TW201134928A - Polishing agent for polishing copper and polishing method using the same - Google Patents

Abstract

The polishing agent for polishing copper of this invention includes: at least one levelling agent selected from a group consisted of tetrazole and its derivative, triazole and its derivative (excluding benzotriazole and its derivative), an inorganic acid, an amino acid, a protective film forming agent, abrasives, an oxidizing agent and water. A content of inorganic acid is 0.080 mol/kg or more, a content of amino acid is 0.200 mol/kg or more, a content of protective film forming agent is 0.020 mol/kg or more, and a ratio of the content of inorganic acid to the content of protective film forming agent is 3.0 or higher.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an abrasive for copper polishing and a polishing method using the same. Further, the present invention relates in particular to an abrasive for copper polishing which is suitable for use in a chemical mechanical polishing (CMP) step, and which has a high polishing rate, and a polishing method using the same. [Prior Art] In order to improve the performance of a large-scale integrated circuit (LSI), a copper alloy has been used as a wiring material instead of the prior aluminum alloy. Steel alloys are difficult to perform microfabrication by dry etching which is frequently used in the formation of prior aluminum alloy wiring. Therefore, in the microfabrication of the copper alloy, a so-called damascene method is mainly used, that is, a copper alloy film is deposited on an insulating film in which a groove portion (concave portion) and a ridge portion (protrusion portion) are formed in advance, and a copper alloy is buried in the groove portion, and secondly, A copper alloy film (a copper alloy film other than the groove portion) deposited on the ridge portion is removed by CMP to form a buried wiring (see, for example, Japanese Laid-Open Patent Publication No. Hei No. Hei. The general method for CMP of a metal such as a copper alloy is as follows: a polishing cloth (polishing pad) is attached to a circular polishing platen, and the metal is impregnated with the abrasive to the surface of the polishing cloth to form a substrate. The surface of the metal film is pressed against the surface of the polishing cloth, and a predetermined pressure (hereinafter referred to as "polishing pressure") is applied to the metal film from the back surface thereof to rotate the polishing plate, and the polishing agent and the ridge portion are formed. The metal film on the ridge is removed by mechanical friction of the metal film. 201134928 The metal grinding ship used in the CMP often contains an oxidizing agent and solid abrasive grains (hereinafter referred to as "abrasive grains"), and further contains a metal oxide dissolving agent and a protective film forming agent as needed. The basic mechanism of CMp using an abrasive containing an oxidizing agent is: first, the surface of the metal film is oxidized by an oxidizing agent to form an oxide layer, and the oxide layer is removed by grinding particles, thereby polishing the metal film. . In such a polishing method, the oxide layer on the surface of the metal film deposited on the groove portion of the insulating film is not sufficiently in contact with the polishing cloth, and the effect of removing the abrasive grains is not obtained, but the metal film deposited on the ridge portion is formed. The oxide layer of the surface is removed by contact with the abrasive cloth. Therefore, as the CMp progresses, the metal film on the ridge portion is removed to planarize the surface of the substrate (for example,

Of Electrochemical Society, Vol. 138, No. 11 (issued in 1991), pp. 3460~3464). In the production of LSI, the thickness of the copper alloy to be polished is about 丨μηη, and an abrasive having a polishing rate of about 5000 A/min is used (for example, refer to Japanese Laid-Open Patent Publication No. 2003-124160). On the other hand, in recent years, CMP processing of copper alloys has begun to be applied to the formation of high-performance, fine wiring boards such as package substrates or the formation of TSV (through silicon Via) which has attracted attention as a new packaging method. However, in these applications, since the thickness of the metal film is thicker than that of the LSI, the conventional LSI polishing agent has a problem that the polishing rate is low and the productivity is lowered. In particular, in the case of forming a TSV, for example, a copper alloy having a thickness of 1 Gpm or more is required to be polished, so that an abrasive can be required. In addition, in order to further increase the polishing rate, the copper bathing agent in the polishing agent is increased in increments, and the female impurities are high. Therefore, there is a tendency that the copper surface after polishing becomes thick. And the flatness is lowered. On the other hand, in order to prevent the copper surface from becoming thick and the protective film forming agent (anti-side) in the abrasive is excessively increased, the hydrophobicity of the copper reaction layer formed by the copper and the abrasive becomes too high, so There is a problem of coloring the polishing pad after grinding. The coloring of the mat is caused by the copper reaction layer remaining on the polishing pad after the polishing process, which causes deterioration of polishing properties such as a decrease in polishing rate. SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object thereof is to provide an abrasive for copper polishing which can polish a copper film by a high polishing rate and which is smooth and does not cause pad coloring, and a polishing agent using the same. Grinding method. The present invention has been found to be obtained by controlling the content of a mineral acid, an amino acid, and a protective film forming agent, a kind of a levelling agent, etc., thereby obtaining a high grinding speed and being smooth and not produced. An abrasive for copper polishing in which a pad is colored to polish a copper film. That is, the abrasive for copper polishing of the present invention comprises: a derivative selected from the group consisting of four U, a derivative of tetras, a triazole, and a derivative of the triazole (except for the derivatives of benzotriazole and the benzotriazole) a smoothing agent of at least one of the group consisting of inorganic acid, amino acid, detailed film forming agent, abrasive particles, oxidizing agent, and water; and the content of the inorganic acid is 0.080 mol/kg or more, and the amino acid The content of the protective film forming agent is more than 0.200 mol/kg, and the content is 0.020 mol/kg or more.

S 6 201134928r The content of the inorganic acid relative to the content of the protective film forming agent/the content of the protective film forming agent is 30 or more. In the case of the inorganic acid, the polishing agent for copper polishing of the invention can be used to produce a film such as a high-performance wiring board or a TSV by smoothing and polishing the copper film without causing enamel coloring (for example, film thickness). In the present invention, the metal containing the copper is a metal containing copper (for example, copper). Alloy two 'oxygen: set: =::). Further, in the present invention, if the metal film is not particularly cut, the metal film is preferably cut, and the smoothing agent is selected from the group consisting of the compound represented by the following formula (I) and the following formula (11). At least 1 in the group of the compounds represented by the above == In this case, the effect of improving the polishing rate can be more highly achieved, and (surfacer〇ughness) 201134928 ' ·(!) R1V>

N-N

Wherein R1 represents a hydrogen atom, an alkyl group having a carbon number of 丨~12, or an amine group] [Chemical 2] R2

(H) wherein R2 and R3 each independently represent a hydrogen atom, a carbon group having 12 carbon atoms or an amine group, and preferably the inorganic acid is at least one selected from the group consisting of sulfuric acid and phosphoric acid. . A preferred guanamine acid has a pKal of 2 to 3. In addition, "pKal is a common logarithm indicating that the acid disolvent tilt (add di-n constant) of the i-th dissociable acidic group is negative of the equilibrium constant Ka of the radical. - It is also preferable to protect the shape of the rider. It is preferable that at least one of the group consisting of the three bonds and the derivative of the benzoquinone dioxin is at least one selected from the group consisting of colloidal gas hydrated fossils and colloidal oxidized 201134928 aluminum, and The average particle diameter of the abrasive grains is not more than 10 nm. Further, it is preferable that the oxidizing agent is at least one selected from the group consisting of hydrogen peroxide, persulfuric acid, and persulfate. The polishing agent for copper polishing of the present invention has a pH of 1.5 to 4.0. In this case, the abrasive for copper polishing of the present invention contains a strong dissolving inorganic acid and an amino acid, and has a pH of 丨5 to 4 Since the pH is a buffer solution, it is difficult to cause a pH change even if the steel as the object to be polished is dissolved in the polishing agent. Therefore, it is possible to stably maintain a high polishing rate without depending on the progress of the polishing. The invention provides a grinding method The polishing method includes a step of polishing a copper-containing metal film by using the above-described copper polishing abrasive to remove at least a part of the metal film. By such a polishing method, it is smooth and non-produced by a high polishing rate. The mat is colored to polish the crucible. Even in the case where it is necessary to polish a thick metal film such as a high-performance wiring board or a TSV, it can be sufficiently polished by a short time to ensure sufficient Productivity. The improvement of productivity and the improvement of product yield can be achieved by the above-mentioned polishing method. [Effect of the Invention] According to the present invention, a copper abrasive grinding agent and a grinding method for the agent can be provided. For the sake of detail, in the state where the polished copper surface is smooth, no pad coloring is produced and the grinding speed is faster than usual. With the present invention, the special limb obtains the 201134928 grinding of the steel. An abrasive having a speed of more than 30,000 A/min (preferably 40,000 A/min), so that it is desirable to manufacture a fabric such as a high-performance wiring board or a TSV, which is necessary for a short period of time. The polishing agent for steel polishing and the polishing method using the same in the case of polishing the copper in a large amount. [Embodiment] The polishing agent for copper polishing of the present embodiment (hereinafter simply referred to as "abrasive agent") includes: At least one smoothing agent of tetrazolium, a derivative of the tetrazole, a triazole, and a derivative of the triazole (except for benzotriazole and a derivative of the benzotriazole), inorganic Acid, amino acid, protective film former 'abrasive grain, oxidant, and water. In the present embodiment, the content of the inorganic acid is 0.080 mol/kg or more, and the content of the amino acid is 0200 mol/kg or more. The content of the protective film forming agent is 〇〇2〇m〇i/kg or more, and the inorganic acid is The ratio of the content to the content of the protective film forming agent is 3 Å or more. Further, although the use of the inorganic acid or the amino acid alone can also increase the polishing rate to some extent, in this case, the polishing rate improving effect in accordance with the content cannot be obtained. On the other hand, the polishing agent of the present embodiment can be used in combination with an inorganic acid and an amino acid, and the content of the above-mentioned specific amount can be drastically improved. Further, on the other hand, the polishing agent of the present embodiment has an effect that it is possible to reduce the effect of obtaining a predetermined polishing rate and extracting the south effect as compared with the case where the inorganic acid or the amino acid is used alone. The content of the inorganic acid and the amino acid 〇 In addition, in the prior abrasive, the use of the protective film forming agent has 201134928. The effect of suppressing the etching of copper due to the formation of a protective film on the surface of the copper, and the suppression of the polishing rate on the other hand. situation. On the other hand, according to the polishing agent of the present embodiment, the specific amount of the inorganic acid and the amino acid are used in combination, and a specific amount of the protective film forming agent is used, whereby the polishing rate can be maintained at a high level and the surname speed can be obtained. The suppression effect. Further, the reason why the polishing speed is improved by the polishing agent of the present embodiment is not necessarily clear, but the inventors of the present invention presume the following. That is, a "reaction layer" containing a protective film forming agent and copper ions is formed on the surface of the copper by the action of the film-forming film forming agent and the inorganic acid. Further, the amino acid is chelated on the copper ion, so that the reaction layer becomes more easily removed and the grinding is promoted. Such multiple polishing processes are not performed separately and simultaneously in parallel, but each polishing process is performed in association with other polishing processes. Therefore, the grinding process which causes only one of the inorganic acid, the amino acid, and the protective film forming agent to be added to the 'other components' also becomes a bottleneck (speed limiting process), and the polishing rate as a whole is not efficiently improved. . On the other hand, in the polishing agent of the present embodiment, by using a specific amount of each component, each polishing process can be promoted to increase the polishing rate efficiently. Further, in order to further increase the polishing rate, when the amount of the copper solubilizing agent such as the inorganic acid or the organic compound is increased, the content of the protective film forming agent is relatively small, and the corrosion resistance to copper is improved. Therefore, there is a tendency that the surface of the copper after polishing becomes thick and the flatness is lowered. On the other hand, in order to prevent the copper surface from becoming thick and the protective film forming agent in the abrasive is excessively increased, there is a problem that the hydrophobicity of the copper reaction layer formed by copper and the abrasive is too high. The polishing pad is colored after grinding. Therefore, by merely adjusting the content of the protective film forming agent, it is difficult to achieve a high balance between the suppression of the coloration of the polishing pad and the reduction of the roughness of the copper surface after polishing. Further, in order to eliminate the coloration of the mat, in addition to reducing the content of the protective film forming agent, it is also considered to increase the amount of the dissolving agent such as a mineral acid or an organic acid, but the surface roughness is adversely affected as described above. . Therefore, the present inventors have found that the content of the protective film forming agent is sufficiently low in the degree of coloration of the mat and the copper etching rate is sufficiently low, and the smoothing agent is added, whereby the effect of improving the polishing rate can be highly achieved. The effect of reducing the surface roughness and the suppression effect of the mat coloring. By adding a certain amount of the protective film forming agent, the roughness of the copper surface after polishing can be reduced by the suppression effect of copper etching, but at the same time, it is possible to produce a color. On the other hand, the smoothing agent contained in the polishing agent of the present embodiment does not necessarily lower the etching rate. Such a smoothing agent can reduce the roughness of the surface of the copper after polishing even if the etching rate is not lowered, and is different from the protective film forming agent in that the coloring of the mat is not caused. The reason why the smoothing agent reduces the roughness is not necessarily clear, but the reason is as follows. That is, although the protective film forming agent can exert a protective effect on the surface of the copper on the entire surface to lower the y-speed, the effect of reducing the unevenness of the copper surface is low. On the other hand, the smoothing agent locally applies the protective effect of the copper surface to the concave portion, thereby promoting the polishing of the convex portion, thereby reducing the unevenness. Hereinafter, the components contained in the polishing agent of the present embodiment will be described more specifically.

S 12 201134928 (pH of the abrasive) The pH of the abrasive is preferably in the range of 1.5 to 4.0 in terms of the fact that the copper polishing speed of the CMP is larger and the copper film is not rotted. Further, if the pH is 1.5 or more, the surface roughness of the copper film can be further reduced, and from the same viewpoint, the pH is preferably 2.0 or more. When the pH is 4.0 or less, the polishing rate of CMP is increased to become a more practical abrasive. From the same viewpoint, the pH is preferably 3.0 or less. The polishing agent of this embodiment is a pH buffer solution containing a mineral acid. The inorganic acid is usually a strong acid. If the abrasive contains a large amount of inorganic acid, the pH of the abrasive is excessively lowered to make it difficult to adjust the pH to a range of from 1.5 to 4.0. However, in the abrasive of the present embodiment, an amino acid is contained in addition to the inorganic acid, and by adjusting the contents of the inorganic acid and the amino acid, the abrasive can be easily made into a pH value of 1.5 to 4.0. Buffer solution. The polishing agent of the present embodiment may contain an acidic component or an assay component as a pH adjuster to adjust to a desired pH value. This? Examples of the 11-value adjusting agent include organic acids such as oxalic acid, tartaric acid malonic acid, maleic acid, malic acid, and citric acid, hydrochloric acid, nitric acid, ammonia, sodium hydroxide, and hydrogen hydroxide; ammonium and the like. These compounds may be used alone or in combination of two or more groups. Of course, when the pH of the abrasive is not included in the range of 1.5 to 4.0 without the pH adjusting agent, the abrasive does not have to have a pH value. The pH of the abrasive can be adjusted by a pH meter (for example, Horiba Manufacturing Co., Ltd.) , PH meter F8 £) for measurement. As the measured value of PH value, the buffer (o-dipic acid pH buffer, pH 4 13 201134928 neutral acid pH buffer, pH 6.86 (25 ° C)) 2 After the dot correction, the electrode was placed in the abrasive and stabilized after 2 minutes or more. (Inorganic acid) The inorganic acid can be any known inorganic acid, and examples thereof include hydrochloric acid, hydrobromic acid, hydromoic acid, sulfuric acid, acid acid, and nitric acid. These compounds may be used alone or in combination of two or more. Among the above inorganic acids, at least the polishing rate of CMP is large, and the surface roughness of the copper film can be further reduced, preferably at least one selected from the group consisting of sulfuric acid, squaric acid, sulfuric acid, and a mixture of acid-filled acid. One. Further, a mineral acid similar to the pH adjuster can be used, and a different inorganic acid can also be used. In terms of excellent polishing rate, the content of the inorganic acid is 0.080 mol/kg or more with respect to the total amount of the abrasive, preferably 〇〇9〇m〇1/kg = dying, more preferably 0· More than 100 mol/kg. Since there is a tendency that the polishing rate does not increase even if a certain amount or more of the inorganic acid is added, the content of the inorganic acid is preferably 1.000 mol/kg or less, more preferably in terms of suppressing an increase in the content of the inorganic acid 4. It is 〇m〇1/kg or less. In addition, in the case where the abrasive contains a plurality of inorganic acids, the "inorganic acid content" and the total content of each inorganic acid are used, and when a mineral acid such as (tetra) acid or acid is used as a pH adjuster, The content of the inorganic acid includes the content of the inorganic acid used as the pH adjuster. (Amino acid) 201134928 =, alanine, shaft acid, leucine, isoleucine, serine, threonine Dehydroabietic acid, 西西秦, f thiaminic acid, aspartic acid, amylin, aminic acid, arginine, albinoic acid, _acid, histidine, tryptophan, aminic acid Amine acid and the like. These compounds may be used singly or in combination of two or more. In the above-mentioned amino acid sock, it is preferred to use an amino acid having a pKal of 2 to 3 in terms of a pH of the polishing agent of 1>5 to 4.0. As such an amino acid, specifically, among the above-exemplified compounds, there are glycine =, alanine, _ acid, leucine, isoleucine, serine, sulphate, sulphonic acid, aspartic acid For the combination of proline, glutamic acid, lysine, arginine and tryptophan, glycine acid is particularly preferred in terms of high polishing efficiency and low cost. In addition, the value of "pKal" can be referred to the chemical handbook and the basic compilation (revision of the fifth edition, Maruzen Co., Ltd.). The content of the amino acid is 0.200 mol/kg or more, preferably 0.230 mol/kg or more, more preferably 〇·25 〇mol/kg, based on the total amount of the polishing agent. the above. Since the polishing rate does not increase even if a certain amount or more of the amino acid is added, the content of the amino acid is preferably 2.000 mol/kg or less in terms of suppressing an increase in the content of the amino acid. More preferably, it is 1.800 mol/kg or less. (Protective film forming agent) The protective film forming agent means a substance having a function of forming a protective film on the surface of copper. However, as described above, the protective film forming agent constitutes a "reaction layer" which is removed during polishing, and does not necessarily form a "protection" for preventing copper from being polished.

201134928 L film." The protective film forming agent may have an effective water solubility in order to exhibit the effect of adding the protective film forming agent, and a conventionally known one can be used without particular limitation. The protective film forming agent may, for example, be quinaldic acid, Andoni, liuyi, keweiwei L complex, (iv) compound or the like, and among them, a benzoquinone compound is preferred. These compounds may be used alone or in combination of two or more. The benzoquinone tris-salt compound is preferably at least one selected from the group consisting of benzoquinone trisodium and benzoquinone trisporin in terms of excellent balance between polishing rate and anti-money property. Examples of the benzotriazole derivative include 1-pyridyltriazole, 1-dihydroxypropylbenzotriazole, 2,3-di-reproperylbenzotriazole, and 4-hydroxybenzoquinone. Azole, 4_carboxyl group ("^^ benzotriazole = 4-carboxy(-1H.) benzotriazole methyl ester, 4·carboxyl(1)^^ benzotriazole), 4-carboxyl (-1H·) Phenyltriazole octyl ester, 5-hexyl benzotriazole, • benzoquinone di-sal-1-methyl][1,2,4-triazolyl+methyldeethylhexyl]aminemethylphenylhydrazine Triazole, naphthoquinone triazole, bis[(1-benzotriazolyl)indolyl]phosphonic acid, etc. Examples of the imidazole compound include 2-methylimidazole, 2-ethylimidazole, 2-isopropylidazole, 2 _propylimidazole, 2-butylimidazole, 4-methylimidazole, 2,4-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-aminoimidazole, etc. Examples of the pyrazole compound include 3,5·dimercaptopyrazole, 3-amino-5-nonylpyrazole, 4-methylpyrazole, 3-amino-5-hydroxypyrazole, and the like. In terms of further reducing the etching rate of the metal, the content of the protective film forming agent is 〇.〇2〇m〇1/kg to 201134928, preferably 0.0, relative to the total amount of the abrasive. 25 mol/kg or more, more preferably 〇〇3〇m〇1/kg or more. Since there is a tendency that the polishing rate does not increase even if a certain amount or more of the protective film forming agent is added, the protective film forming agent is inhibited. In terms of the content increase, the content of the protective film forming agent is preferably 〇3〇〇mol/kg or less, and more preferably 〇·25〇mol/kg or less. Since the grinding speed is increased and the enamel color is reduced In view of the above, the ratio of the content of the inorganic acid (mol/kg) to the content of the protective film forming agent (m〇1/kg) (the content of the inorganic acid/the content of the protective film forming agent) is preferably 3 Å or more. The 疋3.2 or more is more preferably 3.5 or more. In terms of further suppressing the increase in surface roughness, the above ratio is preferably 12 or less, more preferably 10 or less. (Smoothing agent) The so-called smoothing agent is It means that the surface of the copper after polishing is kept smooth in a content range which does not greatly affect the etching rate, the polishing rate, and the coloring of the crucible. In the abrasive of the embodiment, the smoothing agent is selected from the group consisting of tetrazole. Derivatization of the tetrazole At least one of the group consisting of a substance, a triterpene, and a derivative of the triterpenoid (except for the benzotriazole and the derivative of the clandaceous triazole). These compounds may be used alone or in combination of two or more. In order to exhibit the effect of adding a smoothing agent, it is preferred to have an effective water solubility. The tetrazole and the derivative of the tetrazole are preferably compounds represented by the following formula d). More preferably, the compound represented by the formula (1) is a derivative such as 1H-tetrasodium; 5-amino-1H-tetrazole, 5-methyl-1H.tetrazole or 5-phenyl-1H.tetrazole. 17 201134928

(1) wherein R1 represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an amine group; and the triazole derivative is preferably 1,2,3-triazole or a derivative thereof, 1,2,4-triazole and its derivatives. Specific examples of the 1,2,3-triazole and derivatives thereof include 1H-1,2,3-triazole, 2H-1,2,3-triazole, 4H-1,2,3-triazole, and the like. 1,2,3-triazole; 1-amino-4-indenyl-1Η-1,2,3-triazole, 5-methyl-1Η-1,2,3-triazol-1-amine, etc. Derivatives, etc. The 1,2,4-triazole and its derivative are preferably a compound represented by the following formula (II), and specific examples thereof include: 1Η-1,2,4-triazole; 3·amino group- 1Η-1,2,4-triazole, 3-mercapto-1,2,4-triazole, 3-nitro-1,2,4-triazole, 1,2,4-triazole-3- Deuteriumamine, 3-amino-5-mercapto-1,2,4-triazole, 3,5-diamino-1,2,4-triazole and the like. [Chemical 4] R2 Ν ΝΗ R3

_. «(Ε) Ν 201134928 [wherein R2 and R3 each independently represent a hydrogen atom, an alkyl group having a carbon number of 1 to 12, or an amine group] to further reduce the roughness of the copper surface after grinding t, the content of the smoothing agent is preferably 〇〇〇〇1 mol/kg or more, more preferably 0.0005 mol/kg or more, still more preferably 0.0010 mol/kg or more, based on the total amount of the abrasive. Since the surface roughness of the copper after polishing does not decrease even if a certain amount or more of the smoothing agent is added, the content of the smoothing agent is preferably 0.500 mol/kg or less in terms of suppressing an increase in the content of the smoothing agent. More preferably, it is 0.250 mol/kg or less.疋 (abrasive grains) The aluminum and cerium oxide abrasive grains are not particularly limited, and examples thereof include a oxidizing agent, a oxidized β ·· '·cerium dioxide, a titanium oxide, a tantalum carbide, and the like. Polyacrylic acid compound, polyethylene gas shaft = abrasive grain. In view of the fact that the dispersion stability in the abrasive is good, and the number of occurrences of scratches (scratches) due to CMp is small, it is preferable that the polishing is bismuth telluride and alumina; In terms of the more excellent grinding properties, the "grain of the granules" is: (4) oxygen odor. The manufacturing method of colloidal dioxolysis is known to be hydrolyzed or stone with sulphur oxide (S1lic0n alkoxide). The method of the replacement of the acid acid sodium. The manufacturing method of the colloidal oxidation is known to be advantageous = = method. The methods can be individually or in combination with the above-mentioned group 7 and the polishing rate is more excellent and can be Further, in terms of reducing the surface roughness of 19 20113492, it is preferred that the average particle diameter of the abrasive grains is 100 mn or less. When the average particle diameter of the abrasive grains is less than or equal to nm, the abrasive grains are more preferably It is at least one selected from the group consisting of colloidal silica dioxide and colloidal oxide. In addition, the average particle diameter of the abrasive particles means a laser diffraction type particle size distribution analyzer (for example, manufactured by Malvem Instruments). Master Sizemicr〇plu s, refractive index: 1.9285, light source, He-Ne laser, absorption is 〇) The D50 value (volume distribution median diameter, cumulative median value) of the abrasive grains in the abrasive is measured. In terms of the grinding action, the polishing rate is further increased, and the content of the abrasive grains is preferably 0.1 wt% or more with respect to the total amount of the abrasives. More preferably, it is 〇 2 wt% or more. The agent contains a large amount of abrasive grains, and the grinding speed is saturated and it becomes difficult to increase the grinding speed. Therefore, in terms of suppressing an increase in the content of the abrasive grains, and improving the aggregation of the abrasive grains or the increase in the abrasive damage, the abrasive grains are used. The content is preferably 20% by weight or less, more preferably 1% by weight or less, still more preferably 5% by weight or less. (Oxidant) The oxidizing agent can be used without particular limitation if it has an oxidation effect on copper. For example, hydrogen peroxide (H202); persulfuric acid; persulfate, potassium persulfate and the like; periodic acid; sodium periodate, periodic acid, etc., etc., wherein the polishing rate is excellent In terms of Preferably, it is at least one selected from the group consisting of hydrogen peroxide, persulfuric acid, and persulfate. These deuterating agents may be used alone or in combination of two or more. In terms of good grinding speed, the oxidation content is preferably 岐Q1 correction% or more, more preferably, relative to the total amount of the abrasive.

Wt% or more. Further, there is also a case where even if the polishing agent excessively contains oxygen = not mentioning 8 grinding speed or vice versa, the oxidizing agent is preferably 岐 2 Gwt% or less, more preferably 15 wt% (water) = grinding water , silk _ _, preferably the shirt for water 'ultra-pure water. The content of water in the abrasive may be the remainder of the content, if it contains GeΓ = mosquito in the abrasive. Further, the abrasive may optionally contain a water/troreal agent such as a polar solvent such as ethanol, acetic acid or propylene. = Qian Qiang ingredients, can also be used in the abrasives, such as dispersing agents or fresh colors, usually used in abrasives. (Method for Preserving the Abrasive Agent) The method for preserving the agent is not particularly limited, and may be prepared by containing all of the liquid-based abrasives, or may be prepared by reducing the amount of water from the one-liquid 5 abrasive. By concentrating the one-liquid type abrasive and maintaining (4): L can also be mixed with each other to form a target abrasive. The two liquids are divided into a first liquid and a second liquid. It can be stored in the case of a two-liquid abrasive. For example, a material such as a granule, a smoothing agent, an inorganic acid, an amino acid or a protective film may be added to the material of the sister material. = 21 201134928 == (4) Water content' is divided into a moisture-reducing slurry and a concentrated additive. The slurry and the additive are not mixed for benign. In addition, the abrasive may be used to extract more than three types of knife knives. (Grinding method) The polishing method of the present embodiment is characterized in that the polishing step includes polishing the metal film containing steel with the polishing agent, and removing the metal component in the polishing step. Is based on the formation of a metal film (the film to be polished) The metal film is applied to the polishing plate and the polishing cloth. The surface of the polishing film is applied between the metal film and the polishing cloth to polish the substrate and the grinding machine (4). In the case of the polishing method of the present embodiment, for example, the steps of polishing the coffee process, (4) the material and the additive liquid are mixed to obtain an abrasive; the polishing step, using the obtained abrasive, and the substrate by the polishing method The polishing agent of the present embodiment has a ship that is extremely brittle in comparison with the conventional polishing agent for copper polishing, and is suitable for high performance such as a package substrate such as LSI. In the manufacturing step of the micro-wiring board, the thick metal film is polished. More specifically, it is particularly suitable when the substrate of the copper-containing metal film to be polished has a thickness of, for example, 4 μm or more. As described above, as a step of polishing a very thick metal film, a TSV: Through Silicon Via formation step can be cited. 22 201134928 — Γ-1 TSV formation method Various methods have been proposed, and a specific example is a method called VIA-LAST which forms a via hole after forming a component. Hereinafter, referring to the drawing, in the VIA-LAST step A method of using the polishing agent of the present embodiment will be described. Fig. 1 (a), Fig. 1 (b), and Fig. 1 (c) are schematic cross-sectional views showing a step of forming a copper layer 4 on the ruthenium substrate 1. In the figure, the element 2 is formed at a predetermined position on the substrate 1 . Next, as shown in Fig. (b), the concave portion 3 for forming the through hole is formed by the plasma # scribe method. Next, a copper layer 4' is formed by laminating copper into the concave portion 3 by a method such as recording or electrolytic electrowinning to obtain a substrate 1A having a structure as shown in Fig. 1(c). Fig. 2 (a), Fig. 2 (b), and Fig. 2 (c) are schematic cross-sectional views showing a step of polishing the substrate 100 thus formed to form the bumps 5 on one side. While the abrasive is supplied between the surface of the copper layer 4 and the polishing cloth (not shown) in Fig. 2(a), the copper layer 4 is polished as shown in Fig. 2(b) until the element 2 is exposed. More specifically, the abrasive is supplied between the copper layer 4 of the substrate 1 and the surface of the polishing cloth of the polishing plate, while the copper layer 4 is pressed against the polishing cloth of the polishing plate. The copper layer 4 is polished by moving the polishing plate relative to the substrate 1A. Instead of the polishing cloth, a metal or resin brush can also be used. Further, the polishing can be carried out by blowing the abrasive at a predetermined pressure. As the polishing apparatus, for example, when grinding by a polishing cloth, a motor that can be connected to a motor that can change the rotational speed can be used, and a polishing plate with a polishing cloth attached thereto can hold the substrate to be polished. Retainer 23 201134928 (holder) of the usual grinding device. The material of the polishing cloth can be, for example, a general non-woven fabric, a foamed polyurethane, a porous fluorine resin, or the like, and is not particularly limited. The polishing conditions are not limited, and the rotational speed of the polishing plate is preferably a low-speed rotation of 200 rpm or less which does not fly out of the substrate. The pressure (grinding pressure) for pressing the substrate having the surface to be polished against the polishing cloth is preferably from 1 kPa to 100 kPa, and is preferable in order to improve the uniformity of the CMP speed in the surface to be polished and the flatness of the pattern. It is 5 kPa to 50 kPa. When the polishing is performed, the abrasive can be continuously supplied to the polishing cloth by a pump or the like. The amount of supply is not limited, and it is preferred that the abrasive always covers the surface of the abrasive cloth. After the completion of the polishing, the substrate is preferably sufficiently washed in running water, and then the water adhering to the substrate is dropped by a spin dryer or the like to be dried. In order to make the surface state of the polishing cloth always the same, it is preferable to increase the step of the polishing cloth before the polishing. For example, 'with diamond (dia_d) particles attached, the dresser adjusts the polishing cloth with a liquid containing at least water. Then, the CMP polishing step of the present embodiment is carried out, and it is preferable to increase the substrate cleaning step. Then, as shown in Fig. 2(c), on the surface portion of the exposed copper layer 4, the de-energizing method (4) is formed into a bump 5, and a substrate 2GG having a bump $ on one side is obtained. The material f of the bump 5 may be copper or the like. (f) (a), Fig. 3 (1), and Fig. 3 (C) are schematic cross-sectional views showing the steps of drawing the other surface. The method of " + CMP in the state shown in Fig. 3 (a) is a bump 5 for the wire 1

The surface of S 24 201134928r (the opposite surface on which the surface of the bump 5 is formed) is polished to expose the copper layer 4 (Fig. 3(b)). Next, the bumps 6 are formed by the same method as the above-described bump 5, and the TSV-formed substrate 3 is obtained (Fig. 3(c)). [Examples] Hereinafter, the present invention will be described by way of examples, but the present invention is not limited to the examples. In addition, "%" means "wt%" unless otherwise specified. (Preparation of abrasive) (Example 1) 1〇2 g of 96% sulfuric acid, 11 5 g of phosphoric acid with a concentration of 85%, 40_6 g of glycine, and 4g3 of benzoquinone l, 2,4-tris-sodium 〇g and an average particle #70 nm colloidal cerium oxide (solid content: 2% by weight) prepared by hydrolysis of tetraethoxy decane as an abrasive particle in an ammonia solution 5〇g was added to 600 g of pure water to dissolve the components other than the colloidal cerium oxide. After further adding 25% ammonia water to adjust the pH of the liquid to 2.6, pure water was further added to make the total amount 700 g. Add 300 g of hydrogen peroxide (reagent grade, 30% aqueous solution) to obtain a total of 1000 g of abrasive 1 ° (Example 2) Add 3-amino-1H-1,2,4-triazole 1.〇g instead The polishing agent 2 was produced in the same manner as in Example 1 except that H4·triazole i 〇g was used. (Example 3) The polishing agent 3 was produced in the same manner as in Example 1 of 25 201134928 except that lH, i〇.lg was added instead of 1,2,4-triazole 1. (Example 4) 5-amine was added. The polishing agent 4 was produced in the same manner as in Example 1 except that the radical -1H, 〇.lg was used instead of the 1,2,4-triazole 1 〇g. ', (Example 5) 5-Mercapto-1H- was added. The polishing agent 5 was prepared in the same manner as in Example 1 except that tetrazolium.1 g was used instead of 12,4-teraxazole! 〇g. (Comparative Example 1) The amount of sulfuric acid was set to 2.6 g, and the acid was filled. The amount was set to 2.9 g, the glycine acid was set to 10.2 g, the amount of benzoquinone trisal was set to 2 〇g, and the amount of 1,2,4-triazole was not used, and the same procedure as in Example 丨In the same manner as in Comparative Example 1, the polishing agent X2 was produced in the same manner as in Comparative Example 1, except that the amount of the sulfuric acid was changed to 5.1 g and the amount of the phosphoric acid was changed to 5 8 g. 3) The abrasive X3 was produced in the same manner as in Comparative Example 1 except that the amount of glycine was 20.3 g, and 36% hydrochloric acid was used instead of the water in the pH adjustment. (Comparative Example 4) Benzene The ruthenium triazole was set to 4.0 g, and the same as the comparative example. The polishing agent X4 was produced. (Comparative Example 5) The amount of sulfuric acid was set to 5.1 g, the amount of phosphoric acid was set to 5 8 g, and the amount of glycine 26 201134928 aminic acid was set to 20.3 g, and benzoquinone was used. In the same manner as in Comparative Example 1, the abrasive crucible 5 was produced in the same manner as in Comparative Example 1. (Comparative Example 6) The amount of sulfuric acid was set to 1 〇·2 g, and the amount of phosphoric acid was set to u 5 g. In the same manner as in Comparative Example 1, except that the amount of glycine was 4 G _ 6 g ' * 幷 幷 唾 唾 设为 研磨 。 。 。 研磨 研磨 研磨 研磨 研磨 研磨 研磨 研磨 研磨 研磨 研磨 研磨 研磨 研磨 研磨 研磨 研磨 研磨 研磨In the same manner as in Comparative Example 6, the abrasive X7 was produced in the same manner as in Comparative Example 6. (Comparative Example 8) The amount of benzoquinone di-sal was set to 4. 〇g, and Comparative Example 6 was used. The polishing agent X8 was prepared in the same manner. In the same manner as in Comparative Example 8, an abrasive X9 was further added to prepare an abrasive X9. (Comparative Example 10) g 'Other than Example 8 Further, 2,4-dimercaptoimidazole was added in the same manner to prepare an abrasive ΧΙΟ. (Comparative Example 11) g, in addition to the same as Comparative Example 8, further addition was made. The polishing agent Xu was produced in the course of 1Q. (Comparative Example 12) In the same manner as in the comparative example, 3,5-dimethylpyrazole 1. 〇8 was further added to prepare an abrasive χι2. 27 201134928 (Comparative Example 13) The same procedure as in the comparative example was carried out except that 1 hydroxybenzotriazole L〇g was added in the same manner as in the above, and an abrasive X13 was produced. (Comparative Example 14) Further, the polishing agent X14 was prepared by performing the above-described addition of 1 g of decyl dodecylbenzenesulfonate. (Measurement of pH of Abrasive Agent) The pH value of the above-mentioned abrasive 1 abrasive 5' abrasive XI to abrasive X14 was measured using a pH meter F8E manufactured by Horiba. The pH value can be measured using standard buffer (o-phthalate pH buffer, pH 4.01 (25. (:); neutral phosphate pH buffer, pH (C)). After the 2-point calibration, the electrode is placed in the abrasive and stabilized after 2 minutes or more. (Mapping of the substrate) Prepared on a substrate with a direct control of 8 吋 (20.3 cm) (Φ). A film having a copper film having a thickness of 20 μm (purchased from Advantech Co., Ltd.). Using the substrate, the polishing agent 1 to the abrasive 5 and the polishing agent XI to the abrasive χ 14 were dropped onto the fixing plate of the polishing apparatus. On the attached abrasive cloth, CMP polishing is performed on one side. The 'grinding conditions are as follows. Grinding device: The fixed plate size is 600 mm (Φ) in diameter, rotary type abrasive cloth: foamed polyurethane resin with closed cells (IC-1010) , manufactured by Rohm and Haas Company, trade name) Grinding pressure: 32kPa

S 28 201134928 Grinding platen/head rotation speed: 93/87 rpm Abrasive flow rate: 200 ml/min [Evaluation item and evaluation method of grinding test] (Polishing speed, surface roughness, pad coloring) Grinding as described above The substrate was measured for the copper polishing rate of CMp (hereinafter referred to as "polishing speed") and the surface roughness, and the degree of coloration of the surface of the pad after polishing (hereinafter referred to as "pad coloring") was evaluated. The polishing rate was calculated by calculating the difference in film thickness between the substrate before and after CMP in accordance with the change in sheet resistance. As the measuring device, a resistivity meter M〇delRT-7 manufactured by NAPSON Corporation was used. The average value of 77 points in the diameter direction of the wafer (except for the 5 mm portion from the edge) was calculated as the resistance value. Surface roughness (contour arithmetic mean deviation Ra): The surface roughness of the polished copper film was measured by AFM (Atom Force Microscope. SPA-400, manufactured by SII NanoTechnology Inc.). The measurement was carried out at a position 50 mm from the center of the substrate in the radial direction, in the range of 5 μηη><5 μιη. Pad coloring: The surface of the crucible after the end of the polishing was visually observed and evaluated according to the following criteria. No coloring was observed: A only a slight coloration was observed: B sufficient color was observed: C (etching speed) The above abrasive was stirred at room temperature (25 ° C) (600 rpm), and a thickness of 1500 was deposited. The tantalum substrate (copper substrate) of the steel film of nm was impregnated in the 29 201134928 abrasive. The difference in film thickness of the copper film of the copper substrate before and after the impregnation was obtained from the resistance value conversion. The contents of the polishing agent 1 to the polishing agent 5, the polishing agent XI to the polishing agent X14, the pH of each polishing agent, and the evaluation results of the polishing test are shown in Tables 1 to 3. 201134928.

[Table i] Example 1 Example 2 Example 3 Example 4 Example 5 Abrasive grain (wt%) Colloidal ceria 1.000 1.000 1.000 1.000 1.000 Inorganic acid (mol/kg) Sulfuric acid 0.100 0.100 0.100 0.100 0.100 Phosphoric acid 0.100 0.100 0.100 0.100 0.100 Inorganic acid Total 0.200 0.200 0.200 0.200 0.200 Protective film forming agent (mol/kg) Benzotriazole 0.034 0.034 0.034 0.034 0.034 Inorganic acid/protective film forming agent 5.882 5.882 5.882 5.882 5.882 Amino acid (mol/kg) Glycine 0.541 0.541 0.541 0.541 0.541 Oxidizer (wt%) Hydrogen peroxide 9.000 9.000 9.000 9.000 9.000 Smoothing agent (mol/kg) 1,2,4-1σ_^ 0.015 - - - - 3-Amino-1Η-1,2,4-triazole - 0.012 - - - 1Η-四零坐- - 0.001 - 5-amino-1Η-tetrazole- - - 0.001 - 5-methyl-1Η-tetrazole - - - - 0.001 Additive (mol/kg) σ m" sit - - - - - 2,4-dimethylimidazole - - - - - ° ratio. Sit - - - - - 3,5-Dimethyl 0 嗤 - - - - - 3-hydroxy alum-triazole - - - - - 12 yards of acid - - - - - pH adjuster ammonia Ammonia ammonia Ammonia Ammonia pH 2.4 2.4 2.4 2.4 Touch rate (A/min) 280 270 260 270 280 Grinding speed (A/min) 45600 44300 46200 45800 46700 Pad coloring AAAAA Surface roughness (nm) 8.0 9.0 7.0 6.0 6.0 31 X201134928 [Table 2] Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 Abrasive Grain (wt%) Jiao Zhao Dioxide 1.000 1.000 1.000 1.000 1.000 1.000 1.000 1.000 Inorganic acid (mol/kg) Sulfuric acid 0.025 0.050 0.025 0.025 0.050 0.100 0.100 0.100 Phosphoric acid 0.025 0.050 0.025 0.025 0.050 0.100 0.100 0.1(8) Total inorganic acid 0.050 0.100 0.167 * 0.050 0.100 0.200 0.200 0.200 Protective film forming agent (mol/kg) Clumsy three Oxazole 0.017 0.017 0.017 0.034 0.034 0.067 0.051 0.034 Inorganic acid/protective film formation 丨 2.941 5.882 9.820 1.471 2.941 2.985 3.922 5.882 Amino acid (mol/kg) Glycine 0.136 0.136 0.270 0.136 0.270 0.541 0.541 0.541 Oxidizer (wt%) Hydrogen peroxide 9.000 9.000 9.000 9.000 9.000 9.000 9.000 9.000 Smoothing agent (mol/kg) 1,2,4- = «^ • - - - - 3·Amino-1H-1,2,4- Triazole 1H-four bites • • - - - - 5 · Amino-1H- Four-split - 5-mercapto-1H- Four-spot sitting _ - Additive (mol/kg) 0 m saliva _ - - - - 2, 4-Dimethyl Miso • • 〇 0 0 sitting _ • • - - - 3,5-dimethyl fluorene than 0 sitting - 3-hydroxybenzotriazole • - dodecylbenzene sulfonic acid. • - nH value 智智 ammonia water ammonia hydrochloric acid ammonia water ammonia water gas water ammonia water pH 2.4 2.4 2.4 2.4 2.4 2.4 2.4 etching speed (A / min) 190 310 200 70 200 200 230 280 32 201134928r grinding speed (A / min) 21000 24000 18000 18000 32000 42000 44000 46000 Pad coloring CACCC c BA Surface roughness (nm) 2.4 13.0 5.6 1.3 1.1 2.1 11.0 25.0 合 The total value of the inorganic acid of Comparative Example 3 indicates the total amount of sulfuric acid, phosphoric acid and hydrochloric acid used as a pH adjuster. the amount. 33 201134928 [Table 3] Comparative Example 9 Comparative Example 10 Comparative Example 11 Comparative Example 12 Comparative Example 13 Comparative Example 14 Abrasive particles (wt%) Colloidal ceria 1.000 1.000 1.000 1.000 1.000 1.000 Inorganic acid (mol/kg) Sulfuric acid 0.100 0.100 0.100 0.100 0.100 0.100 Phosphoric acid 0.100 0.100 0.100 0.100 0.100 0.100 Total inorganic acid 0.200 0.200 0.200 0.200 0.200 0.200 Protective film forming agent (mol/kg) Benzotriazole 0.034 0.034 0.034 0.034 0.034 0.034 Inorganic acid / Bao Yun [Film forming agent 5.882 5.882 5.882 5.882 5.882 5.882 Amino acid (mol/kg) Glycine 0.541 0.541 0.541 0.541 0.541 0.541 Oxidizer (wt%) Hydrogen peroxide 9.000 9.000 9.000 9.000 9.000 9.000 Smoothing agent (mol/kg) 1,2,4-triazole - - - - - - 3-amino-1H-1,2,4-triazole 1H-tetrazole- - - - - 5-amino-1H-tetrazole - - - - 5- 5-yl- 1H-tetrazole - - - - - - Additive (mol/kg) Flavored salsa 0.015 - - - - - 2,4-Dimercaptoimidazole - 0.010 - - - • .比峻 - - 0.015 - - - 3,5-dimethyl "biazole - - - 0.010 --3-hydroxybenzotriazole - - - - 0.007 - dodecylbenzene benzoic acid - - - - - 0.0003 pH Adjuster Ammonia Ammonia Ammonia Ammonia Ammonia Water pH 2.4 2.4 2.4 2.4 2.4 Unique Speed (A/min) 290 260 290 300 160 60 Grinding Speed (A/min) 44300 45100 46700 47800 43000 44800 Pad Coloring AAAACA Surface Roughness (nm) 24.0 25.0 26.0 23.0 13.0 23.0 The following facts can be seen from the results shown in Tables 1 to 3. That is, 34 201134928 Α 1 Each of the abrasives of Example 1 to Example 5 showed a good polishing rate β, and the surface roughness and the buttoning speed were also good, and no mat coloring was observed. The polishing rate of Comparative Example 1 was used as a standard, and the polishing rates of Comparative Examples 2 to 4 were increased or decreased as follows. When the content of the inorganic acid was changed to 0.080 mol/kg or more, except that it was carried out in the same manner as in Comparative Example 1, (Comparative Example 2), the polishing rate was increased by 3 〇〇〇A/mh^ to the amino acid. When the content was changed to 0.200 mol/kg or more, the polishing rate was reduced by 3000 A/min when it was carried out in the same manner as in Comparative Example i (Comparative Example 3). When the content of the protective film forming agent was changed to 〇 〇 2 〇 m 〇 1 kg or more, the polishing speed was reduced by 3000 A/min when it was carried out in the same manner as in Comparative Example 1 (Comparative Example 4). According to the change in the polishing rate of Comparative Examples 2 to 4, it is expected that the same amount of the inorganic acid as in Comparative Example 2, the amino acid equivalent to Comparative Example 3, and the protective film of Comparative Example 4 were contained. The polishing rate in the case of forming the agent was reduced by 3000 A/min obtained by adding and subtracting the polishing rates of Comparative Examples 2 to 4 with respect to Comparative Example 1. However, in Comparative Example 5 containing a mineral acid, an amino acid, and a protective film forming agent in such a content, the polishing rate was increased by 11,000 A/min. Further, the content of the inorganic acid is 0.080 mol/kg or more, the content of the amino acid is 〇.2〇〇m〇1/kg or more, and the content of the film forming agent is 〇〇2〇mol/kg or more. In Comparative Example 6, the polishing rate was increased by 2100 Å A/min as compared with Comparative Example 1. From these results, it was confirmed that if the content of each component reaches a necessary amount, the increase in the surface roughness can be suppressed and the polishing rate can be increased. However, in Comparative Example 5 and Comparative Example 6', the problem of mat coloring was observed, and it was not possible to simultaneously achieve the improvement of the grinding speed, the reduction of the surface roughness, and the suppression of the coloration of the mat. On the other hand, as shown in Comparative Example 7 and Comparative Example 8, when the content of benzoquinone was reduced as compared with Comparative Example 6, although the ruthenium coloring was suppressed and the polishing rate was improved, the surface was rough. Degree deteriorated. In Example 1 to Example 5, a necessary amount of a smoothing agent was added to Comparative Example 8 having insufficient surface roughness as described above, and the polishing rate was maintained high, and the coloring of the mat was suppressed, and the effect of the smoothing agent was added. Reduce surface roughness to below 10 nm. On the other hand, in the case where a substance similar to the structure of the smoothing agent of Example 5 was added to Comparative Example 8 (Comparative Example 9 to Comparative Example 12), the effect of improving the surface roughness could not be confirmed. Further, in Comparative Example 13 in which a benzotriazole derivative was added, the effect of reducing the surface roughness and the etching rate was confirmed, but pad coloration occurred. Further, in Comparative Example 14, in which the dodecylbenzene acid was added, although the surname speed was greatly lowered, the effect of improving the surface roughness was not confirmed. From the above, it was confirmed that by optimizing the content of the inorganic acid, the amino acid, and the protective film forming agent, and adding a suitable smoothing agent, it is possible to obtain a polishing speed which is significantly faster for the steel than the usual abrasive. It produces an abrasive that is colored and smoothed after grinding. In particular, an abrasive having a grinding speed of more than 30,000 A/min for copper is most suitable for use in which a large amount of copper must be ground in a short time (for example, TSV forming use). BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 (a), Fig. 1 (b), and Fig. 1 (c) show a method of use 36 201134928 when an abrasive according to an embodiment of the present invention is used in VIA-LAST. The first step of the diagram. Fig. 2 (a), Fig. 2 (b), and Fig. 2 (c) are views showing a second step of the method of using the polishing agent according to the embodiment of the present invention in the case of VIA-LAST. Fig. 3 (a), Fig. 3 (b), and Fig. 3 (c) are diagrams showing a third step of the method of using the polishing agent according to the embodiment of the present invention in the case of VIA-LAST. [Description of main component symbols] 1 : 矽 substrate 2 : component 3 : recess 4 : copper layer 5 , 6 : bumps 100 , 200 , 300 : substrate 37

Claims (1)

201134928 Λ. VII. Patent application scope: 1. A copper grinding abrasive comprising: selected from the group consisting of four tr, the four-spotted derivative, three P sitting and the derivative of the triazole (but benzotriazole) And at least one of a smoothing agent, a mineral acid, an amino acid, a protective film forming agent, an abrasive granule, an oxidizing agent, and water, and a mixture of the inorganic acid, and a group of the abbreviated triazole derivatives The content is 0.080 m〇i/kg or more, the content of the amino acid is 0.200 m〇i/kg or more, and the content of the protective film forming agent is 〇(^omol/kg or more, and the content of the inorganic acid is relatively The polishing agent for copper polishing according to the above aspect of the invention, wherein the smoothing agent is selected from the group consisting of the following formula (I) At least one of the group consisting of the compound and the compound represented by the following formula (II), [Chemical Formula 1] [wherein R1 represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or an amine group] [Chemical 2] S 38 201134928. [wherein R2 and R3 each independently represent a hydrogen atom, a carbon group having 12 or an amine group]. 3. The polishing agent for copper polishing according to the first or second aspect of the invention, wherein the inorganic acid is at least one selected from the group consisting of sulfuric acid and phosphoric acid. 4. The abrasive for copper polishing according to any one of claims 3 to 3, wherein the amino acid has a pKal of 2 to 3. 5. The abrasive for copper polishing according to any one of claims 1 to 4, wherein the protective film forming agent is selected from the group consisting of benzotriazole and a derivative of the benzotriazole At least one of the groups formed. The abrasive for copper polishing according to any one of claims 1 to 5, wherein the abrasive particles are at least one selected from the group consisting of colloidal dioxide and colloidal alumina. The abrasive grains have an average particle diameter of 100 nm or less. The copper polishing abrasive according to any one of the preceding claims, wherein the oxidizing agent is selected from the group consisting of hydrogen peroxide, persulfuric acid and persulfate. At least 丨. 8. The steel according to any one of the above-mentioned items of the present invention, wherein the pH is from 1.5 to 4.0. A polishing method comprising the steps of: grinding a copper-containing metal film using a copper polishing abrasive according to any one of claims 1 to 8 At least a portion of the metal film is removed.