的層進行化學機械研磨，其中在使上述研磨液與鈷基板接觸24小時時，在上述鈷基板上形成含有鈷原子之厚度0.5～20nm的反應層。 [2]如[1]所述之研磨液，其中，上述締合度1～3的膠體二氧化矽的含量相對於研磨液總質量係0.01～1質量%，作為上述有機酸，含有胺基酸，作為上述唑系化合物，含有苯并***系化合物及與苯并***系化合物不同之唑系化合物， pH係6.5～8.0，使上述研磨液與包括選自包括Ta、TaN、Ti、TiN、Ru及Mn之群組中的任一種金屬之阻擋基板接觸24小時時，在上述阻擋基板上形成含有上述金屬的原子之厚度0.01～5nm的反應層。 [3]如[2]所述之研磨液，其中，由下述式（3）計算之研磨速度比R1係250～2500。式（3）： R1=基於上述研磨液之鈷基板的研磨速度/基於上述研磨液之阻擋基板的研磨速度 [4]如[1]所述之研磨液，其中，上述締合度1～3的膠體二氧化矽的含量相對於研磨液總質量係0.5～5質量%，作為上述唑系化合物，含有苯并***系化合物及與苯并***系化合物不同之唑系化合物， pH係8.0～10.5，使上述研磨液與包括選自包括Ta、TaN、Ti、TiN、Ru及Mn之群組中的任一種金屬之阻擋基板接觸24小時時，在上述阻擋基板上形成含有上述金屬的原子之厚度0.01～5nm的反應層，使上述研磨液與包括選自包括SiOx及SiOC之群組中的任一種無機成分之絕緣膜基板接觸24小時時，在上述絕緣膜基板上形成含有矽原子之厚度0.01～10nm的反應層。 [5]如[4]所述之研磨液，其中，上述有機酸係順丁烯二酸、反丁烯二酸、2-羥基苯甲酸、3-羥基苯甲酸、4-羥基苯甲酸、鄰苯二甲酸、間苯二甲酸、對苯二甲酸、1,2,3-苯三甲酸、1,2,4-苯三甲酸、1,3,5-苯三甲酸、1,2,3,5-苯四甲酸、1,2,3,4-苯四甲酸、1,2,4,5-苯四甲酸、苯六甲酸、聯苯二甲酸、檸檬酸、琥珀酸、蘋果酸、丙二酸及鄰胺苯甲酸之群組中的至少一種，上述有機酸的含量相對於研磨液總質量係0.01～0.3質量%。 [6]如[4]或[5]所述之研磨液，其中，由下述式（4）計算之研磨速度比R2係0.01～2.0，由下述式（5）計算之研磨速度比R3係0.05～2.0。式（4）： R2=基於上述研磨液之鈷基板的研磨速度/基於上述研磨液之阻擋基板的研磨速度式（5）： R3=基於上述研磨液之鈷基板的研磨速度/基於上述研磨液之絕緣膜基板的研磨速度 [7]如[1]～[6]中任一項所述之研磨液，其中，上述過氧化氫的含量係0.001～5質量%。 [8]如[1]～[7]中任一項所述之研磨液，其還含有含金屬原子之金屬雜質，上述金屬雜質含有選自包括Fe原子、Cu原子、Ag原子及Zn原子之群組中的至少一種特定金屬原子，在上述特定金屬原子係選自包括Fe原子、Cu原子、Ag原子及Zn原子之一種之情況下，上述特定金屬原子的含量相對於研磨液總質量係0.01～100質量ppb，在上述特定金屬原子係選自包括Fe原子、Cu原子、Ag原子及Zn原子之兩種以上之情況下，各自的上述特定金屬原子的含量相對於研磨液總質量係0.01～100質量ppb。 [9]如[8]所述之研磨液，其中，上述金屬雜質含有金屬粒子，該金屬粒子含有選自包括Fe原子、Cu原子、Ag原子及Zn原子之群組中的至少一種特定金屬原子，在上述金屬粒子所含有之上述特定金屬原子係選自包括Fe原子、Cu原子、Ag原子及Zn原子之一種之情況下，上述金屬粒子所含有之上述特定金屬原子的含量相對於研磨液總質量係0.01～50質量ppb，在上述金屬粒子所含有之上述特定金屬原子係選自包括Fe原子、Cu原子、Ag原子及Zn原子之兩種以上之情況下，上述金屬粒子所含有之各自的上述特定金屬原子的含量相對於研磨液總質量係0.01～50質量ppb。 [10]如[8]或[9]所述之研磨液，其中，由下述式（1）計算之含量比T1係30000～500000。式（1）：T1=上述過氧化氫的含量/上述金屬雜質所含有之選自包括Fe原子、Cu原子、Ag原子及Zn原子之群組中的特定金屬原子的總計含量 [11]如[1]～[10]中任一項所述之研磨液，其還含有由後述之通式（1）表示之化合物，上述通式（1）所表示之化合物相對於研磨液總質量係0.00001～1000質量ppb。 [12]如[1]～[11]中任一項所述之研磨液，其還含有有機溶劑，其中，上述有機溶劑的含量相對於研磨液總質量係0.01～20質量%。 [13]如[1]～[12]中任一項所述之研磨液，其還含有選自包括N-椰油醯基肌胺酸鹽、N-月桂醯肌胺酸鹽、N-硬脂醯肌胺酸鹽、N-油醯肌胺酸鹽、N-肉荳蔻醯肌胺酸鹽、N-月桂醯甘胺酸、N-肉荳蔻醯甘胺酸、N-棕櫚醯甘胺酸、N-月桂醯谷胺酸、N-椰油醯谷胺酸、N-椰油醯谷胺酸鉀、N-月桂醯肌胺酸鉀、N-月桂醯丙胺酸鹽、N-肉荳蔻醯丙胺酸鹽及N-椰油丙胺酸鉀之群組中的至少一種化合物，上述化合物的總含量相對於研磨液總質量係0.001～5質量%。 [14]如[2]～[13]中任一項所述之研磨液，其中，作為上述唑系化合物，含有苯并***系化合物及選自包括1,2,4-***系化合物、吡唑系化合物及咪唑系化合物之群組中的任一種以上。 [15]如[1]～[14]中任一項所述之研磨液，其中，上述締合度1～3的膠體二氧化矽的由下述式（2）計算之化學機械研磨前後的平均粒徑之比T2係1～5。式（2）： T2=化學機械研磨後的平均粒徑/化學機械研磨前的平均粒徑 [16]一種研磨液之製造方法，其含有稀釋步驟，對含有締合度1～3的膠體二氧化矽、有機酸、唑系化合物及過氧化氫之研磨液原液混合水，獲得[1]～[15]中任一項所述之研磨液。 [17]一種研磨液原液，其含有締合度1～3的膠體二氧化矽、有機酸、唑系化合物及過氧化氫，其中，為了製備[1]～[15]中任一項所述之研磨液，稀釋成2～50倍而使用。 [18]如[17]所述之研磨液原液，其中，用水稀釋成2～50倍時，稀釋前後的pH變化小於0.01～1。 [19]一種研磨液原液收容體，其具有：如[17]或[18]所述之研磨液原液；以及收容上述研磨液原液之由不含鐵之金屬材料形成之容器。 [20]一種化學機械研磨方法，其包括如下步驟：對安裝於研磨平台之研磨墊，一邊供給如[1]～[15]中任一項所述之研磨液，一邊使被研磨體的被研磨面與上述研磨墊接觸，使上述被研磨體及上述研磨墊相對移動而研磨上述被研磨面，從而獲得已研磨之被研磨體。 [21]如[20]所述之化學機械研磨方法，其中，上述被研磨體含有包括選自包括鈷及鈷合金之群組中的至少一種之含鈷的層。 [發明效果][1] A polishing liquid containing: colloidal silica having an association degree of 1 to 3; an organic acid; an azole compound; and hydrogen peroxide; and for chemical mechanical polishing of a cobalt-containing layer, wherein the above When the polishing liquid is in contact with the cobalt substrate for 24 hours, a reaction layer having a thickness of 0.5 to 20 nm containing cobalt atoms is formed on the cobalt substrate. [2] The polishing liquid according to [1], wherein the content of the colloidal silica having an association degree of 1 to 3 is 0.01 to 1 mass % with respect to the total mass of the polishing liquid, and an amino acid is contained as the organic acid , as the above-mentioned azole-based compound, it contains benzotriazole-based compound and azole-based compound different from benzotriazole-based compound, pH is 6.5-8.0, and the above-mentioned polishing liquid is made of a compound selected from the group consisting of Ta, TaN, Ti, TiN When the barrier substrate of any metal in the group of Ru and Mn is in contact with the barrier substrate for 24 hours, a reaction layer with a thickness of 0.01-5 nm containing atoms of the metal is formed on the barrier substrate. [3] The polishing liquid according to [2], wherein the polishing rate ratio R1 calculated from the following formula (3) is 250 to 2500. Formula (3): R1=the polishing rate of the cobalt substrate based on the above-mentioned polishing liquid/the polishing rate of the barrier substrate based on the above-mentioned polishing liquid The content of colloidal silica is 0.5 to 5 mass % with respect to the total mass of the polishing liquid. As the azole-based compound, a benzotriazole-based compound and an azole-based compound different from the benzotriazole-based compound are contained, and the pH is 8.0 to 8.0 10.5, when the above-mentioned polishing liquid is contacted with a barrier substrate comprising any one metal selected from the group consisting of Ta, TaN, Ti, TiN, Ru and Mn for 24 hours, a metal atom containing the above-mentioned metal is formed on the above-mentioned barrier substrate. A reaction layer with a thickness of 0.01 to 5 nm is formed on the insulating film substrate with a thickness of silicon atoms when the above-mentioned polishing liquid is brought into contact with an insulating film substrate comprising any inorganic component selected from the group consisting of SiOx and SiOC for 24 hours 0.01～10nm reaction layer. [5] The polishing liquid according to [4], wherein the organic acid is maleic acid, fumaric acid, 2-hydroxybenzoic acid, 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, o- Phthalic acid, isophthalic acid, terephthalic acid, 1,2,3-benzenetricarboxylic acid, 1,2,4-benzenetricarboxylic acid, 1,3,5-benzenetricarboxylic acid, 1,2,3, 5-Mellitic acid, 1,2,3,4-Mellitic acid, 1,2,4,5-Mellitic acid, Mellitic acid, Biphthalic acid, Citric acid, Succinic acid, Malic acid, Malondi At least one of the group of acid and anthranilic acid, the content of the organic acid is 0.01 to 0.3 mass % with respect to the total mass of the polishing liquid. [6] The polishing liquid according to [4] or [5], wherein the polishing rate ratio R2 calculated by the following formula (4) is 0.01 to 2.0, and the polishing rate ratio R3 calculated by the following formula (5) Department of 0.05 ~ 2.0. Equation (4): R2=Polishing rate of the cobalt substrate based on the above-mentioned polishing liquid/Polishing rate of the barrier substrate based on the above-mentioned polishing liquid Equation (5): R3=Polishing rate of the cobalt substrate based on the above-mentioned polishing liquid/Based on the above-mentioned polishing liquid The polishing rate of the insulating film substrate [7] The polishing liquid according to any one of [1] to [6], wherein the content of the hydrogen peroxide is 0.001 to 5 mass %. [8] The polishing liquid according to any one of [1] to [7], further comprising a metal impurity containing a metal atom, wherein the metal impurity contains a metal impurity selected from the group consisting of Fe atoms, Cu atoms, Ag atoms, and Zn atoms At least one specific metal atom in the group, when the above-mentioned specific metal atom is selected from one of Fe atoms, Cu atoms, Ag atoms and Zn atoms, the content of the above-mentioned specific metal atoms is 0.01 relative to the total mass of the polishing liquid ～100 mass ppb, when the above-mentioned specific metal atom is selected from two or more types including Fe atom, Cu atom, Ag atom and Zn atom, the content of each above-mentioned specific metal atom relative to the total mass of the polishing liquid is 0.01～ 100 quality ppb. [9] The polishing liquid according to [8], wherein the metal impurity contains metal particles containing at least one specific metal atom selected from the group consisting of Fe atoms, Cu atoms, Ag atoms, and Zn atoms In the case where the above-mentioned specific metal atoms contained in the above-mentioned metal particles are selected from one of Fe atoms, Cu atoms, Ag atoms and Zn atoms, the content of the above-mentioned specific metal atoms contained in the above-mentioned metal particles is relative to the total amount of the polishing liquid. The mass is 0.01 to 50 mass ppb, and when the specific metal atoms contained in the metal particles are selected from two or more types including Fe atoms, Cu atoms, Ag atoms, and Zn atoms, the respective metal atoms contained in the metal particles are selected. The content of the above-mentioned specific metal atoms is 0.01 to 50 mass ppb with respect to the total mass of the polishing liquid. [10] The polishing liquid according to [8] or [9], wherein the content ratio T1 calculated from the following formula (1) is 30,000 to 500,000. Formula (1): T1=the content of the above-mentioned hydrogen peroxide/the total content of the specific metal atoms contained in the above-mentioned metal impurities selected from the group consisting of Fe atoms, Cu atoms, Ag atoms and Zn atoms [11] such as [ The polishing liquid according to any one of 1] to [10], which further contains a compound represented by the general formula (1) described later, and the compound represented by the general formula (1) is 0.00001 to 0.00001 to the total mass of the polishing liquid. 1000 quality ppb. [12] The polishing liquid according to any one of [1] to [11], further comprising an organic solvent, wherein the content of the organic solvent is 0.01 to 20 mass % with respect to the total mass of the polishing liquid. [13] The polishing liquid according to any one of [1] to [12], further comprising a compound selected from the group consisting of N-cocoyl sarcosinate, N-lauro sarcosinate, N-hard sarcosinate Fatty sarcosinate, N-oleosine sarcosinate, N-myristyl sarcosinate, N-lauroglycine, N-myristyl glycine, N-palmitosylglycine , N-Lauroglutamic Acid, N-Cocoglutamic Acid, Potassium N-Cocoglutamate, Potassium N-Laurosarcosine, N-Lauryl Alanine, N-Myristate At least one compound in the group of alanine and potassium N-cocoalanine, the total content of the above compounds is 0.001 to 5% by mass relative to the total mass of the grinding liquid. [14] The polishing liquid according to any one of [2] to [13], wherein the azole-based compound contains a benzotriazole-based compound and a 1,2,4-triazole-based compound selected from the group consisting of , any one or more of the group of pyrazole-based compounds and imidazole-based compounds. [15] The polishing liquid according to any one of [1] to [14], wherein the average values of the colloidal silica having an association degree of 1 to 3 before and after chemical mechanical polishing are calculated by the following formula (2). The particle size ratio T2 is 1-5. Formula (2): T2=average particle size after chemical mechanical polishing/average particle size before chemical mechanical polishing The polishing liquid according to any one of [1] to [15] is obtained by mixing water with a polishing liquid stock solution of silicon, an organic acid, an azole-based compound, and hydrogen peroxide. [17] A polishing liquid stock solution containing colloidal silica having an association degree of 1 to 3, an organic acid, an azole-based compound, and hydrogen peroxide, in order to prepare the colloidal silica according to any one of [1] to [15] The polishing liquid is diluted 2 to 50 times and used. [18] The polishing liquid stock solution according to [17], wherein the pH change before and after dilution is less than 0.01 to 1 when diluted with water to 2 to 50 times. [19] A polishing liquid stock solution container comprising: the polishing liquid stock solution as described in [17] or [18]; and a container formed of a non-ferrous metal material that accommodates the foregoing polishing liquid stock solution. [20] A chemical mechanical polishing method, comprising the steps of: supplying the polishing liquid according to any one of [1] to [15] to a polishing pad mounted on a polishing platform, while making the surface of the object to be polished be polished. The polishing surface is brought into contact with the polishing pad, and the body to be polished and the polishing pad are relatively moved to polish the surface to be polished, thereby obtaining a polished body to be polished. [21] The chemical mechanical polishing method according to [20], wherein the body to be polished contains a cobalt-containing layer including at least one selected from the group consisting of cobalt and a cobalt alloy. [Inventive effect]

依本發明，能夠提供一種適用於包含含鈷的層之被研磨體的CMP時，在被研磨面難以產生凹陷及缺陷之研磨液。又，依本發明，能夠提供一種研磨液之製造方法、研磨液原液、研磨液原液收容體及化學機械研磨方法。According to the present invention, it is possible to provide a polishing liquid which is suitable for CMP of a to-be-polished body including a cobalt-containing layer, and which makes it difficult to generate pits and defects on the to-be-polished surface. Furthermore, according to the present invention, a method for producing a polishing liquid, a polishing liquid stock solution, a polishing liquid stock solution container, and a chemical mechanical polishing method can be provided.

以下，依據實施形態對本發明詳細地進行說明。另外，以下所記載之構成要件的說明係依據本發明的實施形態而完成者，因此本發明並不限定於該種實施形態。另外，在本說明書中，用「～」來表示之數值範圍係指將記載於「～」前後之數值作為下限值及上限值而包括之範圍。Hereinafter, the present invention will be described in detail based on embodiments. In addition, since the description of the structural requirements described below is based on the embodiment of the present invention, the present invention is not limited to this embodiment. In addition, in this specification, the numerical range represented by "-" means the range which includes the numerical value described before and after "-" as a lower limit and an upper limit.

[研磨液] 本發明的研磨液，其含有締合度1～3的膠體二氧化矽、有機酸、唑系化合物及過氧化氫，用於對含鈷的層進行化學機械研磨，且在使上述研磨液與鈷基板接觸24小時時，在上述鈷基板上形成含有鈷原子之厚度0.5～20nm的反應層（以下，亦稱為「反應層1」。）。[Polishing Liquid] The polishing liquid of the present invention contains colloidal silica with an association degree of 1 to 3, an organic acid, an azole-based compound, and hydrogen peroxide, and is used for chemical mechanical polishing of a cobalt-containing layer. When the polishing liquid is in contact with the cobalt substrate for 24 hours, a reaction layer (hereinafter, also referred to as "reaction layer 1") containing cobalt atoms and having a thickness of 0.5 to 20 nm is formed on the cobalt substrate.

作為上述研磨液的特徵點之一，可舉出在使研磨液與鈷基板接觸24小時時，在鈷基板上形成含有鈷原子之厚度為0.5～20nm的反應層之特徵點。One of the characteristic points of the above-mentioned polishing liquid is that when the polishing liquid is brought into contact with the cobalt substrate for 24 hours, a reaction layer containing cobalt atoms and having a thickness of 0.5 to 20 nm is formed on the cobalt substrate.

上述反應層的厚度係0.5nm以上，2nm以上為較佳。又，上述反應層的厚度係20nm以下，15nm以下為較佳，10nm以下為更佳。若上述反應層的厚度小於0.5nm，則不易獲得充分之研磨速度。另一方面，若上述反應層的厚度大於20nm，則在被研磨面容易產生凹陷。上述研磨液為了提高研磨速度而含有膠體二氧化矽。膠體二氧化矽在CMP中與反應層接觸並削去反應層，因此在規定的條件下產生大於20nm的反應層之研磨液之情況下，可推測會比預期削去更多被研磨面，從而產生凹陷。又，若膠體二氧化矽的締合度大於3，則在被研磨面容易產生缺陷，又，亦容易產生凹陷。締合度大於3之膠體二氧化矽的粒子的形狀與締合度1～3的膠體二氧化矽相比較為彎曲，因此相對於粒子的被研磨面之接觸面積較小，接近點接觸。因此，可推測被研磨面的面粗糙度變得粗糙而產生缺陷。又，即使在上述反應層的厚度變薄之情況下，若藉由締合度大於3之膠體二氧化矽進行切削，則亦確認到在被研磨面容易產生凹陷。又，可推測研磨液所含有之有機酸及唑系化合物除了有助於上述反應層的形成以外，還有助於抑制在CMP的過程中已削去之金屬的離子化物（含有鈷離子之各種金屬離子）與上述膠體二氧化矽的鍵結。若上述金屬的離子化物與上述膠體二氧化矽鍵結，則膠體二氧化矽的粒徑增大，在被研磨面更容易產生凹陷，又，亦容易產生缺陷。The thickness of the reaction layer is 0.5 nm or more, preferably 2 nm or more. Moreover, the thickness of the said reaction layer is 20 nm or less, Preferably it is 15 nm or less, More preferably, it is 10 nm or less. If the thickness of the reaction layer is less than 0.5 nm, it is difficult to obtain a sufficient polishing rate. On the other hand, when the thickness of the reaction layer is larger than 20 nm, dents are likely to be generated on the surface to be polished. The above-mentioned polishing liquid contains colloidal silica in order to increase the polishing rate. Colloidal silica is in contact with the reaction layer in CMP and removes the reaction layer. Therefore, in the case of producing a polishing liquid with a reaction layer larger than 20 nm under the specified conditions, it can be presumed that more polished surfaces will be removed than expected. produce depressions. In addition, when the degree of association of colloidal silica is greater than 3, defects are likely to be generated on the surface to be polished, and dents are also likely to be generated. The shape of the particles of colloidal silica with an association degree greater than 3 is more curved than that of colloidal silica with an association degree of 1 to 3, so the contact area with respect to the polished surface of the particles is smaller, and is close to point contact. Therefore, it is presumed that the surface roughness of the surface to be polished becomes rough and a defect occurs. In addition, even when the thickness of the reaction layer was reduced, it was confirmed that dents were easily generated on the surface to be polished by cutting with colloidal silica having an association degree of more than 3. In addition, it is presumed that the organic acid and azole-based compound contained in the polishing liquid contribute to the formation of the above-mentioned reaction layer, and also contribute to the suppression of ionized metal (various types of cobalt ions) that have been removed during CMP. metal ions) bonding to the aforementioned colloidal silica. If the ion compound of the above-mentioned metal is bonded to the above-mentioned colloidal silica, the particle size of the colloidal silica increases, and the surface to be polished is more likely to be dented, and more likely to have defects.

本說明書中的反應層係指，將具備10mm×10mm的被研磨面之鈷基板（由鈷組成之基板）浸漬於10mL的研磨液中，在25℃下使鈷基板與研磨液接觸24小時時，形成於鈷基板的被研磨面上之反應層。另外，在將鈷基板浸漬於研磨液時，亦可以是將積層了鈷基板與其他基板（例如矽基板）之積層體浸漬於研磨液中之形態。The reaction layer in this specification refers to the time when a cobalt substrate (substrate composed of cobalt) having a surface to be polished of 10 mm × 10 mm is immersed in 10 mL of polishing liquid, and the cobalt substrate and the polishing liquid are brought into contact at 25°C for 24 hours , the reaction layer formed on the polished surface of the cobalt substrate. In addition, when the cobalt substrate is immersed in the polishing liquid, it is also possible to immerse the layered body of the cobalt substrate and another substrate (eg, a silicon substrate) in the polishing liquid.

上述反應層含有鈷原子。上述反應層還可以含有氧原子等，在反應層的表面含有研磨液中的成分的錯合物為較佳。在此，上述反應層的厚度係指，在使研磨液與鈷基板接觸24小時之後，使用掃描電子顯微鏡（SEM：scanning electron microscope），藉由實施例中所記載的方法來觀察接觸後的鈷基板的剖面而獲得之厚度。The above-mentioned reaction layer contains cobalt atoms. The said reaction layer may contain oxygen atoms etc., and it is preferable to contain the complex compound of the component in a polishing liquid on the surface of a reaction layer. Here, the thickness of the above-mentioned reaction layer refers to the observation of the contacted cobalt by the method described in the examples using a scanning electron microscope (SEM: scanning electron microscope) after the polishing liquid was brought into contact with the cobalt substrate for 24 hours. The thickness obtained from the cross-section of the substrate.

[pH] 上述研磨液的pH並無特別限制，通常1.0～14.0為較佳。[pH] The pH of the polishing liquid is not particularly limited, but is usually preferably 1.0 to 14.0.

如後述，上述研磨液在製造半導體積體電路裝置時，適當地用於為了埋入配線（鈷配線）的平坦化等實施之CMP。例如，上述研磨液適當地用於具有絕緣膜層、阻擋層及含鈷的層之被研磨體的CMP。上述被研磨體通常具有：具有凸部及凹部之絕緣膜層；沿著絕緣膜層的表面的凹凸覆蓋絕緣膜層之阻擋層；及包含選自包括以填充絕緣膜層的凹部的方式覆蓋阻擋層之鈷及其合金之群組中的至少一種之含鈷的層。圖1表示上述被研磨體的一例。被研磨體10具有：基板12；具有配置於基板12上之凹部之絕緣膜層14；追隨絕緣膜層14的表面而配置之阻擋層16；及以填充絕緣膜層14的凹部並覆蓋阻擋層16的方式配置之含鈷的層18。上述被研磨體通常經過2階段來實施研磨。具體而言，實施如圖2所示那樣研磨含鈷的層18直至阻擋層16露出之第1研磨及如圖3所示那樣研磨含鈷的層18及阻擋層16直至絕緣膜層14露出之第2研磨。上述研磨液能夠適當地使用於上述第1研磨及第2研磨中的任一研磨中。As will be described later, the above-mentioned polishing liquid is suitably used for CMP for planarization of buried wirings (cobalt wirings), etc., when manufacturing a semiconductor integrated circuit device. For example, the above-mentioned polishing liquid is suitably used for CMP of an object to be polished having an insulating film layer, a barrier layer, and a layer containing cobalt. The above-mentioned object to be ground usually has: an insulating film layer having a convex portion and a concave portion; a barrier layer covering the insulating film layer with concavities and convexities along the surface of the insulating film layer; Cobalt-containing layers of at least one of the group of cobalt and alloys thereof. An example of the said to-be-polished body is shown in FIG. 1. FIG. The object to be polished 10 has: a substrate 12; an insulating film layer 14 having a recess arranged on the substrate 12; a barrier layer 16 arranged following the surface of the insulating film layer 14; and filling the recess of the insulating film layer 14 and covering the barrier layer Cobalt-containing layer 18 configured in the manner of 16. The above-mentioned to-be-polished body is generally ground in two stages. Specifically, as shown in FIG. 2 , the first polishing in which the cobalt-containing layer 18 is polished until the barrier layer 16 is exposed, and the cobalt-containing layer 18 and the barrier layer 16 are polished as shown in FIG. 3 until the insulating film layer 14 is exposed are performed. 2nd grinding. The above-mentioned polishing liquid can be suitably used for any one of the above-mentioned first polishing and second polishing.

在將研磨液使用於上述第1研磨之情況下，研磨液的pH係6.5～8.0為更佳。若pH在6.5～8.0的範圍內，則在將研磨液使用於CMP之情況下，因容易將特定條件中的反應層的厚度調整成所期望的範圍，凹陷更難以產生。從凹陷的產生更進一步得到抑制之方面而言，其中，pH在6.8～7.8的範圍內為較佳，6.8～7.2的範圍內為更佳。又，缺陷之一亦即研磨劃傷受被研磨面的狀態及研磨液所含有之有機酸的種類的強烈影響。在將研磨液使用於上述第1研磨之情況下，研磨液如後述那樣作為有機酸含有胺基酸為較佳，並確認到在含有胺基酸之研磨液在pH係6.5以上的情況下能夠顯著抑制研磨劃傷，缺陷的產生進一步得到抑制。When the polishing liquid is used for the above-mentioned first polishing, the pH of the polishing liquid is more preferably 6.5 to 8.0. When the pH is in the range of 6.5 to 8.0, when the polishing liquid is used for CMP, it is easy to adjust the thickness of the reaction layer under specific conditions to a desired range, and it is more difficult to generate dents. Among them, the pH is preferably in the range of 6.8 to 7.8, and more preferably in the range of 6.8 to 7.2, from the viewpoint of further suppressing the generation of depressions. In addition, one of the defects, that is, polishing scratches is strongly influenced by the state of the surface to be polished and the type of organic acid contained in the polishing liquid. When the polishing liquid is used for the above-mentioned first polishing, it is preferable that the polishing liquid contains an amino acid as an organic acid as described later, and it has been confirmed that the polishing liquid containing the amino acid can be pH 6.5 or more. Grinding scratches are significantly suppressed, and the generation of defects is further suppressed.

在將研磨液使用於上述第2研磨之情況下，研磨液的pH係8.0～10.5為更佳。若pH在8.0～10.5的範圍內，則在將研磨液使用於CMP之情況下，因容易將特定條件中的反應層的厚度調整成所期望的範圍，凹陷的產生進一步得到抑制。又，缺陷之一亦即研磨劃傷受被研磨面的狀態及研磨液所含有之有機酸的種類的強烈影響。在將研磨液使用於上述第2研磨之情況下，研磨液如後述那樣作為有機酸含有選自包括順丁烯二酸、反丁烯二酸、2-羥基苯甲酸、3-羥基苯甲酸、4-羥基苯甲酸、鄰苯二甲酸、間苯二甲酸、對苯二甲酸、1,2,3-苯三甲酸、1,2,4-苯三甲酸、1,3,5-苯三甲酸、1,2,3,5-苯四甲酸、1,2,3,4-苯四甲酸、1,2,4,5-苯四甲酸、苯六甲酸、聯苯二甲酸、檸檬酸、琥珀酸、蘋果酸、丙二酸及鄰胺苯甲酸之群組中的至少一種為較佳，在含有該等有機酸之研磨液在pH係8.0以上的情況下（8.2以上的情況為較佳）確認到，能夠顯著抑制研磨劃傷，缺陷的產生進一步得到抑制。從被研磨面中的凹陷及缺陷的產生更進一步得到抑制之方面而言，pH在8.2～9.5的範圍內為較佳，8.7～9.5的範圍內為更佳。When the polishing liquid is used for the above-mentioned second polishing, the pH of the polishing liquid is more preferably 8.0 to 10.5. When the pH is in the range of 8.0 to 10.5, when the polishing liquid is used for CMP, the thickness of the reaction layer under specific conditions can be easily adjusted to a desired range, and the generation of pits is further suppressed. In addition, one of the defects, that is, polishing scratches is strongly influenced by the state of the surface to be polished and the type of organic acid contained in the polishing liquid. When the polishing liquid is used for the above-mentioned second polishing, the polishing liquid contains as an organic acid selected from the group consisting of maleic acid, fumaric acid, 2-hydroxybenzoic acid, 3-hydroxybenzoic acid, 4-Hydroxybenzoic acid, phthalic acid, isophthalic acid, terephthalic acid, 1,2,3-benzenetricarboxylic acid, 1,2,4-benzenetricarboxylic acid, 1,3,5-benzenetricarboxylic acid , 1,2,3,5-mellitic acid, 1,2,3,4-mellitic acid, 1,2,4,5-mellitic acid, mellitic acid, biphthalic acid, citric acid, succinic acid At least one of the group of acid, malic acid, malonic acid and anthranilic acid is preferred, and the pH of the polishing liquid containing these organic acids is above 8.0 (the situation above 8.2 is preferred) It was confirmed that polishing scratches were remarkably suppressed, and the occurrence of defects was further suppressed. The pH is preferably in the range of 8.2 to 9.5, and more preferably in the range of 8.7 to 9.5, from the viewpoint of further suppressing the occurrence of pits and defects in the surface to be polished.

[膠體二氧化矽] 上述研磨液含有締合度1～3的膠體二氧化矽。膠體二氧化矽具有削去形成於被研磨體中之反應層之作用。可推測發揮本發明的效果之理由之一係，上述研磨液含有膠體二氧化矽且依據規定的條件而形成之上述反應層的厚度係0.5～20nm。[Colloidal silica] The above-mentioned polishing liquid contains colloidal silica having an association degree of 1 to 3. Colloidal silica has the function of cutting off the reaction layer formed in the body to be ground. It is presumed that one of the reasons for exhibiting the effects of the present invention is that the polishing liquid contains colloidal silica, and the thickness of the reaction layer formed under predetermined conditions is 0.5 to 20 nm.

本說明書中，締合度藉由締合度=平均二次粒徑/平均一次粒徑而求出。平均一次粒徑係測量從使用JEOL Co.,Ltd.製造的透射型電子顯微鏡TEM2010（加壓電壓200kV）進行拍攝之圖像任意選擇之一次粒子1000個的粒徑（等效圓直徑），並將該些進行算術平均而求出。另外，等效圓直徑係指假設具有與觀察時的粒子的投影面積相同的投影面積之正圓時的該圓的直徑。平均二次粒徑與為凝聚之狀態之二次粒子的平均粒徑（等效圓直徑）相等，能夠藉由與上述之平均一次粒徑相同的方法求出。膠體二氧化矽的締合度係1～3，從研磨速度更優異之方面而言，1.5～2.5為較佳。在締合度大於3之情況下，機械研磨力變得過剩，凹陷容易產生。又，藉由被研磨面變得粗糙，缺陷亦變得容易產生。另一方面，在締合度小於1之情況下，所期望的研磨速度難以獲得。另外，膠體二氧化矽的平均一次粒徑並無特別限制，但從研磨液具有更優異之分散穩定性之方面而言，1～100nm為較佳。In this specification, the degree of association is determined by degree of association=average secondary particle size/average primary particle size. The average primary particle diameter was measured by measuring the particle diameter (equivalent circle diameter) of 1000 primary particles arbitrarily selected from an image photographed using a transmission electron microscope TEM2010 (applied voltage 200 kV) manufactured by JEOL Co., Ltd., and These are calculated|required by arithmetic mean. In addition, the equivalent circle diameter refers to the diameter of the circle when it is assumed that a perfect circle has the same projected area as the projected area of the particle at the time of observation. The average secondary particle diameter is equal to the average particle diameter (equivalent circle diameter) of the secondary particles in a state of aggregation, and can be determined by the same method as the above-mentioned average primary particle diameter. The degree of association of the colloidal silica is in the range of 1 to 3, and 1.5 to 2.5 is preferable from the viewpoint of a more excellent polishing rate. When the degree of association is greater than 3, the mechanical polishing force becomes excessive, and dents tend to be generated. Moreover, as the to-be-polished surface becomes rough, it becomes easy to generate|occur|produce a defect. On the other hand, when the degree of association is less than 1, it is difficult to obtain a desired polishing rate. In addition, the average primary particle size of the colloidal silica is not particularly limited, but from the viewpoint of the polishing liquid having more excellent dispersion stability, it is preferably 1 to 100 nm.

作為締合度1～3的膠體二氧化矽的市售品，例如可舉出PL2、PL3、PL3H及PL3L等（均為商品名，FUSO CHEMICAL CO.,LTD.製造）。As a commercial item of the colloidal silica with an association degree of 1-3, PL2, PL3, PL3H, and PL3L etc. are mentioned, for example (all are trade names, FUSO CHEMICAL CO., LTD. make).

作為締合度1～3的膠體二氧化矽的含量，並無特別限制，相對於研磨液總質量係0.01質量%以上為較佳，0.05質量%以上為更佳，10質量%以下為較佳，5質量%以下為更佳，3質量%以下為進一步較佳，1質量%以下尤為佳。The content of colloidal silica with an association degree of 1 to 3 is not particularly limited, but is preferably 0.01 mass % or more, more preferably 0.05 mass % or more, and preferably 10 mass % or less relative to the total mass of the polishing liquid. 5 mass % or less is more preferable, 3 mass % or less is more preferable, and 1 mass % or less is especially preferable.

在將研磨液使用於上述第1研磨之情況下，作為締合度1～3的膠體二氧化矽的含量，相對於研磨液總質量係0.01～1質量%為更佳。若締合度1～3的膠體二氧化矽的含量在上述範圍內，則被研磨面中的凹陷更難以產生，又，獲得更優異之研磨速度。其中，若締合度1～3的膠體二氧化矽的含量相對於研磨液總質量在0.01～0.15質量%的範圍內，則凹陷的產生更進一步得到抑制。When the polishing liquid is used for the above-mentioned first polishing, the content of the colloidal silica having an association degree of 1 to 3 is more preferably 0.01 to 1 mass % with respect to the total mass of the polishing liquid. When the content of the colloidal silica having an association degree of 1 to 3 is within the above-mentioned range, pits in the surface to be polished are less likely to be generated, and a more excellent polishing rate can be obtained. Among them, when the content of the colloidal silica having an association degree of 1 to 3 is in the range of 0.01 to 0.15 mass % with respect to the total mass of the polishing liquid, the occurrence of dents is further suppressed.

另一方面，在將研磨液適用於上述第2研磨之情況下，作為締合度1～3的膠體二氧化矽的含量，相對於研磨液總質量係0.5～5質量%為更佳。若締合度1～3的膠體二氧化矽的含量在上述範圍內，則被研磨面中的凹陷更難以產生，又，獲得更優異之研磨速度。其中，若締合度1～3的膠體二氧化矽的含量相對於研磨液總質量在0.5～3質量%的範圍內，則凹陷的產生更進一步得到抑制。On the other hand, when applying the polishing liquid to the second polishing, the content of the colloidal silica having an association degree of 1 to 3 is more preferably 0.5 to 5 mass % relative to the total mass of the polishing liquid. When the content of the colloidal silica having an association degree of 1 to 3 is within the above-mentioned range, pits in the surface to be polished are less likely to be generated, and a more excellent polishing rate can be obtained. Among them, when the content of the colloidal silica having an association degree of 1 to 3 is in the range of 0.5 to 3 mass % with respect to the total mass of the polishing liquid, the occurrence of dents is further suppressed.

另外，締合度1～3的膠體二氧化矽可以單獨使用一種，亦可併用兩種以上。在併用兩種以上的締合度1～3的膠體二氧化矽之情況下，總計含量在上述範圍內為較佳。In addition, the colloidal silica having an association degree of 1 to 3 may be used alone or in combination of two or more. When two or more types of colloidal silica having an association degree of 1 to 3 are used in combination, the total content is preferably within the above range.

研磨液中，締合度1～3的膠體二氧化矽的由下述式（2）計算之化學機械研磨（CMP）前後的平均粒徑之比T2係5以下為較佳。在上述T2係5以下的情況下，在被研磨面更難以產生缺陷。上述T2的下限係1以上為較佳。上述T2係2.5以下為更佳，2以下為進一步較佳。式（2）： T2=化學機械研磨後的平均粒徑/化學機械研磨前的平均粒徑In the polishing liquid, the ratio T2 of the average particle size before and after chemical mechanical polishing (CMP) calculated by the following formula (2) of colloidal silica having an association degree of 1 to 3 is preferably 5 or less. In the case of the above-mentioned T2 series of 5 or less, it is more difficult to generate defects on the surface to be polished. The lower limit of the above-mentioned T2 is preferably 1 or more. The above-mentioned T2 is more preferably 2.5 or less, and more preferably 2 or less. Formula (2): T2=average particle size after chemical mechanical polishing/average particle size before chemical mechanical polishing

可推測締合度1～3的膠體二氧化矽與在CMP的過程中削去之金屬的離子化物（含有鈷離子之各種金屬離子）鍵結而平均粒徑增大。It is presumed that the colloidal silica having an association degree of 1 to 3 binds to ionized compounds of metals (various metal ions including cobalt ions) that have been removed in the CMP process to increase the average particle size.

[過氧化氫] 上述研磨液作為氧化劑含有過氧化氫。氧化劑具有將存在於被研磨體的被研磨面上之成為研磨對象之金屬進行氧化之功能。[Hydrogen peroxide] The above-mentioned polishing liquid contains hydrogen peroxide as an oxidizing agent. The oxidizing agent has the function of oxidizing the metal to be polished on the polished surface of the polished body.

作為過氧化氫的含量，並無特別限制，但是相對於研磨液總質量係0.001～5質量%為較佳。The content of hydrogen peroxide is not particularly limited, but is preferably 0.001 to 5% by mass relative to the total mass of the polishing liquid.

在將研磨液適用於上述第1研磨之情況下，從被研磨面中的凹陷更難以產生之方面而言，作為研磨液中的過氧化氫的含量，相對於研磨液總質量係0.001～2.5質量%為更佳，0.06～2質量%為進一步較佳。In the case where the polishing liquid is applied to the above-mentioned first polishing, the content of hydrogen peroxide in the polishing liquid is 0.001 to 2.5 relative to the total mass of the polishing liquid because it is more difficult to generate dents in the surface to be polished. The mass % is more preferable, and 0.06 to 2 mass % is further preferable.

另一方面，在將研磨液適用於上述第2研磨之情況下，從被研磨面中的凹陷更難以產生之方面而言，作為研磨液中的過氧化氫的含量，相對於研磨液總質量係0.001～3質量%為更佳，0.1～1.2質量%為進一步較佳，0.6～1質量%尤為佳。On the other hand, in the case where the polishing liquid is applied to the above-mentioned second polishing, since it is more difficult to generate dents in the surface to be polished, the content of hydrogen peroxide in the polishing liquid is determined relative to the total mass of the polishing liquid. 0.001-3 mass % is more preferable, 0.1-1.2 mass % is more preferable, 0.6-1 mass % is especially preferable.

[有機酸] 上述研磨液含有有機酸。有機酸具有作為金屬的氧化促進、研磨液的pH調整及緩衝劑的作用。本說明書中，有機酸係指在1分子內具有一個以上的酸性基之化合物，酸性基可舉出羧基、磺酸基及磷酸基等。作為有機酸，並無特別限制，能夠使用公知的有機酸。作為有機酸，例如可舉出甲酸、乙酸、丙酸、丁酸、戊酸、2-甲基丁酸、正己酸、3,3-二甲基丁酸、2-乙基丁酸、4-甲基戊酸、正庚酸、2-甲基己酸、正辛酸、2-乙基己酸、苯甲酸、乙醇酸、水楊酸、丙三醇酸、草酸、戊二酸、己二酸、庚二酸、順丁烯二酸、反丁烯二酸、2-羥基苯甲酸、3-羥基苯甲酸、4-羥基苯甲酸、鄰苯二甲酸、間苯二甲酸、對苯二甲酸、1,2,3-苯三甲酸、1,2,4-苯三甲酸、1,3,5-苯三甲酸、1,2,3,5-苯四甲酸、1,2,3,4-苯四甲酸、1,2,4,5-苯四甲酸、苯六甲酸、聯苯二甲酸、檸檬酸、琥珀酸、蘋果酸、丙二酸、鄰胺苯甲酸、酒石酸、乳酸、羥乙基亞胺基二乙酸及亞胺基二乙酸以及該等銨鹽及鹼金屬鹽等鹽；甘胺酸、α-丙胺酸、β-丙胺酸、N-甲基甘胺酸、L-2-胺基丁酸、L-戊胺酸、L-纈胺酸、L-白胺酸或其衍生物、L-脯胺酸、L-鳥胺酸、L-離胺酸、牛磺酸、L-絲胺酸、L-蘇胺酸、L-別蘇胺酸、L-高絲胺酸、L-酪胺酸、L-甲狀腺素、4-羥基-L-脯胺酸、L-半胱胺酸、L-甲硫胺酸、L-乙硫胺基酪酸、L-胱胺酸或其衍生物、L-磺基丙胺酸、L-天冬胺酸、L-麩胺酸、4-胺基丁酸、L-天冬醯胺、L-麩胺醯胺、氮絲胺酸、L-精胺酸、L-刀豆胺酸、L-瓜胺酸、δ-羥基-L-離胺酸、肌胺酸、L-犬尿胺酸、L-組胺酸或其衍生物及L-色胺酸等胺基酸。[Organic acid] The above-mentioned polishing liquid contains an organic acid. The organic acid functions as an oxidation accelerator of metals, pH adjustment of polishing liquids, and buffering agents. In the present specification, an organic acid refers to a compound having one or more acidic groups in one molecule, and examples of the acidic group include a carboxyl group, a sulfonic acid group, and a phosphoric acid group. It does not specifically limit as an organic acid, A well-known organic acid can be used. Examples of the organic acid include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, 2-methylbutyric acid, n-hexanoic acid, 3,3-dimethylbutyric acid, 2-ethylbutyric acid, 4- Methylvaleric acid, n-heptanoic acid, 2-methylhexanoic acid, n-octanoic acid, 2-ethylhexanoic acid, benzoic acid, glycolic acid, salicylic acid, glyceric acid, oxalic acid, glutaric acid, adipic acid , pimelic acid, maleic acid, fumaric acid, 2-hydroxybenzoic acid, 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, phthalic acid, isophthalic acid, terephthalic acid, 1,2,3-benzenetricarboxylic acid, 1,2,4-benzenetricarboxylic acid, 1,3,5-benzenetricarboxylic acid, 1,2,3,5-benzenetetracarboxylic acid, 1,2,3,4- Mellitic acid, 1,2,4,5-Mellitic acid, mellitic acid, biphthalic acid, citric acid, succinic acid, malic acid, malonic acid, anthranilic acid, tartaric acid, lactic acid, hydroxyethyl Iminodiacetic acid and iminodiacetic acid and salts such as ammonium and alkali metal salts; glycine, α-alanine, β-alanine, N-methylglycine, L-2-amine Butyric acid, L-pentanine, L-valine, L-leucine or its derivatives, L-proline, L-ornithine, L-lysine, taurine, L- Serine, L-threonine, L-allothreonine, L-homoserine, L-tyrosine, L-thyroxine, 4-hydroxy-L-proline, L-cysteine , L-methionine, L-ethionine butyric acid, L-cystine or its derivatives, L-sulfoalanine, L-aspartic acid, L-glutamic acid, 4-amino Butyric acid, L-aspartamide, L-glutamine, azaserine, L-arginine, L-canavaline, L-citrulline, delta-hydroxy-L-lysine , creatine, L-kynurenine, L-histidine or its derivatives and amino acids such as L-tryptophan.

作為有機酸的含量，並無特別限制，但是相對於研磨液總質量係0.01～30質量%為較佳。另外，有機酸可以單獨使用一種，亦可併用兩種以上。在併用兩種以上的有機酸之情況下，總計含量在上述範圍內為較佳。The content of the organic acid is not particularly limited, but is preferably 0.01 to 30% by mass relative to the total mass of the polishing liquid. Moreover, an organic acid may be used individually by 1 type, and may use 2 or more types together. When two or more organic acids are used in combination, the total content is preferably within the above range.

在將研磨液適用於上述第1研磨之情況下，從被研磨面中的凹陷更難以產生和/或缺陷更難以產生之方面而言，研磨液作為有機酸含有胺基酸為較佳，其中，甘胺酸、α-丙胺酸、β-丙胺酸、L-天冬胺酸或N-甲基甘胺酸為更佳，甘胺酸或N-甲基甘胺酸為進一步較佳，甘胺酸尤為佳。In the case where the polishing liquid is applied to the above-mentioned first polishing, it is preferable that the polishing liquid contains an amino acid as an organic acid, in terms of the fact that depressions and/or defects in the surface to be polished are more difficult to be generated, and wherein , glycine, α-alanine, β-alanine, L-aspartic acid or N-methylglycine are more preferred, glycine or N-methylglycine is further preferred, glycine Amino acids are particularly preferred.

在將研磨液適用於上述第1研磨之情況下，研磨液中的有機酸的含量並無特別限制，相對於研磨液總質量係0.1質量%以上為較佳，0.8質量%以上為更佳，30質量%以下為較佳，15質量%以下為更佳，8質量%以下為進一步較佳，4質量%以下尤為佳。在有機酸的含量相對於研磨液總質量係0.8～4質量%的情況下，被研磨面中的凹陷及缺陷更難以產生。有機酸可以單獨使用一種，亦可併用兩種以上。又，從被研磨面中的凹陷更難以產生和/或缺陷更難以產生之方面而言，組合胺基酸與其他有機酸（不包含胺基酸。）而使用亦較佳。作為上述有機酸，例如順丁烯二酸、反丁烯二酸、2-羥基苯甲酸、3-羥基苯甲酸、4-羥基苯甲酸、鄰苯二甲酸、間苯二甲酸、對苯二甲酸、1,2,3-苯三甲酸、1,2,4-苯三甲酸、1,3,5-苯三甲酸、1,2,3,5-苯四甲酸、1,2,3,4-苯四甲酸、1,2,4,5-苯四甲酸、苯六甲酸、聯苯二甲酸、檸檬酸、琥珀酸、蘋果酸、丙二酸或鄰胺苯甲酸為較佳。另外，在組合胺基酸與其他有機酸（不包含胺基酸。）而使用之情況下，其他有機酸的含量相對於有機酸的總量係30質量%以下為較佳，10質量%為更佳。另外，其下限係1質量%以上為較佳。在併用兩種以上的有機酸之情況下，總計含量在上述範圍內為較佳。In the case of applying the polishing liquid to the above-mentioned first polishing, the content of the organic acid in the polishing liquid is not particularly limited, and is preferably 0.1 mass % or more relative to the total mass of the polishing liquid, more preferably 0.8 mass % or more, 30 mass % or less is preferable, 15 mass % or less is more preferable, 8 mass % or less is further more preferable, and 4 mass % or less is particularly preferable. When the content of the organic acid is 0.8 to 4 mass % with respect to the total mass of the polishing liquid, dents and defects in the surface to be polished are more difficult to generate. An organic acid may be used individually by 1 type, and may use 2 or more types together. In addition, it is also preferable to use amino acids in combination with other organic acids (excluding amino acids) from the viewpoints that pits and/or defects are more difficult to generate in the polished surface. As the above-mentioned organic acid, for example, maleic acid, fumaric acid, 2-hydroxybenzoic acid, 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, phthalic acid, isophthalic acid, terephthalic acid , 1,2,3-benzenetricarboxylic acid, 1,2,4-benzenetricarboxylic acid, 1,3,5-benzenetricarboxylic acid, 1,2,3,5-benzenetetracarboxylic acid, 1,2,3,4 -Mellitic acid, 1,2,4,5-mellitic acid, mellitic acid, biphthalic acid, citric acid, succinic acid, malic acid, malonic acid or anthranilic acid are preferred. Moreover, when combining amino acid and other organic acid (amino acid is not included.) when using, the content of other organic acid is preferably 30 mass % or less with respect to the total amount of organic acid, and 10 mass % is better. Moreover, it is preferable that the lower limit is 1 mass % or more. When two or more organic acids are used in combination, the total content is preferably within the above range.

另一方面，在將研磨液適用於上述第2研磨之情況下，研磨液中，作為有機酸含有選自包括甲酸、乙酸、丙酸、丁酸、戊酸、2-甲基丁酸、正己酸、3,3-二甲基丁酸、2-乙基丁酸、4-甲基戊酸、正庚酸、2-甲基己酸、正辛酸、2-乙基己酸、苯甲酸、乙醇酸、水楊酸、丙三醇酸、草酸、戊二酸、己二酸、庚二酸、順丁烯二酸、反丁烯二酸、2-羥基苯甲酸、3-羥基苯甲酸、4-羥基苯甲酸、鄰苯二甲酸、間苯二甲酸、對苯二甲酸、1,2,3-苯三甲酸、1,2,4-苯三甲酸、1,3,5-苯三甲酸、1,2,3,5-苯四甲酸、1,2,3,4-苯四甲酸、1,2,4,5-苯四甲酸、苯六甲酸、聯苯二甲酸、檸檬酸、琥珀酸、蘋果酸、丙二酸、鄰胺苯甲酸、酒石酸、乳酸、羥乙基亞胺基二乙酸及亞胺基二乙酸以及該等銨鹽及鹼金屬鹽等鹽之群組中的任一種或兩種以上為較佳。其中，從被研磨面中的凹陷更難以產生和/或缺陷更難以產生之方面而言，順丁烯二酸、反丁烯二酸、2-羥基苯甲酸、3-羥基苯甲酸、4-羥基苯甲酸、鄰苯二甲酸、間苯二甲酸、對苯二甲酸、1,2,3-苯三甲酸、1,2,4-苯三甲酸、1,3,5-苯三甲酸、1,2,3,5-苯四甲酸、1,2,3,4-苯四甲酸、1,2,4,5-苯四甲酸、苯六甲酸、聯苯二甲酸、檸檬酸、琥珀酸、蘋果酸、丙二酸或鄰胺苯甲酸為較佳，順丁烯二酸、2-羥基苯甲酸、4-羥基苯甲酸、鄰苯二甲酸、1,2,4-苯三甲酸、檸檬酸、琥珀酸、蘋果酸、丙二酸或鄰胺苯甲酸為更佳，順丁烯二酸或檸檬酸為進一步較佳，順丁烯二酸尤為佳。又，在併用兩種以上的有機酸而使用之情況下，從被研磨面中的凹陷更難以產生和/或缺陷更難以產生之方面而言，其中，順丁烯二酸與選自包括檸檬酸、琥珀酸、蘋果酸、丙二酸、鄰苯二甲酸、4-羥基苯甲酸、2-羥基苯甲酸、鄰胺苯甲酸及1,2,4-苯三甲酸之群組中的至少一種的組合為較佳，順丁烯二酸與選自包括檸檬酸、丙二酸、4-羥基苯甲酸、2-羥基苯甲酸、鄰胺苯甲酸及1,2,4-苯三甲酸之群組中的至少一種的組合為更佳，順丁烯二酸與選自包括檸檬酸、4-羥基苯甲酸、2-羥基苯甲酸、鄰胺苯甲酸及1,2,4-苯三甲酸之群組中的至少一種的組合為進一步較佳。On the other hand, when the polishing liquid is applied to the above-mentioned second polishing, the polishing liquid contains as an organic acid selected from the group consisting of formic acid, acetic acid, propionic acid, butyric acid, valeric acid, 2-methylbutyric acid, n-hexane acid, 3,3-dimethylbutyric acid, 2-ethylbutyric acid, 4-methylvaleric acid, n-heptanoic acid, 2-methylhexanoic acid, n-octanoic acid, 2-ethylhexanoic acid, benzoic acid, Glycolic acid, salicylic acid, glyceric acid, oxalic acid, glutaric acid, adipic acid, pimelic acid, maleic acid, fumaric acid, 2-hydroxybenzoic acid, 3-hydroxybenzoic acid, 4-Hydroxybenzoic acid, phthalic acid, isophthalic acid, terephthalic acid, 1,2,3-benzenetricarboxylic acid, 1,2,4-benzenetricarboxylic acid, 1,3,5-benzenetricarboxylic acid , 1,2,3,5-mellitic acid, 1,2,3,4-mellitic acid, 1,2,4,5-mellitic acid, mellitic acid, biphthalic acid, citric acid, succinic acid Any of the group of acid, malic acid, malonic acid, anthranilic acid, tartaric acid, lactic acid, hydroxyethyliminodiacetic acid and iminodiacetic acid and salts of these ammonium and alkali metal salts or two or more are preferred. Among them, maleic acid, fumaric acid, 2-hydroxybenzoic acid, 3-hydroxybenzoic acid, 4- Hydroxybenzoic acid, phthalic acid, isophthalic acid, terephthalic acid, 1,2,3-benzenetricarboxylic acid, 1,2,4-benzenetricarboxylic acid, 1,3,5-benzenetricarboxylic acid, 1 ,2,3,5-Mellitic acid, 1,2,3,4-Mellitic acid, 1,2,4,5-Mellitic acid, Mellitic acid, Biphthalic acid, Citric acid, Succinic acid, Malic acid, malonic acid or anthranilic acid are preferred, maleic acid, 2-hydroxybenzoic acid, 4-hydroxybenzoic acid, phthalic acid, 1,2,4-benzenetricarboxylic acid, citric acid , succinic acid, malic acid, malonic acid or anthranilic acid are more preferred, maleic acid or citric acid is further preferred, and maleic acid is particularly preferred. In addition, when two or more organic acids are used in combination, in terms of the fact that depressions in the surface to be polished are more difficult to generate and/or defects are more difficult to generate, wherein maleic acid and a group selected from the group consisting of lemon at least one of the group consisting of acid, succinic acid, malic acid, malonic acid, phthalic acid, 4-hydroxybenzoic acid, 2-hydroxybenzoic acid, anthranilic acid, and 1,2,4-benzenetricarboxylic acid Preferably, the combination of maleic acid and maleic acid is selected from the group consisting of citric acid, malonic acid, 4-hydroxybenzoic acid, 2-hydroxybenzoic acid, anthranilic acid and 1,2,4-benzenetricarboxylic acid The combination of at least one of the group is more preferably, maleic acid and selected from the group consisting of citric acid, 4-hydroxybenzoic acid, 2-hydroxybenzoic acid, anthranilic acid and 1,2,4-benzenetricarboxylic acid. A combination of at least one of the groups is further preferred.

在將研磨液使用於上述第2研磨之情況下，研磨液中的有機酸的含量並無特別限制，相對於研磨液總質量係0.01～30質量%為較佳，0.01～12質量%為更佳，0.01～5質量%為更佳，0.01～0.3質量%為進一步較佳。另外，在使用兩種以上的有機酸之情況下，總計含量在上述範圍內為較佳。When the polishing liquid is used in the above-mentioned second polishing, the content of the organic acid in the polishing liquid is not particularly limited, but is preferably 0.01 to 30 mass % relative to the total mass of the polishing liquid, more preferably 0.01 to 12 mass % Preferably, 0.01-5 mass % is more preferable, 0.01-0.3 mass % is more preferable. Moreover, when using two or more types of organic acids, it is preferable that the total content is within the above-mentioned range.

[唑系化合物] 上述研磨液含有唑系化合物。唑系化合物具有在被研磨面的金屬表面形成反應層之作用。又，具有提高基於後述之過氧化氫之氧化作用之功能。在本說明書中，唑系化合物係指含有包含1個以上的氮原子之五元雜環之化合物，作為氮原子數，1～4個為較佳。又，唑系化合物亦可以含有除了氮原子以外的原子作為雜原子。又，唑系化合物亦在上述複數五員環上具有取代基。[AZOLE COMPOUND] The above-mentioned polishing liquid contains an azole compound. The azole compound has the function of forming a reaction layer on the metal surface of the polished surface. In addition, it has a function of enhancing the oxidative action by hydrogen peroxide which will be described later. In the present specification, the azole-based compound refers to a compound containing a five-membered heterocyclic ring containing one or more nitrogen atoms, and the number of nitrogen atoms is preferably 1 to 4. In addition, the azole-based compound may contain atoms other than nitrogen atoms as hetero atoms. In addition, the azole-based compound also has a substituent on the above-mentioned plural five-membered ring.

作為上述唑系化合物，可舉出例如具有吡咯骨架、咪唑骨架、吡唑骨架、異噻唑骨架、異㗁唑骨架、***骨架、四唑骨架、噻唑骨架、㗁唑骨架、異㗁唑骨架、噻二唑骨架、㗁二唑骨架或、四氮唑骨架之化合物等。作為上述唑系化合物，可以是在上述骨架還具有由芳香族烴環或芳香族雜環縮合之多環結構之唑系化合物。作為含有上述多環結構之唑系化合物，可舉出例如具有吲哚骨架、嘌呤骨架、吲唑骨架、苯并咪唑骨架、咔唑骨架、苯并㗁唑骨架、苯并噻唑骨架、苯并噻二唑骨架或、萘并咪唑骨架之化合物等。Examples of the azole-based compound having a pyrrole skeleton, an imidazole skeleton, a pyrazole skeleton, an isothiazole skeleton, an isoxazole skeleton, a triazole skeleton, a tetrazole skeleton, a thiazole skeleton, an oxazole skeleton, an isoxazole skeleton, Compounds of thiadiazole skeleton, oxadiazole skeleton or tetrazole skeleton, etc. The azole-based compound may be an azole-based compound further having a polycyclic structure condensed with an aromatic hydrocarbon ring or an aromatic heterocyclic ring in the skeleton. Examples of the azole-based compound having the above-mentioned polycyclic structure include an indole skeleton, a purine skeleton, an indazole skeleton, a benzimidazole skeleton, a carbazole skeleton, a benzoxazole skeleton, a benzothiazole skeleton, and a benzothiazole skeleton. A compound with an oxadiazole skeleton or a naphthimidazole skeleton, etc.

作為唑系化合物可含有之取代基，並無特別限制，可舉出例如鹵素原子（氟原子、氯原子、溴原子或碘原子）、烷基（直鏈、支鏈狀或環狀烷基，其可以是多環烷基如雙環烷基，或者可以包含活性次甲基）、烯基、炔基、芳基、雜環基（任意的取代位置）、醯基、烷氧羰基、芳氧羰基、雜環氧羰基、胺基甲醯基（作為具有取代基之胺基甲醯基，可舉出例如N-羥基胺基甲醯基、N-醯基胺基甲醯基、N-磺醯基胺基甲醯基、N-胺基甲醯胺基甲醯基、硫代胺基甲醯基及N-胺磺醯胺基甲醯基等。）、咔唑基、羧基或其鹽、草醯基、草胺醯基、氰基、碳亞胺基、甲醯基、羥基、烷氧基（包含亞乙氧基或者將亞乙氧基作為重複單元而包含之基團）、芳氧基、雜環氧基、醯氧基、羰基氧基、胺基甲醯氧基、磺醯氧基、胺基、醯胺基、磺醯胺基、脲基、硫代脲基、N-羥基脲基、醯亞胺基、羰基胺基、胺磺醯胺基、胺基脲基、硫代胺基脲基、肼基、銨基、草胺醯胺基、N-（烷基或芳基）磺醯脲基、N-醯基脲基、N-醯基胺磺醯胺基、羥基胺基、硝基、包含季氮原子之雜環基（可舉出例如吡啶鎓基、咪唑基、喹啉基及異喹啉基）、異氰基、亞胺基、巰基、（烷基、芳基或雜環基）硫基、（烷基、芳基或雜環基）二硫基、（烷基、芳基）磺醯基、（烷基或芳基）亞磺醯基、磺基或其鹽、胺磺醯基（作為具有取代基之胺磺醯基，可舉出例如N-醯基胺磺醯基及N-磺醯基胺磺醯基）或其鹽、膦基、氧膦基、氧膦基氧基、氧膦基胺基及甲矽烷基等。其中，鹵素原子、烷基、烯基、炔基、芳基或雜環基為較佳。The substituent which the azole-based compound may contain is not particularly limited, and examples thereof include a halogen atom (fluorine atom, chlorine atom, bromine atom, or iodine atom), an alkyl group (straight chain, branched chain, or cyclic alkyl group, It may be a polycyclic alkyl group such as a bicycloalkyl group, or may contain reactive methine groups), alkenyl, alkynyl, aryl, heterocyclyl (in any position of substitution), acyl, alkoxycarbonyl, aryloxycarbonyl , heterooxycarbonyl, aminocarboxy (as the substituted aminocarboxy, for example, N-hydroxyaminocarboxy, N-carbamoyl, N-sulfonamido aminocarbamoyl, N-aminocarbamoyl, thioaminocarbamoyl, and N-sulfamolamidocarboxy, etc.), carbazolyl, carboxyl or its salts, oxalyl, oxalyl, cyano, carboimide, carboxyl, hydroxyl, alkoxy (groups including ethyleneoxy or ethyleneoxy as a repeating unit), aryloxy group, heterocyclic oxy, acyloxy, carbonyloxy, aminocarboxy, sulfonyloxy, amine, amide, sulfonamido, ureido, thiourea, N-hydroxy Urea group, imino group, carbonyl amine group, sulfamoyl amine group, amino urea group, thioamine urea group, hydrazine group, ammonium group, amine group, N-(alkyl or aryl group ) sulfonylurea group, N-sulfonylurea group, N-sulfonamidosulfoamide group, hydroxylamine group, nitro group, heterocyclic group containing a quaternary nitrogen atom (for example, pyridinium group, imidazolyl group, quinolinyl and isoquinolinyl), isocyano, imino, mercapto, (alkyl, aryl or heterocyclyl)thio, (alkyl, aryl or heterocyclyl)dithio, ( Alkyl, aryl) sulfonyl group, (alkyl or aryl) sulfinyl group, sulfo group or its salt, sulfasulfonyl group (as the sulfasulfonyl group having a substituent, for example, N-sulfonyl group can be mentioned sulfonamidosulfonyl and N-sulfonamidosulfonamido) or its salts, phosphine, phosphinyl, phosphinyloxy, phosphinylamino and silyl, etc. Among them, a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group is preferable.

另外，在此，「活性次甲基」係指被2個吸電子基取代之次甲基。「吸電子基」係指例如醯基、烷氧羰基、芳氧羰基、胺基甲醯基、烷基磺醯基、芳基磺醯基、胺磺醯基、三氟甲基、氰基、硝基或碳醯亞胺基。又，2個吸電子基可以彼此鍵合而構成環狀結構。又，「鹽」係指鹼金屬、鹼土類金屬及重金屬等陽離子；銨離子及鏻離子等有機陽離子。Here, the "active methine group" refers to a methine group substituted with two electron withdrawing groups. "Electron withdrawing group" refers to, for example, acyl, alkoxycarbonyl, aryloxycarbonyl, aminocarboxy, alkylsulfonyl, arylsulfonyl, sulfamoyl, trifluoromethyl, cyano, Nitro or carboimide. In addition, two electron withdrawing groups may be bonded to each other to form a cyclic structure. In addition, "salt" refers to cations such as alkali metals, alkaline earth metals, and heavy metals; and organic cations such as ammonium ions and phosphonium ions.

作為唑系化合物，從被研磨面中的凹陷更難以產生和/或缺陷更難以產生之方面而言，具有***骨架之化合物（***系化合物）、吡唑系化合物或具有咪唑骨架之化合物（咪唑系化合物）為較佳，具有***骨架之化合物為更佳。As the azole-based compound, a compound having a triazole skeleton (triazole-based compound), a pyrazole-based compound, or a compound having an imidazole skeleton is more difficult to generate depressions and/or defects in the surface to be polished. (imidazole type compound) is preferable, and the compound which has a triazole skeleton is more preferable.

又，具有***骨架之化合物中，從更難以產生被研磨面中的凹陷和/或更難以產生缺陷之方面而言，具有苯并***骨架之化合物（苯并***系化合物）或具有1,2,4-***骨架之化合物（1,2,4-***系化合物）為較佳，具有苯并***骨架之化合物為更佳。作為具有苯并***骨架之化合物，例如可舉出5-甲基苯并***、5-胺基苯并***、苯并***及5,6-二甲基苯并***等。又，作為具有1,2,4-***骨架之化合物，例如可舉出3-胺基-1,2,4-***或1,2,4-***等。In addition, among compounds having a triazole skeleton, from the viewpoint that it is more difficult to generate depressions and/or defects in the surface to be polished, a compound having a benzotriazole skeleton (benzotriazole-based compound) or a compound having a benzotriazole skeleton A compound having a 1,2,4-triazole skeleton (1,2,4-triazole-based compound) is preferable, and a compound having a benzotriazole skeleton is more preferable. As a compound which has a benzotriazole skeleton, 5-methylbenzotriazole, 5-aminobenzotriazole, benzotriazole, 5, 6- dimethylbenzotriazole, etc. are mentioned, for example. Moreover, as a compound which has a 1, 2, 4- triazole skeleton, 3-amino- 1, 2, 4- triazole, 1, 2, 4- triazole etc. are mentioned, for example.

唑系化合物可以單獨使用一種，亦可以併用兩種以上，但是從被研磨面中的凹陷更難以產生和/或缺陷更難以產生之方面而言，組合具有苯并***骨架之化合物與和苯并***系化合物不同之化合物（不含有苯并***骨架之化合物）而使用為較佳。含有苯并***骨架之化合物與藉由氧化劑亦即過氧化氫被氧化之鈷較強地進行配位而容易形成反應層。另一方面，即使係唑系化合物，不含有苯并***骨架之化合物與被氧化之鈷相對較弱地進行配位而容易形成反應層。可推測將含有苯并***系化合物與和苯并***之化合物不同之研磨液使用於CMP時所形成之反應層，含有由苯并***系化合物形成之層和由和苯并***不同之化合物形成之層。藉由與被氧化之鈷更強地進行配位之苯并***系化合物形成之層係緻密，可推測具有更抑制凹陷的產生之作用。另一方面，由於由與和被氧化之鈷較弱地進行配位之苯并***系化合物不同之化合物形成之層更容易被去除，其結果，可推測係容易獲得優異之研磨速度者。結果，藉由協同上述作用，將含有具有苯并***骨架之化合物及與苯并***系化合物不同之化合物（不含有苯并***骨架之化合物）之研磨液使用於CMP之情況下，能夠獲得更優異之研磨速度，並且在研磨面更難以產生凹陷。The azole-based compound may be used alone or in combination of two or more. However, from the viewpoint that it is more difficult to generate depressions and/or defects in the surface to be polished, a compound having a benzotriazole skeleton is combined with benzene. It is preferable to use a compound different from the triazole-based compound (a compound not containing a benzotriazole skeleton). The compound containing a benzotriazole skeleton is strongly coordinated with cobalt oxidized by hydrogen peroxide, which is an oxidizing agent, to easily form a reaction layer. On the other hand, even if it is an azole-based compound, a compound not containing a benzotriazole skeleton is relatively weakly coordinated with oxidized cobalt, and a reaction layer is easily formed. It can be presumed that the reaction layer formed when a polishing liquid containing a benzotriazole-based compound and a compound different from benzotriazole is used in CMP contains a layer formed of a benzotriazole-based compound and a layer composed of Layers of different compounds. The layer system formed by the benzotriazole-based compound that is more strongly coordinated with the oxidized cobalt is dense, and it is presumed that it has an effect of suppressing the generation of pits. On the other hand, since a layer formed of a compound different from a benzotriazole-based compound that is weakly coordinated with oxidized cobalt is more easily removed, it is presumed that an excellent polishing rate is easily obtained as a result. As a result, when the polishing liquid containing a compound having a benzotriazole skeleton and a compound different from the benzotriazole-based compound (a compound not containing a benzotriazole skeleton) is used in CMP by synergizing the above-mentioned action, A better grinding speed can be obtained, and it is more difficult to generate dents on the grinding surface.

作為不含有上述苯并***骨架之化合物，並無特別限制，但是從被研磨面中的凹陷更難以產生和/或缺陷更難以產生之方面而言，選自包括具有1,2,4-***骨架之化合物、吡唑系化合物及具有咪唑骨架之化合物之群組中的至少一種為較佳。The compound that does not contain the above-mentioned benzotriazole skeleton is not particularly limited, but from the viewpoint of making it more difficult to generate depressions and/or defects in the surface to be polished, it is selected from the group consisting of compounds having 1,2,4- At least one kind selected from the group of a compound having a triazole skeleton, a pyrazole-based compound, and a compound having an imidazole skeleton is preferable.

唑系化合物的含量並無特別限制，相對於研磨液總質量係0.001～10質量%為較佳。另外，使用兩種以上的唑系化合物之情況下，總計含量在上述範圍內為較佳。在將研磨液使用於上述第1研磨之情況下，唑系化合物的含量相對於研磨液總質量係0.001質量%以上為較佳，0.01質量%以上為更佳，2質量%以下為較佳，1.3質量%以下為更佳，0.4質量%以下為進一步較佳。若唑系化合物的含量係0.01質量%以上，則在被研磨面更難以產生凹陷。若唑系化合物的含量係1.3質量%以下，則在被研磨面更難以產生凹陷，又，經時穩定性更優異。在將研磨液使用於上述第1研磨之情況下，研磨液含有兩種以上的唑系化合物（含有具有苯并***骨架之化合物及與苯并***系化合物不同之化合物為較佳）時，作為各自的含量，並無特別限制，研磨液中相對於含量最少之唑系化合物之除此以外的唑系化合物的含量的質量比係5以上為較佳，100以上為更佳，1800以下為較佳，1300以下為更佳，400以下為進一步較佳。又，具有苯并***骨架之化合物的含量比與苯并***系化合物不同之化合物的含量少為較佳。The content of the azole-based compound is not particularly limited, but is preferably 0.001 to 10% by mass relative to the total mass of the polishing liquid. Moreover, when using two or more types of azole-based compounds, it is preferable that the total content is within the above-mentioned range. When the polishing liquid is used for the above-mentioned first polishing, the content of the azole compound is preferably 0.001 mass % or more, more preferably 0.01 mass % or more, and preferably 2 mass % or less, relative to the total mass of the polishing liquid. 1.3 mass % or less is more preferable, and 0.4 mass % or less is more preferable. When the content of the azole-based compound is 0.01 mass % or more, it is more difficult to generate dents on the surface to be polished. When the content of the azole-based compound is 1.3% by mass or less, it is more difficult to generate dents on the surface to be polished, and the stability over time is more excellent. In the case where the polishing liquid is used for the above-mentioned first polishing, when the polishing liquid contains two or more azole-based compounds (preferably a compound having a benzotriazole skeleton and a compound different from the benzotriazole-based compound) , as the respective content, there is no particular limitation, the mass ratio of the content of the azole compounds other than the azole compounds with the least content in the polishing liquid is preferably 5 or more, more preferably 100 or more, and 1800 or less. It is more preferable, less than 1300 is more preferable, and less than 400 is further preferable. In addition, it is preferable that the content of the compound having a benzotriazole skeleton is smaller than the content of the compound different from the benzotriazole-based compound.

在將研磨液使用於上述第2研磨之情況下，唑系化合物的含量相對於研磨液總質量係0.1質量%以上為較佳，0.12質量%以上為更佳，6質量%以下為較佳，3.5質量%以下為更佳，0.8質量%以下為進一步較佳，0.5質量%以下尤為佳。若唑系化合物的含量係0.12質量%以上，則在被研磨面更難以產生凹陷。若唑系化合物的含量係5質量%以下，則在被研磨面更難以產生凹陷，又，經時穩定性更優異。另一方面，在將研磨液適用於上述第2研磨之情況下，研磨液含有兩種以上的唑系化合物（含有具有苯并***骨架之化合物及與苯并***系化合物不同之化合物為較佳）時，作為各自的含量，並無特別限制，研磨液中相對於含量最少之唑系化合物的除此以外的唑系化合物的含量的質量比係0.05以上為較佳，0.5以上為更佳，50以下為較佳，10以下為更佳。又，具有苯并***骨架之化合物的含量比與苯并***系化合物不同之化合物的含量多為較佳。若係上述範圍內，則被研磨面中的凹陷更難以產生，和/或缺陷更難以產生。另外，在研磨液中含量最少的唑系化合物係指在兩種以上的唑系化合物中含量最少者，兩種以上的唑系化合物和複數種唑系化合物亦可適用。另外，唑系化合物可以併用3種以上。在併用3種以上的唑系化合物之情況下，各唑系化合物的含量分別在上述範圍內為較佳。When the polishing liquid is used for the above-mentioned second polishing, the content of the azole compound is preferably 0.1 mass % or more, more preferably 0.12 mass % or more, and preferably 6 mass % or less with respect to the total mass of the polishing liquid, 3.5 mass % or less is more preferable, 0.8 mass % or less is further more preferable, and 0.5 mass % or less is particularly preferable. When the content of the azole-based compound is 0.12 mass % or more, it is more difficult to generate dents on the surface to be polished. When the content of the azole-based compound is 5 mass % or less, it is more difficult to generate dents on the surface to be polished, and the stability over time is more excellent. On the other hand, when the polishing liquid is applied to the above-mentioned second polishing, the polishing liquid contains two or more azole-based compounds (a compound having a benzotriazole skeleton and a compound different from the benzotriazole-based compound are: In the case of preferably), the respective contents are not particularly limited, and the mass ratio of the content of other azole-based compounds relative to the azole-based compound with the least content in the polishing liquid is preferably 0.05 or more, and more preferably 0.5 or more. Better, less than 50 is more preferred, less than 10 is more preferred. In addition, it is preferable that the content of the compound having a benzotriazole skeleton is larger than the content of the compound different from the benzotriazole-based compound. Within the above range, it is more difficult to generate depressions and/or defects in the surface to be polished. In addition, the azole-based compound with the smallest content in the polishing liquid refers to the one with the smallest content among two or more azole-based compounds, and two or more azole-based compounds and a plurality of azole-based compounds are also applicable. In addition, three or more types of azole-based compounds may be used in combination. When three or more azole-based compounds are used in combination, it is preferable that the content of each azole-based compound is within the above range, respectively.

[任意成分] 上述研磨液可以含有上述以外的成分作為任意成分。以下，關於任意成分進行說明。[Optional Components] The polishing liquid may contain components other than those described above as optional components. Hereinafter, the optional components will be described.

＜研磨粒＞上述研磨液還可以含有除了膠體二氧化矽以外的研磨粒。<Abrasive grains> The above-mentioned polishing liquid may contain abrasive grains other than colloidal silica.

作為上述研磨粒並無特別限制，能夠使用除了膠體二氧化矽以外的公知的研磨粒。作為研磨粒，可舉出例如二氧化矽（除了膠體二氧化矽以外的沉澱二氧化矽或氣相二氧化矽）、氧化鋁、氧化鋯、氧化鈰、二氧化鈦、氧化鍺及碳化矽等無機物研磨粒；聚苯乙烯、聚丙烯酸及聚氯乙烯等有機物研磨粒。There is no restriction|limiting in particular as said abrasive grain, A well-known abrasive grain other than colloidal silica can be used. Examples of abrasive grains include silica (precipitated silica other than colloidal silica or fumed silica), alumina, zirconia, ceria, titania, germanium oxide, and inorganic abrasives such as silicon carbide. Granules; organic abrasive particles such as polystyrene, polyacrylic acid and polyvinyl chloride.

＜有機溶劑＞上述研磨液含有有機溶劑為較佳。作為有機溶劑，並無特別限制，能夠使用公知的有機溶劑。其中，水溶性有機溶劑為較佳。作為有機溶劑，可舉出例如酮系溶劑、醚系溶劑、醇系溶劑、二醇系溶劑、二醇醚系溶劑及醯胺系溶劑等。更具體而言，可舉出例如丙酮、甲乙酮、四氫呋喃、二㗁烷、二甲基乙醯胺、N-甲基吡咯烷酮、二甲基亞碸、乙腈、甲醇、乙醇、1-丙醇、2-丙醇、1-丁醇、乙二醇、丙二醇及乙氧基乙醇等。其中，甲乙酮、四氫呋喃、二㗁烷、N-甲基吡咯烷酮、甲醇、乙醇、丙二醇或乙二醇為較佳，甲醇、乙醇、丙二醇或乙二醇為更佳，甲醇、丙二醇或乙二醇為進一步較佳。<Organic solvent> It is preferable that the said polishing liquid contains an organic solvent. It does not specifically limit as an organic solvent, A well-known organic solvent can be used. Among them, water-soluble organic solvents are preferred. Examples of the organic solvent include ketone-based solvents, ether-based solvents, alcohol-based solvents, glycol-based solvents, glycol ether-based solvents, and amide-based solvents. More specifically, acetone, methyl ethyl ketone, tetrahydrofuran, diethane, dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, acetonitrile, methanol, ethanol, 1-propanol, 2 -Propanol, 1-butanol, ethylene glycol, propylene glycol and ethoxyethanol, etc. Among them, methyl ethyl ketone, tetrahydrofuran, diethylene, N-methylpyrrolidone, methanol, ethanol, propylene glycol or ethylene glycol are preferable, methanol, ethanol, propylene glycol or ethylene glycol are more preferable, and methanol, propylene glycol or ethylene glycol are preferable Further preferred.

作為有機溶劑的含量，並無特別限制，但是從本發明的效果更優異之方面而言，相對於研磨液總質量係0.01～20質量%為較佳，0.01～10質量%為更佳，0.01～8質量%為進一步較佳。若有機溶劑的含量在0.01～20質量%的範圍內，則被研磨面中的缺陷變得更難以產生。另外，有機溶劑可以單獨使用一種，亦可以併用兩種以上。在併用兩種以上的有機溶劑之情況下，總計含量在上述範圍內為較佳。The content of the organic solvent is not particularly limited, but from the viewpoint that the effect of the present invention is more excellent, it is preferably 0.01 to 20 mass %, more preferably 0.01 to 10 mass %, and 0.01 to the total mass of the polishing liquid. -8 mass % is more preferable. When the content of the organic solvent is in the range of 0.01 to 20 mass %, it becomes more difficult to generate defects in the surface to be polished. In addition, an organic solvent may be used individually by 1 type, and may use 2 or more types together. When two or more organic solvents are used in combination, the total content is preferably within the above range.

＜表面活性劑和/或親水性聚合物＞上述研磨液可以含有表面活性劑和/或親水性聚合物。表面活性劑及親水性聚合物（以下，亦稱作「親水性高分子」。）具有減小研磨液對被研磨面之接觸見方之作用，研磨液在被研磨面上容易潤濕擴展。作為表面活性劑，並無特別限制，能夠使用選自包括陰離子表面活性劑、陽離子表面活性劑、兩性表面活性劑及非離子表面活性劑等之組中之公知的表面活性劑。作為陰離子表面活性劑，可舉出例如羧酸鹽、烷基苯磺酸等磺酸鹽、硫酸酯鹽及磷酸酯鹽等。作為陽離子表面活性劑，可舉出例如脂肪族胺鹽、脂肪族四級銨鹽、苯紮氯銨鹽、芐索氯銨、吡啶鎓鹽及咪唑啉鎓鹽。作為兩性表面活性劑，可舉出例如羧基甜菜鹼類、胺基羧酸鹽、咪唑啉鎓甜菜鹼、卵磷脂及烷基胺氧化物等。作為非離子表面活性劑，可舉出例如醚型、醚酯型、酯型、含氮型、二醇型及氟系表面活性劑等。作為親水性聚合物，可舉出例如聚乙二醇等聚乙醇類、聚乙醇類的烷基醚、聚乙烯醇、聚乙烯基吡咯烷酮、海藻酸等多糖類、聚甲基丙烯酸及聚丙烯酸等含羧酸的聚合物、聚丙烯醯胺、聚甲基丙烯醯胺以及、聚乙亞胺等。作為該種親水性聚合物的具體例，可舉出在日本特開2009-88243號公報0042～0044段落、日本特開2007-194261號公報0026段落中所記載之水溶性高分子。<Surfactant and/or Hydrophilic Polymer> The above-mentioned polishing liquid may contain a surfactant and/or a hydrophilic polymer. Surfactants and hydrophilic polymers (hereinafter, also referred to as "hydrophilic polymers".) have the effect of reducing the contact between the polishing liquid and the surface to be polished, and the polishing liquid is easy to wet and spread on the surface to be polished. The surfactant is not particularly limited, and known surfactants selected from the group consisting of anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, and the like can be used. Examples of the anionic surfactant include carboxylate, sulfonate such as alkylbenzenesulfonic acid, sulfate, and phosphate. Examples of the cationic surfactant include aliphatic amine salts, aliphatic quaternary ammonium salts, benzalkonium chloride salts, benzethonium chloride, pyridinium salts, and imidazolinium salts. Examples of the amphoteric surfactant include carboxybetaines, aminocarboxylates, imidazolinium betaines, lecithin, and alkylamine oxides. As the nonionic surfactant, for example, ether type, ether ester type, ester type, nitrogen-containing type, glycol type, fluorine type surfactant, etc. are mentioned. Examples of hydrophilic polymers include polyethanols such as polyethylene glycol, alkyl ethers of polyethanols, polysaccharides such as polyvinyl alcohol, polyvinylpyrrolidone, and alginic acid, polymethacrylic acid, and polyacrylic acid. Carboxylic acid-containing polymers, polypropylene amides, polymethacrylamides, and polyethyleneimine, etc. Specific examples of such hydrophilic polymers include water-soluble polymers described in paragraphs 0042 to 0044 of JP 2009-88243 A and paragraph 0026 of JP 2007-194261 A.

在上述實施態樣中，水溶性高分子係選自聚丙烯醯胺、聚甲基丙烯醯胺、聚乙亞胺及聚乙烯基吡咯烷酮之水溶性高分子為較佳。作為聚丙烯醯胺或聚甲基丙烯醯胺，在氮原子上具有羥基烷基者（例如N-（2-羥乙基）丙烯醯胺聚合物等）或者具有包含聚環氧烷鏈之取代基者為較佳，重均分子量係2000～50000為更佳。作為聚乙亞胺，在氮原子上具有聚環氧烷鏈者為較佳，具有由下述通式表示之重複單元者為更佳。In the above embodiment, the water-soluble polymer is preferably a water-soluble polymer selected from the group consisting of polyacrylamide, polymethacrylamide, polyethyleneimine and polyvinylpyrrolidone. As polyacrylamide or polymethacrylamide, those having a hydroxyalkyl group on the nitrogen atom (such as N-(2-hydroxyethyl)acrylamide polymers, etc.) or those having substitutions containing polyalkylene oxide chains The base is preferred, and the weight-average molecular weight is more preferably 2,000 to 50,000. As the polyethyleneimine, those having a polyalkylene oxide chain on a nitrogen atom are preferred, and those having a repeating unit represented by the following general formula are more preferred.

[化學式1]

[Chemical formula 1]

在上述式中，n表示2～200的數（在係混合物之情況下為其平均數）。又，聚乙亞胺使用HLB（HydropHile-LipopHile Balance：親水-親油平衡）值係16～19者為較佳。In the above formula, n represents a number of 2 to 200 (in the case of a mixture, it is an average number). In addition, it is preferable to use a polyethyleneimine with an HLB (HydropHile-LipopHile Balance: hydrophilic-lipophilic balance) value of 16 to 19.

作為界面活性劑或親水性聚合物的含量，並無特別限制，但是相對於研磨液總質量係0.00001～2質量%為較佳，0.0001～1質量%為更佳，0.0001～0.5質量%為進一步較佳。若界面活性劑或親水性聚合物的含量係0.0001～0.5質量%，則將研磨液適用於CMP時，締合度1～3的膠體二氧化矽在化學機械研磨後其平均粒徑難以變動，本發明的效果更優異。另外，表面活性劑或親水性聚合物可以單獨使用一種，亦可併用兩種以上。另外，可以併用表面活性劑和親水性聚合物。在併用兩種以上的表面活性劑、兩種以上的親水性聚合物或表面活性劑及親水性聚合物之情況下，總計含量在上述範圍內為較佳。The content of the surfactant or hydrophilic polymer is not particularly limited, but is preferably 0.00001 to 2 mass %, more preferably 0.0001 to 1 mass %, and more preferably 0.0001 to 0.5 mass % relative to the total mass of the polishing liquid. better. If the content of surfactant or hydrophilic polymer is 0.0001 to 0.5 mass %, when the polishing liquid is applied to CMP, the average particle size of colloidal silica with an association degree of 1 to 3 is difficult to change after chemical mechanical polishing. The effect of the invention is more excellent. Moreover, a surfactant or a hydrophilic polymer may be used individually by 1 type, and may use 2 or more types together. In addition, a surfactant and a hydrophilic polymer may be used in combination. When two or more surfactants, two or more hydrophilic polymers, or a surfactant and a hydrophilic polymer are used in combination, the total content is preferably within the above range.

＜pH調整劑和/或pH緩衝劑＞上述研磨液為了設為規定的pH而還可以含有pH調整劑和/或pH緩衝劑。作為pH調整劑和/或pH緩衝劑，可舉出酸劑和/或鹼劑。另外，pH調整劑及pH緩衝劑係與上述有機酸不同之化合物。作為酸劑，並無特別限制，無機酸為較佳。作為無機酸，可舉出例如硫酸、硝酸、硼酸及磷酸等。其中，硝酸為更佳。作為鹼劑，並無特別限制，但是可舉出氫氧化銨及有機氫氧化銨；氫氧化鈉、氫氧化鉀及氫氧化鋰等鹼金屬氫氧化物；碳酸鈉等碳酸鹽；磷酸三鈉等磷酸鹽；硼酸鹽及四硼酸鹽；等。作為pH調整劑和/或pH緩衝劑的含量，只要係pH維持在所期望的範圍時所需要之量，則無特別的限制，通常在研磨液的總質量中，0.0001～0.1質量%為較佳。<pH adjuster and/or pH buffer> The said polishing liquid may further contain a pH adjuster and/or a pH buffer in order to make predetermined pH. As a pH adjuster and/or pH buffer, an acid agent and/or an alkali agent are mentioned. In addition, the pH adjuster and pH buffer are compounds different from the above-mentioned organic acids. Although it does not specifically limit as an acid agent, Mineral acid is preferable. As an inorganic acid, sulfuric acid, nitric acid, boric acid, phosphoric acid, etc. are mentioned, for example. Among them, nitric acid is more preferable. The alkaline agent is not particularly limited, but includes ammonium hydroxide and organic ammonium hydroxide; alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, and lithium hydroxide; carbonates such as sodium carbonate; trisodium phosphate, etc. Phosphates; Borate and Tetraborate; etc. The content of the pH adjuster and/or pH buffer is not particularly limited as long as it is an amount required to maintain the pH in a desired range, but usually 0.0001 to 0.1% by mass in the total mass of the polishing liquid good.

＜鈷防腐劑＞上述研磨液中，作為鈷的防腐劑，含有選自包括N-椰油醯基肌胺酸鹽、N-月桂醯肌胺酸鹽、N-硬脂醯肌胺酸鹽、N-油醯肌胺酸鹽、N-肉荳蔻醯肌胺酸鹽、N-月桂醯甘胺酸、N-肉荳蔻醯甘胺酸、N-棕櫚醯甘胺酸、N-月桂醯谷胺酸、N-椰油醯谷胺酸、N-椰油醯谷胺酸鉀、N-月桂醯肌胺酸鉀、N-月桂醯丙胺酸鹽、N-肉荳蔻醯丙胺酸鹽及N-椰油丙胺酸鉀之群組中的至少一種化合物為較佳。鈷防腐劑具有藉由與被研磨體面內的鈷進行配位而形成錯合物（複合化合物）來抑制鈷的過渡腐蝕之功能。作為上述鈷防腐劑的含量，並無特別限制，但是相對於研磨液總質量係0.001～5質量%為較佳，0.001～1質量%為更佳，0.001～0.5質量%為進一步較佳。若上述鈷防腐劑的含量係0.001～5質量%，則在被研磨面更難以產生凹陷，又，在被研磨面更難以產生缺陷。另外，上述鈷防腐劑可以單獨使用一種，亦可以併用兩種以上。在併用兩種以上的上述鈷防腐劑之情況下，總計含量在上述範圍內為較佳。<Cobalt preservative> The above-mentioned polishing liquid, as a cobalt preservative, contains a compound selected from the group consisting of N-coco sarcosinate, N-lauro sarcosinate, N-stearyl sarcosinate, N-oleosinate, N-myristate sarcosinate, N-lauroglycine, N-myristylglycine, N-palmitoglycine, N-lauroglutamine Acid, N-Cocoglutamate, Potassium N-Cocoglutamate, Potassium N-Laurosarcosinate, N-Lauryl Alanine, N-Myristate Alanine and N-Coconut At least one compound in the group of potassium oleylalanine is preferred. The cobalt corrosion inhibitor has the function of inhibiting the excessive corrosion of cobalt by coordinating with the cobalt in the surface of the polished body to form a complex (composite compound). The content of the cobalt preservative is not particularly limited, but is preferably 0.001 to 5% by mass, more preferably 0.001 to 1% by mass, and even more preferably 0.001 to 0.5% by mass relative to the total mass of the polishing liquid. When the content of the cobalt antiseptic agent is 0.001 to 5% by mass, it is more difficult to generate dents on the surface to be polished, and it is more difficult to generate defects on the surface to be polished. Moreover, the said cobalt antiseptic|preservative may be used individually by 1 type, and may use 2 or more types together. When two or more kinds of the above-mentioned cobalt antiseptics are used in combination, the total content is preferably within the above-mentioned range.

＜水＞上述研磨液含有水為較佳。作為上述研磨液所含有之水，並無特別限制，能夠使用離子交換水或純水等。作為水的含量，並無特別限制，在研磨液的總質量中，通常，90～99質量%為較佳。<Water> It is preferable that the said polishing liquid contains water. It does not specifically limit as water contained in the said polishing liquid, Deionized water, pure water, etc. can be used. Although there is no restriction|limiting in particular as content of water, Usually, 90-99 mass % is preferable in the total mass of a polishing liquid.

＜金屬雜質＞上述研磨液可以含有含金屬原子之金屬雜質。另外，本說明書中，「含金屬原子之金屬雜質」係指作為金屬離子及固體（金屬單體及、含粒子狀金屬的化合物等。以下，將該等總稱為「金屬粒子」。）在研磨液中所含有之金屬雜質。例如，在金屬原子係Fe原子之情況下，Fe離子及含有Fe原子之固體亦可適用。又，本說明書中，研磨液中的金屬雜質所含有之金屬原子的含量係指藉由ICP-MS（inductively coupled plasma mass spectrometry，感應耦合電漿質譜儀）測量之金屬原子的含量。另外，使用ICP-MS之金屬原子的含量的測量方法如後述之實施例中所記載。又，研磨液中的金屬粒子所含有之金屬原子的含量係指藉由SNP-ICP-MS（single nanoparticle inductively coupled plasma mass spectrometry，單奈米粒子感應耦合電漿質譜儀）測量之金屬原子的含量。另外，使用SNP-ICP-MS之金屬原子的含量的測量方法如後述之實施例中所記載。<Metal impurities> The above-mentioned polishing liquid may contain metal impurities containing metal atoms. In addition, in this specification, "metal impurity containing metal atom" refers to metal ions and solids (metal monomers and particulate metal-containing compounds, etc. Hereinafter, these are collectively referred to as "metal particles"). Metal impurities contained in the liquid. For example, in the case where the metal atom is Fe atom, Fe ions and solids containing Fe atoms are also applicable. In addition, in this specification, the content of metal atoms contained in the metal impurities in the polishing liquid refers to the content of metal atoms measured by ICP-MS (inductively coupled plasma mass spectrometry). In addition, the measurement method of the content of the metal atom using ICP-MS is as described in the Example mentioned later. In addition, the content of metal atoms contained in the metal particles in the polishing liquid refers to the content of metal atoms measured by SNP-ICP-MS (single nanoparticle inductively coupled plasma mass spectrometry, single nanoparticle inductively coupled plasma mass spectrometry). . In addition, the measurement method of the content of the metal atom using SNP-ICP-MS is as described in the Example mentioned later.

金屬雜質中所含有之金屬原子的種類並無特別限制，例如可舉出Fe原子、Cu原子、Ag原子及Zn原子等。又，上述金屬原子中選自包括Fe原子、Cu原子、Ag原子及Zn原子之群組中的至少一種特定金屬原子的含量如以下所述。在上述研磨液含有選自包括Fe原子、Cu原子、Ag原子及Zn原子之一種特定金屬原子之情況下，其一種特定金屬原子的含量相對於研磨液總質量設為0.001～200質量ppb為較佳，0.01～200質量ppb為更佳，0.01～100質量ppb為進一步較佳，0.01～50質量ppb尤為佳、0.01～20質量ppb最為佳。若上述特定金屬原子的含量相對於研磨液總質量在上述範圍內，則被研磨面中的凹陷及缺陷更難以產生，經時穩定性更優異。又，在含有兩種以上選自包括Fe原子、Cu原子、Ag原子及Zn原子之特定金屬原子之情況下，各自的特定金屬原子的含量相對於研磨液總質量係0.001～200質量ppb為較佳，0.01～200質量ppb為更佳，0.01～100質量ppb為進一步較佳，0.01～50質量ppb尤為佳、0.01～20質量ppb最為佳。亦即，例如在研磨液中含有Fe原子及Cu原子的兩種特定金屬原子之情況下，Fe原子的含量及Cu原子的含量這兩者在0.001～200質量ppb的範圍內為較佳。The type of metal atoms contained in the metal impurities is not particularly limited, and examples thereof include Fe atoms, Cu atoms, Ag atoms, and Zn atoms. In addition, the content of at least one specific metal atom selected from the group consisting of Fe atom, Cu atom, Ag atom, and Zn atom in the above-mentioned metal atom is as follows. When the above-mentioned polishing liquid contains a specific metal atom selected from Fe atoms, Cu atoms, Ag atoms and Zn atoms, the content of the specific metal atom is set to be 0.001-200 mass ppb relative to the total mass of the polishing liquid. 0.01-200 mass ppb is more preferable, 0.01-100 mass ppb is further preferable, 0.01-50 mass ppb is particularly preferable, and 0.01-20 mass ppb is most preferable. When the content of the specific metal atom is within the above-mentioned range with respect to the total mass of the polishing liquid, it is more difficult to generate dents and defects in the surface to be polished, and the stability over time is more excellent. In addition, in the case of containing two or more kinds of specific metal atoms selected from the group consisting of Fe atoms, Cu atoms, Ag atoms and Zn atoms, the content of each specific metal atom is relatively high relative to the total mass of the polishing liquid from 0.001 to 200 mass ppb. 0.01-200 mass ppb is more preferable, 0.01-100 mass ppb is further preferable, 0.01-50 mass ppb is particularly preferable, and 0.01-20 mass ppb is most preferable. That is, for example, when two kinds of specific metal atoms of Fe atoms and Cu atoms are contained in the polishing liquid, both the content of Fe atoms and the content of Cu atoms are preferably in the range of 0.001 to 200 mass ppb.

又，從更降低被研磨面的缺陷之觀點而言，將含有研磨液中選自包括Fe原子、Cu原子、Ag原子及Zn原子之群組中的至少一種特定金屬原子之金屬粒子的含量控制在特定範圍內為較佳。換言之，適當地調整研磨液的固體狀金屬雜質量為較佳。在上述研磨液含有上述金屬粒子之情況下，在上述金屬粒子所含有之特定金屬原子係一種時，其一種含量相對於研磨液總質量係0.01～50質量ppb為較佳，0.01～8質量ppb為更佳。在上述研磨液含有上述金屬粒子之情況下，上述金屬粒子所含有之特定金屬原子係兩種以上時，各自的含量相對於研磨液總質量係0.01～50質量ppb為較佳，0.01～8質量ppb為更佳。亦即，例如，在研磨液中含有含Fe原子之金屬粒子及含有Cu原子之金屬粒子之情況下，Fe原子的含量及Cu原子的含量這兩者在0.01～50質量ppb的範圍內為較佳。Also, from the viewpoint of further reducing the defects of the surface to be polished, the content of metal particles containing at least one specific metal atom selected from the group consisting of Fe atoms, Cu atoms, Ag atoms and Zn atoms in the polishing liquid is controlled It is preferable to be within a specific range. In other words, it is preferable to appropriately adjust the amount of solid metal impurities in the polishing liquid. In the case where the above-mentioned polishing liquid contains the above-mentioned metal particles, when the specific metal atom contained in the above-mentioned metal particles is one type, the content of one type is preferably 0.01-50 mass ppb relative to the total mass of the polishing liquid, 0.01-8 mass ppb for better. In the case where the above-mentioned polishing liquid contains the above-mentioned metal particles, when the specific metal atoms contained in the above-mentioned metal particles are two or more kinds, the respective contents are preferably 0.01-50 mass ppb relative to the total mass of the polishing liquid, 0.01-8 mass ppb ppb is better. That is, for example, when the polishing liquid contains Fe atom-containing metal particles and Cu atom-containing metal particles, both the Fe atom content and the Cu atom content are in the range of 0.01 to 50 mass ppb. good.

含上述金屬原子之金屬雜質可以添加於研磨液中，亦可以在研磨液的製造步驟中不可避免地混合於藥液中。作為在研磨液的製造步驟中不可避免地混合之情況，例如可舉出在用於研磨液的製造中之原料（例如，有機溶劑）中含有含上述金屬原子之金屬雜質之情況及在研磨液的製造步驟中混合（例如，污染）等，但是並非限制於上述。The metal impurities containing the above-mentioned metal atoms may be added to the polishing liquid, or may be inevitably mixed in the chemical liquid in the production process of the polishing liquid. Examples of the case where mixing is unavoidable in the production step of the polishing liquid include the case where the raw material (for example, an organic solvent) used in the production of the polishing liquid contains the metal impurities containing the above-mentioned metal atoms, and the case where the metal impurity containing the above-mentioned metal atom is contained in the polishing liquid. mixing (eg, contamination), etc. in the manufacturing steps, but not limited to the above.

又，研磨液的由下述式（1）計算之過氧化氫與上述金屬雜質所含有之選自包括Fe原子、Cu原子、Ag原子及Zn原子之群組中的特定金屬原子的含量比T1係30000～500000為較佳。式（1）：T1=過氧化氫的含量/金屬雜質所含有之選自包括Fe原子、Cu原子、Ag原子及Zn原子之群組中的特定金屬原子的總計含量Also, the content ratio T1 of the hydrogen peroxide in the polishing liquid calculated by the following formula (1) and the specific metal atom contained in the above-mentioned metal impurity selected from the group consisting of Fe atom, Cu atom, Ag atom and Zn atom It is preferably 30000-500000. Formula (1): T1=content of hydrogen peroxide/total content of specific metal atoms selected from the group consisting of Fe atoms, Cu atoms, Ag atoms and Zn atoms contained in metal impurities

過氧化氫藉由將Fe等金屬原子作為觸媒而分解，產生氧化力較強的氫過氧化物。另一方面，鈷原子的氧化電位與配線金屬元素亦即銅原子等相比較低，存在相對容易被氧化之傾向。因此，將被研磨體設為含鈷的層之情況下，藉由上述生成之氫過氧化物容易削去被研磨面，又，產生過渡的腐蝕，其結果可推測，容易產生凹陷。研磨液中，在上述T1係30000以上之情況下，因能夠更抑制上述氫過氧化物的生成，在被研磨面更難以產生凹陷，又，被研磨面的缺陷亦更難以產生。又，研磨液中，在上述T1係500000以下之情況下，過氧化氫的含量與金屬離子的含量之差足夠大（亦即，金屬本身的氧化力很難），藉此在被研磨面更難以產生凹陷，又，被研磨面的缺陷亦更難以產生。在將研磨液使用於上述第1研磨之情況下，從被研磨面中的凹陷及缺陷更難以產生之方面而言，上述T1係110000以下為更佳，80000以下為進一步較佳。在將研磨液使用於上述第2研磨之情況下，從被研磨面中的凹陷及缺陷更難以產生之方面而言，上述T1係100000以上為更佳，250000以上為進一步較佳。Hydrogen peroxide is decomposed by using a metal atom such as Fe as a catalyst to generate hydroperoxide having a strong oxidizing power. On the other hand, the oxidation potential of cobalt atoms is lower than that of copper atoms, which are wiring metal elements, and tends to be oxidized relatively easily. Therefore, when the body to be polished is made of a layer containing cobalt, the surface to be polished is easily shaved by the hydroperoxide produced as described above, and excessive corrosion occurs. As a result, it is presumed that dents are likely to be generated. In the polishing liquid, when the above-mentioned T1 series is 30,000 or more, the generation of the above-mentioned hydroperoxide can be further suppressed, so that pits are more difficult to be generated on the surface to be polished, and defects of the surface to be polished are also more difficult to occur. In addition, in the polishing liquid, when the above-mentioned T1 series is 500,000 or less, the difference between the content of hydrogen peroxide and the content of metal ions is sufficiently large (that is, the oxidizing power of the metal itself is difficult), thereby making the surface to be polished more stable. It is difficult to generate dents, and it is also more difficult to generate defects on the surface to be polished. When the polishing liquid is used for the above-mentioned first polishing, the above-mentioned T1 series is more preferably 110,000 or less, and even more preferably 80,000 or less, from the viewpoint of less generation of dents and defects in the surface to be polished. When the polishing liquid is used for the second polishing, the above-mentioned T1 series is more preferably 100,000 or more, and even more preferably 250,000 or more, from the viewpoint of less generation of dents and defects in the surface to be polished.

＜通式（1）所表示之化合物＞上述研磨液可含有下述通式（1）所表示之化合物。通式（1）： N（R¹ ）（R² ）（R³ ）通式（1）中，R¹ ～R³ 分別獨立地表示氫原子或烷基。<The compound represented by general formula (1)> The said polishing liquid may contain the compound represented by following general formula (1). General formula (1): N(R ¹ )(R ² )(R ³ ) In the general formula (1), R ¹ to R ³ each independently represent a hydrogen atom or an alkyl group.

作為上述通式（1）所表示之化合物，例如可舉出氨；乙醇胺、二乙醇胺、三乙醇胺及三異丙醇胺等烷醇胺類；等鹼劑。上述研磨液中的上述通式（1）所表示之化合物的含量相對於研磨液總質量係1500質量ppb以下為較佳，1000質量ppb以下為更佳，250質量ppb以下為進一步較佳，8質量ppb以下尤為佳。研磨液中，若上述通式（1）所表示之化合物的含量係1500質量ppb以下，則基於上述化合物之向被研磨面上的鈷的配位得到抑制，另一方面，形成基於唑系化合物之與上述鈷的錯合物層變得容易。該結果，在被研磨面更難以產生凹陷，又，被研磨面的缺陷亦更難以產生。研磨液中，上述通式（1）所表示之化合物的含量的下限並無特別限定，例如係0.00001質量ppb以上。另外，上述研磨液中的通式（1）所表示之化合物的含量能夠使用GCMS（氣相色譜質量分析裝置；gas chromatography mass spectrometry）來測定。另外，測量條件等如實施例中所記載。Examples of the compound represented by the general formula (1) include ammonia; alkanolamines such as ethanolamine, diethanolamine, triethanolamine, and triisopropanolamine; and alkaline agents such as the like. The content of the compound represented by the above-mentioned general formula (1) in the above-mentioned grinding liquid is preferably below 1500 mass ppb with respect to the total mass of the grinding liquid, more preferably below 1000 mass ppb, and further preferably below 250 mass ppb, 8 The quality below ppb is especially good. In the polishing liquid, when the content of the compound represented by the general formula (1) is 1500 mass ppb or less, the coordination of cobalt on the surface to be polished by the compound is suppressed, and on the other hand, the azole-based compound is formed. The complex layer with the above-mentioned cobalt becomes easy. As a result, it is more difficult to generate dents on the surface to be polished, and it is also more difficult to generate defects on the surface to be polished. In the polishing liquid, the lower limit of the content of the compound represented by the general formula (1) is not particularly limited, but is, for example, 0.00001 mass ppb or more. In addition, content of the compound represented by General formula (1) in the said polishing liquid can be measured using GCMS (gas chromatography mass spectrometry; gas chromatography mass spectrometry). In addition, measurement conditions etc. are as described in the Example.

上述研磨液如上所述那樣製造半導體積體電路裝置時適當地用於為了實施埋入配線（鈷配線）的平坦化等之CMP。在將研磨液使用於上述第1研磨之情況下，研磨液係下述實施方式1的研磨液為較佳，在將研磨液使用於上述第2研磨之情況下，研磨液係下述實施方式2的研磨液為較佳。The above-mentioned polishing liquid is suitably used for CMP in order to perform planarization of buried wirings (cobalt wirings) when manufacturing a semiconductor integrated circuit device as described above. When the polishing liquid is used for the above-mentioned first polishing, it is preferable that the polishing liquid is the polishing liquid of the following Embodiment 1, and when the polishing liquid is used for the above-mentioned second polishing, the polishing liquid is the following embodiment. The polishing liquid of 2 is better.

《實施方式1的研磨液》實施方式1的研磨液，其係含有締合度1～3的膠體二氧化矽、有機酸、唑系化合物及過氧化氫之化學機械研磨用研磨液，其中，上述締合度1～3的膠體二氧化矽的含量相對於研磨液總質量係0.01～1質量%，作為上述有機酸，含有胺基酸，作為上述唑系化合物，含有至少兩種以上***系化合物，pH係6.5～8.0，在使上述研磨液與鈷基板接觸24小時時，在上述鈷基板上形成含有鈷原子厚度0.5～20nm的反應層（反應層1），並且使上述研磨液與包括選自包括Ta、TaN、Ti、TiN、Ru及Mn之群組中的任一種金屬之阻擋基板接觸24小時時，還在上述阻擋基板上形成含上述金屬的原子之厚度0.01～5nm的反應層（以下，亦稱為「反應層2」。）之研磨液為較佳。<<Polishing Liquid of Embodiment 1>> The polishing liquid of Embodiment 1 is a polishing liquid for chemical mechanical polishing containing colloidal silica with an association degree of 1 to 3, an organic acid, an azole-based compound, and hydrogen peroxide, wherein the above The content of colloidal silica with an association degree of 1 to 3 is 0.01 to 1 mass % with respect to the total mass of the polishing liquid, the organic acid contains an amino acid, and the azole compound contains at least two or more triazole based compounds , the pH is 6.5 to 8.0, when the above-mentioned polishing liquid is brought into contact with the cobalt substrate for 24 hours, a reaction layer (reaction layer 1) containing cobalt atoms with a thickness of 0.5 to 20 nm is formed on the above-mentioned cobalt substrate, and the above-mentioned polishing liquid is mixed with the selected When contacted with a barrier substrate of any metal selected from the group consisting of Ta, TaN, Ti, TiN, Ru, and Mn for 24 hours, a reaction layer ( Hereinafter, also referred to as "reaction layer 2") polishing liquid is preferable.

上述反應層2的厚度係0.01nm以上，0.1nm以上為較佳。又，上述反應層2的厚度係5nm以下，3.0nm以下為較佳。若上述反應層2的厚度係0.01nm以上及5nm以下，則本發明的效果更優異。The thickness of the reaction layer 2 is 0.01 nm or more, preferably 0.1 nm or more. In addition, the thickness of the reaction layer 2 is 5 nm or less, preferably 3.0 nm or less. When the thickness of the reaction layer 2 is 0.01 nm or more and 5 nm or less, the effect of the present invention is more excellent.

本說明書中的反應層2係指，將由具備10mm×10mm的被研磨面之選自包括Ta、TaN、Ti、TiN、Ru及Mn之群組中的任一種金屬（阻擋金屬）構成之阻擋基板（由阻擋金屬構成之金屬基板）浸漬於10mL的研磨液中，在25℃下使上述阻擋基板與研磨液接觸24小時時，形成於上述阻擋基板的被研磨面上之反應層。另外，在將上述阻擋基板浸漬於研磨液時，亦可以是將積層了上述阻擋基板與其他基板（例如矽基板）之積層體浸漬於研磨液中之形態。The reaction layer 2 in this specification refers to a barrier substrate that will be composed of any metal (barrier metal) selected from the group consisting of Ta, TaN, Ti, TiN, Ru, and Mn having a surface to be polished of 10 mm×10 mm. (The metal substrate made of barrier metal) was immersed in 10 mL of polishing liquid, and the reaction layer was formed on the polished surface of the barrier substrate when the barrier substrate was brought into contact with the polishing liquid at 25° C. for 24 hours. Moreover, when the said barrier substrate is immersed in a polishing liquid, the form which immersed the laminated body which laminated|stacked the said barrier substrate and another substrate (for example, a silicon substrate) in a polishing liquid may be sufficient.

上述反應層2含有選自包括Ta、TaN、Ti、TiN、Ru及Mn之群組中的任一種金屬的原子（阻擋金屬原子）。上述反應層2還可以含有氧原子等，在反應層的表面含有研磨液中的成分的錯合物為較佳。其中，上述反應層2的厚度係指，使研磨液與上述阻擋基板接觸24小時之後，使用掃描型電子顯微鏡（SEM）藉由實施例中所記載之方法觀察接觸後的上述阻擋基板的截面而得到之厚度。The reaction layer 2 described above contains atoms (barrier metal atoms) of any metal selected from the group consisting of Ta, TaN, Ti, TiN, Ru, and Mn. The said reaction layer 2 may contain oxygen atoms etc., and it is preferable to contain the complex compound of the component in a polishing liquid on the surface of a reaction layer. The thickness of the above-mentioned reaction layer 2 refers to the observation of the cross-section of the above-mentioned barrier substrate after contact with the polishing liquid and the above-mentioned barrier substrate for 24 hours using a scanning electron microscope (SEM) by the method described in the Examples. obtained thickness.

上述研磨液能夠藉由上述特定的條件在由選自包括Ta、TaN、Ti、TiN、Ru及Mn之群組中的任一種金屬構成之阻擋基板上形成反應層2即可，但是能夠在由Ta構成之基板、由TaN構成之基板、由Ti構成之基板、由TiN構成之基板、由Ru構成之基板及由Mn構成之基板的所有基板上各自形成反應層2為較佳。The above-mentioned polishing liquid can form the reaction layer 2 on the barrier substrate composed of any metal selected from the group consisting of Ta, TaN, Ti, TiN, Ru and Mn under the above-mentioned specific conditions, but can be formed by Preferably, the reaction layer 2 is formed on each of the Ta substrate, the TaN substrate, the Ti substrate, the TiN substrate, the Ru substrate, and the Mn substrate.

從更抑制被研磨面中的凹陷的產生之觀點考慮，上述研磨液的由下述式（3）計算之研磨速度比R1調整成250～2500為較佳。式（3）： R1=基於上述研磨液之鈷基板的研磨速度/基於上述研磨液之阻擋基板的研磨速度阻擋層的研磨中，通常有助於機械研磨的量大於化學研磨。換言之，即使形成反應層2，研磨速度亦不會較大地提高。因此，在將研磨速度比R1設為上述特定的數值範圍之情況下，基於研磨液之含鈷的層的研磨速度調整成上升為較佳。另外，關於後述之研磨速度比R2亦相同。From the viewpoint of further suppressing the generation of dents in the surface to be polished, it is preferable to adjust the polishing rate ratio R1 of the polishing liquid calculated by the following formula (3) to 250 to 2500. Formula (3): R1=the polishing rate of the cobalt substrate based on the above-mentioned polishing liquid/the polishing rate of the barrier substrate based on the above-mentioned polishing liquid. In the polishing of the barrier layer, the amount that usually contributes to mechanical polishing is greater than that of chemical polishing. In other words, even if the reaction layer 2 is formed, the polishing speed is not greatly improved. Therefore, when the polishing rate ratio R1 is set to the above-mentioned specific numerical range, it is preferable to adjust the polishing rate of the cobalt-containing layer based on the polishing liquid so as to increase. In addition, it is the same about the polishing rate ratio R2 mentioned later.

關於實施方式1的研磨液所含有之締合度1～3的膠體二氧化矽、有機酸及唑系化合物以及任意成分，分別如上所述，態樣亦相同為較佳。又，關於上述反應層1亦如上所述，態樣亦相同為較佳。Regarding the colloidal silica, the organic acid, the azole-based compound, and the optional components having an association degree of 1 to 3 contained in the polishing liquid of Embodiment 1, they are as described above, and the aspects are preferably the same. In addition, the above-mentioned reaction layer 1 is also as described above, and the aspect is also preferably the same.

《實施方式2的研磨液》實施方式2的研磨液，係其含有締合度1～3的膠體二氧化矽、有機酸、唑系化合物及過氧化氫之化學機械研磨用研磨液，其中，上述締合度1～3的膠體二氧化矽的含量相對於研磨液總質量係0.5～5質量%，作為上述唑系化合物，含有***系化合物， pH係8.0～10.5，在使上述研磨液與鈷基板接觸24小時時，在上述鈷基板上形成含有鈷原子之厚度0.5～20nm的反應層（相當於上述「反應層1」。），使上述研磨液與包括選自包括Ta、TaN、Ti、TiN、Ru及Mn之群組中的任一種金屬之阻擋基板接觸24小時時，在上述阻擋基板上形成含有上述金屬的原子之厚度0.01～5nm的反應層（相當於上述「反應層2」。），使上述研磨液與包括選自包括SiOx及SiOC之群組中的任一種無機成分之絕緣膜基板接觸24小時時，在上述絕緣膜基板上形成含有上述無機成分之厚度0.01～10nm的反應層（以下，亦稱為「反應層3」。）之研磨液為較佳。<<Polishing Liquid of Embodiment 2>> The polishing liquid of Embodiment 2 is a polishing liquid for chemical mechanical polishing containing colloidal silica having an association degree of 1 to 3, an organic acid, an azole-based compound, and hydrogen peroxide, wherein the above-mentioned The content of colloidal silica with an association degree of 1 to 3 is 0.5 to 5 mass % with respect to the total mass of the polishing liquid, the azole-based compound contains a triazole-based compound, and the pH is 8.0 to 10.5. When the substrates were in contact for 24 hours, a reaction layer with a thickness of 0.5 to 20 nm containing cobalt atoms was formed on the cobalt substrate (corresponding to the above-mentioned "reaction layer 1"). When the barrier substrate of any metal in the group of TiN, Ru, and Mn is in contact with the barrier substrate for 24 hours, a reaction layer (equivalent to the above-mentioned "reaction layer 2") having a thickness of 0.01 to 5 nm containing atoms of the metal is formed on the barrier substrate. ), when the above-mentioned polishing liquid is brought into contact with an insulating film substrate including any inorganic component selected from the group consisting of SiOx and SiOC for 24 hours, a reaction with a thickness of 0.01-10 nm containing the above-mentioned inorganic component is formed on the above-mentioned insulating film substrate The polishing liquid of the layer (hereinafter, also referred to as "reaction layer 3") is preferable.

上述反應層3的厚度係0.01nm以上，0.1nm以上為較佳。又，上述反應層3的厚度係10nm以下，5nm以下為較佳。若上述反應層3的厚度係0.01nm以上及10nm以下，則本發明的效果更優異。The thickness of the reaction layer 3 is 0.01 nm or more, preferably 0.1 nm or more. In addition, the thickness of the reaction layer 3 is 10 nm or less, preferably 5 nm or less. When the thickness of the reaction layer 3 is 0.01 nm or more and 10 nm or less, the effect of the present invention is more excellent.

本說明書中的反應層3係指，將由具備10mm×10mm的被研磨面之選自包括SiOx及SiOC之群組中的任一種無機成分構成之絕緣膜基板浸漬於10mL的研磨液中，在25℃下使上述絕緣膜基板與研磨液接觸24小時時，形成於上述絕緣膜基板的被研磨面上之反應層。另外，在將上述絕緣膜基板浸漬於研磨液時，亦可以是將積層了上述絕緣膜基板與其他基板（例如矽基板）之積層體浸漬於研磨液中之形態。The reaction layer 3 in this specification refers to immersing an insulating film substrate composed of any inorganic component selected from the group consisting of SiOx and SiOC and having a surface to be polished of 10 mm × 10 mm in 10 mL of polishing solution, at 25 The reaction layer formed on the surface to be polished of the insulating film substrate was formed when the insulating film substrate was brought into contact with the polishing liquid for 24 hours at ℃. In addition, when the insulating film substrate is immersed in the polishing liquid, the layered product in which the insulating film substrate and other substrates (eg, silicon substrates) are laminated may be immersed in the polishing liquid.

上述反應層3含有上述無機成分。上述反應層3還可以含有氧原子等，在反應層的表面含有研磨液中的成分的錯合物為較佳。其中，上述反應層3的厚度係指，使研磨液與上述絕緣膜基板接觸24小時之後，使用掃描型電子顯微鏡（SEM）藉由實施例中所記載之方法觀察接觸後的上述絕緣膜基板的截面而獲得之厚度。The said reaction layer 3 contains the said inorganic component. The said reaction layer 3 may contain oxygen atoms etc., and it is preferable to contain the complex compound of the component in a polishing liquid on the surface of the reaction layer. The thickness of the above-mentioned reaction layer 3 refers to the observation of the thickness of the above-mentioned insulating film substrate after contacting the polishing liquid with the above-mentioned insulating film substrate for 24 hours using a scanning electron microscope (SEM) by the method described in the Examples. The thickness obtained from the section.

上述研磨液能夠藉由上述特定的條件在由選自包括SiOx及SiOC之群組中的任一種無機成分構成之絕緣膜基板上形成反應層3即可，與能夠在由SiOx構成之基板及由SiOC構成之基板的所有基板上各自形成反應層3為較佳。The above-mentioned polishing liquid can form the reaction layer 3 on the insulating film substrate composed of any inorganic component selected from the group including SiOx and SiOC under the above-mentioned specific conditions, and can form the reaction layer 3 on the substrate composed of SiOx and the It is preferable to form the reaction layer 3 on all the substrates of the SiOC-constituted substrates.

從更抑制被研磨面中的凹陷的產生之觀點考慮，上述研磨液的由下述式（4）計算之研磨速度比R2調整成0.01～2.0為較佳。又，由下述式（5）計算之研磨速度比R3調整成0.05～2.0為較佳。式（4）： R2=基於上述研磨液之鈷基板的研磨速度/基於上述研磨液之阻擋基板的研磨速度式（5）： R3=基於上述研磨液之鈷基板的研磨速度/基於上述研磨液之絕緣膜基板的研磨速度From the viewpoint of further suppressing the generation of dents in the surface to be polished, it is preferable to adjust the polishing rate ratio R2 of the polishing liquid calculated by the following formula (4) to 0.01 to 2.0. Moreover, it is preferable to adjust the grinding|polishing rate ratio R3 calculated by following formula (5) to 0.05-2.0. Equation (4): R2=Polishing rate of the cobalt substrate based on the above-mentioned polishing liquid/Polishing rate of the barrier substrate based on the above-mentioned polishing liquid Equation (5): R3=Polishing rate of the cobalt substrate based on the above-mentioned polishing liquid/Based on the above-mentioned polishing liquid The polishing speed of the insulating film substrate

關於實施方式2的研磨液所含有之締合度1～3的膠體二氧化矽、有機酸及唑系化合物以及任意成分，分別如上所述。又，關於上述反應層1及上述反應層2亦如上所述。The colloidal silica, the organic acid, the azole-based compound, and the optional components having an association degree of 1 to 3 contained in the polishing liquid of Embodiment 2 are as described above, respectively. In addition, the above-mentioned reaction layer 1 and the above-mentioned reaction layer 2 are also as described above.

[研磨液的製備方法] 上述研磨液能夠藉由公知的方法而製造。例如，能夠藉由混合上述各成分而製造。混合上述各成分之順序和/或時機並無特別限制，可以預先將締合度1～3的膠體二氧化矽分散於已調整pH之水中，將規定的成分依次進行混合。又，將過氧化氫、水或過氧化氫及水另行保管直至使用研磨劑之前，亦可以在使用之前混合。又，上述研磨液藉由具有在使用之前用水稀釋之稀釋步驟之下述方法來製造為較佳。[Method for Preparing Polishing Liquid] The above-mentioned polishing liquid can be produced by a known method. For example, it can be produced by mixing the above-mentioned components. The order and/or timing of mixing the above components is not particularly limited, and colloidal silica having an association degree of 1 to 3 may be dispersed in pH-adjusted water in advance, and the predetermined components may be mixed in order. In addition, hydrogen peroxide, water, or hydrogen peroxide and water are separately stored until the abrasive is used, and may be mixed before use. Moreover, it is preferable to manufacture the said polishing liquid by the following method which has the dilution process of diluting with water before use.

[研磨液之製造方法] 本發明的一的實施態樣之研磨液之製造方法係含有對含有締合度1～3的膠體二氧化矽、有機酸、唑系化合物及過氧化氫之研磨液原液混合水而獲得上述研磨液之步驟（以下，亦稱為「稀釋步驟」。）之研磨液之製造方法。[Method for producing a polishing liquid] A method for producing a polishing liquid according to an embodiment of the present invention comprises a polishing liquid stock solution containing colloidal silica having an association degree of 1 to 3, an organic acid, an azole compound, and hydrogen peroxide. The manufacturing method of the polishing liquid of the step (hereinafter, also referred to as "dilution step") of mixing water to obtain the above-mentioned polishing liquid.

[稀釋步驟] 稀釋步驟係對含有規定的成分之研磨液原液混合水而獲得研磨液之步驟。作為研磨液的態樣與已說明內容相同。又，作為混合水之方法，並無特別限制，能夠使用公知的方法。[Dilution step] The dilution step is a step of obtaining a polishing liquid by mixing water with a polishing liquid stock solution containing predetermined components. The aspect as a polishing liquid is the same as that which has already been described. In addition, there is no restriction|limiting in particular as a method of mixing water, A well-known method can be used.

＜研磨液原液＞上述稀釋步驟中所使用之研磨液原液係含有締合度1～3的膠體二氧化矽、有機酸、唑系化合物及過氧化氫之研磨液原液，進一步用於與水混合來製造研磨液之研磨液原液。作為研磨液原液，藉由混合水等溶劑來獲得上述研磨液即可，除了上述成分以外，還可以依據所期望含有有機溶劑、界面活性劑、親水性聚合物、pH調整劑、pH緩衝劑及鈷防腐劑等。研磨液原液實際上將用於CMP時的研磨液濃縮成2～50倍之液為較佳。亦即，研磨液原液稀釋成2～50倍而使用。稀釋時，使用水為較佳。作為研磨液原液之製造方法，並無特別限制，能夠藉由公知的方法而製造。例如，能夠藉由混合上述各成分而製造。混合上述各成分之順序等並無特別限制，亦可以預先將膠體二氧化矽分散於已調整pH之水和/或有機溶劑中，並依次混合規定的成分。又，研磨液原液用水稀釋成2～50倍時，稀釋前後的pH變化小於0.01～1為較佳。本發明人檢測上述研磨原液的稀釋前後的性能狀態的結果確認到，在稀釋前後的pH變化小於0.01～1的情況下，基於稀釋之性能變化得到抑制。具體而言，確認到若研磨液原液的稀釋前後的pH變化係0.01以上，則伴隨稀釋之性能變化實質上不會產生。另一方面，確認到小於研磨液原液的稀釋前後的pH變化，則伴隨稀釋之性能變化較少，性能不會較大地損失。<Polishing liquid stock solution> The polishing liquid stock solution used in the above-mentioned dilution step is a polishing liquid stock solution containing colloidal silica with an association degree of 1 to 3, an organic acid, an azole compound and hydrogen peroxide, and is further used for mixing with water. A polishing liquid stock solution for the manufacture of polishing liquids. As a polishing liquid stock solution, the polishing liquid may be obtained by mixing a solvent such as water. In addition to the above components, an organic solvent, a surfactant, a hydrophilic polymer, a pH adjuster, a pH buffer and Cobalt preservatives, etc. It is preferable that the polishing liquid stock solution actually concentrates the polishing liquid used for CMP to 2 to 50 times. That is, the polishing liquid stock solution is diluted 2 to 50 times and used. When diluting, it is better to use water. There is no restriction|limiting in particular as a manufacturing method of a polishing liquid undiluted|stock solution, It can manufacture by a well-known method. For example, it can be produced by mixing the above-mentioned components. The order of mixing the above components is not particularly limited, and colloidal silica may be dispersed in pH-adjusted water and/or an organic solvent in advance, and the predetermined components may be mixed in order. In addition, when the polishing liquid stock solution is diluted with water to 2 to 50 times, it is preferable that the pH change before and after the dilution is less than 0.01 to 1. As a result of examining the performance state of the above-mentioned polishing stock solution before and after dilution, the present inventors confirmed that when the pH change before and after dilution is less than 0.01 to 1, the performance change due to dilution is suppressed. Specifically, it was confirmed that if the pH change before and after the dilution of the polishing liquid stock solution is 0.01 or more, the performance change accompanying the dilution does not substantially occur. On the other hand, it was confirmed that the pH change before and after the dilution of the polishing liquid stock solution was smaller than the change in performance accompanying the dilution, and the performance was not greatly lost.

又，作為研磨液之製造方法的其他態樣，可舉出準備含有規定的成分之研磨液的濃縮液，向其加入過氧化氫或、過氧化氫及水，從而製造具有特定的特性之研磨液之方法。In addition, as another aspect of the manufacturing method of the polishing liquid, a concentrated liquid of the polishing liquid containing predetermined components is prepared, and hydrogen peroxide or hydrogen peroxide and water are added thereto, thereby producing polishing with specific characteristics. liquid method.

[研磨液原液收容體] 本發明的研磨液原液收容體具有上述研磨液原液、收容上述研磨液原液之由不含鐵之金屬材料形成之容器而構成。其中，「不含有鐵之金屬材料」係指實質上不含有鐵之金屬材料，例如係指鐵原子的含量相對於總原子量係30%以下，20%以下的金屬材料為較佳。從難以增加雜質含量之方面又抑制過氧化氫的分解之方面而言，特定期間曝光研磨液原液之情況下，上述研磨液原液亦期望容納於由不含有鐵之金屬材料（以下，亦稱為「非鐵金屬材料」。）形成之容器中。上述容器中與研磨液原液接觸之內壁由非鐵金屬材料形成即可，關於其他構成，並無特別限定。作為內壁由非鐵金屬材料形成之容器，內壁由選自包括非金屬材料及被電解研磨之非金屬材料之群組中的至少一種材料覆蓋或內壁由材料形成之容器為較佳。另外，本說明書中，「覆蓋」係指上述內壁由上述材料包覆。作為上述內壁由上述材料包覆之態樣，內壁的總表面積的70%以上由上述材料包覆為較佳。[Polishing liquid stock solution container] The polishing liquid stock liquid container of the present invention includes the above-mentioned polishing liquid stock solution and a container made of a non-ferrous metal material that accommodates the above-mentioned polishing liquid stock solution. Among them, "iron-free metal material" refers to a metal material that does not substantially contain iron, for example, a metal material with an iron atom content of 30% or less, preferably 20% or less, relative to the total atomic weight. In terms of the difficulty of increasing the impurity content and the suppression of the decomposition of hydrogen peroxide, in the case of exposing the polishing liquid stock solution for a certain period of time, the polishing liquid stock solution is also desirably contained in a metal material (hereinafter, also referred to as a metal material that does not contain iron). "Non-ferrous metal material".) in the container formed. The inner wall of the container in contact with the polishing liquid stock solution may be formed of a non-ferrous metal material, and other structures are not particularly limited. As the container whose inner wall is formed of a non-ferrous metal material, a container whose inner wall is covered with at least one material selected from the group consisting of non-metallic materials and electrolytically ground non-metallic materials or a container whose inner wall is formed of a material is preferable. In addition, in this specification, "covering" means that the said inner wall is covered with the said material. As an aspect in which the inner wall is covered with the material, it is preferable that 70% or more of the total surface area of the inner wall is covered with the material.

作為非金屬材料，例如可舉出聚乙烯樹脂、聚丙烯樹脂、聚乙烯-聚丙烯樹脂、四氟化乙烯樹脂、四氟化乙烯-全氟烷基乙烯醚共聚物、四氟化乙烯-六氟化丙烯共聚樹脂、四氟化乙烯-乙烯共聚物樹脂、三氟化氯化乙烯-乙烯共聚樹脂、氟化偏乙烯樹脂、三氟化氯化乙烯共聚樹脂及氟化乙烯樹脂等樹脂材料；鉻及鎳等金屬材料。Examples of non-metallic materials include polyethylene resin, polypropylene resin, polyethylene-polypropylene resin, tetrafluoroethylene resin, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene-hexafluoroethylene Fluorinated propylene copolymer resin, tetrafluoroethylene-ethylene copolymer resin, chlorinated ethylene trifluoride-ethylene copolymer resin, fluorinated vinylidene resin, chlorinated ethylene trifluoride copolymer resin and fluorinated ethylene resin and other resin materials; Metal materials such as chromium and nickel.

作為上述金屬材料，其中，鎳-鉻合金為較佳。作為鎳-鉻合金，並無特別限制，能夠使用公知的鎳-鉻合金。其中，鎳含量係40～75質量%且鉻含量係1～30質量%的鎳-鉻合金為較佳。作為鎳-鉻合金，例如可舉出赫史特合金（商品名，以下相同。）、蒙乃爾合金（商品名，以下相同）及英高鎳合金（商品名，以下相同）等。更具體而言，可舉出赫史特合金C-276（Ni含量63質量%、Cr含量16質量%）、赫史特合金-C（Ni含量60質量%、Cr含量17質量%）、赫史特合金C-22（Ni含量61質量%、Cr含量22質量%）等。又，鎳-鉻合金依據需要除了含有上述之合金以外，還可以含有硼、矽、鎢、鉬、銅及鈷等。Among the above-mentioned metal materials, nickel-chromium alloys are preferred. It does not specifically limit as a nickel-chromium alloy, A well-known nickel-chromium alloy can be used. Among them, a nickel-chromium alloy having a nickel content of 40 to 75 mass % and a chromium content of 1 to 30 mass % is preferable. Examples of the nickel-chromium alloy include Hearst (trade name, the same below), Monel (trade name, the same below), Inconel (trade name, the same below), and the like. More specifically, Hearst Alloy C-276 (Ni content 63 mass %, Cr content 16 mass %), Hearst Alloy-C (Ni content 60 mass %, Cr content 17 mass %), Stealloy C-22 (Ni content 61 mass %, Cr content 22 mass %) etc. Further, the nickel-chromium alloy may contain boron, silicon, tungsten, molybdenum, copper, cobalt, and the like, in addition to the above-mentioned alloys, if necessary.

作為對上述金屬材料進行電解研磨之方法，並無特別限制，能夠使用公知的方法。例如，能夠使用日本特開2015-227501號公報的[0011]-[0014]段及日本特開2008-264929號公報的[0036]-[0042]段等中所記載之方法。There is no restriction|limiting in particular as a method of electropolishing the said metal material, A well-known method can be used. For example, the methods described in paragraphs [0011] to [0014] of JP 2015-227501 A and paragraphs [0036] to [0042] of JP 2008-264929 A can be used.

另外，上述金屬材料可以進行拋光。拋光的方法並無特別限制，能夠使用公知的方法。用於精拋之研磨粒的尺寸並無特別限制，但是從上述金屬材料的表面的凹凸容易變得更小之方面而言，#400以下為較佳。另外，拋光在電解研磨之前進行為較佳。In addition, the above-mentioned metal materials may be polished. The method of polishing is not particularly limited, and a known method can be used. The size of the abrasive grains used for finish polishing is not particularly limited, but #400 or less is preferable because the unevenness of the surface of the metal material is easily reduced. In addition, polishing is preferably performed before electrolytic grinding.

[化學機械研磨方法] 本發明的一實施形態之化學機械研磨方法係包括如下步驟（以下，亦稱作「研磨步驟」。）之化學機械研磨方法（以下，亦稱作「CMP方法」。）：對安裝於研磨平台上之研磨墊，一邊供給上述研磨液，一邊使被研磨體的被研磨面與研磨墊接觸，使研磨體及研磨墊相對移動而研磨被研磨面，從而獲得已研磨的被研磨體。[Chemical Mechanical Polishing Method] The chemical mechanical polishing method according to one embodiment of the present invention is a chemical mechanical polishing method (hereinafter, also referred to as "CMP method") including the following steps (hereinafter, also referred to as "polishing step".) : For the polishing pad mounted on the polishing platform, while supplying the above-mentioned polishing liquid, the surface to be polished of the body to be polished is brought into contact with the polishing pad, and the polishing body and the polishing pad are moved relatively to polish the surface to be polished, thereby obtaining a polished surface. body to be ground.

[被研磨體] 作為能夠使用上述實施態樣之CMP方法之被研磨體，並無特別限制，含有選自包括鈷及鈷合金之組中之至少一種含鈷的層之被研磨體（帶金屬層基板）為較佳。作為上述鈷合金，並無特別限制，但是含有鎳之鈷合金為較佳。在鈷合金含有鎳之情況下，作為鎳的含量，在鈷合金總質量中係10質量%以下為較佳，1質量%以下為更佳，0.1質量%以下為進一步較佳，0.00001質量%以上為較佳。電極的形態亦可以是矽貫通電極。[Object to be polished] The body to be polished that can use the CMP method of the above-described embodiment is not particularly limited, and the body to be polished (with metal layer substrate) is preferred. The above-mentioned cobalt alloy is not particularly limited, but a cobalt alloy containing nickel is preferable. When the cobalt alloy contains nickel, the content of nickel in the total mass of the cobalt alloy is preferably 10 mass % or less, more preferably 1 mass % or less, further preferably 0.1 mass % or less, and 0.00001 mass % or more is better. The shape of the electrode may also be a through-silicon electrode.

作為在上述實施形態之CMP方法中使用之被研磨體，能夠藉由以下方法而製造。首先，在矽基板上積層二氧化矽等層間絕緣膜。接著，藉由抗蝕層形成、蝕刻等公知的方法，在層間絕緣膜表面形成規定圖案的凹部（基板露出部），設為包括凸部和凹部之層間絕緣膜。在該層間絕緣膜上作為沿著表面的凸凹覆蓋層間絕緣膜之阻擋層，藉由蒸鍍或CVD（chemical vapor deposition，化學氣相沉積）等對金屬或金屬氮化物（例如選自包括Ta、TaN、Ti、TiN、Ru及Mn之群組中的任一種金屬或金屬氮化物為較佳。）等進行成膜。進而，藉由蒸鍍、電鍍或CVD等形成以填充凹部的方式覆蓋阻擋層之由選自包括鈷及鈷合金之群組中的至少一種構成之含鈷的層（以下，亦稱為金屬層。）而獲得具有積層結構之被研磨體。層間絕緣膜、阻擋層及金屬層的厚度分別係0.01～2.0μm、1～100nm、0.01～2.5μm左右為較佳。作為構成上述阻擋層之材料，並無特別限制，能夠使用公知的低電阻的金屬材料。作為低電阻的合金材料，Ta、TaN、Ti、TiN、Ru及Mn為更佳。As a to-be-polished body used in the CMP method of the said embodiment, it can manufacture by the following method. First, an interlayer insulating film such as silicon dioxide is laminated on a silicon substrate. Next, concave portions (substrate exposed portions) of a predetermined pattern are formed on the surface of the interlayer insulating film by known methods such as resist formation and etching to form an interlayer insulating film including protrusions and concave portions. On the interlayer insulating film, as a barrier layer covering the interlayer insulating film along the surface convex and concave, by evaporation or CVD (chemical vapor deposition, chemical vapor deposition) or the like, metal or metal nitride (for example, selected from including Ta, Any metal or metal nitride in the group of TaN, Ti, TiN, Ru and Mn is preferable.) etc. to form a film. Furthermore, a cobalt-containing layer (hereinafter, also referred to as a metal layer) composed of at least one selected from the group consisting of cobalt and a cobalt alloy and covering the barrier layer so as to fill the recess is formed by evaporation, electroplating, CVD, or the like. .) to obtain a ground object with a layered structure. The thicknesses of the interlayer insulating film, the barrier layer, and the metal layer are preferably about 0.01 to 2.0 μm, 1 to 100 nm, and 0.01 to 2.5 μm, respectively. It does not specifically limit as a material which comprises the said barrier layer, A well-known low-resistance metal material can be used. As low-resistance alloy materials, Ta, TaN, Ti, TiN, Ru and Mn are more preferable.

（被研磨面）上述實施態樣之CMP方法中所使用之被研磨體中，被研磨面不特別限定。使用上述被研磨體之金屬配線的製造步驟中，因被研磨體中的阻擋層所含有之金屬原子與含鈷的層所含有之金屬原子彼此化學及物理性質不同，通常分成2階段來實施CMP。亦即，如上所述，在第1階段的步驟中實施對含鈷的層之CMP，在第2階段的步驟中實施對阻擋層之CMP。另外，在該第1階段的CMP過程中容易產生金屬配線過渡研磨之凹陷，在第2階段的CMP過程中容易產生上述凹陷及隨著上述凹陷細微的金屬配線緻密地配列之部位的絕緣膜（絕緣膜配置於各金屬配線之間。）過渡研磨之腐蝕。(Surface to be polished) In the body to be polished used in the CMP method of the above-described embodiment, the surface to be polished is not particularly limited. In the manufacturing process of the metal wiring using the above-mentioned object to be polished, since the chemical and physical properties of the metal atoms contained in the barrier layer in the object to be polished and the metal atoms contained in the cobalt-containing layer are different from each other, CMP is usually carried out in two stages. . That is, as described above, the CMP of the cobalt-containing layer is performed in the steps of the first stage, and the CMP of the barrier layer is performed in the steps of the second stage. In addition, in the CMP process of the first stage, pits due to over-polishing of the metal wiring are likely to occur, and in the CMP process of the second stage, the pits and the insulating film ( The insulating film is arranged between the metal wirings.) Corrosion by over-polishing.

[研磨裝置] 作為能夠實施上述CMP方法之研磨裝置，並無特別限制，能夠使用公知的化學機械研磨裝置（以下，亦稱作「CMP裝置」。）。作為CMP裝置，能夠使用例如通常的CMP裝置，該CMP裝置具備保持具有被研磨面之被研磨體（例如，半導體基板等）之支架和貼附研磨墊之（安裝有轉速可變之馬達等）研磨平台。作為市售品，能夠使用例如Reflexion（Applied Materials,Inc.製造）。[Polishing Apparatus] There is no particular limitation as a polishing apparatus capable of implementing the above-mentioned CMP method, and a known chemical mechanical polishing apparatus (hereinafter, also referred to as "CMP apparatus") can be used. As a CMP apparatus, for example, a general CMP apparatus can be used, which is provided with a holder for holding a to-be-polished body (for example, a semiconductor substrate, etc.) having a surface to be polished, and a polishing pad (with a variable-speed motor, etc.) attached thereto. Grinding platform. As a commercial item, for example, Reflexion (manufactured by Applied Materials, Inc.) can be used.

＜研磨壓力＞在上述實施形態之CMP方法中，以研磨壓力亦即在被研磨面與研磨墊的接觸面產生之壓力3000～25000Pa進行研磨為較佳，以6500～14000Pa進行研磨為更佳。<Polishing pressure> In the CMP method of the above-mentioned embodiment, the polishing pressure, that is, the pressure generated at the contact surface between the surface to be polished and the polishing pad, is preferably 3000 to 25000 Pa, and more preferably 6500 to 14000 Pa.

＜研磨平台的轉速＞上述實施態樣之CMP方法中，以研磨平台的轉速係50～200rpm進行研磨為較佳，以60～150rpm進行研磨為更佳。另外，為了使研磨體及研磨墊相對移動，進而，可以使支架旋轉和/或擺動，亦可以使研磨平台進行行星旋轉，亦可以使帶狀研磨墊沿長尺寸方向的一者以直線狀移動。另外，支架可以是固定、旋轉或擺動中的任意狀態。該等研磨方法只要使研磨體及研磨墊相對移動，則能夠依據被研磨面和/或研磨裝置而適當地選擇。<Rotational speed of the polishing table> In the CMP method of the above-described embodiment, the polishing is preferably performed at a rotation speed of the polishing table at 50 to 200 rpm, and more preferably at 60 to 150 rpm. In addition, in order to relatively move the polishing body and the polishing pad, the holder may be rotated and/or oscillated, the polishing platform may be planetary rotated, or the belt-shaped polishing pad may be moved linearly in one of the longitudinal directions. . In addition, the bracket can be in any state of being fixed, rotating or swinging. These polishing methods can be appropriately selected depending on the surface to be polished and/or the polishing apparatus as long as the polishing body and the polishing pad are relatively moved.

＜研磨液的供給方法＞在上述實施形態之CMP方法中，在研磨被研磨面期間，用泵等將研磨液連續供給到研磨平台上的研磨墊。對該供給量沒有限制，但研磨墊的表面始終被研磨液包覆為較佳。另外，關於研磨液的態樣，如上所述。<Method of Supplying Polishing Liquid> In the CMP method of the above-described embodiment, the polishing liquid is continuously supplied to the polishing pad on the polishing table by a pump or the like while the surface to be polished is polished. The supply amount is not limited, but it is preferable that the surface of the polishing pad is always covered with the polishing liquid. In addition, the aspect of the polishing liquid is as described above.

作為上述實施態樣之CMP方法，在上述研磨步驟之前，還可以包括以下步驟。作為上述步驟，例如可舉出對含有締合度1～3的膠體二氧化矽、有機酸、唑系化合物及過氧化氫之研磨液原液混合水之步驟。另外，研磨液、研磨液原液及濃縮液的態樣與已說明內容相同。 [實施例]As the CMP method of the above-mentioned embodiment, before the above-mentioned polishing step, the following steps may be further included. As the above-mentioned step, for example, a step of mixing water with a polishing liquid stock solution containing colloidal silica having an association degree of 1 to 3, an organic acid, an azole-based compound, and hydrogen peroxide can be mentioned. In addition, the aspect of the polishing liquid, the polishing liquid stock solution, and the concentrated liquid is the same as that described above. [Example]

以下，依據實施例對本發明進而詳細地進行說明。以下實施例所示之材料、使用量、比例、處理內容及處理步驟等只要不脫離本發明的主旨便能夠適當地變更。從而，本發明的範圍並非係被以下所示之實施例限定地解釋者。另外，只要無特別說明，「%」係指「質量%」，「ppb」係指「質量ppb」。Hereinafter, the present invention will be described in further detail based on examples. The materials, usage amounts, ratios, processing contents, processing steps, and the like shown in the following examples can be appropriately changed without departing from the gist of the present invention. Therefore, the scope of the present invention is not to be construed as being limited by the embodiments shown below. In addition, unless otherwise specified, "%" means "mass %", and "ppb" means "mass ppb".

[原料等的純化] 以下所示之各實施例中所使用之各原料、各觸媒使用純度99質量%以上的高純度品級，進而在事先藉由蒸餾、離子交換、過濾等進行純化。[Purification of raw materials, etc.] Each raw material and each catalyst used in the following examples were purified by distillation, ion exchange, filtration, etc. using high-purity grades with a purity of 99% by mass or more.

用於製備各研磨液之超純水藉由日本特開2007-254168號公報中所記載之方法進行了純化。之後，藉由基於後述之SNP-ICP-MS法之測量確認到Na、Ca及Fe的各自的元素的含量相對於各藥液的總質量小於10質量ppt之後使用。The ultrapure water used for preparing each polishing liquid was purified by the method described in Japanese Patent Laid-Open No. 2007-254168. Then, it was used after confirming that the content of each element of Na, Ca, and Fe was less than 10 mass ppt with respect to the total mass of each chemical solution by measurement by the SNP-ICP-MS method described later.

各實施例及比較例的研磨液的製備、填充、保管及分析均在滿足ISO級別2以下之水平的無塵室中進行。又，各實施例及比較例中所使用之容器用各自的實施例或比較例的研磨液清洗之後使用。為了提高測量精度，關於金屬成分的含量的測量及水的含量的測量，在通常的測量中處於檢測限界以下的測量，以體積換算濃縮成100分之1而進行測量，並換算成濃縮前的研磨液的濃度來進行含量的計算。The preparation, filling, storage, and analysis of the polishing liquids of the respective Examples and Comparative Examples were all performed in a clean room satisfying ISO class 2 or lower. In addition, the container used in each Example and the comparative example was used after washing|cleaning with the polishing liquid of each Example or the comparative example. In order to improve the measurement accuracy, the measurement of the content of the metal component and the measurement of the water content, in the normal measurement, the measurement below the detection limit, the volume conversion is concentrated to 1/100, and the measurement is carried out, and converted into the concentration before concentration. The concentration of the polishing liquid is used to calculate the content.

[實施例1A] 將下述所示之各成分進行混合，製備出化學機械研磨液。・膠體二氧化矽（締合度：2、平均一次粒徑：35nm、產品名「PL3」、FUSO CHEMICAL CO.,LTD.製造）0.1質量% ・甘胺酸（相當於胺基酸。）1.5質量% ・5-甲基苯并***（相當於含有苯并***骨架之唑類化合物。）0.001質量% ・3-胺基-1,2,4-***（相當於不含有苯并***骨架之化合物，並且含有1,2,4-***骨架之化合物。）0.2質量% ・乙二醇（相當於有機溶劑，一部分作為溶解5-甲基苯并***之溶劑而使用。）0.05質量% ・過氧化氫（相當於氧化劑。）1.0質量% ・水（純水）殘餘部分[Example 1A] The components shown below were mixed to prepare a chemical mechanical polishing liquid.・Colloidal silica (degree of association: 2, average primary particle size: 35 nm, product name "PL3", manufactured by FUSO CHEMICAL CO., LTD.) 0.1 mass% ・Glycine (equivalent to amino acid.) 1.5 mass % ・5-Methylbenzotriazole (corresponds to an azole compound containing a benzotriazole skeleton.) 0.001 mass% ・3-amino-1,2,4-triazole (corresponds to no benzotriazole A compound of an azole skeleton, and a compound containing a 1,2,4-triazole skeleton.) 0.2% by mass ・Ethylene glycol (corresponding to an organic solvent, and a part of it was used as a solvent for dissolving 5-methylbenzotriazole.) 0.05% by mass ・Hydrogen peroxide (equivalent to oxidizing agent.) 1.0% by mass ・Residual portion of water (pure water)

另外，表1中的研磨液的pH，依據需要，使用硫酸和/或氫氧化鉀調整成規定值。In addition, the pH of the polishing liquid in Table 1 was adjusted to a predetermined value using sulfuric acid and/or potassium hydroxide as needed.

另外，本實施例中，「表1」係指表1A1、表1A2、表1B1、表1B2、表1C1、表1C2、表1D1、表1D2。In addition, in this Example, "Table 1" means Table 1A1, Table 1A2, Table 1B1, Table 1B2, Table 1C1, Table 1C2, Table 1D1, Table 1D2.

[實施例2A～83A、比較例1A～5A] 將表1所示之各成分，藉由與實施例1A相同的方法進行混合而獲得了各研磨液。另外，表1中的各縮寫符號表示以下化合物等。・PL3（膠體二氧化矽，產品名「PL3」、FUSO CHEMICAL CO.,LTD.製造，締合度：2、平均一次粒徑：35nm。）・PL2（膠體二氧化矽，產品名「PL2」、FUSO CHEMICAL CO.,LTD.製造，締合度：2、平均一次粒徑：25nm。）・PL3L（膠體二氧化矽，產品名「PL3L」、FUSO CHEMICAL CO.,LTD.製造，締合度：1、平均一次粒徑：35nm。）・PL3H（膠體二氧化矽，產品名「PL3H」、FUSO CHEMICAL CO.,LTD.製造，締合度：3、平均一次粒徑：35nm。）・ST-PS-MO（膠體二氧化矽、產品名「ST-PS-MO」、NISSAN CHEMICAL INDUSTRIES. LTD.製造，締合度：大於3、平均一次粒徑：20nm。）・Gly（甘胺酸，相當於胺基酸。）・Ala（丙胺酸，相當於胺基酸。）・Asp（天冬胺酸，相當於胺基酸。）・NMG（N-甲基甘胺酸，相當於胺基酸。）・5-MBTA（5-甲基苯并***，相當於具有苯并***骨架之唑系化合物。）・BTA（苯并***，相當於具有苯并***骨架之唑系化合物。）・5,6-DMBTA（5,6-二甲基苯并***，相當於含有苯并***骨架之唑系化合物。）・5-ABTA（5-胺基苯并***，相當於含有苯并***骨架之唑系化合物。）・3-AT（3-胺基-1,2,4-***，相當於不含有苯并***骨架之唑系化合物、且含有1,2,4-***骨架之唑系化合物。）・1,2,4-三（1,2,4-***，相當於不含有苯并***骨架之唑系化合物、且含有1,2,4-***骨架之唑系化合物。）・3,5-DP（3,5-二甲基吡唑，相當於不含有苯并***骨架之唑系化合物、且含有吡唑骨架之唑系化合物（吡唑系化合物）。）・Pyraz（吡唑，相當於不含有苯并***骨架之唑系化合物且含有吡唑骨架之唑系化合物。）・Imidaz（咪唑，相當於不含有苯并***骨架之唑系化合物、且含有咪唑骨架之唑系化合物（咪唑系化合物）。）・5-ATZ（5-胺基四氮唑，相當於不含有苯并***骨架之唑系化合物。）・ETG（乙二醇，相當於有機溶劑。）・EtOH（乙醇，相當於有機溶劑。）・PG（丙二醇，相當於有機溶劑。）・4-HA（4-羥基苯甲酸，相當於有機酸。）・2-HA（2-羥基苯甲酸，相當於有機酸。）・PA（鄰苯二甲酸，相當於有機酸。）・SA（水楊酸，相當於有機酸。）・Ant（鄰胺苯甲酸，相當於有機酸。）・TMT（1,2,4-苯三甲酸，相當於有機酸。）・N-cocoyl sarcosinate（N-椰油醯基肌胺酸鹽，相當於鈷防腐劑。）・N-lauroyl sarcosinate（N-月桂醯肌胺酸鹽，相當於鈷防腐劑。）・N-oleoyl sarcosinate（N-油醯肌胺酸鹽，相當於鈷防腐劑。）・N-myristoyl sarcosinate（N-肉荳蔻醯肌胺酸鹽，相當於鈷防腐劑。）・N-myristoyl glycine（N-肉荳蔻醯甘胺酸，相當於鈷防腐劑。）・N-stearoyl sarcosinate（N-硬脂醯肌胺酸鹽，相當於鈷防腐劑。）・N-lauroyl glycine（N-月桂醯甘胺酸，相當於鈷防腐劑。）・N-palmitoyl glycine（N-棕櫚醯甘胺酸，相當於鈷防腐劑。）・N-lauroyl glutamate（N-月桂醯谷胺酸，相當於鈷防腐劑。）・N-cocoyl glutamate（N-椰油醯谷胺酸，相當於鈷防腐劑。）・potassium N-cocoyl glutamate（N-椰油醯谷胺酸鉀，相當於鈷防腐劑。）・potassium N-lauroyl sarcosinate（N-月桂醯肌胺酸鉀，相當於鈷防腐劑。）・N-lauroyl alaninate（N-月桂醯丙胺酸鹽，相當於鈷防腐劑。）・N-myristoyl alaninate（N-肉荳蔻醯丙胺酸鹽，相當於鈷防腐劑。）・potassium N-cocoyl alaninate（N-椰油丙胺酸鉀，相當於鈷防腐劑。）・RE-610（產品名「Rhodafac RE-610」，Rhodia Inc.製造，相當於表面活性劑。）・MD-20（產品名「Surfynol MD-20」，Air Products and Chemicals,Inc.製造，相當於表面活性劑。）・DBSH（十二烷基苯磺酸，相當於表面活性劑。）・PHEAA（N-（2-羥乙基）丙烯醯胺聚合物、重均分子量20000，相當於親水性聚合物。）・PAA（聚丙烯酸、相當於親水性聚合物。）・PEIEO（具有包含由下述式表示之重複單元之氧化乙烯鏈之聚乙亞胺、HLB值18）[Examples 2A to 83A and Comparative Examples 1A to 5A] The respective components shown in Table 1 were mixed by the same method as in Example 1A to obtain respective polishing liquids. In addition, each abbreviation in Table 1 represents the following compounds and the like.・PL3 (Colloidal silica, product name "PL3", manufactured by FUSO CHEMICAL CO., LTD., degree of association: 2, average primary particle size: 35 nm.) ・PL2 (Colloidal silica, product name "PL2", Manufactured by FUSO CHEMICAL CO., LTD., degree of association: 2, average primary particle size: 25 nm.) ・PL3L (colloidal silica, product name "PL3L", manufactured by FUSO CHEMICAL CO., LTD., degree of association: 1, Average primary particle size: 35nm.) ・PL3H (Colloidal silica, product name "PL3H", manufactured by FUSO CHEMICAL CO., LTD., degree of association: 3, average primary particle size: 35nm.) ・ST-PS-MO (Colloidal silica, product name "ST-PS-MO", manufactured by NISSAN CHEMICAL INDUSTRIES. LTD., degree of association: more than 3, average primary particle size: 20 nm.) ・Gly (glycine, equivalent to amino acid) .) ・Ala (Alanine, equivalent to amino acid.) ・Asp (Aspartic acid, equivalent to amino acid.) ・NMG (N-methylglycine, equivalent to amino acid.) ・5 -MBTA (5-methylbenzotriazole, equivalent to an azole compound having a benzotriazole skeleton.) ・BTA (benzotriazole, equivalent to an azole compound having a benzotriazole skeleton.) ・5 ,6-DMBTA (5,6-dimethylbenzotriazole, equivalent to an azole compound containing a benzotriazole skeleton.) ・5-ABTA (5-aminobenzotriazole, equivalent to a benzotriazole containing An azole-based compound with a triazole skeleton.) ・3-AT (3-amino-1,2,4-triazole, equivalent to an azole-based compound not containing a benzotriazole skeleton and containing 1,2,4- An azole-based compound with a triazole skeleton.) ・1,2,4-tris (1,2,4-triazole corresponds to an azole-based compound that does not contain a benzotriazole skeleton and contains 1,2,4-triazole An azole-based compound with an azole skeleton.) ・3,5-DP (3,5-dimethylpyrazole, equivalent to an azole-based compound without a benzotriazole skeleton and an azole-based compound with a pyrazole skeleton (pyrazole) azole-based compound).) ・Pyraz (pyrazole, equivalent to an azole-based compound that does not contain a benzotriazole skeleton and an azole-based compound that contains a pyrazole skeleton.) ・Imidaz (imidazole, equivalent to an azole-based compound that does not contain a benzotriazole skeleton.) azole-based compound containing an imidazole skeleton (imidazole-based compound).) ・5-ATZ (5-aminotetrazole, equivalent to an azole-based compound that does not contain a benzotriazole skeleton.) ・ETG (Ethylene glycol, equivalent to an organic solvent.) ・EtOH (Ethanol, equivalent to an organic solvent.) ・PG (Propylene glycol, equivalent to an organic solvent.) ・4-HA (4-hydroxybenzoic acid, equivalent to an organic acid.)・2-HA (2-hydroxybenzoic acid, equivalent to organic acid.) ・PA (Phthalic acid, equivalent to organic acid. ) ・SA (Salicylic acid, equivalent to an organic acid.) ・Ant (Anthranilic acid, equivalent to an organic acid.) ・TMT (1,2,4-benzenetricarboxylic acid, equivalent to an organic acid.) ・N- cocoyl sarcosinate (N-cocoyl sarcosinate, equivalent to cobalt preservative.) ・N-lauroyl sarcosinate (N-lauroyl sarcosinate, equivalent to cobalt preservative.) ・N-oleoyl sarcosinate (N -Oleosinate, equivalent to a cobalt preservative.) ・N-myristoyl sarcosinate (N-myristoyl sarcosinate, equivalent to a cobalt preservative.) ・N-myristoyl glycine (N-myristoyl glycine Amino acid, equivalent to cobalt preservative.) ・N-stearoyl sarcosinate (N-stearoyl sarcosinate, equivalent to cobalt preservative.) ・N-lauroyl glycine (N-lauroylglycine, equivalent to cobalt preservative.) ・N-palmitoyl glycine (N-palmitoyl glycine, equivalent to cobalt preservative.) ・N-lauroyl glutamate (N-lauroyl glutamate, equivalent to cobalt preservative.) ・N-cocoyl glutamate (N-cocoglutamate, equivalent to cobalt preservative.) ・potassium N-cocoyl glutamate (potassium N-cocoglutamate, equivalent to cobalt preservative.) ・potassium N-lauroyl sarcosinate (N -Potassium lauroyl sarcosinate, equivalent to cobalt preservative.) ・N-lauroyl alaninate (N-lauroyl alaninate, equivalent to cobalt preservative.) ・N-myristoyl alaninate (N-myristoyl alaninate , equivalent to a cobalt preservative.) ・potassium N-cocoyl alaninate (potassium N-cocoalanine, equivalent to a cobalt preservative.) ・RE-610 (product name "Rhodafac RE-610", manufactured by Rhodia Inc., equivalent for surfactant.) ・MD-20 (product name "Surfynol MD-20", manufactured by Air Products and Chemicals, Inc., equivalent to surfactant.) ・DBSH (dodecylbenzenesulfonic acid, equivalent to surface Active agent.) ・PHEAA (N-(2-hydroxyethyl)acrylamide polymer, weight average molecular weight 20,000, equivalent to a hydrophilic polymer.) ・PAA (polyacrylic acid, equivalent to a hydrophilic polymer.) ・PEIEO (polyethyleneimine having an ethylene oxide chain comprising repeating units represented by the following formula, HLB value 18)

[化學式2]

[Chemical formula 2]

[實施例1B] 將下述所示之各成分進行混合，製備出化學機械研磨液。・膠體二氧化矽（締合度：2、平均一次粒徑：35nm、產品名「PL3」、FUSO CHEMICAL CO.,LTD.製造）3.0質量% ・CA（檸檬酸，相當於有機酸。）0.003質量% ・Male（順丁烯二酸，相當於有機酸。）0.05質量% ・苯并***（相當於含有苯并***骨架之唑系化合物。）0.1質量% 3-胺基-1,2,4-***（相當於不含有苯并***骨架之化合物且含有1,2,4-***骨架之化合物。）0.05質量% ・過氧化氫（相當於氧化劑。）1.0質量% ・乙二醇（相當於有機溶劑，一部分作為溶解5-甲基苯并***之溶劑而使用。）0.05質量% ・水（純水）殘餘部分[Example 1B] The components shown below were mixed to prepare a chemical mechanical polishing liquid.・Colloidal silica (degree of association: 2, average primary particle size: 35 nm, product name "PL3", manufactured by FUSO CHEMICAL CO., LTD.) 3.0 mass% ・CA (citric acid, equivalent to organic acid.) 0.003 mass % ・Male (maleic acid, equivalent to an organic acid.) 0.05 mass% ・benzotriazole (corresponding to an azole-based compound containing a benzotriazole skeleton.) 0.1 mass% 3-amino-1,2 ,4-triazole (corresponds to a compound that does not contain a benzotriazole skeleton and contains a 1,2,4-triazole skeleton.) 0.05% by mass ・Hydrogen peroxide (corresponds to an oxidizing agent.) 1.0% by mass ・B Diol (corresponds to an organic solvent, and a part is used as a solvent for dissolving 5-methylbenzotriazole.) 0.05 mass % ・Water (pure water) residue

另外，表2中的研磨液的pH依據需要使用硫酸和/或氫氧化鉀調整成特定的值。In addition, the pH of the polishing liquid in Table 2 was adjusted to a specific value using sulfuric acid and/or potassium hydroxide as needed.

另外，本實施例中，「表2」表示表2A1、表2A2、表2A3、表2B1、表2B2、表2B3、表2C1、表2C2、表2C3、表2D1、表2D2、表2D3。In addition, in this Example, "Table 2" means Table 2A1, Table 2A2, Table 2A3, Table 2B1, Table 2B2, Table 2B3, Table 2C1, Table 2C2, Table 2C3, Table 2D1, Table 2D2, Table 2D3.

[實施例2B～82B、比較例1B～3B] 將表2所示之各成分，藉由與實施例1B相同的方法進行混合而獲得了各研磨液。表2中的各簡稱表示以下的化合物等。另外，關於表2中的各簡稱中與表1中的簡稱相同，如上所述。・CA（檸檬酸，相當於有機酸。）・琥珀酸（相當於有機酸。）・蘋果酸（相當於有機酸。）・丙二酸（相當於有機酸。）・Male（順丁烯二酸，相當於有機酸。）[Examples 2B to 82B and Comparative Examples 1B to 3B] Each of the components shown in Table 2 was mixed by the same method as in Example 1B to obtain each polishing liquid. Each abbreviation in Table 2 represents the following compounds and the like. In addition, the abbreviations in Table 2 are the same as those in Table 1, as described above.・CA (citric acid, equivalent to organic acid.) ・Succinic acid (equivalent to organic acid.) ・Malic acid (equivalent to organic acid.) ・malonic acid (equivalent to organic acid.) ・Male (equivalent to organic acid.) acid, equivalent to organic acid.)

[CMP前後的膠體二氧化矽的平均粒徑比（T2）的測量] 藉由下述方法，測量CMP前後的膠體二氧化矽的平均粒徑，藉由下述式（2）求出了CMP前後的膠體二氧化矽的平均粒徑比（T2）。將結果示於表1及表2。＜＜測量條件＞＞使用粒度分佈儀SALD-2300（Shimadzu Corporation製造），測量CMP前的研磨液中的研磨粒子的粒度分佈而求出了平均粒徑。又，回收CMP後的研磨液，關於上述回收後的研磨液中的研磨粒子亦藉由相同的方法求出了其平均粒徑。使用所獲得之數值，計算出由下述式獲得之T2。式（2）： T2=化學機械研磨後的平均粒徑/化學機械研磨前的平均粒徑[Measurement of the average particle size ratio (T2) of colloidal silica before and after CMP] The average particle size of colloidal silica before and after CMP was measured by the following method, and CMP was obtained by the following formula (2) Average particle size ratio (T2) of colloidal silica before and after. The results are shown in Table 1 and Table 2. <<Measurement Conditions>> Using a particle size distribution analyzer SALD-2300 (manufactured by Shimadzu Corporation), the particle size distribution of the abrasive particles in the polishing liquid before CMP was measured, and the average particle diameter was obtained. In addition, the polishing liquid after CMP was recovered, and the average particle diameter of the polishing particles in the polishing liquid after the recovery was determined by the same method. Using the obtained numerical values, T2 obtained by the following formula was calculated. Formula (2): T2=average particle size after chemical mechanical polishing/average particle size before chemical mechanical polishing

[反應層厚度的測量] ＜將鈷的模型膜設為被研磨面之情況的的反應層的厚度的測量＞將沉積有厚度1500nm的鈷之矽基板裁剪成約10mm見方的基板，將其浸漬於加入了10mL上述的研磨液之內容積約100mL的聚乙烯瓶中，在室溫（約25℃）下靜置24小時。在浸漬之後，對從研磨液取出之試樣進行水洗，進而，使用氮氣進行風乾，從而獲得在鈷表面上形成有反應層之試樣。關於該試樣，在下述所示之測量條件下，進行基於聚焦離子束加工裝置（FIB：Focused Ion Beam）之剖面形成加工及基於掃描電子顯微鏡（SEM）之剖面觀察，測量出反應層的厚度。結果示於表1及表2中。（FIB加工條件）裝置：Hitachi,Ltd.製造 FB-2000A型加速電壓：30kV 預處理：鉑濺射塗層→碳蒸鍍→鎢鍍層（SEM測量條件）裝置：Hitachi,Ltd.製造S-900型加速電壓：3kV 預處理：鉑濺射塗層[Measurement of the thickness of the reaction layer] <Measurement of the thickness of the reaction layer when the model film of cobalt is used as the surface to be polished> The silicon substrate on which the cobalt with a thickness of 1500 nm is deposited is cut out into a substrate of about 10 mm square, and it is immersed in 10 mL of the above-mentioned grinding liquid was added to a polyethylene bottle having an inner volume of about 100 mL, and the solution was left to stand at room temperature (about 25° C.) for 24 hours. After the immersion, the sample taken out from the polishing solution was washed with water, and then air-dried with nitrogen to obtain a sample in which a reaction layer was formed on the cobalt surface. About this sample, under the measurement conditions shown below, cross-sectional formation processing by a focused ion beam processing apparatus (FIB: Focused Ion Beam) and cross-sectional observation by a scanning electron microscope (SEM) were performed, and the thickness of the reaction layer was measured. . The results are shown in Table 1 and Table 2. (FIB processing conditions) Apparatus: FB-2000A manufactured by Hitachi, Ltd. Accelerating voltage: 30 kV Pretreatment: platinum sputter coating → carbon vapor deposition → tungsten coating (SEM measurement conditions) Apparatus: S-900 manufactured by Hitachi, Ltd. Type accelerating voltage: 3kV Pretreatment: Platinum sputter coating

＜將選自包括Ta、TaN、Ti、TiN、Ru及Mn之群組中的任一種模型膜設為被研磨面之情況的反應層的厚度的測量＞將沉積有厚度1500nm的Ta之矽基板裁剪成約10mm見方的基板，將其浸漬於加入了10mL上述的研磨液之內容積約100mL的聚乙烯瓶中，在室溫（約25℃）下靜置24小時。在浸漬之後，對從研磨液取出之試樣進行水洗，進而，使用氮氣進行風乾，從而獲得在Ta表面上形成有反應層之試樣。關於該試樣，在下述所示之測量條件下，進行基於聚焦離子束加工裝置（FIB：Focused Ion Beam）之剖面形成加工及基於掃描電子顯微鏡（SEM）之剖面觀察，測量出反應層的厚度。結果示於表1及表2中。又，關於TaN、Ti、TiN、Ru及Mn的各金屬，亦藉由與上述相同的方法製作了模型膜，從而測量出各反應層的厚度（結果示於表1及表2。）。<Measurement of the thickness of the reaction layer when any model film selected from the group consisting of Ta, TaN, Ti, TiN, Ru, and Mn is used as the surface to be polished> A silicon substrate on which Ta with a thickness of 1500 nm is deposited The substrate was cut out to a square of about 10 mm, immersed in a polyethylene bottle with an inner volume of about 100 mL containing 10 mL of the above-mentioned polishing liquid, and left to stand at room temperature (about 25° C.) for 24 hours. After the immersion, the sample taken out from the polishing liquid was washed with water, and then air-dried using nitrogen gas to obtain a sample in which a reaction layer was formed on the Ta surface. About this sample, under the measurement conditions shown below, cross-sectional formation processing by a focused ion beam processing apparatus (FIB: Focused Ion Beam) and cross-sectional observation by a scanning electron microscope (SEM) were performed, and the thickness of the reaction layer was measured. . The results are shown in Table 1 and Table 2. Moreover, about each metal of TaN, Ti, TiN, Ru, and Mn, the model film was produced by the same method as the above, and the thickness of each reaction layer was measured (results are shown in Table 1 and Table 2.).

＜將選自包括SiOx及SiOC之群組中的任一種模型膜設為被研磨面之情況的反應層的厚度的測量＞將沉積有厚度1500nm的SiOx之矽基板裁剪成約10mm見方的基板，將其浸漬於加入了10mL上述的研磨液之內容積約100mL的聚乙烯瓶中，在室溫（約25℃）下靜置24小時。在浸漬之後，對從研磨液取出之試樣進行水洗，進而，使用氮氣進行風乾，從而獲得在SiOx表面上形成有反應層之試樣。關於該試樣，在下述所示之測量條件下，進行基於聚焦離子束加工裝置（FIB：Focused Ion Beam）之剖面形成加工及基於掃描電子顯微鏡（SEM）之剖面觀察，測量出反應層的厚度。結果示於表2中。又，關於SiOC，亦藉由與上述相同的方法製作了模型膜，測量出反應層的厚度（結果示於表2中。）。<Measurement of the thickness of the reaction layer when any model film selected from the group consisting of SiOx and SiOC is used as the surface to be polished> The silicon substrate on which SiOx with a thickness of 1500 nm is deposited is cut into a substrate of about 10 mm square, and the This was immersed in a polyethylene bottle having an inner volume of about 100 mL to which 10 mL of the above-mentioned polishing liquid was added, and was allowed to stand at room temperature (about 25° C.) for 24 hours. After the immersion, the sample taken out from the polishing liquid was washed with water, and then air-dried using nitrogen gas to obtain a sample in which a reaction layer was formed on the SiOx surface. About this sample, under the measurement conditions shown below, cross-sectional formation processing by a focused ion beam processing apparatus (FIB: Focused Ion Beam) and cross-sectional observation by a scanning electron microscope (SEM) were performed, and the thickness of the reaction layer was measured. . The results are shown in Table 2. In addition, regarding SiOC, a model film was produced by the same method as above, and the thickness of the reaction layer was measured (the results are shown in Table 2).

[各種定量] ＜通式（1）所表示之化合物的含量＞關於在各實施例及比較例中製作之研磨液中所含有之通式（1）所表示之化合物的含量，使用氣相色譜質量分析裝置（產品名「GCMS-2020」、SHIMADZU CORPORATION製造）來進行測量。以下，示出測量條件。另外，關於基於氣相色譜分析質量分析裝置之定量，向研磨液添加氟化氫使研磨粒子完全溶解，之後使用將pH調整成10以上之試樣來實施。[Various Quantifications] <Content of the compound represented by the general formula (1)> About the content of the compound represented by the general formula (1) contained in the polishing liquid prepared in each Example and Comparative Example, a gas chromatograph was used. The mass spectrometer (product name "GCMS-2020", manufactured by SHIMADZU CORPORATION) was used for measurement. Below, measurement conditions are shown. In addition, the quantitative determination by gas chromatography mass spectrometer was performed by adding hydrogen fluoride to the polishing liquid to completely dissolve the polishing particles, and then using a sample whose pH was adjusted to 10 or more.

＜＜測量條件＞＞毛細管柱：InertCap5MS/NP0.25mmI.D.×30mdf=0.25μm 試樣導入法：分流75kPa壓力恆定氣化室溫度：230℃ 管柱烘箱溫度：80℃（2min）-500℃（13min）升溫速度15℃/min 載氣：氦氣隔墊吹掃流量：5mL/min 分流比：25:1 接口溫度：250℃ 離子源溫度：200℃ 測量模式：Scanm/z=85～500 試樣導入量：1μL＜＜Measurement conditions＞ Capillary column: InertCap5MS/NP0.25mmI.D.×30mdf=0.25μm ℃ (13min) heating rate 15℃/min Carrier gas: Helium gas septum purge flow: 5mL/min Split ratio: 25:1 Interface temperature: 250℃ Ion source temperature: 200℃ Measurement mode: Scanm/z=85～ 500 Sample introduction volume: 1 μL

＜特定金屬原子的含量＞（金屬雜質中所含有之特定金屬原子的含量）關於在各實施例及比較例中製作之研磨液中的金屬雜質中所含有之特定金屬原子的含量，使用Agilent8800三重四極ICP-MS（半導體分析用、選項#200）來進行測量。<Content of specific metal atoms> (Content of specific metal atoms contained in metal impurities) For the content of specific metal atoms contained in metal impurities in the polishing liquids prepared in each of the Examples and Comparative Examples, Agilent 8800 Triplex was used. Measurements were performed by quadrupole ICP-MS (for semiconductor analysis, option #200).

＜＜測量條件＞＞樣品導入系統使用了石英火炬與同軸型PFA（全氟烷氧基鏈烷）霧化器（自吸用）及鉑錐接口。冷電漿條件的測量參數如以下所述。・RF（RadioFrequency）輸出（W）：600 ・載氣流量（L/min）：0.7 ・尾吹氣流量（L/min）：1 ・取樣深度（mm）：18<<Measurement conditions>> The sample introduction system used a quartz torch, a coaxial PFA (perfluoroalkoxyalkane) nebulizer (for self-priming) and a platinum cone interface. Measurement parameters for cold plasma conditions are as follows.・RF (RadioFrequency) output (W): 600 ・Carrier gas flow rate (L/min): 0.7 ・Makeup gas flow rate (L/min): 1 ・Sampling depth (mm): 18

（金屬粒子中所含有之特定金屬原子的含量）・基於SNP-ICP-MS（Single NanoParticle-Inductively Coupled Plasma-Mass Spectrometry，單奈米粒子感應耦合電漿質譜儀）之測量關於金屬粒子中所含有之特定金屬原子的含有率，使用PerkinElmer Co., Ltd.製造「Nexion350S」來進行測量。另外，關於基於SNP-ICP-MS之定量，向研磨液添加氟化氫使研磨粒子完全溶解，之後使用將pH調整成10以上之試樣進行了實施。 1）標準物質的準備關於標準物質，向清洗的玻璃容器內稱量加入超純水，將中位數直徑50nm的測量對象金屬粒子成為10000個/ml的濃度的方式添加之後，將用超聲波清洗機處理30分鐘之分散液用作傳輸效率測量用標準物質。 2）測量條件使用PFA製同軸型霧化器、石英製旋流型噴霧室、石英製內徑1mm火炬噴射器，以約0.2mL/min吸引測量對象液。氧添加量以0.1L/min進行了電漿輸出1600W、基於氨氣之清洗。時間解析度以50us進行了解析。 3）關於金屬粒子中所含有之特定金屬原子的含量，使用製造商配件的下述解析軟件而檢測。・金屬粒子中所含有之特定金屬原子的含量：奈米粒子分析「SNP-ICP-MS」專用Syngistix奈米應用模塊(Content of specific metal atoms contained in metal particles) ・Measurement based on SNP-ICP-MS (Single NanoParticle-Inductively Coupled Plasma-Mass Spectrometry) The content of the specific metal atom was measured using "Nexion 350S" manufactured by PerkinElmer Co., Ltd. In addition, regarding the quantitative determination by SNP-ICP-MS, hydrogen fluoride was added to the polishing liquid to completely dissolve the polishing particles, and then the pH was adjusted to 10 or more, and the measurement was carried out using a sample. 1) Preparation of reference material For the reference material, ultrapure water is weighed into a cleaned glass container, and the metal particles to be measured with a median diameter of 50 nm are added to a concentration of 10,000 particles/ml, and then cleaned with ultrasonic waves. The dispersion liquid treated by machine for 30 minutes was used as a standard substance for the measurement of transmission efficiency. 2) Measurement conditions A coaxial atomizer made of PFA, a swirl-type spray chamber made of quartz, and a torch with an inner diameter of 1 mm made of quartz were used to aspirate the liquid to be measured at about 0.2 mL/min. The oxygen addition amount was 0.1 L/min and the plasma output 1600 W and the cleaning by ammonia gas were performed. The time resolution is resolved with 50us. 3) The content of specific metal atoms contained in the metal particles was detected using the following analysis software provided by the manufacturer.・Content of specific metal atoms contained in metal particles: Syngistix Nano Application Module for Nanoparticle Analysis "SNP-ICP-MS"

[研磨速度、凹陷評價及腐蝕評價] 在以下條件下，一邊向拋光墊供給研磨液，一邊進行研磨，對實施例1A～83A、比較例1A～5A進行了研磨速度及凹陷的評價，對實施例1B～82B進行了研磨速度、凹陷及腐蝕的評價。・研磨裝置：Reflexion（Applied Materials,Inc.製造）・被研磨體（晶圓）：（1）研磨速度計算用；在矽基板上形成了厚度1.5μm的上述各模型膜（Co膜、Ta膜、SiOx膜、TaN膜、Ti膜、TiN膜、Mn膜、Ru膜或SiOC膜）之直徑300mm的空白晶圓。（2）凹陷評價用；・實施例1A～83A、比較例1A～5A：使由SiOx構成之絕緣層以厚度5000Å積層於鈷配線的帶有圖案的基板（International SEMATECH製造，矽基板）上之後，藉由「SEMATECH854」遮罩（L/S=10μm/10μm）進行圖案加工，在其上依次積層厚度100Å的阻擋金屬層（阻擋金屬：Ta）及7500Å的鈷層之試驗用基板。・實施例1B～82B：使由SiOx構成之絕緣層以厚度5000Å積層於鈷配線的帶有圖案的基板（International SEMATECH製造，矽基板）上之後，藉由「SEMATECH 854」遮罩（L/S=10μm/10μm）進行圖案加工，在其上依次積層厚度100Å的阻擋金屬層（阻擋金屬：Ta）及7500Å的鈷層之試驗用基板。（3）腐蝕評價用；使由SiOx構成之絕緣層以厚度5000Å積層於鈷配線的帶有圖案的基板（International SEMATECH製造，矽基板）上之後，藉由「SEMATECH 854」遮罩（L/S=9μm/1μm）進行圖案加工，在其上依次積層厚度100Å的阻擋金屬層（阻擋金屬：Ta）及7500Å的鈷層之試驗用基板。[Polishing Speed, Depression Evaluation, and Corrosion Evaluation] Polishing was performed while supplying a polishing liquid to the polishing pad under the following conditions. Examples 1B to 82B were evaluated for polishing rate, sinking, and corrosion.・Polishing device: Reflexion (manufactured by Applied Materials, Inc.) ・Object to be polished (wafer): (1) For calculation of polishing speed; each of the above-mentioned model films (Co film, Ta film) with a thickness of 1.5 μm was formed on a silicon substrate , SiOx film, TaN film, Ti film, TiN film, Mn film, Ru film or SiOC film) blank wafer with a diameter of 300mm. (2) For sag evaluation; ・Examples 1A to 83A, Comparative Examples 1A to 5A: After an insulating layer composed of SiOx was laminated to a thickness of 5000Å on a patterned substrate (manufactured by International SEMATECH, silicon substrate) of cobalt wiring , pattern processing with "SEMATECH854" mask (L/S=10μm/10μm), on which a barrier metal layer (barrier metal: Ta) with a thickness of 100Å and a cobalt layer with a thickness of 7500Å are sequentially laminated on the test substrate.・Examples 1B to 82B: After an insulating layer composed of SiOx was laminated with a thickness of 5000Å on a patterned substrate (manufactured by International SEMATECH, silicon substrate) of cobalt wiring, it was masked by “SEMATECH 854” (L/S = 10 μm/10 μm) for patterning, on which a barrier metal layer (barrier metal: Ta) with a thickness of 100 Å and a cobalt layer with a thickness of 7500 Å are sequentially laminated on the test substrate. (3) For corrosion evaluation: After an insulating layer composed of SiOx was laminated with a thickness of 5000Å on a patterned substrate (manufactured by International SEMATECH, silicon substrate) of cobalt wiring, it was masked by "SEMATECH 854" (L/S = 9 μm/1 μm) for patterning, on which a barrier metal layer (barrier metal: Ta) with a thickness of 100 Å and a cobalt layer with a thickness of 7500 Å are sequentially laminated on the test substrate.

・研磨墊：IC1010（Rodel Inc.製造）・研磨條件；研磨壓力（被研磨面與研磨墊的接觸壓力）：1.5psi（另外，在本說明書中，psi係指pound-force per square inch；磅每平方英寸，係指1psi=6894.76Pa。）研磨液供給速度：200ml/min 研磨平台轉速：110rpm 研磨頭轉速：100rpm・Polishing pad: IC1010 (manufactured by Rodel Inc.) ・Polishing conditions; Polishing pressure (contact pressure between the surface to be polished and the polishing pad): 1.5 psi (in addition, in this specification, psi means pound-force per square inch; pounds Per square inch, refers to 1psi=6894.76Pa.) Grinding liquid supply speed: 200ml/min Grinding platform speed: 110rpm Grinding head speed: 100rpm

（評價方法）・實施例1A～83A、比較例1A～5A：研磨速度的計算：將（1）的空白晶圓研磨60秒鐘，針對晶圓面上的均等間隔的49個部位，由電阻值進行換算而求出研磨前後的金屬膜厚，將金屬膜厚除以研磨時間而求出之值的平均值設為研磨速度（單位：nm/min）。(Evaluation method) ・Examples 1A to 83A and Comparative Examples 1A to 5A: Calculation of polishing speed: The blank wafer of (1) was polished for 60 seconds, and 49 equally spaced locations on the wafer surface were subjected to resistance measurements. The value was converted to obtain the metal film thickness before and after polishing, and the average value of the values obtained by dividing the metal film thickness by the polishing time was defined as the polishing speed (unit: nm/min).

凹陷的評價：對（2）的圖案化晶圓，除了非配線部的鈷完全被研磨為止的時間以外，還額外地進行該時間的20%的研磨，用接觸式段差計DektakV320Si（Veeco Instruments,Inc.製造）測量線和空間部（線10μm，空間10μm）的段差，並依據以下基準進行了評價。另外，評價「G」以上係實用範圍。 A：凹陷係5nm以下。 B：凹陷大於5nm且8nm以下。 C：凹陷大於8nm且12nm以下。 D：凹陷大於12nm且15nm以下。 E：凹陷大於15nm且18nm以下。 F：凹陷大於18nm且21nm以下。 G：凹陷大於21nm且25nm以下。 H：凹陷大於25nm。Evaluation of sag: For the patterned wafer of (2), in addition to the time until the cobalt in the non-wiring portion was completely polished, 20% of the time was additionally polished, using a contact level difference meter DektakV320Si (Veeco Instruments, Inc.) measured the level difference between the line and the space portion (line 10 μm, space 10 μm), and evaluated according to the following criteria. In addition, the evaluation "G" or higher is a practical range. A: The depression is 5 nm or less. B: The depression is larger than 5 nm and 8 nm or less. C: The recess is larger than 8 nm and 12 nm or less. D: The depression is larger than 12 nm and 15 nm or less. E: The recess is larger than 15 nm and 18 nm or less. F: The recess is larger than 18 nm and 21 nm or less. G: The depression is larger than 21 nm and 25 nm or less. H: The pit is larger than 25 nm.

・實施例1B～82B、比較例1B～3B：研磨速度的計算：將（1）的空白晶圓研磨60秒鐘，針對晶圓面上的均等間隔的49個部位，由電阻值進行換算而求出研磨前後的金屬膜厚，將金屬膜厚除以研磨時間而求出之值的平均值設為研磨速度（單位：nm/min）。・Examples 1B to 82B and Comparative Examples 1B to 3B: Calculation of polishing rate: The blank wafer of (1) was polished for 60 seconds, and the resistance values were converted into 49 equally spaced locations on the wafer surface. The metal film thickness before and after polishing was obtained, and the average value of the values obtained by dividing the metal film thickness by the polishing time was defined as the polishing speed (unit: nm/min).

腐蝕的評價：對（3）的圖案化晶圓，除了非配線部的鈷完全被研磨為止的時間以外，還額外進行僅1分鐘的研磨，用接觸式段差計DektakV320Si（Veeco Instruments,Inc.製造）測量線和空間部（線9μm、空間1μm）的段差，並依據以下基準進行了評價。另外，評價「G」以上係實用範圍。 A：腐蝕係3nm以下。 B：腐蝕大於3nm且5nm以下。 C：腐蝕大於5nm且10nm以下。 D：腐蝕大於10nm且15nm以下。 E：腐蝕大於15nm且20nm以下。 F：腐蝕大於20nm且25nm以下。 G：腐蝕大於25nm且30nm以下。 H：腐蝕大於30nm。Evaluation of corrosion: The patterned wafer of (3) was polished for only 1 minute in addition to the time until the cobalt in the non-wiring portion was completely polished, using a contact level difference meter DektakV320Si (manufactured by Veeco Instruments, Inc. ) measured the level difference between the line and the space (line 9 μm, space 1 μm), and evaluated according to the following criteria. In addition, the evaluation "G" or higher is a practical range. A: Corrosion is 3 nm or less. B: Corrosion is more than 3 nm and 5 nm or less. C: Corrosion is more than 5 nm and 10 nm or less. D: Corrosion is more than 10 nm and 15 nm or less. E: Corrosion is more than 15 nm and 20 nm or less. F: Corrosion is more than 20 nm and 25 nm or less. G: Corrosion is more than 25 nm and 30 nm or less. H: Corrosion is more than 30 nm.

[缺陷評價] 對進行至精拋之圖案化晶圓藉由ComPlus（AMAT公司製造，缺陷檢查裝置），進行了研磨液的缺陷評價的評價（60nm以上）。 A：研磨後的缺陷數係20個/Wf以下 B：研磨後的缺陷數大於20個/Wf且30個/Wf以下 C：研磨後的缺陷數大於30個/Wf且50個/Wf以下 D：研磨後的缺陷數大於50個/Wf且60個/Wf以下 E：研磨後的缺陷數大於60個/Wf且80個/Wf以下 F：研磨後的缺陷數大於80個/Wf且100個/Wf以下 G：研磨後的缺陷數大於100個/Wf且120個/Wf以下 H：研磨後的缺陷數大於120個/Wf[Defect evaluation] The evaluation of the defect evaluation of the polishing liquid (60 nm or more) was performed by ComPlus (manufactured by AMAT Corporation, a defect inspection apparatus) on the patterned wafer that was subjected to the finishing polishing. A: The number of defects after polishing is 20/Wf or less B: The number of defects after polishing is more than 20/Wf and 30/Wf or less C: The number of defects after polishing is more than 30/Wf and 50/Wf or less D : The number of defects after polishing is greater than 50/Wf and 60/Wf or less E: The number of defects after polishing is greater than 60/Wf and 80/Wf or less F: The number of defects after polishing is greater than 80/Wf and 100 /Wf or less G: The number of defects after grinding is more than 100 pieces/Wf and 120 pieces/Wf or less H: The number of defects after grinding is more than 120 pieces/Wf

[經時穩定性評價] 在40℃下將各研磨液保管1個月。使用粒度分佈儀SALD-2300（Shimadzu Corporation製造），測量剛製備後（初始）的研磨粒子及保管後的研磨粒子的各粒度分佈（平均粒徑）而求出各平均粒徑，藉由由下述式計算之比，進行了研磨液的經時穩定性的評價。式（6）：T3=保管後的研磨粒子的平均粒徑/初始的研磨粒子的平均粒徑 A：T3係1.1以下 B：T3大於1.1且1.3以下 C：T3大於1.3且1.5以下 D：T3大於1.5[Evaluation of Stability Over Time] Each polishing liquid was stored at 40°C for one month. Using a particle size distribution analyzer SALD-2300 (manufactured by Shimadzu Corporation), each particle size distribution (average particle diameter) of the abrasive particles immediately after preparation (initial) and the abrasive particles after storage was measured, and each average particle diameter was obtained by the following: The ratio was calculated by the above formula, and the time-dependent stability of the polishing liquid was evaluated. Formula (6): T3=average particle diameter of abrasive particles after storage/average particle diameter of initial abrasive particles A: T3 is 1.1 or less B: T3 is more than 1.1 and 1.3 or less C: T3 is more than 1.3 and 1.5 or less D: T3 greater than 1.5

將結果示於表1及表2中。另外，表中，「%」及「ppb」均為質量基準。又，「研磨速度比R1」、「研磨速度比R2」及「研磨速度比R3」係分別由下述式（3）～（5）計算之值。式（3）： R1=基於研磨液之鈷基板的研磨速度/基於研磨液之阻擋基板的研磨速度式（4）： R2=基於研磨液之鈷基板的研磨速度/基於研磨液之阻擋基板的研磨速度式（5）： R3=基於研磨液之鈷基板的研磨速度/基於研磨液之絕緣膜基板的研磨速度又，「金屬雜質量」係指選自包括Fe原子、Cu原子、Ag原子及Zn原子之特定金屬原子相對於研磨液總質量之含量。又，「金屬粒子量」係指上述金屬雜質中固體狀金屬雜質所含有之、選自包括Fe原子、Cu原子、Ag原子及Zn原子之特定金屬原子相對於研磨液總質量之含量。又，「H₂ O₂ /金屬雜質量（T1）」係指由下述式（1）計算之值。式（1）：T1=過氧化氫的含量/金屬雜質所含有之選自包括Fe原子、Cu原子、Ag原子及Zn原子之群組中的特定金屬原子的總計含量又，「胺量（ppb）」係指相對於上述之通式（1）所表示之化合物的研磨液總質量之含量。另外，研磨液用水（殘餘部）調整成總質量成為100質量%。The results are shown in Table 1 and Table 2. In addition, in the table, "%" and "ppb" are quality standards. In addition, "polishing speed ratio R1", "polishing speed ratio R2", and "polishing speed ratio R3" are values calculated from the following formulae (3) to (5), respectively. Equation (3): R1=grinding speed of the cobalt substrate based on the polishing liquid/grinding rate of the barrier substrate based on the polishing liquid Equation (4): R2=grinding rate of the cobalt substrate based on the polishing liquid/the polishing rate of the barrier substrate based on the polishing liquid Polishing rate formula (5): R3 = polishing rate of cobalt substrate based on polishing liquid/grinding rate of insulating film substrate based on polishing liquid. “Amount of metal impurity” refers to selected from the group consisting of Fe atoms, Cu atoms, Ag atoms and The content of specific metal atoms of Zn atoms relative to the total mass of the slurry. In addition, the "amount of metal particles" refers to the content of specific metal atoms selected from the group consisting of Fe atoms, Cu atoms, Ag atoms and Zn atoms contained in the solid metal impurities in the above-mentioned metal impurities relative to the total mass of the polishing liquid. In addition, "H ₂ O ₂ /metal impurity amount (T1)" means a value calculated from the following formula (1). Formula (1): T1=content of hydrogen peroxide/total content of specific metal atoms contained in metal impurities selected from the group consisting of Fe atoms, Cu atoms, Ag atoms and Zn atoms )" refers to the content of the total mass of the polishing liquid relative to the compound represented by the general formula (1). In addition, the polishing liquid was adjusted with water (residual portion) so that the total mass was 100% by mass.

另外，下述表1中，下述表1A2、表1B2、表1C2、表1D2分別示出關於下述表1A1、表1B1、表1C1、表1D1中所示之實施例1A～83A及比較例1A～5A的各研磨液的各種評價結果。亦即，例如，在實施例1A的情況下，表1A2中示出使用表1A1的研磨液之各種評價。實施例1A的研磨液中的Co反應層的厚度係4nm，凹陷評價係4nm（相當於A），缺陷評價係A，經時穩定性係A。又，例如，在將阻擋金屬設為TaN之情況下，TaN反應層的厚度係0.08nm。又，下述表2中，下述表2A2及表2A3、表2B2及表2B3、表2C2及表2C3、表2D2及表2D3分別示出關於下述表2A1、表2B1、表2C1中所示之實施例1B～82B、比較例1B～3B的各研磨液的各種評價結果。亦即，例如，在實施例1B的情況下，表2A2及表2A3中示出使用表2A1的研磨液之各種評價。實施例1B的研磨液中的Co反應層的厚度係1nm，凹陷評價係3.5nm（相當於A），腐蝕評價係8.75nm（相當於C）缺陷評價係A，經時穩定性係A。又，例如，在將阻擋金屬設為TaN之情況下，TaN反應層的厚度係0.212nm。In addition, in the following Table 1, the following Table 1A2, Table 1B2, Table 1C2, and Table 1D2 respectively show Examples 1A to 83A and Comparative Examples shown in the following Tables 1A1, 1B1, 1C1, and 1D1. Various evaluation results of each polishing liquid of 1A to 5A. That is, for example, in the case of Example 1A, various evaluations using the polishing liquid of Table 1A1 are shown in Table 1A2. The thickness of the Co reaction layer in the polishing liquid of Example 1A is 4 nm, the evaluation of depression is 4 nm (corresponding to A), the evaluation of defects is A, and the stability over time is A. Also, for example, when the barrier metal is TaN, the thickness of the TaN reaction layer is 0.08 nm. In addition, in the following Table 2, the following Table 2A2 and Table 2A3, Table 2B2 and Table 2B3, Table 2C2 and Table 2C3, Table 2D2 and Table 2D3 respectively show the following table 2A1, Table 2B1, Table 2C1 Various evaluation results of each polishing liquid of Examples 1B to 82B and Comparative Examples 1B to 3B. That is, for example, in the case of Example 1B, various evaluations using the polishing liquid of Table 2A1 are shown in Table 2A2 and Table 2A3. The thickness of the Co reaction layer in the polishing liquid of Example 1B was 1 nm, the dent evaluation system was 3.5 nm (equivalent to A), the corrosion evaluation system was 8.75 nm (equivalent to C), the defect evaluation system A, and the stability over time system A. Also, for example, when the barrier metal is TaN, the thickness of the TaN reaction layer is 0.212 nm.

[表1]

[Table 1]

[表2]

[Table 2]

[表3]

[table 3]

[表4]

[Table 4]

[表5]

[table 5]

[表6]

[Table 6]

[表7]

[Table 7]

[表8]

[Table 8]

[表9]

[Table 9]

[表10]

[Table 10]

[表11]

[Table 11]

[表12]

[Table 12]

[表13]

[Table 13]

[表14]

[Table 14]

[表15]

[Table 15]

[表16]

[Table 16]

[表17]

[Table 17]

[表18]

[Table 18]

[表19]

[Table 19]

[表20]

[Table 20]

從表1及表2的結果確認到，實施例的研磨液均抑制被研磨面中的凹陷、腐蝕及缺陷的產生。又，確認到經時穩定性亦優異。另一方面，確認到比較例1～5的研磨液產生被研磨面中的凹陷及缺陷。From the results in Tables 1 and 2, it was confirmed that the polishing liquids of Examples all suppressed the occurrence of pitting, corrosion, and defects in the polished surface. In addition, it was confirmed that the stability over time was also excellent. On the other hand, in the polishing liquids of Comparative Examples 1 to 5, it was confirmed that depressions and defects occurred in the surfaces to be polished.

・實施例1A～83A的結果（表1）從實施例1A、8A～11A的對比確認到，在過氧化氫的含量相對於研磨液總質量係0.001～2.5質量%（0.06～2質量%為較佳）的情況下，被研磨面中的凹陷更難以產生。又，從實施例1A、12A～15A的對比確認到，在唑系化合物的含量相對於研磨液總質量係0.01～1.3質量%（0.01～0.4質量%為較佳）的情況下，被研磨面中的凹陷更難以產生，經時穩定性更優異。從實施例1A、19A～21A的對比確認到，締合度1～3的膠體二氧化矽的化學機械研磨前後的平均粒徑之比T2係2.5以下（2以下為較佳）的情況下，被研磨面中的缺陷更難以產生。又，從實施例1A、22A～25A的對比確認到，在研磨液的pH係6.5～8.0（6.8～7.8為較佳，6.8～7.2為更佳）的情況下，被研磨面中的凹陷及缺陷更難以產生，經時穩定性更優異。又，從實施例1A、26A～29A的對比確認到，在上述通式（1）所表示之化合物的含量相對於研磨液總質量係1000質量ppb以下（250質量ppb以下為較佳，8質量ppb以下為更佳）的情況下，被研磨面中的凹陷及缺陷更難以產生，經時穩定性更優異。又，從實施例1A、30A～32A的對比確認到，在金屬雜質所含有之選自包括Fe原子、Cu原子、Ag原子及Zn原子之一種特定金屬原子的含量相對於研磨液總質量係0.01～100質量ppb（0.01～50質量ppb為較佳，0.01～20質量ppb為更佳）的情況下，被研磨面中的凹陷及缺陷更難以產生，經時穩定性更優異。又，在金屬粒子所含有之特定金屬原子且其含量相對於研磨液總質量係0.01～50質量ppb（0.01～8質量ppb為較佳）的情況下，被研磨面中的凹陷及缺陷更難以產生，經時穩定性更優異。又，從實施例1A、33A～35A、54A、55A的對比確認到，在胺基酸的含量相對於研磨液總質量係0.8～4質量%的情況下，被研磨面中的凹陷及缺陷更難以產生，經時穩定性更優異。又，從實施例1A、36A～38A的對比確認到，在作為胺基酸含有甘胺酸或N-甲基甘胺酸（甘胺酸為較佳）之情況下，被研磨面中的凹陷更難以產生。又，從實施例1A、57A、58A的對比確認到，在締合度1～3的膠體二氧化矽的含量相對於研磨液總質量係0.01～0.15質量%的情況下，被研磨面中的凹陷更難以產生。又，從實施例1A、39A～53A的對比確認到，在將含有具有苯并***骨架之化合物及與苯并***系化合物不同之化合物之研磨液使用於CMP之情況下，在被研磨面更難以產生凹陷。又，從實施例1A、8A～11A、30A～32A的對比確認到，研磨液中過氧化氫與金屬雜質所含有之選自包括Fe原子、Cu原子、Ag原子及Zn原子之群組中的特定金屬原子的含量比T1係30000～500000（30000～110000為較佳，30000～80000為更佳）的情況下，被研磨面中的凹陷更難以產生。從實施例1A、39A～41A的對比確認到，在作為具有苯并***骨架之化合物含有5-甲基苯并***之情況下，被研磨面中的凹陷更難以產生。・Results of Examples 1A to 83A (Table 1) From the comparison of Examples 1A and 8A to 11A, it was confirmed that the content of hydrogen peroxide is 0.001 to 2.5 mass % (0.06 to 2 mass % is 0.001 to 2.5 mass % relative to the total mass of the polishing liquid) better), the pits in the polished surface are more difficult to generate. In addition, from the comparison of Examples 1A and 12A to 15A, it was confirmed that when the content of the azole compound is 0.01 to 1.3 mass % (preferably 0.01 to 0.4 mass %) with respect to the total mass of the polishing liquid, the surface to be polished It is more difficult to generate dimples in , and the stability over time is more excellent. From the comparison of Examples 1A and 19A to 21A, it was confirmed that when the ratio T2 of the average particle size before and after chemical mechanical polishing of colloidal silica with an association degree of 1 to 3 is 2.5 or less (preferably 2 or less), the Defects in the ground surface are more difficult to produce. In addition, from the comparison of Examples 1A and 22A to 25A, it was confirmed that when the pH of the polishing liquid is 6.5 to 8.0 (6.8 to 7.8 is preferable, and 6.8 to 7.2 is more preferable), the dents in the surface to be polished and Defects are more difficult to generate, and the stability over time is more excellent. In addition, from the comparison of Examples 1A and 26A to 29A, it was confirmed that the content of the compound represented by the general formula (1) is 1000 mass ppb or less (preferably 250 mass ppb or less, 8 mass ppb or less) relative to the total mass of the polishing liquid ppb or less), it is more difficult to generate dents and defects in the surface to be polished, and the stability over time is more excellent. Also, from the comparison of Examples 1A and 30A to 32A, it was confirmed that the content of a specific metal atom selected from the group consisting of Fe atoms, Cu atoms, Ag atoms and Zn atoms contained in the metal impurities was 0.01 relative to the total mass of the grinding liquid. In the case of ~100 mass ppb (preferably 0.01 to 50 mass ppb, more preferably 0.01 to 20 mass ppb), it is more difficult to generate dents and defects in the surface to be polished, and the stability over time is more excellent. Furthermore, when the specific metal atoms contained in the metal particles are 0.01 to 50 mass ppb (preferably 0.01 to 8 mass ppb) relative to the total mass of the polishing liquid, the surface to be polished is more difficult to have dents and defects produced, and the stability over time is more excellent. In addition, from the comparison of Examples 1A, 33A to 35A, 54A and 55A, it was confirmed that when the content of the amino acid was 0.8 to 4 mass % with respect to the total mass of the polishing liquid, the dents and defects in the surface to be polished were more severe. It is difficult to produce, and the stability over time is more excellent. In addition, from the comparison of Examples 1A and 36A to 38A, it was confirmed that when glycine or N-methylglycine (glycine is preferred) is contained as the amino acid, depressions in the polished surface more difficult to produce. In addition, from the comparison of Examples 1A, 57A, and 58A, it was confirmed that when the content of colloidal silica with an association degree of 1 to 3 was 0.01 to 0.15 mass % with respect to the total mass of the polishing liquid, depressions in the surface to be polished were observed. more difficult to produce. In addition, from the comparison of Examples 1A and 39A to 53A, it was confirmed that when a polishing liquid containing a compound having a benzotriazole skeleton and a compound different from a benzotriazole-based compound was used in CMP, the polishing Faces are more difficult to dent. Also, from the comparison of Examples 1A, 8A-11A, and 30A-32A, it was confirmed that the hydrogen peroxide and metal impurities contained in the polishing liquid were selected from the group consisting of Fe atoms, Cu atoms, Ag atoms, and Zn atoms. When the content of the specific metal atom is 30,000 to 500,000 (preferably 30,000 to 110,000, more preferably 30,000 to 80,000) of the T1 series, it is more difficult to generate dents in the surface to be polished. From the comparison of Examples 1A and 39A to 41A, it was confirmed that when 5-methylbenzotriazole is contained as a compound having a benzotriazole skeleton, it is more difficult to generate dents in the surface to be polished.

・實施例1B～82B的結果（表2）從實施例1B、8B～10B的對比確認到，在過氧化氫的含量相對於研磨液總質量係0.1～1.2質量%（0.6～1質量%為較佳）的情況下，在被研磨面中凹陷及腐蝕更難以產生。又，從實施例1B、11B～14B的對比確認到，在唑系化合物的含量相對於研磨液總質量係0.12～3.5質量%（0.12～0.8質量%為較佳，0.12～0.5質量%為更佳）的情況下，被研磨面中的凹陷及腐蝕更難以產生，經時穩定性更優異。從實施例1B、18B～20B的對比確認到，在締合度1～3的膠體二氧化矽的化學機械研磨前後的平均粒徑之比T2係2.5以下（2以下為較佳）的情況下，被研磨面中的缺陷更難以產生。又，從實施例1B、21B～23B的對比確認到，在研磨液的pH係8.2～9.5（8.7～9.5為較佳）的情況下，被研磨面中的凹陷及腐蝕以及缺陷更難以產生。又，從實施例1B、24B～27B的對比確認到，在上述通式（1）所表示之化合物的含量相對於研磨液總質量係1000質量ppb以下（250質量ppb以下為較佳，8質量ppb以下為更佳）的情況下，被研磨面中的凹陷及腐蝕以及缺陷更難以產生，經時穩定性更優異。又，從實施例1B、28B～30B的對比確認到，在金屬雜質所含有之選自包括Fe原子、Cu原子、Ag原子及Zn原子之一種特定金屬原子的含量相對於研磨液總質量係0.01～100質量ppb（0.01～20質量ppb為較佳）的情況下，被研磨面中的凹陷及腐蝕以及缺陷更難以產生，經時穩定性更優異。又，在金屬粒子所含有之特定金屬原子且其含量相對於研磨液總質量係0.01～50質量ppb（0.01～8質量ppb為較佳）的情況下，被研磨面中的凹陷及腐蝕以及缺陷更難以產生，經時穩定性更優異。・Results of Examples 1B to 82B (Table 2) From the comparison of Examples 1B and 8B to 10B, it was confirmed that the content of hydrogen peroxide is 0.1 to 1.2 mass % (0.6 to 1 mass % is 0.1 to 1.2 mass % relative to the total mass of the polishing liquid) In the case of better), pitting and corrosion are more difficult to generate in the polished surface. In addition, from the comparison of Examples 1B and 11B to 14B, it was confirmed that the content of the azole compound is 0.12 to 3.5 mass % (preferably 0.12 to 0.8 mass %, and more preferably 0.12 to 0.5 mass % with respect to the total mass of the polishing liquid). In the case of good), pits and corrosion in the surface to be polished are more difficult to generate, and the stability over time is more excellent. From the comparison of Examples 1B and 18B to 20B, it was confirmed that when the ratio T2 of the average particle size before and after chemical mechanical polishing of colloidal silica with an association degree of 1 to 3 is 2.5 or less (preferably 2 or less), Defects in the ground surface are more difficult to produce. In addition, from the comparison of Examples 1B and 21B to 23B, it was confirmed that when the pH of the polishing liquid is 8.2 to 9.5 (preferably 8.7 to 9.5), pits, corrosion, and defects in the polished surface are more difficult to occur. In addition, from the comparison of Examples 1B and 24B to 27B, it was confirmed that the content of the compound represented by the general formula (1) is 1000 mass ppb or less (preferably 250 mass ppb or less, 8 mass ppb or less) relative to the total mass of the polishing liquid ppb or less), pits, corrosion, and defects in the surface to be polished are more difficult to generate, and the stability over time is more excellent. Also, from the comparison of Examples 1B and 28B to 30B, it was confirmed that the content of a specific metal atom selected from the group consisting of Fe atoms, Cu atoms, Ag atoms and Zn atoms contained in the metal impurities was 0.01 relative to the total mass of the grinding liquid. In the case of to 100 mass ppb (preferably 0.01 to 20 mass ppb), pits, corrosion, and defects in the surface to be polished are more difficult to generate, and the stability over time is more excellent. In addition, when the specific metal atoms contained in the metal particles and the content of the specific metal atoms are 0.01 to 50 mass ppb (preferably 0.01 to 8 mass ppb) relative to the total mass of the polishing liquid, pitting, corrosion and defects in the surface to be polished It is more difficult to produce, and the stability over time is more excellent.

又，從實施例1B、31B～36B的對比確認到，在有機酸的含量相對於研磨液總質量係0.01～0.3質量%的情況下，被研磨面中的凹陷及腐蝕以及缺陷更難以產生，經時穩定性更優異。又，從實施例1B、37B～39B的對比確認到，在作為有機酸組合順丁烯二酸及檸檬酸或丙二酸而使用（組合順丁烯二酸及檸檬酸而使用為較佳）之情況下，被研磨面中的凹陷及腐蝕更難以產生，經時穩定性更優異。從實施例1B、40B～42B的對比確認到，在作為具有苯并***骨架之化合物含有苯并***、5-胺基苯并***或5,6-二甲基苯并***之情況下，被研磨面中的凹陷及腐蝕更難以產生。又，從實施例1B、40B～48B、52B、53B的對比確認到，在將作為唑系化合物含有具有苯并***骨架之化合物及與苯并***系化合物不同之化合物研磨液使用於CMP之情況下，在被研磨面更難以產生凹陷及腐蝕。又，從實施例1B、55B、56B的對比確認到，在締合度1～3的膠體二氧化矽的含量相對於研磨液總質量係0.5～3質量%的情況下，在被研磨面更難以產生凹陷及腐蝕。又，從實施例1B、8B～10B、28B～30B的對比確認到，在研磨液中過氧化氫與金屬雜質所含有之選自包括Fe原子、Cu原子、Ag原子及Zn原子之群組中的特定金屬原子的含量比T1係30000～500000（100000～500000為較佳，250000～500000為更佳）的情況下，在被研磨面更難以產生凹陷及腐蝕。In addition, from the comparison of Examples 1B and 31B to 36B, it was confirmed that when the content of the organic acid is 0.01 to 0.3 mass % with respect to the total mass of the polishing liquid, pits, corrosion and defects in the surface to be polished are more difficult to generate, The stability over time is more excellent. In addition, it was confirmed from the comparison of Examples 1B and 37B to 39B that as the organic acid, it is used in combination with maleic acid and citric acid or malonic acid (it is preferable to use in combination with maleic acid and citric acid) In this case, pits and corrosion in the surface to be polished are less likely to occur, and the stability over time is more excellent. From the comparison of Examples 1B and 40B to 42B, it was confirmed that when the compound having a benzotriazole skeleton contains benzotriazole, 5-aminobenzotriazole or 5,6-dimethylbenzotriazole In this case, pitting and corrosion in the polished surface are more difficult to produce. In addition, from the comparison of Examples 1B, 40B to 48B, 52B, and 53B, it was confirmed that the polishing liquid containing a compound having a benzotriazole skeleton as an azole compound and a compound different from the benzotriazole compound was used in CMP. In this case, pitting and corrosion are more difficult to occur on the surface to be polished. In addition, from the comparison of Examples 1B, 55B, and 56B, it was confirmed that when the content of colloidal silica with an association degree of 1 to 3 is 0.5 to 3 mass % with respect to the total mass of the polishing liquid, the surface to be polished is more difficult to be polished. Depression and corrosion occur. In addition, from the comparison of Examples 1B, 8B-10B, and 28B-30B, it was confirmed that the hydrogen peroxide and metal impurities contained in the polishing liquid were selected from the group consisting of Fe atoms, Cu atoms, Ag atoms, and Zn atoms. When the content of the specific metal atoms is 30,000-500,000 (100,000-500,000 is better, 250,000-500,000 is better) than the T1 series, it is more difficult to produce pitting and corrosion on the polished surface.

[實施例84A] 將各成分設為如表3所示，除此以外，藉由與實施例1A相同的方法，製備了實施例84A。另外，實施例84A相當於研磨液原液。進而，作為稀釋液使用水，將上述實施例84A的研磨液稀釋成10倍。稀釋前後的pH變化係0.01，能夠確認在稀釋前後對研磨液的性能無差異。[Example 84A] Example 84A was prepared by the same method as Example 1A except that each component was as shown in Table 3. In addition, Example 84A corresponds to a polishing liquid stock solution. Furthermore, using water as a dilution liquid, the polishing liquid of the said Example 84A was diluted 10 times. The pH change before and after the dilution was 0.01, and it was confirmed that there was no difference in the performance of the polishing liquid before and after the dilution.

[實施例85A] 將各成分設為如表3所示，除此以外，藉由與實施例1A相同的方法，製備了實施例85A。另外，實施例85A相當於研磨液原液。進而，作為稀釋液使用水，將上述實施例85A的研磨液稀釋成50倍。稀釋前後的pH變化係0.1，能夠確認在稀釋前後對研磨液的性能無差異。[Example 85A] Example 85A was prepared by the same method as Example 1A except that each component was as shown in Table 3. In addition, Example 85A corresponds to a polishing liquid stock solution. Furthermore, using water as a dilution liquid, the polishing liquid of the said Example 85A was diluted 50 times. The pH change before and after the dilution was 0.1, and it was confirmed that there was no difference in the performance of the polishing liquid before and after the dilution.

[表21]

[Table 21]

[實施例1B（A）～實施例1B（E）] 使用實施例1B的研磨液，將凹陷評價用基板及腐蝕評價用的試驗基板替換成下述，除此以外，進行了與實施例1B相同的評價。將該結果作為實施例1B（A）～實施例1B（E）分別示於表4～8。（1）凹陷評價用；使由SiOx構成之絕緣層以厚度5000Å積層於鈷配線的帶有圖案的基板（International SEMATECH製造，矽基板）上之後，藉由「SEMATECH 854」遮罩（L/S=10μm/10μm）進行圖案加工，在其上依次積層厚度100Å的阻擋金屬層（阻擋金屬：TaN、Ti、TiN、Ru或Mn）及7500Å的鈷層之試驗用基板。（2）腐蝕評價用；使由SiOx構成之絕緣層以厚度5000Å積層於鈷配線的帶有圖案的基板（International SEMATECH製造，矽基板）上之後，藉由「SEMATECH 854」遮罩（L/S=9μm/1μm）進行圖案加工，在其上依次積層厚度100Å的阻擋金屬層（阻擋金屬：TaN、Ti、TiN、Ru或Mn）及7500Å的鈷層子試驗用基板。[Example 1B(A) to Example 1B(E)] The same procedure as Example 1B was carried out, except that the polishing liquid of Example 1B was used, and the substrate for dent evaluation and the test substrate for corrosion evaluation were replaced with the followings. same rating. The results are shown in Tables 4 to 8 as Examples 1B(A) to 1B(E), respectively. (1) For sag evaluation: After an insulating layer composed of SiOx was laminated with a thickness of 5000Å on a patterned substrate (manufactured by International SEMATECH, silicon substrate) of cobalt wiring, it was masked with “SEMATECH 854” (L/S =10μm/10μm) for patterning, on which a barrier metal layer with a thickness of 100Å (barrier metal: TaN, Ti, TiN, Ru or Mn) and a cobalt layer with a thickness of 7500Å are sequentially laminated on the test substrate. (2) For corrosion evaluation: After an insulating layer composed of SiOx was laminated with a thickness of 5000Å on a patterned substrate (manufactured by International SEMATECH, silicon substrate) of cobalt wiring, it was masked by "SEMATECH 854" (L/S = 9 μm/1 μm) for patterning, on which a barrier metal layer (barrier metal: TaN, Ti, TiN, Ru or Mn) with a thickness of 100 Å and a 7500 Å cobalt layer sub-test substrate are sequentially laminated.

如表4～8所示那樣確認到，實施例1B的研磨液相對於具有Ta、TaN、Ti、TiN、Ru及Mn中的任一個阻擋金屬層之基板，凹陷及腐蝕的產生亦得到抑制。As shown in Tables 4 to 8, it was confirmed that the polishing liquid of Example 1B also suppressed the occurrence of pitting and corrosion with respect to the substrate having any one of Ta, TaN, Ti, TiN, Ru, and Mn barrier metal layers.

[表22]

[Table 22]

[表23]

[Table 23]

[表24]

[Table 24]

[表25]

[Table 25]

[表26]

[Table 26]

[實施例83B] 將各成分設為表9所示，除此以外，藉由與實施例1B相同的方法，製備了實施例83B。另外，實施例83B相當於研磨液原液。進而，作為稀釋液使用水，將上述實施例83B的研磨液稀釋成2倍。稀釋前後的pH變化係0.1，確認到在稀釋前後對研磨液的性能無差異。[Example 83B] Example 83B was prepared by the same method as Example 1B except that each component was shown in Table 9. In addition, Example 83B corresponds to a polishing liquid stock solution. Furthermore, using water as a dilution liquid, the polishing liquid of the said Example 83B was diluted 2 times. The pH change before and after the dilution was 0.1, and it was confirmed that there was no difference in the performance of the polishing liquid before and after the dilution.

[表27] 進而，作為稀釋液使用水，將上述實施例83B的研磨液稀釋成2倍。

[Table 27] Furthermore, using water as a diluent, the polishing liquid of the above-mentioned Example 83B was diluted twice.

10‧‧‧被研磨體12‧‧‧基板14‧‧‧絕緣膜層16‧‧‧阻擋層18‧‧‧含鈷的層10‧‧‧Object to be ground 12‧‧‧Substrate 14‧‧‧Insulating film layer 16‧‧‧Barrier layer 18‧‧‧Cobalt-containing layer

圖1係表示被研磨體的一例之剖面圖。圖2係對被研磨體進行第1研磨之後的剖面圖。圖3係進一步對被研磨體進行第2研磨之後的剖面圖。FIG. 1 is a cross-sectional view showing an example of a to-be-polished body. FIG. 2 is a cross-sectional view after the first polishing of the body to be polished. FIG. 3 is a cross-sectional view after the object to be polished is further subjected to second polishing.

10‧‧‧被研磨體 10‧‧‧The body to be ground

12‧‧‧基板 12‧‧‧Substrate

14‧‧‧絕緣膜層 14‧‧‧Insulating film

16‧‧‧阻擋層 16‧‧‧Barrier layer

18‧‧‧含鈷的層 18‧‧‧Cobalt-containing layers

Claims

一種研磨液，其含有：締合度1~3的膠體二氧化矽；有機酸；唑系化合物；以及過氧化氫；並且用於對含鈷的層進行化學機械研磨，其中在使該研磨液與鈷基板接觸24小時時，在該鈷基板上形成含有鈷原子之厚度0.5~20nm的反應層，作為該唑系化合物，含有苯并***系化合物及與苯并***系化合物不同之唑系化合物。 A grinding liquid, which contains: colloidal silica with an association degree of 1 to 3; an organic acid; an azole compound; and hydrogen peroxide; When the cobalt substrate is in contact with the cobalt substrate for 24 hours, a reaction layer with a thickness of 0.5 to 20 nm containing cobalt atoms is formed on the cobalt substrate. As the azole compound, a benzotriazole compound and an azole compound different from the benzotriazole compound are contained. compound.

如申請專利範圍第1項所述之研磨液，其中該締合度1~3的膠體二氧化矽的含量相對於研磨液總質量係0.01~1質量%，作為該有機酸，含有胺基酸，pH係6.5~8.0，使該研磨液與包括選自包括Ta、TaN、Ti、TiN、Ru及Mn之群組中的任一種金屬之阻擋基板接觸24小時時，在該阻擋基板上形成含有該金屬的原子之厚度0.01~5nm的反應層。 The polishing liquid according to item 1 of the scope of the application, wherein the content of the colloidal silica with a degree of association of 1 to 3 is 0.01 to 1 mass % relative to the total mass of the polishing liquid, and as the organic acid, it contains an amino acid, The pH is between 6.5 and 8.0. When the polishing liquid is brought into contact with a barrier substrate including any metal selected from the group consisting of Ta, TaN, Ti, TiN, Ru and Mn for 24 hours, a formation containing the barrier substrate is formed on the barrier substrate. A reactive layer with a thickness of 0.01 to 5 nm of metal atoms.

如申請專利範圍第2項所述之研磨液，其中由下述式(3)計算之研磨速度比R1係250~2500，式(3)： R1=基於該研磨液之該鈷基板的研磨速度/基於該研磨液之該阻擋基板的研磨速度。 The polishing liquid described in the second item of the scope of the application, wherein the polishing rate ratio R1 calculated by the following formula (3) is 250~2500, and the formula (3): R1=the polishing rate of the cobalt substrate based on the polishing liquid/the polishing rate of the barrier substrate based on the polishing liquid.

如申請專利範圍第1項所述之研磨液，其中該締合度1~3的膠體二氧化矽的含量相對於研磨液總質量係0.5~5質量%，pH係8.0~10.5，使該研磨液與包括選自包括Ta、TaN、Ti、TiN、Ru及Mn之群組中的任一種金屬之阻擋基板接觸24小時時，在該阻擋基板上形成含有該金屬的原子之厚度0.01~5nm的反應層，使該研磨液與包括選自包括SiOx及SiOC之群組中的任一種無機成分之絕緣膜基板接觸24小時時，在該絕緣膜基板上形成含有矽原子之厚度0.01~10nm的反應層。 The polishing liquid according to item 1 of the scope of the application, wherein the content of the colloidal silica with an association degree of 1-3 is 0.5-5 mass % relative to the total mass of the polishing liquid, and the pH is 8.0-10.5, so that the polishing liquid is When in contact with a barrier substrate comprising any one metal selected from the group consisting of Ta, TaN, Ti, TiN, Ru, and Mn for 24 hours, a reaction with a thickness of 0.01 to 5 nm of atoms containing the metal is formed on the barrier substrate layer, when the polishing liquid is brought into contact with an insulating film substrate including any inorganic component selected from the group including SiOx and SiOC for 24 hours, a reaction layer with a thickness of 0.01-10 nm containing silicon atoms is formed on the insulating film substrate .

如申請專利範圍第4項所述之研磨液，其中該有機酸係選自包括順丁烯二酸、反丁烯二酸、2-羥基苯甲酸、3-羥基苯甲酸、4-羥基苯甲酸、鄰苯二甲酸、間苯二甲酸、對苯二甲酸、1,2,3-苯三甲酸、1,2,4-苯三甲酸、1,3,5-苯三甲酸、1,2,3,5-苯四甲酸、1,2,3,4-苯四甲酸、1,2,4,5-苯四甲酸、苯六甲酸、聯苯二甲酸、檸檬酸、琥珀酸、蘋果酸、丙二酸及鄰胺苯甲酸之群組中的至少一種，該有機酸的含量相對於研磨液總質量係0.01~0.3質量%。 The polishing liquid as described in claim 4, wherein the organic acid is selected from the group consisting of maleic acid, fumaric acid, 2-hydroxybenzoic acid, 3-hydroxybenzoic acid, and 4-hydroxybenzoic acid , phthalic acid, isophthalic acid, terephthalic acid, 1,2,3-benzenetricarboxylic acid, 1,2,4-benzenetricarboxylic acid, 1,3,5-benzenetricarboxylic acid, 1,2, 3,5-Mellitic acid, 1,2,3,4-Mellitic acid, 1,2,4,5-Mellitic acid, Mellitic acid, Biphthalic acid, Citric acid, Succinic acid, Malic acid, At least one in the group of malonic acid and anthranilic acid, the content of the organic acid is 0.01-0.3 mass % relative to the total mass of the polishing liquid.

如申請專利範圍第4項或第5項所述之研磨液，其中由下述式(4)計算之研磨速度比R2係0.01~2.0，由下述式(5)計算之研磨速度比R3係0.05~2.0，式(4)：R2=基於該研磨液之該鈷基板的研磨速度/基於該研磨液之該阻擋基板的研磨速度，式(5)：R3=基於該研磨液之該鈷基板的研磨速度/基於該研磨液之該絕緣膜基板的研磨速度。 The polishing liquid according to item 4 or item 5 of the scope of the application, wherein the polishing rate ratio R2 calculated by the following formula (4) is 0.01~2.0, and the polishing rate ratio R3 calculated by the following formula (5) is 0.05~2.0, Formula (4): R2=grinding speed of the cobalt substrate based on the grinding liquid/grinding speed of the barrier substrate based on the grinding liquid, formula (5): R3=grinding speed of the cobalt substrate based on the grinding liquid/ The polishing rate of the insulating film substrate based on the polishing liquid.

如申請專利範圍第1項至第5項中任一項所述之研磨液，其中該過氧化氫的含量係0.001~5質量%。 The polishing liquid according to any one of items 1 to 5 of the claimed scope, wherein the content of the hydrogen peroxide is 0.001-5 mass %.

如申請專利範圍第1項至第5項中任一項所述之研磨液，其還含有含金屬原子之金屬雜質，該金屬雜質含有選自包括Fe原子、Cu原子、Ag原子及Zn原子之群組中的至少一種特定金屬原子，在該特定金屬原子係選自包括Fe原子、Cu原子、Ag原子及Zn原子之一種之情況下，該特定金屬原子的含量相對於研磨液總質量係0.01~100質量ppb，在該特定金屬原子係選自包括Fe原子、Cu原子、Ag原子及Zn原子之兩種以上之情況下，各自的該特定金屬原子的含量相對於研磨液總質量係0.01~100質量ppb。 The polishing liquid according to any one of items 1 to 5 of the scope of the application further contains a metal impurity containing a metal atom, and the metal impurity contains a metal impurity selected from the group consisting of Fe atom, Cu atom, Ag atom and Zn atom At least one specific metal atom in the group, when the specific metal atom is selected from one of Fe atoms, Cu atoms, Ag atoms and Zn atoms, the content of the specific metal atoms is 0.01 relative to the total mass of the polishing liquid ~100 mass ppb, when the specific metal atom is selected from two or more types including Fe atom, Cu atom, Ag atom and Zn atom, the content of each specific metal atom relative to the total mass of the polishing liquid is 0.01~ 100 quality ppb.

如申請專利範圍第8項所述之研磨液，其中該金屬雜質含有金屬粒子，該金屬粒子含有選自包括Fe原子、Cu原子、Ag原子及Zn原子之群組中的至少一種特定金屬原子，在該金屬粒子所含有之該特定金屬原子係選自包括Fe原子、Cu原子、Ag原子及Zn原子之一種之情況下，該金屬粒子所含有之該特定金屬原子的含量相對於研磨液總質量係0.01~50質量ppb，在該金屬粒子所含有之該特定金屬原子係選自包括Fe原子、Cu原子、Ag原子及Zn原子之兩種以上之情況下，該金屬粒子所含有之各自的該特定金屬原子的含量相對於研磨液總質量係0.01~50質量ppb。 The polishing liquid as described in claim 8, wherein the metal impurity contains metal particles, and the metal particles contain at least one specific metal atom selected from the group consisting of Fe atoms, Cu atoms, Ag atoms, and Zn atoms, When the specific metal atoms contained in the metal particles are selected from one of Fe atoms, Cu atoms, Ag atoms and Zn atoms, the content of the specific metal atoms contained in the metal particles is relative to the total mass of the polishing liquid It is 0.01 to 50 mass ppb, and when the specific metal atom contained in the metal particle is selected from two or more types including Fe atom, Cu atom, Ag atom and Zn atom, the respective metal atoms contained in the metal particle are The content of specific metal atoms is 0.01 to 50 ppb by mass relative to the total mass of the polishing liquid.

如申請專利範圍第8項所述之研磨液，其中由下述式(1)計算之含量比T1係30000~500000，式(1)：T1=該過氧化氫的含量/該金屬雜質所含有之選自包括Fe原子、Cu原子、Ag原子及Zn原子之群組中的特定金屬原子的總計含量。 The polishing liquid described in item 8 of the scope of the application, wherein the content ratio T1 calculated by the following formula (1) is 30000~500000, and the formula (1): T1=the content of the hydrogen peroxide/the metal impurity contained It is the total content of specific metal atoms selected from the group consisting of Fe atoms, Cu atoms, Ag atoms, and Zn atoms.

如申請專利範圍第1項至第5項中任一項所述之研磨液，其還含有下述通式(1)所表示之化合物，該通式(1)所表示之化合物相對於研磨液總質量係0.00001~1000質量ppb，通式(1)：N(R¹)(R²)(R³)，通式(1)中，R¹~R³分別獨立地表示氫原子或烷基。 The polishing liquid according to any one of items 1 to 5 of the scope of application, further comprising a compound represented by the following general formula (1), which is relative to the polishing liquid The total mass is 0.00001~1000 mass ppb, general formula (1): N(R ¹ )(R ² )(R ³ ), in general formula (1), R ¹ to R ³ each independently represent a hydrogen atom or an alkyl group .

如申請專利範圍第1項至第5項中任一項所述之研磨液，其還含有選自包括N-椰油醯基肌胺酸鹽、N-月桂醯肌胺酸鹽、N-硬脂醯肌胺酸鹽、N-油醯肌胺酸鹽、N-肉荳蔻醯肌胺酸鹽、N-月桂醯甘胺酸、N-肉荳蔻醯甘胺酸、N-棕櫚醯甘胺酸、N-月桂醯谷胺酸、N-椰油醯谷胺酸、N-椰油醯谷胺酸鉀、N-月桂醯肌胺酸鉀、N-月桂醯丙胺酸鹽、N-肉荳蔻醯丙胺酸鹽及N-椰油丙胺酸鉀之群組中的至少一種化合物，該化合物的總含量相對於研磨液總質量係0.001~5質量%。 The polishing liquid according to any one of items 1 to 5 of the scope of the application, further containing a compound selected from the group consisting of N-coco sarcosinate, N-lauro sarcosinate, N-hard sarcosinate Fatty sarcosinate, N-oleosine sarcosinate, N-myristyl sarcosinate, N-lauroglycine, N-myristyl glycine, N-palmitosylglycine , N-Lauroglutamic Acid, N-Cocoglutamic Acid, Potassium N-Cocoglutamate, Potassium N-Laurosarcosine, N-Lauryl Alanine, N-Myristate Alanine At least one compound in the group of salt and potassium N-cocoalanine, the total content of the compound is 0.001 to 5% by mass relative to the total mass of the grinding liquid.

如申請專利範圍第1項至第5項中任一項所述之研磨液，其中作為該唑系化合物，含有苯并***系化合物及選自包括1,2,4-***系化合物、吡唑系化合物及咪唑系化合物之群組中的任一種以上。 The polishing liquid according to any one of items 1 to 5 of the claimed scope, wherein as the azole compound, a benzotriazole compound and a compound selected from the group consisting of 1,2,4-triazole compound, Any one or more of the group of pyrazole-based compounds and imidazole-based compounds.

如申請專利範圍第1項至第5項中任一項所述之研磨液，其中該締合度1~3的膠體二氧化矽的由下述式(2)計算之化學機械研磨前後的平均粒徑之比T2係1~5，式(2)：T2=化學機械研磨後的平均粒徑/化學機械研磨前的平均粒徑。 The polishing liquid according to any one of items 1 to 5 of the scope of the application, wherein the average particle size of the colloidal silica with an association degree of 1 to 3 is calculated by the following formula (2) before and after chemical mechanical polishing The diameter ratio T2 is 1 to 5, and formula (2): T2=average particle size after chemical mechanical polishing/average particle size before chemical mechanical polishing.

一種研磨液，其含有：締合度1~3的膠體二氧化矽；有機酸；唑系化合物；過氧化氫；以及有機溶劑；並且用於對含鈷的層進行化學機械研磨，其中在使該研磨液與鈷基板接觸24小時時，在該鈷基板上形成含有鈷原子之厚度0.5~20nm的反應層，且該有機溶劑的含量相對於研磨液總質量係0.01~20質量%。 A polishing liquid, which contains: colloidal silica with an association degree of 1 to 3; an organic acid; an azole compound; hydrogen peroxide; and an organic solvent; When the polishing liquid is in contact with the cobalt substrate for 24 hours, a reaction layer with a thickness of 0.5-20 nm containing cobalt atoms is formed on the cobalt substrate, and the content of the organic solvent is 0.01-20 mass % relative to the total mass of the polishing liquid.

如申請專利範圍第15項所述之研磨液，其中該有機酸係選自包括順丁烯二酸、反丁烯二酸、2-羥基苯甲酸、3-羥基苯甲酸、4-羥基苯甲酸、鄰苯二甲酸、間苯二甲酸、對苯二甲酸、1,2,3-苯三甲酸、1,2,4-苯三甲酸、1,3,5-苯三甲酸、1,2,3,5-苯四甲酸、1,2,3,4-苯四甲酸、1,2,4,5-苯四甲酸、苯六甲酸、聯苯二甲酸、檸檬酸、琥珀酸、蘋果酸、丙二酸及鄰胺苯甲酸之群組中的至少一種，該有機酸的含量相對於研磨液總質量係0.01~0.3質量%。 The polishing liquid according to claim 15, wherein the organic acid is selected from the group consisting of maleic acid, fumaric acid, 2-hydroxybenzoic acid, 3-hydroxybenzoic acid, and 4-hydroxybenzoic acid , phthalic acid, isophthalic acid, terephthalic acid, 1,2,3-benzenetri Formic acid, 1,2,4-benzenetricarboxylic acid, 1,3,5-benzenetricarboxylic acid, 1,2,3,5-benzenetetracarboxylic acid, 1,2,3,4-benzenetetracarboxylic acid, 1,2, At least one selected from the group consisting of 4,5-benzenetetracarboxylic acid, mellitic acid, biphthalic acid, citric acid, succinic acid, malic acid, malonic acid and anthranilic acid, the content of the organic acid is relative to grinding The total mass of the liquid is 0.01 to 0.3 mass %.

如申請專利範圍第15項所述之研磨液，其中該過氧化氫的含量係0.001~5質量%。 The polishing liquid according to claim 15, wherein the content of the hydrogen peroxide is 0.001-5 mass %.

如申請專利範圍第15項所述之研磨液，其還含有含金屬原子之金屬雜質，該金屬雜質含有選自包括Fe原子、Cu原子、Ag原子及Zn原子之群組中的至少一種特定金屬原子，在該特定金屬原子係選自包括Fe原子、Cu原子、Ag原子及Zn原子之一種之情況下，該特定金屬原子的含量相對於研磨液總質量係0.01~100質量ppb，在該特定金屬原子係選自包括Fe原子、Cu原子、Ag原子及Zn原子之兩種以上之情況下，各自的該特定金屬原子的含量相對於研磨液總質量係0.01~100質量ppb。 The polishing liquid as described in item 15 of the claimed scope further contains metal impurities containing metal atoms, the metal impurities containing at least one specific metal selected from the group consisting of Fe atoms, Cu atoms, Ag atoms and Zn atoms Atom, in the case where the specific metal atom is selected from one of Fe atoms, Cu atoms, Ag atoms and Zn atoms, the content of the specific metal atoms is 0.01 to 100 mass ppb relative to the total mass of the grinding liquid. When the metal atom is selected from two or more types including Fe atom, Cu atom, Ag atom, and Zn atom, the content of each specific metal atom is 0.01 to 100 mass ppb relative to the total mass of the polishing liquid.

如申請專利範圍第18項所述之研磨液，其中該金屬雜質含有金屬粒子，該金屬粒子含有選自包括Fe原子、Cu原子、Ag原子及Zn原子之群組中的至少一種特定金屬原子，在該金屬粒子所含有之該特定金屬原子係選自包括Fe原子、Cu原子、Ag原子及Zn原子之一種之情況下，該金屬粒子所含有之該特定金屬原子的含量相對於研磨液總質量係0.01~50質量ppb，在該金屬粒子所含有之該特定金屬原子係選自包括Fe原子、Cu原子、Ag原子及Zn原子之兩種以上之情況下，該金屬粒子所含有之各自的該特定金屬原子的含量相對於研磨液總質量係0.01~50質量ppb。 The polishing liquid according to claim 18, wherein the metal impurities contain metal particles, and the metal particles contain at least one specific metal atom selected from the group consisting of Fe atoms, Cu atoms, Ag atoms, and Zn atoms, When the specific metal atoms contained in the metal particles are selected from one of Fe atoms, Cu atoms, Ag atoms and Zn atoms, the content of the specific metal atoms contained in the metal particles is relative to the total mass of the polishing liquid Department of 0.01~50 quality ppb, When the specific metal atom contained in the metal particle is selected from two or more types including Fe atom, Cu atom, Ag atom and Zn atom, the content of the specific metal atom contained in the metal particle is relative to The total mass of the grinding liquid is 0.01~50 mass ppb.

如申請專利範圍第18項所述之研磨液，其中由下述式(1)計算之含量比T1係30000~500000，式(1)：T1=該過氧化氫的含量/該金屬雜質所含有之選自包括Fe原子、Cu原子、Ag原子及Zn原子之群組中的特定金屬原子的總計含量。 The polishing liquid described in item 18 of the scope of the application, wherein the content ratio T1 calculated by the following formula (1) is 30,000~500,000, and the formula (1): T1=the content of the hydrogen peroxide/the metal impurity contained It is the total content of specific metal atoms selected from the group consisting of Fe atoms, Cu atoms, Ag atoms, and Zn atoms.

如申請專利範圍第15項所述之研磨液，其還含有下述通式(1)所表示之化合物，該通式(1)所表示之化合物相對於研磨液總質量係0.00001~1000質量ppb，通式(1)：N(R¹)(R²)(R³)，通式(1)中，R¹~R³分別獨立地表示氫原子或烷基。 The polishing liquid described in item 15 of the scope of the application further contains a compound represented by the following general formula (1), and the compound represented by the general formula (1) is 0.00001-1000 mass ppb relative to the total mass of the polishing liquid , general formula (1): N(R ¹ )(R ² )(R ³ ), in general formula (1), R ¹ to R ³ independently represent a hydrogen atom or an alkyl group.

如申請專利範圍第15項所述之研磨液，其還含有選自包括N-椰油醯基肌胺酸鹽、N-月桂醯肌胺酸鹽、N-硬脂醯肌胺酸鹽、N-油醯肌胺酸鹽、N-肉荳蔻醯肌胺酸鹽、N-月桂醯甘胺酸、N-肉荳蔻醯甘胺酸、N-棕櫚醯甘胺酸、N-月桂醯谷胺酸、N-椰油醯谷胺酸、N-椰油醯谷胺酸鉀、N-月桂醯肌胺酸鉀、N-月桂醯丙胺酸鹽、N-肉荳蔻醯丙胺酸鹽及N-椰油丙胺酸鉀之群組中的至少一種化合物，該化合物的總含量相對於研磨液總質量係0.001~5質量%。 The polishing liquid as described in item 15 of the claimed scope further contains a compound selected from the group consisting of N-cocoyl sarcosinate, N-lauro sarcosinate, N-stearyl sarcosinate, N- - Oleosarcosinate, N-Myristylsarcosinate, N-Laurylglycine, N-Myristylglycine, N-Palmitosylglycine, N-Laurylglutamate , N-Cocoglutamate, Potassium N-Cocoglutamate, Potassium N-Laurosarcosinate, N-Laureate, N-Myristate and N-Coconut Oil At least one compound in the group of potassium alanine, the total content of the compound is 0.001 to 5% by mass relative to the total mass of the polishing liquid.

如申請專利範圍第15項所述之研磨液，其中作為該唑系化合物，含有苯并***系化合物及選自包括1,2,4-***系化合物、吡唑系化合物及咪唑系化合物之群組中的任一種以上。 The polishing liquid as described in item 15 of the scope of the application, wherein The azole-based compound includes a benzotriazole-based compound and any one or more selected from the group consisting of a 1,2,4-triazole-based compound, a pyrazole-based compound, and an imidazole-based compound.

一種研磨液之製造方法，其含有稀釋步驟，對含有締合度1~3的膠體二氧化矽、有機酸、唑系化合物及過氧化氫之研磨液原液混合水，獲得如申請專利範圍第1項至第23項中任一項所述之研磨液。 A method for manufacturing a polishing liquid, comprising a dilution step, mixing water with a polishing liquid stock solution containing colloidal silica with an association degree of 1 to 3, an organic acid, an azole compound and hydrogen peroxide, and obtaining the first item in the scope of the patent application. To the polishing liquid described in any one of item 23.

一種研磨液原液，其含有締合度1~3的膠體二氧化矽、有機酸、唑系化合物及過氧化氫，其中為了製備如申請專利範圍1項至第23項中任一項所述之研磨液，稀釋成2~50倍而使用。 A lapping liquid stock solution, which contains colloidal silica with an association degree of 1 to 3, an organic acid, an azole compound and hydrogen peroxide, wherein in order to prepare the lapping as described in any one of the claims 1 to 23 of the patent application scope liquid, diluted 2 to 50 times and used.

如申請專利範圍第25項所述之研磨液原液，其中用水稀釋成2~50倍時，稀釋前後的pH變化小於0.01~1。 The polishing liquid stock solution as described in item 25 of the patent application scope, wherein when diluted with water to 2-50 times, the pH change before and after the dilution is less than 0.01-1.

一種研磨液原液收容體，其具有：如申請專利範圍第25項或第26項所述之研磨液原液；以及收容該研磨液原液之由不含鐵之金屬材料形成之容器。 A polishing liquid stock solution container, comprising: the polishing liquid stock liquid as described in item 25 or 26 of the scope of the patent application; and a container formed of a non-ferrous metal material for accommodating the polishing liquid stock liquid.

一種化學機械研磨方法，其包括如下步驟：對安裝於研磨平台之研磨墊，一邊供給如申請專利範圍第1項至第23項中任一項所述之研磨液，一邊使被研磨體的被研磨面與該研磨墊接觸，使該被研磨體及該研磨墊相對移動而研磨該被研磨面，從而獲得已研磨之被研磨體。 A chemical mechanical polishing method, comprising the steps of: supplying the grinding liquid as described in any one of the 1st to 23rd items of the patent application scope to the polishing pad installed on the polishing platform, while making the surface of the body to be ground be ground. The polishing surface is in contact with the polishing pad, and the body to be polished and the polishing pad are moved relatively to polish the surface to be polished, thereby obtaining a polished body to be polished.

如申請專利範圍第28項所述之化學機械研磨方法，其中該被研磨體含有包括選自包括鈷及鈷合金之群組中的至少一種之含鈷的層。 The chemical mechanical polishing method of claim 28, wherein the body to be ground contains a cobalt-containing layer including at least one selected from the group consisting of cobalt and a cobalt alloy.