CN102888208B

CN102888208B - Abrasive and substrate polishing method

Info

Publication number: CN102888208B
Application number: CN201210253479.0A
Authority: CN
Inventors: 三嶋公二; 飞田文子
Original assignee: Hitachi Chemical Co Ltd
Current assignee: Lishennoco Co ltd
Priority date: 2011-07-20
Filing date: 2012-07-20
Publication date: 2015-02-25
Anticipated expiration: 2032-07-20
Also published as: KR101437725B1; KR20140019464A; JP2013042123A; JP6051632B2; KR101846607B1; KR20130011943A; TW201311841A; CN102888208A; TWI600731B

Abstract

The invention provides an abrasive for polishing cobalt-containing layers. The abrasive comprises a carboxylic acid derivative, a metal corrosion inhibitor and water, the carboxylic acid derivative consisting of at least one selected from a phthalic compound, an isophthalic compound, an alkyl dicarboxylic compound represented by the formula (I), and salts and anhydrides of the phthalic compound, the isophthalic compound and the alkyl dicarboxylic compound. The pH is below 4.0. Formula (I): HOOC-R-COOH.

Description

The Ginding process of grinding agent and substrate

Technical field

The present invention relates to the Ginding process of grinding agent and substrate.

Background technology

In recent years, (be designated as below " LSI " along with semiconductor integrated circuit.) Highgrade integration, high performance, develop new Micrometer-Nanometer Processing Technology.Cmp (is designated as " CMP " below.) method is also wherein a kind of, is the technology of frequent utilization in the planarization of the insulator in LSI manufacturing process, especially multilayer wiring formation process, metallic plug is formationed, embedded wiring formation etc.

In addition, recently in order to make LSI high performance, attempting utilizing copper alloy as wiring material.But copper alloy is difficult to the microfabrication of carrying out the frequent dry etching method used in the formation based on aluminium alloy wiring in the past.Therefore, such as, main employing is so-called inlays (damascene) method, the dielectric film being pre-formed with groove is piled up, embeds copper alloy thin films, remove the copper alloy thin films beyond groove portion by CMP, forms embedded wiring (for example, referring to patent documentation 1.）。

The conventional method of the CMP of metal is, abrasive cloth pasted by the grinding plate (Platen) of circle, the metal grinding agent that the surface of abrasive cloth is liquid infiltrates, and pressing forms the face of the metal film of substrate, (is designated as below " grinding pressure " with the pressure applying regulation from the back side.) state rotate grinding plate, by the mechanical friction between metal grinding agent and the protuberance of metal film, removing protuberance metal film.

The metal grinding agent used in CMP, generally containing oxidant and abrasive particle, adds dissolving metal agent, corrosion inhibitor for metal etc. as required further.When adding these, think that basic mechanism is with dissolving metal agent oxidized metal film surface, scrape oxide layer with abrasive particle.Think the oxide layer of the metallic film surface becoming recess, contact with abrasive cloth hardly, do not reach the effect that polished abrasive particle scrapes off, therefore along with the carrying out of CMP, the metal level of protuberance is removed, substrate surface planarization.

On the other hand, as shown in Fig. 1 (a), in the lower floor of the conductive material layer 5 formed with metal by the wiring of copper or copper alloy etc., diffusion in the insulator 2 formed on silicon substrate 1 to prevent copper and improve adaptation, and form barrier metal electrically conductive film 3(hereinafter also referred to as " barrier metal layer 3 ").Thus, the barrier metal layer 3 exposed beyond the wiring portion of embedded wiring metal, needs to be removed by CMP.

Therefore, general applicable two sections of Ginding process, namely " the 1st grinding step " that be divided into the state grinding conductive material layer 5 shown in from the state shown in Fig. 1 (a) to Fig. 1 (b) and, the state shown in from the state shown in Fig. 1 (b) to Fig. 1 (c) are ground " the 2nd grinding step " of barrier metal layer 3, grind respectively with different grinding agents.

, along with the miniaturization of design rule, each layer of above-mentioned wiring formation process also tends to thinning.But, because above-mentioned barrier metal layer 3 is thinning, prevent the diffusion effect containing the conductive material of at least a kind be such as selected from copper or copper alloy and their oxide from just reducing.In addition, because wiring width narrows, the embeddability of conductive material reduces, and wiring portion produces the emptying aperture being called void.Further, the tendency of reduction is also had with the adaptation of conductive material layer.Therefore, study the metal used in the barrier metal layer 3 in Fig. 1 is replaced to containing Co(cobalt) metal of element.In addition, suggestion as shown in Figure 2 (a) shows, makes the metal level (hereinafter also referred to as " cobalt layers 4 ") containing cobalt element be interposed between barrier metal layer 3 and conductive material layer 5.By using cobalt layers 4, not only inhibit the diffusion of conductive material, and due to cobalt and high as the compatibility between the widely used copper of conductive material, therefore the embeddability of layers of copper in wiring portion improves, and can make up the adaptation with layers of copper further.

When using cobalt as barrier metal layer, metal grinding agent is needed to remove unnecessary cobalt layers.Known many kinds of substance is as metal grinding agent, and on the other hand, when having certain metal grinding agent, it differs and removes arbitrary metal surely.As metal grinding agent in the past, known using the metal of copper, tantalum, titanium, tungsten, aluminium etc. as grinding object (object of removing redundance), but also not too know the grinding agent using cobalt as grinding object.

But, due to cobalt with compared by the conductive material of the copper that uses as wiring metal etc. in the past, corrosivity is strong, if therefore directly use grinding agent in the past, cobalt is just by excessive erosion (etching), or slit is produced in wiring layer, therefore can not play the function as barrier metal layer, have the possibility that metal ion spreads.In insulator when metal ion diffusion, the possibility of semiconductor device short circuit uprises.On the other hand, if prevent such thing, add the corrosion inhibitor that corrosion-resisting function is strong, or increase the addition of corrosion inhibitor, then to have the problem reducing overall grinding rate.

For such problem, the grinding agent of the specific corrosion inhibitor for metal of known use, this corrosion inhibitor for metal is the heterocyclic compound of four-membered ring ~ hexatomic ring, containing more than 2 double bonds, containing the nitrogen-atoms of more than 1 (for example, referring to patent documentation 2.）。According to such grinding agent, while protection wiring layer, can prevent there is slit in wiring layer.

Prior art

Patent documentation

Patent documentation 1: Japanese Patent Laid-Open 2-278822 publication

Patent documentation 2: Japanese Patent Laid-Open 2011-91248 publication

Summary of the invention

The problem that invention will solve

But, only rely on the effect of corrosion inhibitor for metal, although the etching of cobalt can be suppressed, be not easy to maintain the high grinding rate for cobalt simultaneously, seek more to improve the grinding rate to cobalt.The present invention wants to solve above-mentioned problem, and object suppresses the grinding agent that cobalt layers burn into suppresses slit to produce and the substrate Ginding process using this grinding agent while being to provide and keeping the good grinding rate to cobalt layers.

Solve the means of problem

In order to solve so wholwe-hearted result of study of problem in the past, the present inventor finds, by using specific carboxylic acid derivates, while can keeping the good grinding rate to cobalt layers, the corrosion-inhibiting of cobalt layers is excellent, suppresses the generation of slit.

The concrete method solving above-mentioned problem is as described below.

< 1 > grinding agent, for grinding the layer containing cobalt element, it contains the carboxylic acid derivates, corrosion inhibitor for metal and the water that are made up of at least one be selected from alkyl dicarboxylic aid's compound and their salt and acid anhydrides that phthalic compounds, M-phthalic acid compound and following general formula (I) represent, and the pH of grinding agent is below 4.0.

HOOC-R-COOH…(I)

(in above-mentioned general formula (I), R represents that carbon number is the alkylidene of 4 ~ 10.）

By being set as such grinding agent, while the good grinding rate for cobalt layers can be kept, improve corrosion-inhibiting.

< 2 > grinding agent, for grinding the layer containing cobalt element, it contains carboxylic acid derivates, corrosion inhibitor for metal and water more than by least one be selected from alkyl dicarboxylic aid's compound and their salt and acid anhydrides that phthalic compounds, M-phthalic acid compound and following general formula (I) represent, the pH of grinding agent below 4.0, in the grinding agent of 50 DEG C for the etching speed of cobalt at below 10.0nm/min.

HOOC-R-COOH…(I)

Grinding agent described in <1> or <2> described in < 3 >, described corrosion inhibitor for metal contains the compound with triazole skeleton.

Thus, more effectively corrosivity can be suppressed.

The grinding agent described in any one in < 4 > above-mentioned < 1 > ~ < 3 >, further containing oxidant.

Thus, when polished film contains the layer beyond cobalt layers, more can improve the grinding rate of the layer beyond cobalt layers.

The grinding agent described in any one in < 1 > ~ < 4 > described in < 5 >, further containing organic solvent.

Thus, when polished film contains the layer beyond cobalt layers, because the wetability for the layer beyond cobalt layers improves, therefore more can improve grinding rate.

The grinding agent described in any one in < 1 > ~ < 5 > described in < 6 >, further containing water-soluble polymer.

Thus, the polished face of protection, suppresses corrosion, can reduce the generation of the defect of wound etc.

The grinding agent described in any one in < 1 > ~ < 6 > described in < 7 >, further containing abrasive particle.

< 8 > mono-kind removes the substrate Ginding process of the redundance containing cobalt element, uses the grinding of the grinding agent described in any one in described <1> ~ <7> at least one polished film containing cobalt element formed on the surface of substrate.

According to Ginding process of the present invention, the polished film containing cobalt element can be ground at a high speed and with suppressing excessive corrosion.

The effect of invention

According to the present invention, a kind of maintenance can be provided the grinding agent of the corrosion-inhibiting excellence of cobalt layers while the good grinding rate of cobalt layers and the substrate Ginding process using it.

Accompanying drawing explanation

Fig. 1 is the pattern sectional view of the cloth wire forming proces shown in mosaic procedure in the past.

Fig. 2 is the pattern sectional view that display uses the cloth wire forming proces in the mosaic procedure of cobalt layers.

Fig. 3 is the sectional view of display with an example of the substrate after Ginding process grinding of the present invention.

Symbol description

1 silicon substrate

2 insulators

3 barrier metal layers

4 cobalt layers

5 conductive material layers (wiring metal)

Embodiment

Word " operation " in this specification, is not only independently operation, even when can not clearly distinguish with other operation, as long as reach the object desired by its operation, is just included in this word.In addition the number range using " ~ " to represent, represents that the numerical value recorded the front and back of " ~ " is respectively as the scope contained by minimum value and maximum.The content of each composition further in grinding agent, exists multiple when being equivalent to the material of each composition, except as otherwise noted, means total metering of the plurality of material existed in grinding agent in grinding agent.

Below, to the grinding agent for grinding the layer containing cobalt element of the present invention (hereinafter simply referred to as " grinding agent ".) and the suitable execution mode of substrate Ginding process be described in detail.

[grinding agent]

Grinding agent of the present invention contains the carboxylic acid derivates, corrosion inhibitor for metal and the water that are made up of at least one be selected from alkyl dicarboxylic aid's compound and their salt and acid anhydrides that phthalic compounds, M-phthalic acid compound and following general formula (I) represent, and pH is below 4.0.

HOOC-R-COOH…(I)

< carboxylic acid derivates >

Grinding agent of the present invention contains the carboxylic acid derivates (hereinafter referred to as " specific carboxylic acid derivates ") of at least one in the dicarboxylic acid compound (be " specific dicarboxylic acid compound " hereinafter referred to as them) and their salt and acid anhydrides being selected from phthalic compounds, M-phthalic acid compound and following general formula (I) and representing.Above-mentioned specific carboxylic acid derivates, can one be used alone, or two or more used in combination.By the above-mentioned specific carboxylic acid derivates selected from the carboxylic acid and carboxylic acid derivates of countless existence, while keeping the good grinding rate to cobalt layers, moderately can control etching speed, suppress corrosion, obtain good abradant surface.Even if further under harsher condition (such as 50 DEG C), the etching speed of cobalt layers is also more effectively suppressed, excellent corrosion-inhibiting can be reached.Corrosion-inhibiting excellence comprises herein: on polished face, effectively suppresses cobalt layers to be etched, or produces slit in wiring layer.

Obtain the reason of such effect and unclear, the present inventor infers as follows.That is, think such as there is the effect working as dissolving metal agent, improve the grinding rate to cobalt layers by above-mentioned specific carboxylic acid derivates.Inferring that above-mentioned specific carboxylic acid derivates has such function simultaneously, by two carboxyls and cobalt atom chelating structure circlewise, controlling etching speed to form stable complex compound state that there is the function of the corrosion suppressed in polished face.The formation of this stable complex status in addition, may also be of value to corrosion inhibitor for metal described later.

From the viewpoint of to the grinding rate of cobalt layers, the controlling of etching speed and corrosion-inhibiting, above-mentioned specific carboxylic acid derivates is selected from dicarboxylic acid compound, their salt and their acid anhydrides.Acid compound beyond above-mentioned specific carboxylic acid derivates, is sometimes difficult to two to the good grinding rate of cobalt layers with the etching speed of suppression cobalt layers and stands.This is presumably because that the formation of complex status stable is described above important, the stereochemical structure of acid compound becomes important factor.In addition, even containing above-mentioned specific carboxylic acid derivates, if containing other acid compound in addition, the etching speed of cobalt layers significantly rises sometimes.This is presumably because that the effect of other acid compound etching cobalt layers has precedence over the formation of complex status as above.

First form of the present invention is, above-mentioned carboxylic acid derivates is made up of at least one be selected from alkyl dicarboxylic aid's compound and their salt and acid anhydrides that phthalic compounds, M-phthalic acid compound and above-mentioned general formula (I) represent.But, above-mentioned carboxylic acid derivates is not significantly damaging the scope of effect of the present invention, can comprise other carboxylic acid derivates, it is selected from least one in dicarboxylic acid compound beyond alkyl dicarboxylic aid's compound that phthalic compounds, M-phthalic acid compound and above-mentioned general formula (I) represent and their salt and their acid anhydrides.Namely, above-mentioned carboxylic acid derivates is, the material be substantially made up of the specific carboxylic acid derivates of at least one be selected from alkyl dicarboxylic aid's compound and their salt and acid anhydrides that phthalic compounds, M-phthalic acid compound and above-mentioned general formula (I) represent." substantially " herein refers to the scope significantly not damaging effect of the present invention, particularly, means that the containing ratio of other carboxylic acid derivates above-mentioned is below 10 quality % relative to the gross mass of specific carboxylic acid derivates.The containing ratio of other carboxylic acid derivates above-mentioned preferably below 5 quality %, more preferably below 1 quality % further.

Same viewpoint, the second form of grinding agent of the present invention is, above-mentioned carboxylic acid derivates contains: be selected from least one in the alkyl dicarboxylic aid's compound and their salt and acid anhydrides that phthalic compounds, M-phthalic acid compound and above-mentioned general formula (I) represent, in the grinding agent of 50 DEG C for the etching speed of cobalt at below 10.0nm/min.In second form, above-mentioned carboxylic acid derivates can contain other carboxylic acid derivates, these other carboxylic acid derivates are selected from least one in dicarboxylic acid compound beyond alkyl dicarboxylic aid's compound that phthalic compounds, M-phthalic acid compound and above-mentioned general formula (I) represent and their salt and their acid anhydrides, but need in the grinding agent of 50 DEG C, the preferable range of 10.0nm/min about the containing ratio of other carboxylic acid derivates above-mentioned to be no more than for the etching speed of cobalt, with above-mentioned first homomorphosis.

Can measure as following for the etching speed of cobalt in the grinding agent of 50 DEG C.Namely, prepared silicon substrate defines the square chip of the 20mm of the cobalt layers of 0.3 μm (evaluation chip), above-mentioned evaluation chip is put in the beaker adding 50g grinding agent, to be immersed in the thermostat of 50 DEG C 1 minute, by measuring the film thickness of the cobalt layers before and after soaking, try to achieve as (thickness of the cobalt layers after the thickness-immersion of the cobalt layers before immersion)/1 minute [nm/min].

In the second form of grinding agent of the present invention, above-mentioned etching speed at below 10.0nm/min, from the viewpoint of improving corrosion-inhibiting better, preferred below 9.0nm/min, more preferably below 8.0nm/min.

In the first form of grinding agent of the present invention, also from the viewpoint of more improving corrosion-inhibiting, above-mentioned etching speed preferably at below 10.0nm/min, more preferably below 9.0nm/min, further preferably below 8.0nm/min.

In above-mentioned specific dicarboxylic acid compound, phthalic compounds comprises at least a kind that phthalic acid (benzene-1,2-dicarboxylic acids) and phenyl ring has more than one substituent phthalic acid derivatives.Described substituting group citing is as methyl, amino, nitro etc.Wherein, at least one in preferred nitro and methyl, more preferably nitro.

As above-mentioned phthalic compounds, can enumerate particularly, the alkyl phthalic acid of phthalic acid, 3-methylphthalic acid, 4-methylphthalic acid etc.; The aminophthalic acid of 3-aminophthalic acid, 4-aminophthalic acid etc.; The nitrophthalic acid etc. of 3-nitrophthalic acid, 4-nitrophthalic acid etc.Wherein, the phthalic compounds (nitrophthalic acid) preferably containing nitro alternatively base, at least one more preferably in 3-nitrophthalic acid and 4-nitrophthalic acid, particularly preferably 3-nitrophthalic acid.Above-mentioned phthalic compounds, can use with anhydride form, also can use in a salt form.

In above-mentioned M-phthalic acid compound, comprise at least a kind of M-phthalic acid (benzene-1,3-dicarboxylic acids) and phenyl ring having in more than one substituent isophthalic acid derivatives.Above-mentioned substituting group citing is as nitro, methyl, amino, hydroxyl etc.Wherein, preferred nitro.

Above-mentioned M-phthalic acid compound, specifically can enumerate as, M-phthalic acid, 5-nitroisophthalic acid etc.Above-mentioned M-phthalic acid compound, can use salt form.

Alkyl dicarboxylic aid's compound that above-mentioned general formula (I) represents can be alkyl dicarboxylic aid's compound of the alkylidene with carbon number 4 ~ 10.Moreover above-mentioned carbon number is the carbon number of alkylidene, the carbon atom comprised in carboxyl not can be regarded as described carbon number.Above-mentioned alkylidene can be any one in ring-type, straight-chain and branched.Wherein, preferred straight-chain.To the grinding rate of cobalt layers, from the viewpoint of controlling and the corrosion suppression of etching speed, preferred carbon number is 4 ~ 8, and more preferably carbon number is 4 ~ 6.

As the alkyl dicarboxylic aid of alkylidene with carbon number 4 ~ 10, specifically can enumerate, adipic acid, pimelic acid, suberic acid, azelaic acid etc.Wherein, preferred adipic acid, pimelic acid, more preferably pimelic acid.

With the gross mass of grinding agent for benchmark, the content of above-mentioned carboxylic acid derivates is preferably in the scope of 0.001 quality % ~ 10 quality %.Above-mentioned scope is adjusted to by the content of above-mentioned carboxylic acid derivates, the good grinding rate of the layer (the wiring metal of the copper of the conductive material layer 5 such as, represented in Fig. 2 (a) etc. or barrier metal layer 3 etc.) beyond the neighbouring cobalt layers arranged of cobalt layers can be obtained.

From the viewpoint of grinding rate, content more preferably more than the 0.01 quality % of above-mentioned carboxylic acid derivates, further preferably more than 0.03 quality %, particularly preferably more than 0.05 quality %.In addition, from the viewpoint of to the etching inhibition of cobalt layers and corrosion-inhibiting, content preferably below the 5.0 quality % of above-mentioned dicarboxylic acids, more preferably below 3.0 quality %, preferably below 1.0 quality %, very preferably below 0.7 quality %, extremely preferably below 0.5 quality % further.

Above-mentioned grinding agent, from the viewpoint of grinding rate, preferably as carboxylic acid derivates contain more than 0.01 quality % be selected from alkyl phthalic acid, aminophthalic acid, nitrophthalic acid, M-phthalic acid, 5-nitroisophthalic acid and represent as general formula (I), R is alkyl dicarboxylic aid's compound of the straight-chain alkylidene of carbon number 4 ~ 8 and at least one in their salt and acid anhydrides.

In addition above-mentioned grinding agent, from the viewpoint of the etch effect suppressed cobalt layers, as carboxylic acid derivates, that alkyl phthalic acid, aminophthalic acid, nitrophthalic acid, M-phthalic acid, 5-nitroisophthalic acid and general formula (I) represent, that R is the straight-chain alkylidene of carbon number 4 ~ 8 alkyl dicarboxylic aid's compound is selected from preferably containing below 5.0 quality %, and at least one in their salt and acid anhydrides.

< corrosion inhibitor for metal >

The corrosion inhibitor for metal comprised in grinding agent of the present invention has no particular limits, known as there being the compound of corrosion-resisting function to use to metal.Particularly, at least one be selected from triazole compounds, pyridine compounds, pyrazole compound, pyrimidine compound, imidazolium compounds, guanidine compound, thiazolium compounds, tetrazole compound, triaizine compounds, hexa can be used." compound " herein refers to the general name of the compound with its skeleton, and such as triazole compounds refers to the compound with triazole skeleton.

Triazole compounds can be enumerated as, 1,2,3-triazoles, 1,2,4-triazole, 3-amino-1H-1,2,4-triazole, BTA, I-hydroxybenzotriazole, 1-dihydroxypropyl BTA, 2,3-dicarboxypropyl BTA, 4-hydroxybenzotriazole, 4-carboxyl-1H-BTA, 4-carboxyl-1H-BTA methyl esters (1H-BTA-4-carboxylate methyl ester), 4-carboxyl-1H-BTA butyl ester (1H-BTA-4-butyl carboxylate), 4-carboxyl-1H-BTA monooctyl ester (1H-BTA-4-carboxylic acid monooctyl ester), 5-hexyl BTA, (1,2,3-BTA-1-methyl) (1,2,4-BTA-1-methyl) (2-ethylhexyl) amine, tolyl-triazole, aphthotriazoles, two [(1-BTA base) methyl] phosphonic acids, 3H-1,2,3-triazol [4,5-b] pyridine-3-alcohol, 1H-1,2,3-triazol [4,5-b] pyridine, 1-acetyl group-1H-1,2,3-triazol [4,5-b] pyridine, 3-pyridone, 1,2,4-triazol [1,5-a] pyrimidine, 1,3,4,6,7,8-six hydrogen-2H-pyrimido [1,2-a] pyrimidine, 2-methyl-5,7-diphenyl-[1,2,4] triazol [1,5-a] pyrimidine, 2-sulfonyloxy methyl-5,7-diphenyl-[1,2,4] triazol [1,5-a] pyrimidine, 2-sulfonyloxy methyl-5,7-diphenyl-4,7-dihydro-[1,2,4] triazol [1,5-a] pyrimidine etc.Moreover, when there is in a part triazole skeleton and skeleton in addition, be categorized as triazole compounds.

As pyridine compounds, can illustrate as, oxine, protionamide, 2-nitropyridine-3-alcohol, pyridoxamine, niacinamide, iproniazid (Iproniazid), isonicotinic acid, benzo [f] quinoline, 2,5-Pyridinedicarboxylic acid, 4-stibazole, anabasine, 4-nitropyridine-1-oxide, pyridine-3-ethyl acetate, quinoline, 2-ethylpyridine, quinolinic acid, arecaline, citrazinic acid, pyridine-3-methyl alcohol, 2-methyl-5-ethylpyridine, 2-fluorine pyridine, five fluorine pyridines, 6-picoline-3-alcohol, pyridine-2-ethyl acetate etc.

As pyrazole compound, can illustrate as, pyrazoles, 1-pi-allyl-3,5-dimethyl pyrazole, 3,5-bis-(2-pyridine radicals) pyrazoles, 3,5-diisopropyl pyrazoles, 3,5-dimethyl-1-hydroxymethylpyrazolcompounds, 3,5-dimethyl-1-Phenylpyrazole, 3,5-dimethyl pyrazoles, 3-amino-5-hydroxypyrazoles, 4-methylpyrazole, N-methylpyrazole, 3-amino-pyrazol, 3-amino-pyrazol etc.

As pyrimidine compound, can enumerate as, pyrimidine, 1,3-diphenyl-pyrimidine-2,4,6-triketone, Isosorbide-5-Nitrae, 5,6-tetrahydropyrimidine, 2,4,5,6-tetraminopyrimidine sulfate, 2,4,5-trihydroxy-pyrimidine, 2,4,6-Triaminopyrimidine, 2,4,6-trichloropyrimidines, 2,4,6-trimethoxy-pyrimidine, 2,4,6-triphenyl pyrimidines, 2,4-diaminourea-6-hydroxy pyrimidine, 2,4-di-amino-pyrimidines, 2-ethanamide pyrimidine, 2-aminopyrimidine, 4-amino-pyrazol be [3,4-d] pyrimidine etc. also.

As imidazolium compounds, can illustrate as, 1,1'-carbonyl two (1H-imidazoles), 1,1'-oxalyl diimidazole, 1,2,4,5-tetramethyl imidazoles, 1,2-dimethyl-5-nitroimidazole, 1,2-methylimidazole, 1-(3-aminopropyl) imidazoles, 1-butyl imidazole, 1-ethyl imidazol(e), 1-methylimidazole, benzimidazole etc.

As guanidine compound, can illustrate as, 1,1,3,3-TMG, 1,2,3-triphenyl guanidine, 1,3-bis--o-tolyl guanidine, 1,3-diphenylguanidine etc.

As thiazolium compounds, can illustrate as 2-mercaptobenzothiazole, 2,4-dimethylthiazoles etc.

As tetrazole compound, can illustrate as, tetrazolium, 5-methyl tetrazolium, 5-amino-1H-TETRAZOLE, 1-(2-dimethyl aminoethyl)-5-mercapto-tetrazole etc.

As triaizine compounds, can illustrate as, 3,4-dihydro-3-hydroxy-4-oxo-1,2,4-triazine etc.

Above-mentioned corrosion inhibitor for metal can be used alone one or mixes two or more use.The content of above-mentioned corrosion inhibitor for metal, consider from the angle that can obtain for the good grinding rate of the polished film containing cobalt element, be preferably 0.001 quality % ~ 10 quality % in the gross mass of grinding agent.Based on same viewpoint, the content of above-mentioned corrosion inhibitor for metal, more preferably more than 0.01 quality %, further preferred more than 0.02 quality %.In addition, based on same viewpoint, the content of above-mentioned corrosion inhibitor for metal preferably less than 5.0 % by weight, more preferably 0.5 % by weight.

Above-mentioned corrosion inhibitor for metal, by combined with above-mentioned carboxylic acid derivates, even (such as, 50 DEG C) also significantly can suppress the etching speed of cobalt layers under harsh temperature conditions, simultaneously with suitable speed grinding cobalt layers, can suppress the corrosion of cobalt layers.This is presumably because such as, under corrosion inhibitor for metal and above-mentioned specific dicarboxylic acid compound coexist, play as excellent complex-forming agents and the protectant function of film.

From the viewpoint, in above-mentioned corrosion inhibitor for metal, preferably be selected from triazole compounds, pyridine compounds, imidazolium compounds, tetrazole compound, at least a kind in triaizine compounds and hexa, be more preferably and be selected from 3H-1, 2, 3-triazol [4, 5-b] pyridine-3-alcohol, I-hydroxybenzotriazole, 1H-1, 2, 3-triazol [4, 5-b] pyridine, the triazole compounds of BTA etc., 3-pyridone, benzimidazole, 5-amino-1H-TETRAZOLE, 3, 4-dihydro-3-hydroxy-4-oxo-1, 2, at least one in 4-triazine and hexa.

From the viewpoint of controlling etching speed and grinding rate well, the ratio (carboxylic acid derivates/corrosion inhibitor for metal) of carboxylic acid derivates and corrosion inhibitor for metal in above-mentioned grinding agent, preferred mass compares the scope 10/1 ~ 1/5, more preferably 7/1 ~ 1/5 scope, further preferably 5/1 ~ 1/5 scope, particularly preferably in the scope of 5/1 ~ 1/1.

From the viewpoint of controlling etching speed and grinding rate well, further, in above-mentioned grinding agent, carboxylic acid derivates is preferably 10/1 ~ 1/5 with the ratio (carboxylic acid derivates/anticolodal) being selected from least one corrosion inhibitor for metal in triazole compounds, pyridine compounds, imidazolium compounds, tetrazole compound, triaizine compounds and hexa

The ratio (carboxylic acid derivates/anticolodal) of the corrosion inhibitor for metal of at least one in above-mentioned carboxylic acid derivates and triazole compounds, pyridine compounds, imidazolium compounds, tetrazole compound, triaizine compounds and hexa is more preferably 5/1 ~ 1/5

Above-mentioned carboxylic acid derivates, be selected from 3H-1,2,3-triazol [4,5-b] pyridine-3-alcohol, I-hydroxybenzotriazole, 1H-1,2,3-triazol [4,5-b] triazole compounds of pyridine, BTA etc., and be selected from 3-pyridone, benzimidazole, 5-amino-1H-TETRAZOLE, 3,4-dihydro-3-hydroxy-4-oxos-1, the ratio (carboxylic acid derivates/corrosion inhibitor for metal) of the corrosion inhibitor for metal of at least a kind in 2,4-triazine and hexa further preferably 5/1 ~ 1/1.

< oxidant >

Above-mentioned grinding agent is preferably further containing at least a kind of oxidant.By further containing oxidant, can more improve the grinding rate of the layer beyond cobalt layers.Above-mentioned oxidant has no particular limits, selection that can be suitable from normally used oxidant.Particularly, as hydrogen peroxide, sulfuric peroxide hydrochlorate, nitric acid, Potassium periodate, hypochlorous acid, Ozone Water etc., wherein preferred hydrogen peroxide.These metal onidiges can be used alone one or mix two or more use.

When grinding agent contains oxidant, the content of metal onidiges is preferably 0.01 quality % ~ 50 quality % in the gross mass of grinding agent.From the view point of preventing that the oxidation of metal is insufficient, grinding rate declines, and described content is more than 0.02 quality % preferably, further preferred more than 0.05 quality %.In addition, occur that from polished face can be prevented coarse angle is considered, preferably below 30 quality %, further preferred below 15 quality %.

< organic solvent >

In above-mentioned grinding agent, organic solvent can also be contained further.By adding organic solvent, the wetability of the layer beyond the cobalt layers that is arranged near cobalt layers can be improved, more can improve grinding rate.As above-mentioned organic solvent, be not particularly limited, preferred water miscible material.Water miscible definition is herein, for 100g water, dissolves the material of more than 0.1g in 25 DEG C.

As above-mentioned organic solvent, can illustrate as, the carbonate solvent of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate etc.; The interior ester solvent of butyrolactone, propiolactone etc.; The diol solvent of ethylene glycol, propylene glycol, diethylene glycol, DPG alcohol, triethylene glycol, tripropylene glycol etc.; The ether solvents of oxolane, diox, dimethoxy-ethane, poly(ethylene oxide), ethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetic acid esters, propylene glycol methyl ether acetate etc.; The alcohols solvent of methyl alcohol, ethanol, propyl alcohol, n-butanol, n-amyl alcohol, n-hexyl alcohol, isopropyl alcohol, MMB etc.; The ketone solvent of acetone, methyl ethyl ketone etc.; Other organic solvents etc. of dimethyl formamide, 1-METHYLPYRROLIDONE, ethyl acetate, ethyl lactate, sulfolane etc.

In addition, organic solvent also can be the derivative of diol solvent.Can enumerate as, glycol monoethyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, Tripropylene glycol monomethyl Ether, ethylene glycol monoethyl ether, dihydroxypropane single-ether, diethylene glycol monoethyl ether, DPE, Triethylene glycol ethyl ether, tripropylene glycol list ether, ethylene glycol ether, propylene glycol monopropyl ether, Diethylene glycol monopropyl ether, Triethylene glycol Monoisopropyl Ether, Tripropylene glycol Propyl Ether, ethylene glycol monobutyl ether, propylene glycol monobutyl ether, diethylene glycol monobutyl ether, Tri(propylene glycol)butyl ether,mixture of isomers, triethylene glycol butyl ether, the glycol monoethers solvent of Tri(propylene glycol)butyl ether,mixture of isomers etc., glycol dimethyl ether, Propylene Glycol Dimethyl Ether, diethylene glycol dimethyl ether, dimethyl ether, triethylene glycol dimethyl ethyl ether, tripropylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol diethyl ether, diethylene glycol diethyl ether, dipropylene glycol diethyl ether, triethylene glycol diethyl ether, tripropylene glycol diethyl ether, ethylene glycol bisthioglycolate propyl ether, propylene glycol dipropyl ether, diethylene glycol dipropyl ether, DPG dipropyl ether, triethylene glycol dipropyl ether, tripropylene glycol dipropyl ether, butyl cellosolve, propylene glycol butyl oxide, dibutyl ethylene glycol ether, DPG butyl oxide, triethylene glycol butyl oxide, the glycol ether solvent etc. of tripropylene glycol butyl oxide etc.

Wherein, organic solvent is preferably selected from least one in diol solvent, the derivative of diol solvent, alcoholic solvent and carbonate solvent, at least one more preferably in alcohols solvent.These organic solvents can be used alone one or mix two or more use.

When grinding agent contains organic solvent, the content of organic solvent is preferably 0.1 quality % ~ 95 quality % in the gross mass of grinding agent.Consider from the angle that prevents from reducing for the wettability of the substrate of grinding agent, content more preferably more than the 0.2 quality % of above-mentioned organic solvent, further preferred more than 0.5 quality %.In addition, from making the preparation, use, waste water treatment etc. of grinding agent become to be easy to angle to consider, more preferably below 50 quality %, further preferred below 10 quality %.

< water-soluble polymer >

Above-mentioned grinding agent is preferably containing at least a kind of water-soluble polymer.More effectively reach the suppression of corrosive effect, the protection on film surface, the minimizing etc. of defect generation thus.Herein, water miscible definition is, at 25 DEG C, for the material of 100g water-soluble solution more than 0.1g.

As above-mentioned water-soluble polymer, can enumerate, there is the water-soluble polymer etc. of carboxylic acid group or carboxylate group.As such water-soluble polymer, the autopolymer with the monomer of carboxylic acid group of acrylic acid, methacrylic acid, maleic acid etc. can be enumerated; Carboxylic acid group's part of this polymer is the autopolymer etc. that the carboxylate group becoming ammonium salt etc. is formed.In addition, the copolymer of the monomer also preferably with carboxylic acid group and the derivative with the monomer of carboxylate group and the Arrcostab of carboxylic acid etc.As water-soluble polymer can enumerate particularly as, polyacrylic acid, polyacrylic carboxylic acid group at least partially by polymer (hereinafter referred to as " ammonium polyacrylate salt ") etc. that carboxylic acid ammonium's alkali replaces.

In addition, as other water-soluble polymers other than the above, can illustrate as, the polysaccharide of alginic acid, pectic acid, carboxymethyl cellulose, agar, curdlan, pulullan polysaccharide etc.; The polybasic carboxylic acid of poly-aspartate, polyglutamic acid, polylysine, polymalic acid, polyamic acid, polyamic acid ammonium salt, polyamic acid sodium salt, metacetaldehyde acid etc. and salt thereof; The vinyl polymers etc. of polyvinyl alcohol, polyvinylpyrrolidone, polyacrolein etc.

When the substrate of grinding object is semiconductor integrated circuit substrate etc., from the viewpoint of the pollution avoiding above-mentioned alkali metal, alkaline-earth metal, halide etc. to cause, above-mentioned water-soluble polymer preferably has polymer or their ammonium salt of acidic groups.But, when the substrate of grinding object is glass substrate etc., there is no such restriction.

In above-mentioned water-soluble polymer, be preferably selected from the group of water-soluble polymer, pectic acid, agar, polymalic acid, polyacrylamide, polyvinyl alcohol and the polyvinylpyrrolidone composition with carboxylic acid group or carboxylate group (when being formed and obtain ester, salt, comprise these) in water-soluble polymer, more preferably there is the water-soluble polymer (comprising ester, salt) of carboxylic acid group or carboxylate group, further optimization polypropylene acid (comprising salt), particularly preferably ammonium polyacrylate salt.These can be used alone one or mix two or more use.

The weight average molecular weight of water-soluble polymer preferably 500 ~ 1,000,000, more preferably 1,000 ~ 500,000, further preferably 2,000 ~ 200,000, particularly preferably 5,000 ~ 150,000.

Above-mentioned weight average molecular weight, such as, based on following method, can be measured by gel permeation chromatography (GPC), the value being converted into standard polypropylene acid can be used to measure.

(condition)

Sample: 10 μ L

Standard polypropylene acid: Hitachi changes into テ Network ノサー PVC ス Co., Ltd. trade name: PMAA-32

Detector: Hitachi Co., Ltd's system, RI-detector, trade name " L-3000 "

Integrator (integrator): Hitachi Co., Ltd's system, GPC-integrator, trade name " D-2200 "

Pump: Hitachi Co., Ltd's system, trade name " L-6000 "

Degasser: Showa Denko K. K's system, trade name " Shodex DEGAS "

Chromatographic column: Hitachi Chemical Co., Ltd.'s system, with the use that is linked in sequence of trade name " GL-R440 ", " GL-R430 ", " GL-R420 "

Eluent: oxolane (THF)

Measure temperature: 23 DEG C

Flow velocity: 1.75mL/ minute

Minute: 45 minutes

During grinding agent containing water-soluble polymer, the content of water-soluble polymer in the gross mass of grinding agent is 0.001 quality % ~ 10 quality % preferably.From the viewpoint of good corrosion-inhibiting can be guaranteed, preferably more than 0.001 quality %, more preferably more than 0.01 quality %, further preferred more than 0.02 quality %.In addition, consider from the angle that can maintain sufficient grinding rate, preferably below 10 quality %, more preferably below 5.0 quality %, further preferred below 1.0 quality %.

< abrasive particle >

Above-mentioned grinding agent is preferably containing at least a kind of abrasive particle.By containing abrasive particle, the grinding rate of the layer beyond the cobalt layers that is arranged near cobalt layers can be improved.

As main abrasive particle, can illustrate as, the organic substance polishing particles etc. of the inorganic matter polishing particles, polystyrene, polyacrylic acid, polyvinyl chloride etc. of silicon dioxide, aluminium oxide, zirconia, ceria, titanium dioxide, germanium oxide, carborundum etc.This is wherein preferably selected from the inorganic matter polishing particles of silicon dioxide, aluminium oxide, zirconia, ceria, titanium dioxide and germanium oxide, especially, is more preferably selected from the inorganic matter polishing particles of silicon dioxide and aluminium oxide.

Good from the dispersion stabilization grinding agent, to be produced by CMP grinding damage (scratch, scratch) the few angle of generation quantity consider, by cataloid preferred in the inorganic matter polishing particles selected in silicon dioxide and aluminium oxide or colloidal alumina, more preferably cataloid.These abrasive particles can be used alone one or mix two or more use.

Consider from the angle that can obtain good grinding rate, the average grain diameter of abrasive particle is preferably at 10nm ~ 100nm, more preferably at 20nm ~ 90nm, preferred at 40nm ~ 80nm further.

The average grain diameter of abrasive particle is the value measured with light diffraction scattering formula particle size distribution meter (such as, the trade name of COULTER ELectronics society: COULTER N4SD).The condition determination of Coulter is, measure temperature 20 DEG C, solvent refractive index 1.333(and aqueous phase when), particle refractive index Unknown(sets), solvent viscosity 1.005MPaS(and aqueous phase ought), Run Time 200sec, laser incidence angle 90 °, Intensity(is made to be equivalent to scattering strength, turbidity) in the scope of 5E+04 ~ 4E+05, during higher than 4E+05, measure after dilute with water.

When grinding agent contains abrasive particle, the content of abrasive particle is preferably more than 1.0 quality %, more preferably more than 3.0 quality % in the gross mass of grinding agent, further preferred 3.0 quality % ~ 5.0 quality %.By the content of above-mentioned abrasive particle is set in above-mentioned scope, good grinding rate can be obtained.

< water >

There is no particular limitation for the water that the present invention uses, and preferably can use pure water.As long as water is mixed as the remainder of the constituent material of above-mentioned grinding agent, content has no particular limits.

Other > of <

Can make an addition to other compositions in above-mentioned grinding agent, citing is as, the colouring agent of the pigment of the dyestuff, phthalocyanine green etc. of surfactant, Victoria pure blue etc. etc.

The pH of above-mentioned grinding agent is below 4.0.If pH is more than 4.0, then the conductive material layer formed by wiring metal and the grinding rate of cobalt layers may decline.On the other hand, from can suppress at leisure corrosion of wirings metal in addition, because the strong and reluctant angle of acidity is set out, above-mentioned pH preferably more than 1.0, more preferably more than 2.0.

PH adjusts by the addition of acid compound.In addition, also can be adjusted by the interpolation of the alkali compounds such as ammonia, NaOH, Tetramethylammonium hydroxide (TMAH).

(the Model F-51 that such as, Horiba Ltd (HORIBA, Ltd.) makes measures the mensuration pH meter of the pH of above-mentioned grinding agent.Standard buffer solution (phthalate pH pH of buffer: 4.21(25 DEG C), neutral phosphate pH pH of buffer: 6.86(25 DEG C can be used), borate pH pH of buffer: 9.04(25 DEG C)) carry out 3 point calibrations after, electrode is inserted in grinding agent, measure the value after more than 3 minutes stable.

Above-mentioned grinding agent can be taken care of, during grinding, by suitably used in combination to this grinding agent, other constituent materials and water as the grinding agent (stock solution) containing carboxylic acid derivates, corrosion inhibitor for metal and water.Or, also can take care of with the state of the grinding agent suitably mixing other constituent materials in carboxylic acid derivates, corrosion inhibitor for metal and water and use.

Above-mentioned grinding agent is applicable to the formation of the wiring layer in semiconductor device.As the polished film of grinding object, as long as containing the part (hereinafter referred to as " cobalt part ") at least containing cobalt element, further, also can containing the conductive material be arranged near cobalt portion, barrier metal or insulator.

Namely, other forms of the present invention, that grinding agent contains the purposes in the layer of cobalt element in grinding, described grinding agent contains the carboxylic acid derivates, corrosion inhibitor for metal and the water that are made up of at least one be selected from alkyl dicarboxylic carboxylic acid compound and their salt and acid anhydrides that phthalic compounds, M-phthalic acid compound and following general formula (I) represent, and pH is below 4.0.

HOOC-R-COOH…(I)

In addition, other forms of the present invention are, grinding agent contains the purposes in the layer of cobalt element in grinding, described grinding agent contains at least one carboxylic acid derivates, corrosion inhibitor for metal and the water that are selected from alkyl dicarboxylic aid's compound and their salt and acid anhydrides that phthalic compounds, M-phthalic acid compound and following general formula (I) represent, pH is below 4.0,50 DEG C time, for the etching speed of cobalt at below 10.0nm/min.

HOOC-R-COOH…(I)

[substrate Ginding process]

Substrate Ginding process of the present invention is, uses at least one polished film containing cobalt element formed on the surface of above-mentioned grinding agent grinding base plate, removes the Ginding process containing the unnecessary part of cobalt element.More specifically, between the abrasive cloth on the polished film containing cobalt element and grinding plate of at least one surface formation of substrate, supply above-mentioned grinding agent, under the state simultaneously described substrate surface of the side, face being provided with above-mentioned polished film being pressed into abrasive cloth, by making this substrate and grinding plate relative movement, the Ginding process at least partially of the polished film of removing.

Below, with reference to Fig. 2, that use substrate Ginding process of the present invention, that wiring layer in semiconductor device is formed series of processes is described.But the purposes of grinding agent of the present invention is not limited to following operation.

As shown in Figure 2 (a) shows, substrate 10 before grinding, have at silicon substrate 1: barrier metal layer 3 and the cobalt layers 4 covering barrier metal layer 3 of the insulator 2 have the insulator 2 of the recess of predetermined pattern, covering along the convex-concave on the surface of this insulator 2, cobalt layers 4 is formed conductive material layer 5.

Silicon system insulator, organic polymer system insulator etc. is there can be exemplified as insulator 2.As silicon system insulator, can enumerate, the silica-based insulator of the organic silicate glass obtained for initiation material with silicon dioxide, fluorosilicate glass, trimethyl silane or dimethoxydimethylsilane, silicon oxynitride, hydrogen silsesquioxanes etc. or, carborundum and silicon nitride etc.In addition, as organic polymer system insulator, all aromatic system low dielectric constant insulator can be enumerated.Wherein, especially preferred silicon dioxide.

Insulator 2 is by CVD(chemical gaseous phase deposition) method, spin-coating method, dip coating or spraying process film forming.As the object lesson of insulator 2, can enumerate as the insulator etc. in LSI manufacturing process, particularly multilayer wiring formation process.

Barrier metal layer 3 is in order to prevent conductive material to be diffused in insulator 2 and the adaptation improved between insulator 2 and conductive material layer 5 is formed.As for the barrier metal in barrier metal layer 3, for example there are the tantalum compound of tantalum, tantalum nitride, tantalum alloy etc., the titanium compound of titanium, titanium nitride, titanium alloy etc., the tungsten compound of tungsten, tungsten nitride, tungsten alloy etc., the ruthenium compound etc. of ruthenium etc.Barrier metal layer 3 can be the single layer structure formed by 1 in these kind, also can be the lamination structure of two or more formation.Barrier metal layer 3 is by evaporation, CVD(chemical gaseous phase deposition) etc. film forming.In addition, as barrier metal layer 3, can cobalt layers 4 be only set.

As the cobalt class adopted in cobalt layers 4, cobalt, cobalt alloy, the oxide of cobalt, the oxide etc. of cobalt alloy can be enumerated.Cobalt layers is by film forming such as known gunitees.

As the conductive material adopted in conductive material 5, the noble metals etc. such as what can enumerate copper, copper alloy, the oxide of copper, the oxide of copper alloy etc. take copper as the metal of main component, the tungsten metal of tungsten, tungsten alloy etc., silver-colored, golden.Wherein the oxide of preferably copper, copper alloy, copper, the oxide of copper alloy etc. take copper as the metal of principal component.Conductive material layer 5 is by film forming such as known gunite, galvanoplastic.

The thickness of preferred insulator 2 is at 0.01 μm ~ about 2.0 μm, and the thickness of barrier metal layer 3 is at 0.01 μm ~ about 2.5 μm, and the thickness of cobalt layers 4 is at 0.01 μm ~ 2.5 μm, and the thickness of conductive material layer 5 is at 0.01 μm ~ about 2.5 μm.

Be ground to the 1st grinding step of the conductive material layer 5 of state shown in Fig. 2 (b) from state Fig. 2 (a) Suo Shi, use such as, the conductive material layer 5 on the surface of the substrate 10 before grinding, than the grinding agent of enough large conductive material, is ground by CMP by the grinding rate of conductive material layer 5/ cobalt layers 4.Thus the cobalt layers 4 obtaining the protuberance on substrate is exposed in surface, recess the substrate 20 with conductive pattern remaining conductive material layer 5.Grinding rate as conductive material layer 5/ cobalt layers 4 compares the grinding agent of enough large above-mentioned conductive material, can use the grinding agent recorded in such as Japan Patent No. 3337464 specification.Also the part that conductive material layer 5 grinds the cobalt layers 4 of protuberance together can be ground in 1st grinding step.

In ensuing 2nd grinding step, using the conductive pattern that obtained by the 1st grinding step as the polished film of the 2nd grinding step, grinding agent of the present invention is used to grind.

In 2nd grinding step, under the state that the abrasive cloth of grinding plate presses substrate 20, between abrasive cloth and substrate, supplying grinding agent of the present invention, simultaneously by making grinding plate and substrate 20 relatively move, grinding the cobalt layers 4 by exposing in the 1st grinding step.

As lapping device, general lapping device can be used, there is in its device the holder of the substrate keeping polished, be connected with the motor etc. of modifiable rotating speed and pasted the grinding plate of abrasive cloth.As abrasive cloth, common nonwoven fabrics, polyurethane foam, Porous fluororesin etc. can be used, have no particular limits.

Grinding condition has no particular limits, but the low rotation of preferred below the 200rpm of the rotary speed of grinding plate.Do not fly out to make substrate.On abrasive cloth, pressing has the pressure of the substrate of polished film, preferred 1kPa ~ 100kPa, in order to the homogeneity of grinding rate in satisfied polished face and the flatness of pattern, more preferably 5kPa ~ 50kPa.

In grinding, use pump etc. are supplied grinding agent of the present invention between abrasive cloth and polished film continuously.This quantity delivered has no particular limits, but preferably the total surface of abrasive cloth is that polished agent covers.Substrate after grinding terminates, makes it dry after brushing lightly the water droplet falling to being attached on substrate after preferably carefully washing in flowing water with Rotary drying etc.

In 2nd grinding step, at least grind the cobalt layers 4 exposed, remove unnecessary cobalt part.In 2nd grinding step, grinding cobalt layers 4, if expose barrier metal layer 3 just terminate grinding, also can use barrier metal layer abradant grinding agent grinding barrier metal layer 3 in addition.In addition, as shown in from Fig. 2 (b) to Fig. 2 (c), in the 2nd grinding step, also can be ground to metal level 3 from cobalt layers 4 a series ofly.Further, the conductive layer 5 being embedded in recess can be polished together with cobalt layers 4 and barrier metal layer 3.

When obtaining substrate 30 with desired pattern, terminate grinding, desired pattern is as follows, insulator 2 under the barrier metal layer 3 of protuberance all exposes, remain the conductive material layer 5 becoming wiring layer in recess, in the border between protuberance and recess, the cross section of barrier metal layer 3 and cobalt layers 4 is exposed.

In order to ensure the more excellent flatness at the end of grinding, further, as shown in Figure 3, overmastication (such as, when the 2nd grinding step time obtained till desired pattern was 100 seconds, add again except this grinding of 100 seconds and grind for 50 seconds, be called overmastication 50%) also passable.During overmastication, a part for insulator 2 is also because grinding is removed.

On the metal line formed like this, after the insulator further forming the 2nd layer and metal line, grinding, makes whole faces of semiconductor substrate become level and smooth face.Repeat this operation by stipulated number, the semiconductor device with the desired wiring number of plies can be manufactured.

Grinding agent of the present invention is not only the grinding of the metal film formed in semiconductor substrate described above, also can be used in the substrate of lapping magnetic heads etc.

[embodiment]

Below, by embodiment, more specific description is carried out to the present invention, but the present invention being not limited to these examples.

< is for the evaluation > of the etch quantity of cobalt

［ embodiment and comparative example ］

(manufacture method of grinding agent)

Corrosion inhibitor for metal shown in table 1 and table 2 and carboxylic acid derivates are joined in container respectively, using make the amount as final grinding agent become as in table 1 record combined amount, and (Hitachi changes into テ Network ノサー PVC ス system to add the ammonium polyacrylate salt made as water-soluble polymer, molecular weight 8000) become the amount of 0.02 quality % of final grinding agent, the MMB as organic solvent is made to be the amount of 1.4 quality % of final grinding agent, inject ultra-pure water wherein, be uniformly mixed, dissolve whole composition.

Then, add the amount of 4.0 quality % in the gross mass being equivalent to the slurries prepared, as the cataloid (Fukawa Chemical Industries Co., Ltd.'s system, particle diameter 60nm) of the silicon dioxide granule of abrasive particle, re-inject ultra-pure water, obtain slurries.In the gross mass of the slurries obtained, the hydrogen peroxide adding 30 quality % is 0.2 quality %, obtains various grinding agent.

Measure the pH of each grinding agent obtained, the results are shown in Table 1 and table 2.

(evaluating the etch quantity for cobalt)

Prepare to define by CVD the housing base (a) that thickness is the cobalt layers of 300nm on the silicon substrate of 8 inches.Above-mentioned housing base (a) is cut into the square chip of 20mm, prepares evaluation chip (b).

Add above-mentioned evaluation chip (b) respectively to above-mentioned adding in the beaker of each grinding agent 50g, soak 1 minute in the thermostat of 50 DEG C.Take out the chip (b) after soaking, after fully washing with pure water, spray nitrogen makes the moisture drying on chip.The resistance resistivity measurement of dried evaluation chip (b) is fixed, is converted into the thickness of the cobalt layers after the immersion in following formula (1).

Obtain lubber-line the information of the resistance value corresponding respectively from each thickness with shell basic unit (a), tried to achieve the thickness of cobalt layers by following formula (1).

The thickness [nm] of the cobalt layers after immersion

=104.5 × (evaluating the resistance value [m Ω]/1000 with chip (b)) ^-0.893

Then, the thickness of the cobalt layers before the thickness and immersion of the cobalt layers after the immersion obtained, according to following formula (2), tries to achieve the etching speed of cobalt layers.

Etching speed (Co-ER) [nm/min] of cobalt layers

=(thickness [nm] of the cobalt layers after thickness [the nm]-immersion of the cobalt layers before immersion)/1 minute ... (2)

To each grinding agent obtained above, try to achieve the etching speed for cobalt layers.This results are shown in Table 1 and table 2.In addition, in table 1 and table 2, "-" in the hurdle of carboxylic acid derivates and anticolodal represents unmixed.

(evaluation for the grinding rate of cobalt layers)

In addition, grinding rate (Co-RR) [nm/min] when using each grinding agent obtained above to grind above-mentioned housing base (a) is under the following conditions evaluated.This result is shown in table 1 and table 2 in the lump.In addition, about several comparative example, because etching speed is too fast, therefore omit the evaluation of grinding rate, be recited as "-".

< grinding condition >

Abrasive cloth: IC1000

Grinding pressure: 10.3kPa(1.5psi)

Rotating speed: platform/grinding head=93/87rpm

The quantity delivered of grinding agent: 200mL/ minute

Milling time: 0.5 minute

[table 1]

[table 2]

From table 1 and table 2 very clear, in embodiment 1 ~ 13, by simultaneously containing specific dicarboxylic acids and corrosion inhibitor for metal, even also significantly suppress the etching speed of cobalt under the condition of 50 DEG C, known can with suitable speed grinding cobalt layers.Thus, enlightenment: containing in the grinding agent of the present invention of above-mentioned carboxylic acid derivates, above-mentioned specific dicarboxylic acid compound has the effect as complex-forming agents and corrosion inhibitor concurrently.That is, according to grinding agent of the present invention, enlightening when grinding the layer containing cobalt element, also effectively suppressing the layer containing cobalt element to be etched excessively with the grinding of good grinding rate, or due to corrosion generation slit.

Claims

1. grinding agent contains the application in the layer of cobalt element in grinding, described grinding agent contains the carboxylic acid derivates, corrosion inhibitor for metal and the water that are made up of at least one be selected from alkyl dicarboxylic carboxylic acid compound and their salt and acid anhydrides that phthalic compounds, M-phthalic acid compound and following general formula (I) represent, the pH of grinding agent is below 4.0

HOOC-R-COOH···(I)

In above-mentioned general formula (I), R represents that carbon number is the alkylidene of 4 ~ 10.

2. grinding agent contains the application in the layer of cobalt element in grinding, described grinding agent contains at least one carboxylic acid derivates, corrosion inhibitor for metal and the water that are selected from alkyl dicarboxylic aid's compound and their salt and acid anhydrides that phthalic compounds, M-phthalic acid compound and following general formula (I) represent, the pH of grinding agent is below 4.0, in the grinding agent of 50 DEG C for the etching speed of cobalt at below 10.0nm/min

HOOC-R-COOH···(I)

3. grinding agent as claimed in claim 2 in grinding containing the application in the layer of cobalt element, in the grinding agent of 50 DEG C for the etching speed of cobalt at below 9.0nm/min.

4. grinding agent as claimed in claim 2 in grinding containing the application in the layer of cobalt element, in the grinding agent of 50 DEG C for the etching speed of cobalt at below 8.0nm/min.

5. the grinding agent as described in any one in claim 1 ~ claim 4 is in grinding containing the application in the layer of cobalt element, and described carboxylic acid derivates comprises at least one in the group being selected from and phthalic acid, phenyl ring have alkyl dicarboxylic aid's compound with the alkylidene of carbon number 4 ~ 8 that more than one substituent phthalic acid derivatives, M-phthalic acid, phenyl ring have more than one substituent isophthalic acid derivatives and described general formula (I) to represent to form.

6. the grinding agent as described in any one in claim 1 ~ claim 4 contains the application in the layer of cobalt element in grinding, described carboxylic acid derivates comprises and is selected from by phthalic acid, phenyl ring is selected from methyl, more than one substituent phthalic acid derivatives in the group that amino and nitro is formed, M-phthalic acid, phenyl ring is selected from nitro, methyl, at least one in the group that alkyl dicarboxylic aid's compound with the alkylidene of carbon number 4 ~ 8 that more than one substituent isophthalic acid derivatives in the group that amino and hydroxyl is formed and described general formula (I) represent is formed.

7. grinding agent as claimed in claim 5 is in grinding containing the application in the layer of cobalt element, and the carbon number of the described alkylidene in described alkyl dicarboxylic aid's compound is 4 ~ 6.

8. the grinding agent as described in any one in claim 1 ~ claim 4 is in grinding containing the application in the layer of cobalt element, and described carboxylic acid derivates comprises at least one in the group being selected from and being made up of phthalic acid, alkyl phthalic acid, aminophthalic acid, nitrophthalic acid, M-phthalic acid, nitroisophthalic acid, adipic acid, pimelic acid, suberic acid and azelaic acid.

9. the grinding agent as described in any one in claim 1 ~ claim 4 is in grinding containing the application in the layer of cobalt element, and with the gross mass of grinding agent for benchmark, the content of described carboxylic acid derivates is 0.001 quality % ~ 10 quality %.

10. the grinding agent as described in any one in claim 1 ~ claim 4 is in grinding containing the application in the layer of cobalt element, and with the gross mass of grinding agent for benchmark, the content of described carboxylic acid derivates is more than 0.01 quality %.

11. grinding agents as described in any one in claim 1 ~ claim 4 are in grinding containing the application in the layer of cobalt element, and with the gross mass of grinding agent for benchmark, the content of described carboxylic acid derivates is more than 0.03 quality %.

12. grinding agents as described in any one in claim 1 ~ claim 4 are in grinding containing the application in the layer of cobalt element, and with the gross mass of grinding agent for benchmark, the content of described carboxylic acid derivates is more than 0.05 quality %.

13. grinding agents as described in any one in claim 1 ~ claim 4 are in grinding containing the application in the layer of cobalt element, and with the gross mass of grinding agent for benchmark, the content of described carboxylic acid derivates is below 5.0 quality %.

14. grinding agents as described in any one in claim 1 ~ claim 4 are in grinding containing the application in the layer of cobalt element, and with the gross mass of grinding agent for benchmark, the content of described carboxylic acid derivates is below 3.0 quality %.

15. grinding agents as described in any one in claim 1 ~ claim 4 are in grinding containing the application in the layer of cobalt element, and with the gross mass of grinding agent for benchmark, the content of described carboxylic acid derivates is below 1.0 quality %.

16. grinding agents as described in any one in claim 1 ~ claim 4 are in grinding containing the application in the layer of cobalt element, and described carboxylic acid derivates comprises at least one be selected from alkyl dicarboxylic aid's compound and their salt that the R represented by alkyl phthalic acid, aminophthalic acid, nitrophthalic acid, M-phthalic acid, 5-nitroisophthalic acid and general formula (I) is the straight-chain alkylidene of carbon number 4 ~ 8 and the group that acid anhydrides is formed of more than 0.01 quality %.

17. grinding agents as described in any one in claim 1 ~ claim 4 are in grinding containing the application in the layer of cobalt element, and described carboxylic acid derivates comprises at least one be selected from alkyl dicarboxylic aid's compound and their salt that the R represented by alkyl phthalic acid, aminophthalic acid, nitrophthalic acid, M-phthalic acid, 5-nitroisophthalic acid and general formula (I) is the straight-chain alkylidene of carbon number 4 ~ 8 and the group that acid anhydrides is formed of below 5.0 quality %.

18. grinding agents as claimed in claim 16 are in grinding containing the application in the layer of cobalt element, and the carbon number of the described straight-chain alkylidene in described alkyl dicarboxylic aid's compound is 4 ~ 6.

19. the grinding agent as described in any one in claim 1 ~ claim 4 is in grinding containing the application in the layer of cobalt element, described corrosion inhibitor for metal is selected from least one in the group of triazole compounds, pyridine compounds, pyrazole compound, pyrimidine compound, imidazolium compounds, guanidine compound, thiazolium compounds, tetrazole compound, triaizine compounds and hexa formation.

20. the grinding agent as described in any one in claim 1 ~ claim 4 is in grinding containing the application in the layer of cobalt element, described corrosion inhibitor for metal is selected from least one in the group of triazole compounds, pyridine compounds, imidazolium compounds, tetrazole compound, triaizine compounds and hexa formation.

21. grinding agents as claimed in claim 19 are in grinding containing the application in the layer of cobalt element, and described corrosion inhibitor for metal is selected from 1,2,3-triazoles, 1,2,4-triazole, 3-amino-1H-1,2,4-triazole, BTA, I-hydroxybenzotriazole, 1-dihydroxypropyl BTA, 2,3-dicarboxypropyl BTA, 4-hydroxybenzotriazole, 4-carboxyl-1H-BTA, 4-carboxyl-1H-BTA methyl esters (1H-BTA-4-carboxylate methyl ester), 4-carboxyl-1H-BTA butyl ester (1H-BTA-4-butyl carboxylate), 4-carboxyl-1H-BTA monooctyl ester (1H-BTA-4-carboxylic acid monooctyl ester), 5-hexyl BTA, (1,2,3-BTA-1-methyl) (1,2,4-triazolyl-1-methyl) (2-ethylhexyl) amine, tolyl-triazole, aphthotriazoles, two [(1-BTA base) methyl] phosphonic acids, 3H-1,2,3-triazol [4,5-b] pyridine-3-alcohol, 1H-1,2,3-triazol [4,5-b] pyridine, 1-acetyl group-1H-1,2,3-triazol [4,5-b] pyridine, 3-pyridone, 1,2,4-triazol [1,5-a] pyrimidine, 1,3,4,6,7,8-six hydrogen-2H-pyrimido [1,2-a] pyrimidine, 2-methyl-5,7-diphenyl-[1,2,4] triazol [1,5-a] pyrimidine, 2-sulfonyloxy methyl-5,7-diphenyl-[1,2,4] triazol [1,5-a] pyrimidine, 2-sulfonyloxy methyl-5,7-diphenyl-4,7-dihydro-[1,2,4] triazol [1,5-a] pyrimidine, oxine, protionamide, 2-nitropyridine-3-alcohol, pyridoxamine, niacinamide, iproniazid, isonicotinic acid, benzo [f] quinoline, 2,5-Pyridinedicarboxylic acid, 4-stibazole, anabasine, 4-nitropyridine-1-oxide, pyridine-3-ethyl acetate, quinoline, 2-ethylpyridine, quinolinic acid, arecaline, citrazinic acid, pyridine-3-methyl alcohol, 2-methyl-5-ethylpyridine, 2-fluorine pyridine, five fluorine pyridines, 6-picoline-3-alcohol, pyridine-2-ethyl acetate, pyrazoles, 1-pi-allyl-3,5-dimethyl pyrazole, 3,5-bis-(2-pyridine radicals) pyrazoles, 3,5-diisopropyl pyrazoles, 3,5-dimethyl-1-hydroxymethylpyrazolcompound, 3,5-dimethyl-1-Phenylpyrazole, 3,5-dimethyl pyrazole, 3-amino-5-hydroxypyrazoles, 4-methylpyrazole, N-methylpyrazole, 3-amino-pyrazol, 3-amino-pyrazol, pyrimidine, 1,3-diphenyl-pyrimidine-2,4,6-triketone, Isosorbide-5-Nitrae, 5,6-tetrahydropyrimidine, 2,4,5,6-tetraminopyrimidine sulfate, 2, 4, 5-trihydroxy-pyrimidine, 2,4,6-Triaminopyrimidine, 2,4,6-trichloropyrimidine, 2,4,6-trimethoxy-pyrimidine, 2,4,6-triphenyl pyrimidine, 2,4-diaminourea-6-hydroxy pyrimidine, 2,4-di-amino-pyrimidine, 2-ethanamide pyrimidine, 2-aminopyrimidine, 4-amino-pyrazol is [3,4-d] pyrimidine also, 1,1'-carbonyl two (1H-imidazoles), 1,1'-oxalyl diimidazole, 1,2,4,5-tetramethyl imidazoles, 1,2-dimethyl-5-nitroimidazole, 1,2-methylimidazole, 1-(3-aminopropyl) imidazoles, 1-butyl imidazole, 1-ethyl imidazol(e), 1-methylimidazole, benzimidazole, 1,1,3,3-TMG, 1,2,3-triphenyl guanidine, 1,3-, bis--o-tolyl guanidine, 1,3-diphenylguanidine, 2-mercaptobenzothiazole, 2,4-dimethylthiazole, tetrazolium, 5-methyl tetrazolium, 5-amino-1H-TETRAZOLE, 1-(2-dimethyl aminoethyl)-5-mercapto-tetrazole, the group that 3,4-dihydro-3-hydroxy-4-oxo-1,2,4-triazine and hexa are formed.

22. grinding agents as claimed in claim 19 are in grinding containing the application in the layer of cobalt element, and described corrosion inhibitor for metal is selected from 1,2,3-triazoles, 1,2,4-triazole, 3-amino-1H-1,2,4-triazole, BTA, I-hydroxybenzotriazole, 1-dihydroxypropyl BTA, 2,3-dicarboxypropyl BTA, 4-hydroxybenzotriazole, 4-carboxyl-1H-BTA, 4-carboxyl-1H-BTA methyl esters (1H-BTA-4-carboxylate methyl ester), 4-carboxyl-1H-BTA butyl ester (1H-BTA-4-butyl carboxylate), 4-carboxyl-1H-BTA monooctyl ester (1H-BTA-4-carboxylic acid monooctyl ester), 5-hexyl BTA, (1,2,3-BTA-1-methyl) (1,2,4-triazolyl-1-methyl) (2-ethylhexyl) amine, tolyl-triazole, aphthotriazoles, two [(1-BTA base) methyl] phosphonic acids, 3H-1,2,3-triazol [4,5-b] pyridine-3-alcohol, 1H-1,2,3-triazol [4,5-b] pyridine, 1-acetyl group-1H-1,2,3-triazol [4,5-b] pyridine, 3-pyridone, 1,2,4-triazol [1,5-a] pyrimidine, 1,3,4,6,7,8-six hydrogen-2H-pyrimido [1,2-a] pyrimidine, 2-methyl-5,7-diphenyl-[1,2,4] triazol [1,5-a] pyrimidine, 2-sulfonyloxy methyl-5,7-diphenyl-[1,2,4] triazol [1,5-a] pyrimidine, 2-sulfonyloxy methyl-5,7-diphenyl-4,7-dihydro-[1,2,4] triazol [1,5-a] pyrimidine, oxine, protionamide, 2-nitropyridine-3-alcohol, pyridoxamine, niacinamide, iproniazid, isonicotinic acid, benzo [f] quinoline, 2,5-Pyridinedicarboxylic acid, 4-stibazole, anabasine, 4-nitropyridine-1-oxide, pyridine-3-ethyl acetate, quinoline, 2-ethylpyridine, quinolinic acid, arecaline, citrazinic acid, pyridine-3-methyl alcohol, 2-methyl-5-ethylpyridine, 2-fluorine pyridine, five fluorine pyridines, 6-picoline-3-alcohol, pyridine-2-ethyl acetate, 1,1'-carbonyl two (1H-imidazoles), 1,1'-oxalyl diimidazole, 1,2,4,5-tetramethyl imidazoles, 1,2-dimethyl-5-nitroimidazole, 1,2-methylimidazole, 1-(3-aminopropyl) imidazoles, 1-butyl imidazole, 1-ethyl imidazol(e), 1-methylimidazole, benzimidazole, tetrazolium, 5-methyl tetrazolium, 5-amino-1H-TETRAZOLE, 1-(2-dimethyl aminoethyl)-5-mercapto-tetrazole, the group that 3,4-dihydro-3-hydroxy-4-oxo-1,2,4-triazine and hexa are formed.

23. grinding agents as described in any one in claim 1 ~ claim 4 are in grinding containing the application in the layer of cobalt element, and described corrosion inhibitor for metal contains the compound with triazole skeleton.

24. grinding agents as claimed in claim 23 in grinding containing the application in the layer of cobalt element, described in there is triazole skeleton compound be selected from 1,2,3-triazoles, 1,2,4-triazole, 3-amino-1H-1,2,4-triazole, BTA, I-hydroxybenzotriazole, 1-dihydroxypropyl BTA, 2,3-dicarboxypropyl BTA, 4-hydroxybenzotriazole, 4-carboxyl-1H-BTA, 4-carboxyl-1H-BTA methyl esters (1H-BTA-4-carboxylate methyl ester), 4-carboxyl-1H-BTA butyl ester (1H-BTA-4-butyl carboxylate), 4-carboxyl-1H-BTA monooctyl ester (1H-BTA-4-carboxylic acid monooctyl ester), 5-hexyl BTA, (1,2,3-BTA-1-methyl) (1,2,4-triazolyl-1-methyl) (2-ethylhexyl) amine, tolyl-triazole, aphthotriazoles, two [(1-BTA base) methyl] phosphonic acids, 3H-1,2,3-triazol [4,5-b] pyridine-3-alcohol, 1H-1,2,3-triazol [4,5-b] pyridine, 1-acetyl group-1H-1,2,3-triazol [4,5-b] pyridine, 3-pyridone, 1,2,4-triazol [1,5-a] pyrimidine, 1,3,4,6,7,8-six hydrogen-2H-pyrimido [1,2-a] pyrimidine, 2-methyl-5,7-diphenyl-[1,2,4] triazol [1,5-a] pyrimidine, the group that 2-sulfonyloxy methyl-5,7-diphenyl-[1,2,4] triazol [1,5-a] pyrimidine and 2-sulfonyloxy methyl-5,7-diphenyl-4,7-dihydro-[1,2,4] triazol [1,5-a] pyrimidine are formed.

25. the grinding agent as described in any one in claim 1 ~ claim 4 is in grinding containing the application in the layer of cobalt element, the content of described corrosion inhibitor for metal is 0.001 quality % ~ 10 quality % in the gross mass of grinding agent.

26. grinding agents as described in any one in claim 1 ~ claim 4 are in grinding containing the application in the layer of cobalt element, and the content of described corrosion inhibitor for metal is more than 0.01 quality % in the gross mass of grinding agent.

27. grinding agents as described in any one in claim 1 ~ claim 4 are in grinding containing the application in the layer of cobalt element, and the content of described corrosion inhibitor for metal is more than 0.02 quality % in the gross mass of grinding agent.

28. grinding agents as described in any one in claim 1 ~ claim 4 are in grinding containing the application in the layer of cobalt element, and the content of described corrosion inhibitor for metal is below 5.0 quality % in the gross mass of grinding agent.

29. grinding agents as described in any one in claim 1 ~ claim 4 are in grinding containing the application in the layer of cobalt element, and the content of described corrosion inhibitor for metal is below 0.5 quality % in the gross mass of grinding agent.

30. grinding agents as described in any one in claim 1 ~ claim 4 in grinding containing the application in the layer of cobalt element, the ratio of described carboxylic acid derivates and corrosion inhibitor for metal, namely carboxylic acid derivates/corrosion inhibitor for metal mass ratio 10/1 ~ 1/5 scope.

31. grinding agents as described in any one in claim 1 ~ claim 4 in grinding containing the application in the layer of cobalt element, the ratio of described carboxylic acid derivates and corrosion inhibitor for metal, namely carboxylic acid derivates/corrosion inhibitor for metal mass ratio 7/1 ~ 1/5 scope.

32. grinding agents as described in any one in claim 1 ~ claim 4 in grinding containing the application in the layer of cobalt element, the ratio of described carboxylic acid derivates and corrosion inhibitor for metal, namely carboxylic acid derivates/corrosion inhibitor for metal mass ratio 5/1 ~ 1/5 scope.

33. grinding agents as described in any one in claim 1 ~ claim 4 in grinding containing the application in the layer of cobalt element, the ratio of described carboxylic acid derivates and corrosion inhibitor for metal, namely carboxylic acid derivates/corrosion inhibitor for metal mass ratio 5/1 ~ 1/1 scope.

34. grinding agents as described in any one in claim 1 ~ claim 4 in grinding containing the application in the layer of cobalt element, the ratio of described carboxylic acid derivates and the corrosion inhibitor for metal of at least one be selected from group that triazole compounds, pyridine compounds, imidazolium compounds, tetrazole compound, triaizine compounds and hexa form, namely carboxylic acid derivates/corrosion inhibitor for metal mass ratio 10/1 ~ 1/5 scope.

35. grinding agents as described in any one in claim 1 ~ claim 4 in grinding containing the application in the layer of cobalt element, the ratio of described carboxylic acid derivates and the corrosion inhibitor for metal of at least one be selected from group that triazole compounds, pyridine compounds, imidazolium compounds, tetrazole compound, triaizine compounds and hexa form, namely carboxylic acid derivates/corrosion inhibitor for metal mass ratio 5/1 ~ 1/5 scope.

36. grinding agents as described in any one in claim 1 ~ claim 4 in grinding containing the application in the layer of cobalt element, described carboxylic acid derivates be selected from 3H-1, 2, 3-triazol [4, 5-b] pyridine-3-alcohol, I-hydroxybenzotriazole, 1H-1, 2, 3-triazol [4, 5-b] pyridine, BTA, 3-pyridone, benzimidazole, 5-amino-1H-TETRAZOLE, 3, 4-dihydro-3-hydroxy-4-oxo-1, 2, the ratio of the corrosion inhibitor for metal of at least one in 4-triazine and hexa, namely carboxylic acid derivates/corrosion inhibitor for metal mass ratio 5/1 ~ 1/1 scope.

37. grinding agents as described in any one in claim 1 ~ claim 4 in grinding containing the application in the layer of cobalt element, further containing oxidant.

38. grinding agents as claimed in claim 37 are in grinding containing the application in the layer of cobalt element, and shown oxidant is selected from least one in the group of hydrogen peroxide, sulfuric peroxide hydrochlorate, nitric acid, Potassium periodate, hypochlorous acid and Ozone Water formation.

39. grinding agents as claimed in claim 37 are in grinding containing the application in the layer of cobalt element, and the content of described oxidant is 0.01 quality % ~ 50 quality % in the gross mass of grinding agent.

40. grinding agents as claimed in claim 37 are in grinding containing the application in the layer of cobalt element, and the content of described oxidant is more than 0.02 quality % in the gross mass of grinding agent.

41. grinding agents as claimed in claim 37 are in grinding containing the application in the layer of cobalt element, and the content of described oxidant is more than 0.05 quality % in the gross mass of grinding agent.

42. grinding agents as claimed in claim 37 are in grinding containing the application in the layer of cobalt element, and the content of described oxidant is below 30 quality % in the gross mass of grinding agent.

43. grinding agents as claimed in claim 37 are in grinding containing the application in the layer of cobalt element, and the content of described oxidant is below 15 quality % in the gross mass of grinding agent.

44. grinding agents as described in any one in claim 1 ~ claim 4 in grinding containing the application in the layer of cobalt element, further containing organic solvent.

45. grinding agents as claimed in claim 44 are in grinding containing the application in the layer of cobalt element, and described organic solvent is water miscible.

46. grinding agents as claimed in claim 44 are in grinding containing the application in the layer of cobalt element, and described organic solvent is selected from least one in the group of the derivative formation of carbonate solvent, interior ester solvent, diol solvent, ether solvents, alcohols solvent, ketone solvent and diol solvent.

47. grinding agents as claimed in claim 44 are in grinding containing the application in the layer of cobalt element, and described organic solvent is selected from ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, butyrolactone, propiolactone, ethylene glycol, propylene glycol, diethylene glycol, DPG alcohol, triethylene glycol, tripropylene glycol, oxolane, diox, dimethoxy-ethane, poly(ethylene oxide), ethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetic acid esters, propylene glycol methyl ether acetate, methyl alcohol, ethanol, propyl alcohol, n-butanol, n-amyl alcohol, n-hexyl alcohol, isopropyl alcohol, MMB, acetone, methyl ethyl ketone, dimethyl formamide, 1-METHYLPYRROLIDONE, ethyl acetate, ethyl lactate, sulfolane, glycol monoethyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, Tripropylene glycol monomethyl Ether, ethylene glycol monoethyl ether, dihydroxypropane single-ether, diethylene glycol monoethyl ether, DPE, Triethylene glycol ethyl ether, tripropylene glycol list ether, ethylene glycol ether, propylene glycol monopropyl ether, Diethylene glycol monopropyl ether, Triethylene glycol Monoisopropyl Ether, Tripropylene glycol Propyl Ether, ethylene glycol monobutyl ether, propylene glycol monobutyl ether, diethylene glycol monobutyl ether, Tri(propylene glycol)butyl ether,mixture of isomers, triethylene glycol butyl ether, Tri(propylene glycol)butyl ether,mixture of isomers, glycol dimethyl ether, Propylene Glycol Dimethyl Ether, diethylene glycol dimethyl ether, dimethyl ether, triethylene glycol dimethyl ethyl ether, tripropylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol diethyl ether, diethylene glycol diethyl ether, dipropylene glycol diethyl ether, triethylene glycol diethyl ether, tripropylene glycol diethyl ether, ethylene glycol bisthioglycolate propyl ether, propylene glycol dipropyl ether, diethylene glycol dipropyl ether, DPG dipropyl ether, triethylene glycol dipropyl ether, tripropylene glycol dipropyl ether, butyl cellosolve, propylene glycol butyl oxide, dibutyl ethylene glycol ether, DPG butyl oxide, triethylene glycol butyl oxide, at least one in the group that tripropylene glycol butyl oxide is formed.

48. grinding agents as claimed in claim 44 are in grinding containing the application in the layer of cobalt element, and the content of described organic solvent is 0.1 quality % ~ 95 quality % in the gross mass of grinding agent.

49. grinding agents as claimed in claim 44 are in grinding containing the application in the layer of cobalt element, and the content of described organic solvent is more than 0.2 quality % in the gross mass of grinding agent.

50. grinding agents as claimed in claim 44 are in grinding containing the application in the layer of cobalt element, and the content of described organic solvent is more than 0.5 quality % in the gross mass of grinding agent.

51. grinding agents as claimed in claim 44 are in grinding containing the application in the layer of cobalt element, and the content of described organic solvent is below 50 quality % in the gross mass of grinding agent.

52. grinding agents as claimed in claim 44 are in grinding containing the application in the layer of cobalt element, and the content of described organic solvent is below 10 quality % in the gross mass of grinding agent.

53. grinding agents as described in any one in claim 1 ~ claim 4 in grinding containing the application in the layer of cobalt element, further containing water-soluble polymer.

54. grinding agents as claimed in claim 53 are in grinding containing the application in the layer of cobalt element, and described water-soluble polymer has carboxylic acid group or carboxylate group.

55. grinding agents as claimed in claim 53 are in grinding containing the application in the layer of cobalt element, and described water-soluble polymer is selected from water-soluble polymer, pectic acid, agar, polymalic acid, polyacrylamide, polyvinyl alcohol and the polyvinylpyrrolidone with carboxylic acid group or carboxylate group.

56. grinding agents as claimed in claim 53 are in grinding containing the application in the layer of cobalt element, and the weight average molecular weight of described water-soluble polymer is 500 ~ 1,000,000.

57. grinding agents as claimed in claim 53 are in grinding containing the application in the layer of cobalt element, and the weight average molecular weight of described water-soluble polymer is 1,000 ~ 500,000.

58. grinding agents as claimed in claim 53 are in grinding containing the application in the layer of cobalt element, and the weight average molecular weight of described water-soluble polymer is 2,000 ~ 200,000.

59. grinding agents as claimed in claim 53 are in grinding containing the application in the layer of cobalt element, and the weight average molecular weight of described water-soluble polymer is 5,000 ~ 150,000.

60. grinding agents as claimed in claim 53 are in grinding containing the application in the layer of cobalt element, and the content of described water-soluble polymer in the gross mass of grinding agent is 0.001 quality % ~ 10 quality %.

61. grinding agents as claimed in claim 53 are in grinding containing the application in the layer of cobalt element, and the content of described water-soluble polymer in the gross mass of grinding agent is more than 0.001 quality %.

62. grinding agents as claimed in claim 53 are in grinding containing the application in the layer of cobalt element, and the content of described water-soluble polymer in the gross mass of grinding agent is more than 0.01 quality %.

63. grinding agents as claimed in claim 53 are in grinding containing the application in the layer of cobalt element, and the content of described water-soluble polymer in the gross mass of grinding agent is more than 0.02 quality %.

64. grinding agents as claimed in claim 53 are in grinding containing the application in the layer of cobalt element, and the content of described water-soluble polymer in the gross mass of grinding agent is below 10 quality %.

65. grinding agents as claimed in claim 53 are in grinding containing the application in the layer of cobalt element, and the content of described water-soluble polymer in the gross mass of grinding agent is below 5.0 quality %.

66. grinding agents as claimed in claim 53 are in grinding containing the application in the layer of cobalt element, and the content of described water-soluble polymer in the gross mass of grinding agent is below 1.0 quality %.

67. grinding agents as described in any one in claim 1 ~ claim 4 in grinding containing the application in the layer of cobalt element, further containing abrasive particle.

68. grinding agents as described in claim 67 in grinding containing the application in the layer of cobalt element, at least one in the group that described abrasive particle is selected from silicon dioxide, aluminium oxide, zirconia, ceria, titanium dioxide, germanium oxide, carborundum, polystyrene, polyacrylic acid, polyvinyl chloride are formed.

69. grinding agents as described in claim 67 are in grinding containing the application in the layer of cobalt element, and described abrasive particle is selected from least one in the group that silicon dioxide and aluminium oxide form.

70. grinding agents as described in claim 67 are in grinding containing the application in the layer of cobalt element, and described abrasive particle is selected from least one in the group that cataloid and colloidal alumina form.

71. grinding agents as described in claim 67 are in grinding containing the application in the layer of cobalt element, and described abrasive particle is cataloid.

72. grinding agents as described in claim 67 are in grinding containing the application in the layer of cobalt element, and the average grain diameter of described abrasive particle is at 10nm ~ 100nm.

73. grinding agents as described in claim 67 are in grinding containing the application in the layer of cobalt element, and the average grain diameter of described abrasive particle is at 20nm ~ 90nm.

74. grinding agents as described in claim 67 are in grinding containing the application in the layer of cobalt element, and the average grain diameter of described abrasive particle is at 40nm ~ 80nm.

75. grinding agents as described in claim 67 are in grinding containing the application in the layer of cobalt element, and the content of described abrasive particle is more than 1.0 quality % in the gross mass of grinding agent.

76. grinding agents as described in claim 67 are in grinding containing the application in the layer of cobalt element, and the content of described abrasive particle is more than 3.0 quality % in the gross mass of grinding agent.

77. grinding agents as described in claim 67 are in grinding containing the application in the layer of cobalt element, and the content of described abrasive particle is 3.0 quality % ~ 5.0 quality % in the gross mass of grinding agent.

78. 1 kinds of substrate Ginding process, by least one the polished film containing cobalt element formed on the surface at substrate of the application grinding described in any one in claim 1 ~ claim 77, remove the redundance containing cobalt element.