CN101058711B - Grinding fluid for metal and grinding method - Google Patents
Grinding fluid for metal and grinding method Download PDFInfo
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- CN101058711B CN101058711B CN2007101046360A CN200710104636A CN101058711B CN 101058711 B CN101058711 B CN 101058711B CN 2007101046360 A CN2007101046360 A CN 2007101046360A CN 200710104636 A CN200710104636 A CN 200710104636A CN 101058711 B CN101058711 B CN 101058711B
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Abstract
The invention discloses a grinding liquid of metal, which comprises the following parts: oxidizer, dissolving agent ofoxidizing metal, metal corrosion inhibitor and water, wherein the corrosion inhibitor is at least one of the compound with amerol frame and the compound with imidazole frame. The grinding liquid can be used to keep low-etching speed and improve the grinding speed, which can form high-reliability imbedding pattern of matallic film.
Description
The application is to be on June 13rd, 2003 applying date, and national applications number is 03826622.9, and international application no is PCT/JP2003/007554, and denomination of invention is divided an application for the patent application of " metal polishing slurry and Ginding process ".
Technical field
The present invention relates to a kind of distribution of semiconducter device that is applicable to and form the metal polishing slurry of operation, and the Ginding process that uses this lapping liquid.
Background technology
In recent years, along with the highly integrated and high performance of semiconductor integrated circuit (LSI), new Micrometer-Nanometer Processing Technology grows up.Chemical mechanical milling method (Chemical Mechanical Polishing) is exactly one of them, in LSI manufacturing process, during forming, the particularly interlayer dielectric planarization in multilayer wired formation operation, metallic plug (plug) formation and embed type distribution frequently use the chemical mechanical milling method technology.This technology for example is disclosed in No. 4944836 specification sheetss of U.S. Patent No..
In recent years, in order to make the LSI high performance, attempt adopting copper alloy as wiring material.But to carry out microfabrication by the dry ecthing method that was used to form the aluminium alloy distribution in the past be difficult to copper alloy.Therefore, the main employing being pre-formed on the insulation layer of irrigation canals and ditches deposition imbedded copper alloy thin films, by chemical mechanical milling method the copper alloy of irrigation canals and ditches outside removed to form the embed type distribution, promptly so-called inlaying process.This technology for example is disclosed in No. 2278822 communique of Japanese kokai publication hei.
Chemical mechanical milling method as metal, general method is that the abrasive disk (platen) in circle is gone up the stickup grinding pad, with metal polishing slurry the grinding pad surface is soaked, the side that then matrix is formed with metallic membrane is pressed on the grinding pad, apply rotation abrasive disk under the specified pressure state of (be called grinding pressure or grind loading) from its back side, the metallic membrane of protuberance is removed by the mechanical friction between the protuberance of lapping liquid and metallic membrane.
The metal polishing slurry that is used for chemical mechanical milling method generally comprises oxygenant and solid abrasive particles, can also add some oxidized metal dissolving agent and corrosion inhibitor for metal as required.Think that its principle is, elder generation with the metallic film surface oxidation, grinds off this zone of oxidation by solid abrasive particles by oxidation then.Because the zone of oxidation of the metallic surface of recess can not contact with grinding pad, can not produce the effect of utilizing solid abrasive particles to grind off zone of oxidation, therefore, when carrying out chemical mechanical milling method, remove the metal level of protuberance and make the matrix surface planarization.Be disclosed in Journal of electrochemicalSociety about its detailed content, in 138,11,3460～3464,1991.
As the method for the grinding rate that improves chemical mechanical milling method, it is effective adding oxidized metal dissolving agent.Its reason is because the metal oxide grain that is ground off by solid abrasive particles is dissolved in the lapping liquid thereby has improved the effect that grinds off of solid abrasive particle.
But, as its problem points, can enumerate the dissolving (below, be called etching) of metallic film surface.The zone of oxidation of the metallic film surface of recess is in case also etched and metallic film surface is exposed, and then oxidized dose of oxidation of metallic film surface so repeats the etching of the metallic membrane of recess, probably will influence the effect of planarization.For example: the surperficial central part branch of embed type metal wiring falls into (dishing) phenomenon because of etching produces dish.And, because etching also can produce corrosion (corrosion) to the metallic surface.
Also add corrosion inhibitor for metal in order to prevent corrosion.And, for suppress dish fall into phenomenon or grind in to the corrosion of copper alloy, form the high LSI distribution of reliability, and the metal polishing slurry that a kind of use contains oxidized metal dissolving agent and BTA (benzotriazole) is proposed, wherein oxidized metal dissolving agent is made of Padils such as glycine or acid amides sulfuric acid, and this technology is disclosed in the Japanese patent laid-open 8-83780 communique.
Yet the interpolation of corrosion inhibitor for metal can reduce grinding rate.In order to keep the characteristic of planarization, the balance that obtains the effect of oxidized metal dissolving agent and corrosion inhibitor for metal is important, with the effectively dissolving and improve the grinding rate of chemical mechanical milling method of the zone of oxidation particle that grinds off, and to make the zone of oxidation of the metallic film surface of recess that etching not take place be preferred.
Add oxidized metal dissolving agent and corrosion inhibitor for metal as mentioned above and increase the effect of chemical reaction, thereby when the grinding rate of chemical mechanical milling method is improved, also obtain to reduce damage (damage) effect of chemical mechanical milling method layer on surface of metal.
On the other hand, at the bottom of distribution copper or copper alloy etc., being formed for the blocking layer that prevents that copper from spreading in interlayer dielectric, is the electrically conductive film of tungsten, tungsten nitride, tungstenalloy or other tungsten compound etc. as this blocking layer.Therefore, except the distribution part of imbedding copper or copper alloy, exposed blocking layer also must be removed with chemical mechanical milling method.Yet, these blocking layer electrically conductive films, therefore its hardness, use copper or the used abrasive substance of copper alloy greater than copper or copper alloy, can't obtain good grinding rate.And when utilizing chemical mechanical milling method to remove the blocking layer, it is etched and make the problem of its thickness attenuation to produce copper or copper alloy distribution.
The invention provides a kind of metal polishing slurry, it fully improves grinding rate in the low etching speed of maintenance, suppresses the corrosion of metallic surface and the generation that dish falls into phenomenon, can form the pattern that the high metallic membrane of reliability is imbedded.
In addition, the present invention also provides a kind of Ginding process of metal, and it can keep low etching speed, fully improve grinding rate, suppress the corrosion of metallic surface and the generation that dish falls into phenomenon, can form the pattern that the high metallic membrane of reliability is imbedded, its productivity, operation are good, the qualification rate height.
Summary of the invention
Lapping liquid of the present invention relates to the metal polishing slurry and the Ginding process of following (1)～(18).
(1) a kind of metal polishing slurry, contain oxygenant, oxidized metal dissolving agent, corrosion inhibitor for metal and water, described corrosion inhibitor for metal contains the compound with imidazoles skeleton that is combined with amino compound with aminotriazole skeleton and following general formula (I) expression on the carbon of triazole ring
(in the general formula (I), R
1, R
2With R
3Represent hydrogen atom, amino or C independently of one another
1～C
12Alkyl chain.But, R
1, R
2With R
3Be all except the situation of hydrogen).
(2) a kind of metal polishing slurry contains oxygenant, oxidized metal dissolving agent, corrosion inhibitor for metal and water, and described corrosion inhibitor for metal contains the compound of the triazole skeleton with nothing amino and the compound with imidazoles skeleton of following general formula (I) expression
(in the general formula (I), R
1, R
2With R
3Represent hydrogen atom, amino or C independently of one another
1～C
12Alkyl chain.But, R
1, R
2With R
3Be all except the situation of hydrogen).
(3) a kind of metal polishing slurry, contain oxygenant, oxidized metal dissolving agent, corrosion inhibitor for metal and water, described corrosion inhibitor for metal contains the compound that is combined with the amino compound with aminotriazole skeleton and has the triazole skeleton that does not have amino on the carbon of triazole ring.
(4) metal polishing slurry put down in writing of above-mentioned (1) or (3), the compound that wherein has the aminotriazole skeleton is a 3-amino-1,2, the 4-triazole.
(5) metal polishing slurry put down in writing of above-mentioned (1) or (2), the compound that wherein has the imidazoles skeleton is selected from glyoxal ethyline, 2-ethyl imidazol(e), 2 isopropyl imidazole, 2-propyl imidazole, 2-butyl imidazole, 4-methylimidazole, 2, at least a in the group that 4-methylimidazole and 2-ethyl-4-methylimidazole are formed.
(6) metal polishing slurry put down in writing of above-mentioned (2) or (3) wherein has the compound that does not have amino triazole skeleton and is selected from 1,2,3-triazoles, 1,2, at least a in the group that 4-triazole, benzotriazole and I-hydroxybenzotriazole are formed.
(7) metal polishing slurry of being put down in writing in each in above-mentioned (1) to (6), wherein corrosion inhibitor for metal contains above-mentioned compound with aminotriazole skeleton, and above-mentioned have compound and an above-mentioned compound with imidazoles skeleton that does not have amino triazole skeleton.
(8) each metal polishing slurry of putting down in writing in above-mentioned (1) to (7) also contains water-soluble polymers.
(9) above-mentioned (8) metal polishing slurry of being put down in writing, wherein water-soluble polymers is selected from least a in the group that Polysaccharides, poly carboxylic acid, polycarboxylate, polycarboxylate, polyacrylamide and vinyl based polymer formed.
(10) each metal polishing slurry of putting down in writing in above-mentioned (1) to (9), wherein the burning agent is selected from least a in the group that hydrogen peroxide, nitric acid, potassium periodate, hypochlorous acid, persulphate, ozone water form.
(11) each metal polishing slurry of putting down in writing in above-mentioned (1) to (10), wherein oxidized metal dissolving agent is selected from least a in the group that organic acid, organic acid acetic, organic acid ammonium salt and sulfuric acid forms.
(12) each metal polishing slurry of putting down in writing in above-mentioned (1) to (11) wherein also comprises abrasive particle.
(13) each metal polishing slurry of putting down in writing in above-mentioned (1) to (12), polished metallic membrane are selected from least a in the group that oxide compound, tantalum and compound thereof, titanium and compound thereof, tungsten and the compound thereof of copper, copper alloy, copper oxide, copper alloy form.
(14) a kind of Ginding process, on one side each metal polishing slurry of putting down in writing in above-mentioned (1) to (13) is supplied on the abrasive cloth of abrasive disk, the matrix that will have metallic membrane press on state abrasive cloth under abrasive disk and matrix relatively moved to grind this metallic membrane on one side.
(15) above-mentioned (14) Ginding process of being put down in writing, wherein metallic membrane be selected from group that oxide compound, tantalum and compound thereof, titanium and compound thereof, tungsten and the compound thereof of copper, copper alloy, copper oxide, copper alloy form at least a.
(16) Ginding process put down in writing of above-mentioned (14) or (15), the lamination of two kinds of its continuously grindings or its above metallic membrane.
(17) above-mentioned (16) Ginding process of being put down in writing, wherein in the stack membrane of two kinds or metal more than it, at first polished first film is selected from one or more in the oxide compound of copper, copper alloy, copper oxide, copper alloy, and secondly polished second film is selected from one or more in tantalum and compound, titanium and compound thereof, tungsten and the compound thereof.
(18) a kind of Ginding process, it comprises first grinding step and second grinding step, wherein, first grinding step grinds the distribution metal level of substrate and the blocking layer of its protuberance is exposed, this substrate has the interlayer dielectric that the surface comprises recess and protuberance, along the blocking layer of the described interlayer dielectric of surface coverage with fill described recess and the distribution metal level of covering barrier layer; Behind this first grinding step, second grinding step grinds the distribution metal level of blocking layer and recess at least and the interlayer dielectric of protuberance is exposed; Wherein, use in second grinding step at least that each metal polishing slurry of putting down in writing grinds in above-mentioned (1) to (13).
Embodiment
Below describe the present invention in detail.
Metal polishing slurry of the present invention contains as the oxygenant of main composition composition, oxidized metal dissolving agent, corrosion inhibitor for metal and water.Wherein corrosion inhibitor for metal contains the compound with imidazoles skeleton (B) that is combined with amino compound with aminotriazole skeleton (A) and following general formula (I) expression on the carbon of triazole ring;
(in the general formula (I), R
1, R
2With R
3Represent hydrogen atom, amino or C independently of one another
1～C
12Alkyl chain.But, R
1, R
2With R
3Be all except the situation of hydrogen.)
Or contain above-claimed cpd (B) and have the compound (C) that does not have amino triazole skeleton;
Or contain above-claimed cpd (A) and above-claimed cpd (C).
Compound with imidazoles skeleton of the present invention, and without particular limitation, can enumerate compound with following general formula (I) expression:
In the general formula (I), R
1, R
2With R
3Represent hydrogen atom, amino or C independently of one another
1～C
12Alkyl chain.But, R
1, R
2With R
3Be all except the situation of hydrogen.
Wherein, compound with imidazoles skeleton, can enumerate glyoxal ethyline, 2-ethyl imidazol(e), 2 isopropyl imidazole, 2-propyl imidazole, 2-butyl imidazole, 4-methylimidazole, 2,4-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecyl imidazole, 2-aminooimidazole etc. particularly.These can use separately, or make up two kinds or its above use.Be preferably selected from glyoxal ethyline, 2-ethyl imidazol(e), 2 isopropyl imidazole, 2-propyl imidazole, 2-butyl imidazole, 4-methylimidazole, 2 especially, 4-methylimidazole and 2-ethyl-4 Methylimidazole.
The preferred carbon atom amino and on the triazole skeleton of compound with aminotriazole skeleton of the present invention combines, and considers that from the industrial production angle with 3-amino-1,2, the 4-triazole is good.
In the metal polishing slurry of the present invention, can also contain compound as corrosion inhibitor for metal with the triazole skeleton that does not have amino.
Can enumerate as having the compound that does not have amino triazole skeleton, 1,2, the 3-triazole, 1,2, the 4-triazole, benzotriazole, I-hydroxybenzotriazole, 1-dihydroxypropyl benzotriazole, 2,3-dicarboxyl propyl group benzotriazole, the 4-hydroxybenzotriazole, 4-carboxyl (1H-) benzotriazole, 4-carboxyl (1H-) benzotriazole methyl ester, 4-carboxyl (1H-) benzotriazole butyl ester, 4-carboxyl (1H-) benzotriazole octyl group ester, 5-hexyl benzotriazole, [1,2,3-benzotriazole base-1-methyl] [1,2,4-triazolyl-1-methyl] [2-ethylhexyl] amine, tolyl-triazole, aphthotriazoles, two [(1-benzotriazole base) methyl] phosphoric acid etc.These corrosion inhibitor for metal can be used alone, and maybe can make up two kinds or its above use.
Corrosion inhibitor for metal is more preferably and use: have the compound of aminotriazole skeleton and have at least a in the compound that does not have amino triazole skeleton, with the compound with imidazoles skeleton.In addition, the further preferred compound of also using compound and having the amino triazole skeleton of nothing with aminotriazole skeleton.
Total use level of corrosion inhibitor for metal of the present invention is preferably 0.001～10 weight % with respect to the total amount of metal polishing slurry, is good with 0.01～8 weight % wherein, with 0.02～5 weight % for better.If use level is less than 0.001 weight %, then can't suppress etching, or have and can not obtain the tendency that grinding rate fully improves, if greater than 10 weight %, then grinding rate can reach capacity or even descend gradually.Under the situation of the compound that only uses skeleton, be preferably 0.05～5 weight % as corrosion inhibitor for metal especially with aminotriazole.
Oxygenant of the present invention can be enumerated hydrogen peroxide (H
2O
2), nitric acid, potassium periodate, hypochlorous acid, persulphate and ozone water etc., wherein with hydrogen peroxide for most preferably, these oxygenants can use separately, or make up two kinds or its above use.
As the applicable object that grinds, matrix is to contain under the situation of unicircuit with the silicon substrate of element, for fear of by pollutions such as basic metal, alkaline earth metal, halogenide, does not therefore preferably contain the oxygenant of nonvolatile component.But the moiety of ozone water is along with the time significantly changes, so preferable with hydrogen peroxide.And matrix is not contain under the situations such as glass substrate of semiconductor element, also has no relations even contain the oxygenant of nonvolatile component.
The oxygenant use level is with respect to the total amount of metal polishing slurry, preferred 0.1～50 weight %, more preferably 0.2～25 weight %, most preferably 0.3～15 weight %.If use level is less than 0.1 weight %, then because the oxidation of metal is incomplete, so can cause the grinding rate of chemical mechanical milling method to reduce; If use level is greater than 50 weight %, then abrasive surface can be coarse.
Oxidized metal dissolving agent of the present invention, so long as water-soluble getting final product, and have no particular limits, can enumerate formic acid, acetate, propionic acid, butyric acid, valeric acid, 2-Methyl Butyric Acid, n-caproic acid, 3, the 3-acid dimethyl, 2 Ethylbutanoic acid, the 4-methylvaleric acid, positive enanthic acid, 2 methyl caproic acid, n-caprylic acid, 2 ethyl hexanoic acid, M-nitro benzoic acid, oxyacetic acid, Whitfield's ointment, R-Glyceric acid, oxalic acid, propanedioic acid, succsinic acid, pentanedioic acid, hexanodioic acid, pimelic acid, maleic acid, phthalic acid, oxysuccinic acid, tartrate, organic acids such as citric acid, above-mentioned organic acid ester and above-mentioned organic acid ammonium salt etc.In addition, also can enumerate mineral acids such as hydrochloric acid, sulfuric acid, nitric acid, the ammonium salt class of above-mentioned mineral acid, for example ammonium persulphate, ammonium nitrate, ammonium chloride etc., chromic acid etc.Wherein consider that from the angle that can effectively grind formic acid, propanedioic acid, oxysuccinic acid, tartrate, citric acid are applicable to the chemical mechanical milling method of metal level.These solvating agents can use separately, or make up two kinds or its above use.
The use level of oxidized metal dissolving agent composition is with respect to the total amount of metal polishing slurry, preferred 0.001～10 weight %, more preferably 0.01～8 weight %, preferred especially 0.02～5 weight %, if use level is less than 0.001 weight %, then grinding rate can sharply reduce, if greater than 10 weight %, then is difficult to suppress etching.
Metal polishing slurry of the present invention can also comprise water-soluble polymers.These polymkeric substance for example are the Polysaccharides of Lalgine, pectic acid, carboxymethyl cellulose, agar, curdlan and amylopectin etc.; The poly carboxylic acid of poly-aminosuccinic acid, polyglutamic acid, polylysine, polymalic acid, polymethyl acrylic acid, polyamino acid, polymaleic acid, poly-methylene-succinic acid, poly-fumaric acid, poly-(to the vinylbenzene carboxylic acid), polyacrylic acid, metaldehyde acid etc.; Polycarboxylate and the ester and the derivative of ammonium polymethacrylate salt, sodium polymethacrylate salt, polyacrylamide, poly-amino acryl amides, ammonium polyacrylate salt, polyacrylic acid sodium salt, polyamino acid ammonium salt, polyamino acid sodium salt etc.; The vinyl based polymer of polyvinyl alcohol, polyvinylpyrrolidone and polyacrolein etc. etc.In addition, also can enumerate the ester and the ammonium salt of above-mentioned polymkeric substance.
Wherein, water-soluble polymers is preferably selected from Polysaccharides, poly carboxylic acid, polycarboxylate, polycarboxylate, polyacrylamide and the vinyl based polymer at least a.Particularly, preferred pectin acid, agar, polymalic acid, polymethyl acrylic acid, polyacrylic acid, polyacrylamide, polyvinyl alcohol and polyvinylpyrrolidone alcohol, and their ester and ammonium salt.But under the situation that the matrix that is suitable for is a semiconductor integrated circuit with silicon plate etc.,, preferably use acid or its ammonium salt for fear of by pollutions such as basic metal, alkaline earths or halogenide.In addition, be under the situation of glass substrate at matrix, then without limits.
The use level of water-soluble polymers is preferably 0～10 weight % with respect to the total amount of metal polishing slurry, more preferably 0.01～8 weight %, preferred especially 0.02～5 weight %.If use level less than 10 weight %, can make grinding rate reduce.
The weight-average molecular weight of water-soluble polymers (GPC measure, polystyrene standard convert) to be good more than or equal to 500, is preferable more than or equal to 1500, more than or equal to 5000 for better.The upper limit of the weight-average molecular weight of water-soluble polymers does not have special stipulation, from deliquescent viewpoint, with better smaller or equal to 5,000,000.If the weight-average molecular weight of water-soluble polymers then can not produce high grinding rate less than 500.The present invention is preferably and utilizes at least a weight-average molecular weight more than or equal to 500 water-soluble polymers.
Lapping liquid of the present invention can contain abrasive particle.Use silicon dioxide film as the copper of LSI etc. or the insulating film layer of copper alloy distribution, after the grinding of blocking layer tantalum etc., when continuing to use lapping liquid of the present invention to come the abrasive silica film, preferably contain abrasive particle in this case.
Abrasive particle of the present invention can be any in the following abrasive particle: inorganics abrasive particles such as silicon-dioxide, aluminum oxide, zirconium white, cerium dioxide, titanium dioxide, germanium dioxide, silicon carbide; Organism abrasive particles such as polystyrene, polyacrylic acid, polyvinyl chloride, wherein abrasive particle is preferably a kind of being selected from silicon-dioxide, aluminum oxide, cerium dioxide, titanium dioxide, zirconium white, the germanium dioxide or more than it.And, preferably disperse stability good and few by the grinding damage (scratch) of chemical mechanical milling method generation at lapping liquid, median size is 150nm or its following colloid silica, colloidal alumina.When the grinding rate that makes the blocking layer was bigger, median size was with 100nm or be preferable below it, and 70nm or its are following for better.Be known that colloid silica by silicon alkoxide hydrolysis or the ion-exchange by water glass are made, colloidal alumina is by making the aluminum nitrate hydrolysis.
Under the situation that cooperates abrasive particle, the concentration of abrasive particle is preferably 0.01～20 weight % with respect to the gross weight of lapping liquid, and more preferably 0.05～15 weight % most preferably is 0.1～8 weight %.If the concentration of abrasive particle then be can't see the effect of the abrasive particle that is added less than 0.01 weight %, if greater than 20 weight %, then not only aggegation easily of abrasive grain, and also the otherness of grinding rate can't be found out.
Metal polishing slurry of the present invention is except above-mentioned material, can also contain 0.01～1 weight % that has an appointment as required, more preferably contain the tinting material of the pigment such as dyestuff, phthalocyanine green such as dispersion agents such as interfacial agent, Victoria's ethereal blue etc. of 0.1～0.8 weight % that has an appointment.And, be that the use level of water is good with the rest part, as long as contain water, have no particular limits.
Of the present invention as being suitable for by the metallic membrane of grinding film, for example (hereinafter referred to as titanium and compound thereof), tungsten, tungsten nitride, tungstenalloys etc. (hereinafter referred to as tungsten and compound thereof) etc. such as (to call tantalum and compound thereof in the following text), titanium, titanium nitride, titanium alloy such as the oxide compound (hereinafter referred to as copper and compound thereof) of copper, copper alloy, copper oxide, copper alloy, tantalum, tantalum nitride, tantalum alloy can pass through sputtering method or electrochemical plating film forming.And metallic membrane also can be the stack membrane that the above above-mentioned metallic substance of two kinds or its combines.
Above-mentioned stack membrane, upper strata (initial polished first film) for example can be selected from copper and compound thereof, and lower floor's (then second film that grinds) for example can be selected from tantalum and compound thereof, titanium and compound thereof, tungsten and compound thereof.
The stack membrane of the metal polishing slurry of the application of the invention can continuously grinding above-mentioned two kinds or its above metallic membrane.In other words, save the formality of the lapping liquid of each replacing metallic membrane.
The present invention's first Ginding process is to supply with above-mentioned metal polishing slurry on one side on the abrasive cloth of abrasive disk, press under the state on the abrasive cloth will having matrix as the metallic membrane of grinding film on one side, grind as by the metallic membrane of grinding film by relatively moving between abrasive disk and the matrix.As milling apparatus, can use to have to be used for controlling controlling device and can pasting abrasive cloth (grinding pad) of matrix with metal level, the abrasive disk of the motor of variable rotation number is installed.
As abrasive cloth, can use general non-woven fabrics, polyurathamc, porous fluoride resin etc., and without particular limitation.Although grinding condition liquid has no particular limits, the speed of rotation of abrasive disk is preferably and can not makes speed 200rpm that matrix flies out or below it.Have by the press pressure (grinding pressure) of the matrix of grinding film on abrasive cloth and be preferably 1～100kPa, for the consistence of grinding rate in wafer face and the flatness of pattern that satisfies chemical mechanical milling method, this pressure with 5～50kpa for more preferably.
As long as Ginding process can make abrasive disk and matrix relatively move, can be according to suitably being selected by grinding film or milling apparatus.Ginding process is except the spin finishing dish, for instance, also can adopt rotation or shake the Ginding process of controlling device, or the Ginding process of planetary spin finishing dish, or make zonal abrasive cloth carry out Ginding process that linearity moves etc. along a direction of long chi direction.Wherein control device and can be state fixing, that rotate or shake.
In process of lapping, to abrasive cloth surface and matrix by abrasive surface between with metal polishing slurries without interruption such as pumps.This feed rate is also unrestricted, the preferred surface of soaking into abrasive cloth usually with lapping liquid.
Matrix after having ground after preferably cleaning with flowing water, uses the Rotary drying method that the water droplet that adheres on the matrix is wiped away and carries out drying afterwards.
Metal polishing slurry of the present invention and with the Ginding process of this lapping liquid, owing to not only have fully high grinding rate, and its etching speed is low, because productivity height, it is few that the corrosion of metallic surface and dish fall into phenomenon, therefore, be applicable to make miniaturization, filming, dimensional precision, with good electric performance, semiconductor device with high reliability and instrument.
Second Ginding process of the present invention is following Ginding process: comprise first grinding step and second grinding step, first grinding step grinds the distribution metal level of substrate and the blocking layer of exposing its protuberance, this substrate have the surface by recess and protuberance constitute interlayer dielectric, cover the blocking layer of described interlayer dielectric surfacewise and fill the distribution metal level of described recess covering barrier layer; Behind this first grinding step, second grinding step grinds the distribution metal level of blocking layer and recess at least, and makes the interlayer dielectric of protuberance expose, and at least the second grinding step uses metal polishing slurry of the present invention.
Interlayer dielectric for example is silicon based coating or organic polymer films etc.As the silicon based coating, for example having with silicon-dioxide, fluoro silicate glass, trimethyl silane or dimethoxy dimethylsilane is the silicon based coating of the resulting organic silicate glass of original raw material, silicon-oxygen nitride (シ リ コ Application オ キ シ Na イ ト ラ イ De), hydrogen silsesquioxane (water elementization シ Le セ ス キ オ キ サ Application) etc., or silicon carbide and silicon nitride etc.And as organic polymer films, can enumerate all aromatic is low-k interlayer insulating film.Be good particularly with organic silicate glass.These films can pass through chemical Vapor deposition process, spin-coating method, and dip coating or sputtering method wait film forming.
The formation on blocking layer is to be used for preventing metal diffusing such as copper to interlayer insulating film, and improves the adherence between metal and the insulation layer.The blocking layer preferably, is selected from the layer of at least a composition in tungsten and compound thereof, tantalum and compound thereof, titanium and the compound thereof, and it can be the single layer structure with a kind of composition, or has the rhythmo structure of the above composition of two kinds or its.
The distribution metal level can be enumerated, and is the layer of principal constituent with the metal of copper and compound, tungsten, tungstenalloy, silver or gold etc.Wherein, the preferred layer that contains at least a composition that is selected from copper and compound thereof that grinds.The distribution metal level can be by known sputtering method, electrochemical plating film forming on the blocking layer.
Below, the embodiment of Ginding process of the present invention is described by the wiring layer forming process in the semiconducter device manufacturing process.
At first, at the interlayer insulating film of silicon substrate superimposed layer silicon-dioxide etc.Then, form resist layer.Afterwards, utilize known means such as etching, form the recess (substrate exposed division) of predetermined pattern, thereby form the interlayer dielectric that constitutes by recess and protuberance in the layer insulation laminar surface.Then, on this interlayer dielectric, become the blocking layer of the tungsten etc. of concavo-convex covering interlayer dielectric surfacewise by vapour deposition method or chemical Vapor deposition process film forming.And then, form the distribution metal level of the copper of filling described recess covering barrier layer etc. by electrochemical plating or chemical Vapor deposition process evaporation.
(first grinding step) followed, this semiconductor substrate is fixed on the milling apparatus, distribution metal level with the surface is by abrasive surface, grind while supplying with lapping liquid, thereby substrate surface is exposed on the blocking layer of interlayer dielectric protuberance, obtains the desired pattern that described metal level residues in the recess of interlayer dielectric.
(second grinding step) after this as by abrasive surface, at least grinds above-mentioned exposed blocking layer and the distribution metal level of recess while supply with lapping liquid of the present invention with above-mentioned conductive pattern.The interlayer dielectric of the below on the blocking layer of protuberance all exposes, and the above-mentioned metal level that becomes wiring layer that is positioned at recess is residual, exposes the section on blocking layer and obtains desired pattern until the boundary at recess and protuberance, stops grinding.(for example also additionally grind in order to ensure better grinding flatness when stopping grinding, obtain time that pattern that the second grinding step desire forms need grind when being 100 seconds, the 50 wonderful grindings that to append outside this 100 wonderful grinding are called extra grinding 50%), this extra grinding can be ground to the degree of depth of the part of the interlayer dielectric that contains protuberance.
In second grinding step, except under the state on the abrasive cloth of being pressed on by abrasive surface of substrate, abrasive cloth and substrate being relatively moved and grinding by the Ginding process of abrasive surface according to the mode of first Ginding process of the present invention, also can adopt the method for the metal system of making or resinous brush contact, or purge the Ginding process of lapping liquid with the pressure of regulation.
In first grinding step and second grinding step, at least the second grinding step lapping liquid of the present invention.Also can in first grinding step and second grinding step, use lapping liquid of the present invention continuously.In the case, between first grinding step and second grinding step, do not need to carry out especially clean operation and drying process by abrasive surface, can shut-down operation changing abrasive disk and abrasive cloth, or change the operation loading.In addition, the employed lapping liquid of the present invention of first grinding step and second grinding step can be identical or different composition.If use the lapping liquid of same composition, then can not shut-down operation and proceed continuously to grind to the 2nd grinding step transit time by first grinding step, so the productivity excellence.
So, on the metal wiring that forms, further form interlayer dielectric, blocking layer and metallic wiring layer, grind then and make whole semiconductor substrate surface planarization, and form the metal wiring of the second layer.By making semiconducter device with desired distribution number of plies with this operation of stipulated number repetitive operation.
Embodiment
The present invention is described by the following examples, but the present invention is not limited in these embodiment.
Embodiment 1～4,6-11, reference example 1,2 and comparative example 1,2
(making method of metal polishing slurry)
Metal polishing slurry is modulated by mixing following substances: with respect to total amount, 0.15 the oxysuccinic acid of weight %, 0.15 the water-soluble polymers (acrylic acid polymer of weight %, weight-average molecular weight about 10,000), 0.2 the amino-triazole compound thing shown in table 1 and table 2 of weight % is as removing the corrosion inhibitor for metal the amino-triazole compound thing shown in table 1 and table 2, the imidazolium compounds of the benzotriazole of 0.2 weight % and/or 0.05 weight %, and the hydrogen peroxide of 9 weight %, all the other are water.
The metal polishing slurry that utilization obtains carries out etching under the following conditions, chemical mechanical milling method grinds and evaluation.The grinding rate, etching speed that in the table 1 the copper matrix are carried out chemical mechanical milling method described with in the table 2 grinding rate, the etching speed of tungsten basal body being incorporated into.
(grinding condition)
The copper matrix: lamination the silicon substrate of copper metal of thickness 1500nm
Tungsten basal body: lamination the silicon substrate of tungsten compound of thickness 600nm
Lapping liquid feed rate: 15cc/ branch
Grinding pad: foaming polyurethane resin (the model IC1000 of ロ デ one Le corporate system)
Grinding pressure: 29.4kPa (300gf/cm
2)
Speed of relative movement between matrix and the abrasive disk: 45m/min
The speed of rotation of abrasive disk: 75rpm
Assessment item
Grinding rate: obtain the film thickness difference that each film grinds front and back by the resistance value conversion.
Etching speed: respectively matrix is immersed in the metal polishing slurry (room temperature, 25 ℃, stirring velocity 600rpm) after stirring, convert by resistance value and obtain the metal level film thickness difference of dipping front and back.
Embodiment 13～20, reference example 3～6 and comparative example 3
(making method of metal polishing slurry)
Metal polishing slurry is modulated by mixing following substances: with respect to total amount, 0.15 the oxysuccinic acid of weight %, 0.15 the water-soluble polymers (acrylic acid polymer of weight %, weight-average molecular weight about 10,000), the imidazolium compounds as shown in table 3 of 0.2 weight %, benzotriazole shown in the table 3 of 0.2 weight % or 3-amino-1,2,4-triazole compounds, and the hydrogen peroxide of 9 weight %, all the other are water.
The metal polishing slurry that utilization obtains carries out etching similarly to Example 1, chemical mechanical milling method grinds and evaluation.With etching speed and be set forth in the table 3.
Table 1
Table 2
Table 3
In embodiment 1～4, reference example 1, the grinding rate of copper all is more than the 130nm/min, to compare the effect that improvement is arranged with comparative example 1 under any situation.On the other hand, etching speed is compared with comparative example, and is quite low.
In embodiment 6～11, reference example 2, the grinding rate of tungsten all more than 80nm/min, is compared the effect that improvement is arranged with comparative example 2 under any situation.On the other hand, etching speed is compared with comparative example, and is quite low.
In embodiment 13～20, the etching speed of copper all below 0.5nm/min, is compared with comparative example 3, significantly improves.On the other hand, the etching speed of tungsten is compared with comparative example, and is quite low.In addition, in reference example 3～6, the etching speed of tungsten is also quite low, reaches practical degree.
In embodiment 13～20, reference example 3～6, the grinding rate of copper, tungsten is respectively at 100nm/min, more than the 20nm/min, reach very practical degree.
Embodiment 25
Metal polishing slurry is modulated by mixing following substances: the oxysuccinic acid of 0.15 weight %, the water-soluble polymers of 0.15 weight % (acrylic acid polymer, weight-average molecular weight about 10,000), 0.3 the 3-amino-1 of weight %, 2,4-triazole, the benzotriazole of 0.14 weight %, 0.05 2 of weight %, the 4-methylimidazole, the abrasive particle of 0.4 weight % (colloid silica, primary particle size 30nm), and the hydrogen peroxide of 9 weight %, all the other are water.
Prepared silicon substrate in the following manner: in silicon-dioxide, form dark 0.5 to 100 micron irrigation canals and ditches; Then, with the tungsten layer of known method formation as the thickness 50nm on blocking layer, layer forms 1.0 microns copper film thereon.Grind until the whole lip-deep silicon-dioxide protuberance of substrate under the grinding condition identical by above-mentioned lapping liquid and to expose with embodiment 1.Its milling time is 2 minutes, obtains about 500nm/min or its above grinding rate.Adopt contact pin type surface topographic apparatus fo (contact pin type section difference meter) to be arranged parallel to each other into the surface shape of the pattern of striated according to the insulation membranous part of 100 microns of distribution metal part, the width of 100 microns of width, obtain the distribution metal part with respect to the insulation membranous part the film reduction be 70nm, the value of the degree that has reached abundant practicality is described.
Embodiment 26
Lapping liquid is modulated by mixing following substances: the oxysuccinic acid of 0.15 weight %, 0.15 the water-soluble polymers (acrylic acid polymer of weight %, weight-average molecular weight about 10,000), the 3-amino-1,2 of 0.3 weight %, the 4-triazole, 0.14 the benzotriazole of weight %, 2 of 0.05 weight %, 4-methylimidazole, and the hydrogen peroxide of 9 weight %, all the other are water.
Except using this lapping liquid, all the other are all identical with embodiment 1, carry out etching.The etching speed of this moment, copper is 0.37nm/min, tungsten is 0.49nm/min.
Grind under the grinding condition identical by above-mentioned lapping liquid, expose the identical silicon substrate used with embodiment 25 until whole lip-deep silicon-dioxide protuberance with embodiment 1.Its milling time is 3 minutes, obtains about 350nm/min or its above grinding rate.Then, adopt contact pin type surface topographic apparatus fo (contact pin type section difference meter) to be arranged parallel to each other into the surface shape of the drafting department of striated according to the insulation membranous part of 100 microns of distribution metal part, the width of 100 microns of width, obtain the distribution metal part with respect to the insulation membranous part the film reduction be 50nm, illustrate to have reached the very value of practical level.
Utilizability on the industry
Metal polishing slurry of the present invention can be kept very low etching speed, and grinding rate is fully improved, and corrosion and the dish that can suppress the metal surface fall into the generation of phenomenon, thereby can carry out the formation of the high metal film flush type pattern of reliability.
Ginding process of the present invention, can keep very low etching speed, and grinding rate is fully improved, can suppress the generation that the corrosion of metal surface and dish fall into phenomenon, thereby can productivity, operation, qualification rate form the pattern that the high metal film of reliability is imbedded goodly.
Claims (14)
1. a metal polishing slurry contains oxygenant, oxidized metal dissolving agent, corrosion inhibitor for metal and water; Described corrosion inhibitor for metal contains the compound that is combined with the amino compound with aminotriazole skeleton and has the triazole skeleton that does not have amino on the carbon of triazole ring, also contains the compound with imidazoles skeleton; The use level of described oxygenant is 0.1～50 weight % with respect to the total amount of metal polishing slurry, the use level of described oxidized metal dissolving agent is 0.001～10 weight % with respect to the total amount of metal polishing slurry, and total use level of described corrosion inhibitor for metal is 0.001～10 weight % with respect to the total amount of metal polishing slurry.
2. metal polishing slurry as claimed in claim 1, wherein this compound with aminotriazole skeleton is a 3-amino-1,2, the 4-triazole.
3. metal polishing slurry as claimed in claim 1 wherein has the compound that does not have amino triazole skeleton and is selected from 1,2,3-triazoles, 1,2, at least a in the group that 4-triazole, benzotriazole and I-hydroxybenzotriazole are formed.
4. metal polishing slurry as claimed in claim 1, it contains water-soluble polymers.
5. metal polishing slurry as claimed in claim 4, wherein this water-soluble polymers is selected from least a in the group that Polysaccharides, poly carboxylic acid, polycarboxylate, polycarboxylate, polyacrylamide and vinyl based polymer formed.
6. metal polishing slurry as claimed in claim 1, wherein this burning agent is selected from least a in the group that hydrogen peroxide, nitric acid, potassium periodate, hypochlorous acid, persulphate and ozone water form.
7. metal polishing slurry as claimed in claim 1, wherein this oxidized metal dissolving agent be selected from group that organic acid, organic acid acetic, organic acid ammonium salt and sulfuric acid forms at least a.
8. metal polishing slurry as claimed in claim 1, it contains abrasive particle.
9. metal polishing slurry as claimed in claim 1, polished metallic membrane are selected from least a in the group that oxide compound, tantalum and compound thereof, titanium and compound thereof, tungsten and its compound of copper, copper alloy, copper oxide, copper alloy form.
10. Ginding process, this method is supplied to the described metal polishing slurry of claim 1 on the abrasive cloth of abrasive disk on one side, the matrix that will have metallic membrane press on state this abrasive cloth under abrasive disk and matrix relatively moved to grind this metallic membrane on one side.
11. Ginding process as claimed in claim 10, wherein this metallic membrane is selected from least a in the group that oxide compound, tantalum and compound thereof, titanium and compound thereof, tungsten and the compound thereof of copper, copper alloy, copper oxide, copper alloy form.
12. Ginding process as claimed in claim 10, wherein two or more the lamination of metallic membrane of this Ginding process continuously grinding.
13. Ginding process as claimed in claim 12, wherein in two or more the stack membrane of metal, at first polished first film is selected from one or more in the oxide compound of copper, copper alloy, copper oxide, copper alloy, and secondly polished second film is selected from one or more in tantalum and compound, titanium and compound thereof, tungsten and the compound thereof.
14. Ginding process, comprise first grinding step and second grinding step, this first grinding step grinds the distribution metal level of substrate the blocking layer of its protuberance is exposed, wherein said substrate has: the surface comprises the interlayer dielectric of recess and protuberance, cover the blocking layer of described interlayer dielectric surfacewise and fill described recess and the distribution metal level of covering barrier layer; This second grinding step grinds the distribution metal level of blocking layer and recess at least behind first grinding step and the interlayer dielectric of protuberance is exposed, and uses the described metal polishing slurry of claim 1 at least in second grinding step.
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| CN2007101046360A CN101058711B (en) | 2003-06-13 | 2003-06-13 | Grinding fluid for metal and grinding method |
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| CNB038266229A Division CN100343362C (en) | 2003-06-13 | 2003-06-13 | Polishing fluid for metal and polishing Method |
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| CN101058711B true CN101058711B (en) | 2011-07-20 |
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| US8883031B2 (en) * | 2009-08-19 | 2014-11-11 | Hitachi Chemical Company, Ltd. | CMP polishing liquid and polishing method |
| CN103865402A (en) * | 2012-12-17 | 2014-06-18 | 安集微电子（上海）有限公司 | Chemically mechanical polishing liquid |
| CN106661429B (en) * | 2014-08-26 | 2019-07-05 | 凯斯科技股份有限公司 | Polishing slurries composition |
| CN107236519A (en) * | 2017-05-19 | 2017-10-10 | 南通华兴石油仪器有限公司 | A kind of oil instrument lapping liquid |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1117531A (en) * | 1994-08-12 | 1996-02-28 | 美克株式会社 | Liquid for corroding copper and copper alloy |
| CN1369530A (en) * | 2001-01-31 | 2002-09-18 | 不二见株式会社 | Polishing compsns. and polishing method using same |
| CN1390979A (en) * | 2001-05-25 | 2003-01-15 | 希普利公司 | Electroplating process |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1117531A (en) * | 1994-08-12 | 1996-02-28 | 美克株式会社 | Liquid for corroding copper and copper alloy |
| CN1369530A (en) * | 2001-01-31 | 2002-09-18 | 不二见株式会社 | Polishing compsns. and polishing method using same |
| CN1390979A (en) * | 2001-05-25 | 2003-01-15 | 希普利公司 | Electroplating process |
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