CN100570827C - The grinding-material of this slurry is starched and used to grinding-material - Google Patents
The grinding-material of this slurry is starched and used to grinding-material Download PDFInfo
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- CN100570827C CN100570827C CNB2006800117038A CN200680011703A CN100570827C CN 100570827 C CN100570827 C CN 100570827C CN B2006800117038 A CNB2006800117038 A CN B2006800117038A CN 200680011703 A CN200680011703 A CN 200680011703A CN 100570827 C CN100570827 C CN 100570827C
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Abstract
The invention provides a kind of grinding-material slurry that suppresses the damage of bottom when can guarantee good grinding rate.This grinding-material slurry comprises resin (A) and the organic resin (B) that contains amide groups.
Description
Technical field
The present invention relates to grinding-material slurry and use the grinding-material of this slurry, particularly relate to the grinding-material slurry that forms metal wirings such as grinding dielectric film surface or tungsten, aluminium, copper in the technology at the distribution that semiconductor device is made.
Background technology
For grinding technique, seeking when guaranteeing good grinding rate, can suppress the technology of bottom damage.
For example, form in the technology at the distribution that semiconductor device is made in recent years, on dielectric film, form distribution formation groove, imbed the distribution metal film by coating method etc., remove superfluous metal film, and make the dielectric film planarization that contains metal wiring, adopted cmp (CMP) as such technology.It is to utilize the slurry that has disperseed abrasive particle mechanically to grind the method for the abradant surface of process chemical modification.
CMP technology is not only for metal materials such as copper wiring, tantalum barrier metal and tungsten plugs, also necessary technology in the processing of insulating film materials such as silica, from now in order to reduce the technology cost, just seeking to obtain high grinding rate, and be difficult to produce the technology of the damage of bottom with few slurry quantity delivered.Damage can be enumerated cut (scratch), depression (dishing), abrasion (erosion) as the bottom among the CMP.
Wherein, cut is the grinding damage of metal surface, and the reason of its generation is that the locality that the existence of hardness of grain, abrasive particle agglutination body causes is superfluous grinds.
In addition, depression and abrasion can become the rising that causes the distribution impedance and fluctuation and then cause the short circuit of the wiring closet that is formed at the upper strata, and reduce the reliability of distribution body device significantly, reduce the reason of rate of finished products significantly.
Wherein, abrasion is that central portion in the intensive part of Wiring pattern is owing to comprising that the dielectric film as bottom is also further ground the phenomenon that forms spill.It is low etc. with the grinding selectivity of bottom that the reason that produces abrasion is the caused undue grinding of hard abrasive, dielectric film and the barrier layer that prevents metal diffusing etc.
In addition, depression is easily owing to produce as the slurry of the acidic region of corrosion of metals scope, complex formation agent, the caused metal stripping of pH conditioning agent (etching) that is included in the slurry.And, be better than the slurry of the mechanism of abrasive particle for the chemical action of additive, be easy to generate depression.
In the CMP technology, used the slurry of inorganic abrasive particles such as metal oxides such as comprising ceria, aluminium oxide or silicon dioxide so far.But, these inorganic hardness of grain height, and the agglutinator of the abrasive particle in the waste liquid and lapping rejects be difficult to discharge, thus when grinding the low metal film of hardness such as copper, produce above-mentioned cut and abrasion sometimes.
That is, in order to improve semi-conductive performance, the 1/2 distribution width (half spacing) on the dielectric film develops into 65nm from the further miniaturization of 90nm, even 45nm now, and its dielectric film surface of grinding object becomes more complicated structure.During the further miniaturization of distribution width, the grinding damage of the metal surface that cut causes can cause broken string, and, abrasion can cause the rising of distribution impedance and fluctuation and then cause the short circuit of the wiring closet that is formed at the upper strata, become the reliability of remarkable reduction semiconductor device, significantly reduce the reason of rate of finished products.
In order to address these problems, the situation of inorganic abrasive particle, developed adopt the ratio aluminum oxide softness silicon dioxide as abrasive particle, form the passive film of metal and the lapping liquid that grinds in neutrality to the alkaline side of not stripping metal.For example, during as abrasive particle, the situation of cut ratio aluminum oxide is few with silicon dioxide.Yet, use the situation of such inorganic particulate, because abrasive metal mechanically, the agglutinator of abrasive particle and metal fillings can cause cut and abrasion, can not fundamentally suppress to produce defective.
The technology that has patent documentation 1～10 record as existing grinding technique.
In patent documentation 1 and 2,, studied the optimization of grinding pad channel patterns in order to effectively utilize the supply slurry.
In addition, in patent documentation 3, disclose with the organic high molecular compound particle as the method for grinding abrasive particle.Organic polymer is methacrylic resin, polystyrene resin etc. as used herein.
Yet, the functional group that these organic polymers do not have easily and metal film reacts.In the document, since with this composition as abrasive particle, and do not contain the oxidant that makes oxidation on metal surface, thereby can not be brought into play fully by the chemical action of the metal film of abrasive body with conduct, the distribution that can not get making at semiconductor device forms the necessary sufficient grinding rate of operation.
In addition, in order to solve the problems referred to above relevant with the organic high molecular compound particle, for example in patent documentation 4, disclose comprise have can with form by the mill water dispersoid of the organic filler of the functional group of the metal reaction of abradant surface.But the technology of document record also fails to solve distribution metal film partly forms spill in the central part over-lapping so-called depressed phenomenon.
The grinding-material slurry that contains chelating resin and inorganic abrasive particle is disclosed in patent documentation 5.
In patent documentation 6 and 7 at being that polyacrylic CMP of containing of purpose puts down in writing with lapping liquid to suppress etching, to reduce depression.
In patent documentation 8 and 9, put down in writing and contained the CMP grinding agent that diaphragm forms agent and water-soluble polymer.
In patent documentation 10, disclose and form agent by complexes such as quinoline carboxylic acids and form weak insoluble petal complex, taken into account the grinding-material slurry of etched inhibition and high grinding rate.
Yet even adopt these technology, also there is room for improvement in the damage aspect that suppresses bottom when guaranteeing good grinding rate.
Patent documentation 1: Japanese kokai publication hei 11-216663 communique
Patent documentation 2: Japanese kokai publication hei 11-333699 communique
Patent documentation 3: Japanese kokai publication hei 7-86216 communique
Patent documentation 4: TOHKEMY 2001-55559 communique
Patent documentation 5: TOHKEMY 2002-261052 communique
Patent documentation 6: Japanese kokai publication hei 11-195628 communique
Patent documentation 7: Japanese Unexamined Patent Application Publication 2004-532521 communique
Patent documentation 8: the international WO00/13217 brochure that discloses
Patent documentation 9: the international WO01/17006 brochure that discloses
Patent documentation 10: TOHKEMY 2000-183003 communique
Summary of the invention
According to the invention provides a kind of grinding-material slurry, it is characterized in that, comprise the water-soluble resin (A) and the organic filler (B) that contain amide groups.
According to the invention provides a kind of grinding-material, it is characterized in that, contain above-mentioned grinding-material slurry, oxidant, can form the water soluble compound and the corrosion inhibitor of complex with metal.
Provide a kind of grinding-material again according to the present invention, it is characterized in that, contain compound and water that above-mentioned grinding-material is starched, can be formed complex with metal.
In the present invention, because grinding-material slurry comprises water-soluble resin (A) and the organic filler (B) that contains amide groups, so can obtain and do not contain the equal grinding rate of inorganic abrasive particle.In addition, owing to comprise water-soluble resin (A) and the organic filler (B) that contains amide groups, so can suppress effectively by the damage of abradant surface.
Like this, can when guaranteeing good grinding rate, suppress the damage of bottom according to the present invention.
Embodiment
Below be that example describes so that grinding-material of the present invention slurry is used for semiconductor fabrication, the suitable application area of grinding-material slurry of the present invention is not particularly limited, for example also can be used for the glass substrate is the grinding etc. of various substrates of representative.
Grinding-material slurry of the present invention comprises water-soluble resin (A) and the organic filler (B) that contains amide groups.
Here, in the present invention, water-soluble resin is meant and forms the resin that is dissolved in the form in this medium that in based on the medium of water organic filler is meant the resin that forms emboliform form in based on the medium of water.
In the present invention, owing to comprise organic filler (B), so can suppress effectively by the damage of abradant surface.This effect does not contain inorganic particulate in grinding-material situation is significantly brought into play.The grinding-material that for example will comprise the organic filler (B) than copper softness is starched when being used to form the copper wiring structure, and with respect to the situation of using inorganic particulate, the abrasion during overmastication can be suppressed.And, owing to do not contain the particle harder than copper, so can not produce damage (cut).
Grinding-material of the present invention slurry, the water-soluble resin (A) and the organic filler (B) that contain amide groups can exist with any form, for example can for:
(i) synthetic respectively water-soluble resin (A) and the organic filler (B) that contains amide groups mixes and the form of the resin combination that obtains again;
(ii) contain the water-soluble resin of amide groups (A) in the presence of polymerization organic filler (B) and the form of the resin combination that obtains; And
(iii) polymerization contains the water-soluble resin (A) of amide groups and the form of the resin combination that obtains in the presence of organic filler (B).
Wherein, consider, more preferably under any one party resin that contains water-soluble resin of amide groups (A) or organic filler (B), synthesize the opposing party's resin and the resin combination that obtains from the angle of the storage stability of emulsion.
In addition, in grinding-material slurry of the present invention, organic filler (B) can be the particle that obtains by the vinyl monomer of polymerizations such as emulsion polymerisation more than a kind.Below be that example describes with the situation of coming polymerization organic filler (B) by emulsion polymerisation.
In this case, the organic filler (B) that contains the water-soluble resin (A) of amide groups and obtain by the vinyl monomer of emulsion polymerisation more than a kind can any form exist, but consider from the angle of the storage stability of emulsion, more preferably contain resin of amide groups (A) or emulsion polymerisation more than a kind vinyl monomer and the synthesizing the opposing party's resin down of any one party resin of the resin (B) that obtains and the resin combination that obtains.
For example, the water-soluble resin (A) that contains amide groups can be polymerization more than a kind vinyl monomer and the organic filler (B) that obtains in the presence of carry out emulsion polymerisation and the resin that obtains.
In addition, by contain the water-soluble resin of amide groups (A) in the presence of the vinyl monomer of emulsion polymerisation more than a kind obtain organic filler (B), can further improve dispersion stabilization.
Below be described more specifically the present invention.
[water-soluble resin (A) that contains amide groups]
The water-soluble resin (A) that contains amide groups of the present invention contains the resin that the compound of amide groups obtains at least for polymerization.
As the special preferable methyl acrylamide of the compound that contains amide groups.
The water-soluble resin (A) that contains amide groups of the present invention can also the vinyl monomer of polymerization more than a kind except the compound that contains amide groups.
At this, the vinyl monomer more than a kind is preferably the vinyl monomer with functional group, for example can enumerate: acrylamide etc. contain the vinyl monomer of amide groups; (methyl) acrylic acid etc. contains the vinyl monomer of carboxyl; (methyl) acrylic acid 2-hydroxy methacrylate etc. contains the vinyl monomer of hydroxyl; (methyl) glycidyl acrylate etc. contains the vinyl monomer of glycidyl; (methyl) acrylonitrile etc. contains the vinyl monomer of cyano group; N, N-dimethylaminoethyl (methyl) acrylate etc. contain amino vinyl monomer; Acetoacetyl oxygen ethyl (methyl) acrylate etc. contains the vinyl monomer of acetoacetoxy groups; Reach the monomer that Sodium styrene sulfonate, SMAS etc. contain sulfonic acid.In addition, can also use hydrophobic vinyl monomers such as styrene, (methyl) acrylate.
For the water-soluble resin that contains amide groups (A), can use the bridging property vinyl monomer, as this monomer can illustration methylene two (methyl) acrylamide, divinylbenzene, contain two (methyl) acrylate of polyglycol chain etc.In addition, the bridging property vinyl monomer can contain the vinyl more than 2.
In order to regulate the molecular weight of the water-soluble resin (A) that contains amide groups, can use chain-transferring agent, other molecular weight regulators such as n-dodecyl mercaptan and 1-thioglycerol.
The molecular weight that contains the water-soluble resin (A) of amide groups considers that from the angle of stablizing grinding rate weight average molecular weight Mw more than 5000, is preferably more than 10000.In addition, contain the molecular weight of the water-soluble resin (A) of amide groups, never make the angle of the excess stickiness increase of grinding-material slurry consider that weight average molecular weight Mw below 500000, is preferably below 200000.
The water-soluble resin (A) that contains amide groups is for example by being that the GPC-MALLS method of benchmark is measured with goods name: PULLULAN (manufacturing of Shodex company).
The water-soluble resin (A) that contains amide groups, be preferably monomer 100～10 weight % that contain amide groups, more preferably 100～50 weight % and other vinyl monomers 0～90 weight %, more preferably 0～50 weight % carries out polymerization and the resin that obtains.
In addition, grinding-material of the present invention slurry also can comprise the water-soluble resin except that the water-soluble resin that contains amide groups (A), and its content is 100～200 weight portions with respect to the water-soluble resin (A) that 100 weight portions contain amide groups preferably.
[manufacture method that contains the water-soluble resin (A) of amide groups]
The synthetic method that contains the water-soluble resin (A) of amide groups is not particularly limited, and preferably carries out polymerization in the solvent that with water is principal component.Particularly preferred polymerization methods is an aqueous solution polymerization.Contain the water-soluble resin (A) of the amide groups polymerization initiator when synthetic without limits, preferred water dissolubility radical initiator, persulfates, 4 such as special initiator system of ammonium persulfate, 4 '-azo two water-soluble azo class initators such as (4-cyanopentanoic acids).
Contain the water-soluble resin (A) of the amide groups polymerization temperature when synthetic without limits, but consider manufacturing time and monomer to the conversion ratio (reactivity) of copolymer etc., preferably synthetic 30～95 ℃ of scopes, preferred especially 50～85 ℃.
In addition, make stability, when polymerization, also can use as the EDTA of pH conditioning agent and metal ion sealer or its salt etc. in order to improve.
[organic filler (B)]
The preferred configuration of organic filler (B) (being total to) polymerized emulsion for obtaining by the vinyl monomer of emulsion polymerisation more than a kind.
Can enumerate as vinyl monomer: hydrophobic vinyl monomers such as styrene, (methyl) alkyl acrylate; (methyl) acrylonitrile etc. contains the vinyl monomer of cyano group; (methyl) acrylamide etc. contains the vinyl monomer of amide groups; (methyl) acrylic acid etc. contains the vinyl monomer of carboxyl; (methyl) acrylic acid 2-hydroxy methacrylate etc. contains the vinyl monomer of hydroxyl; (methyl) glycidyl acrylate etc. contains the vinyl monomer of glycidyl; N, N-dimethylaminoethyl (methyl) acrylate etc. contain amino vinyl monomer; Acetoacetyl oxygen ethyl (methyl) acrylate etc. contains the vinyl monomer of acetoacetoxy groups; Sodium styrene sulfonate etc. contain vinyl monomer of sulfonic acid etc. and contain vinyl monomer of functional group etc.
As required, can use the bridging property vinyl monomer, as this monomer can illustration methylene two (methyl) acrylamide, divinylbenzene, contain two (methyl) acrylate of polyglycol chain etc.In addition, also can use the monomer that contains 2 above vinyl as the bridging property vinyl monomer.
In addition, in order to regulate molecular weight, can use chain-transferring agent, other various molecular weight regulators such as n-dodecyl mercaptan and 1-thioglycerol.
In the present invention, emulsion polymerisation more than a kind vinyl monomer and the organic filler (B) that obtains is preferably containing that the vinyl monomer of emulsion polymerisation more than a kind obtains (being total to) polymer emulsion in the presence of the water-soluble resin of amide groups (A).At this moment, be preferably polymerization as the water-soluble resin that contains amide groups (A) and comprised the resin of the monomer of Methacrylamide at least.
[manufacture method of organic filler (B)]
The synthetic method of organic filler (B) is not particularly limited, and is preferably the emulsion polymerisation of carrying out in the solvent of principal component with water being.For the polymerization stability that improves organic filler (B), storage stability etc., can use surfactant and water soluble polymer aptly.
Wherein, can enumerate anionic surfactant, cationic surfactant, nonionic surfactant etc. as surfactant.Particularly preferred surfactant is not for containing the metallic surface activating agent in the manufacturing process of semiconductor device.
The for example salt of DBSA, lauryl sulfate, alkyl diphenyl base ether disulfonic acid, alkyl naphthalene sulfonic acid, dialkyl sulfosuccinate butanedioic acid, stearic acid, oleic acid, dioctyl sulfosuccinate, polyoxyethylene alkyl ether sulfuric acid, polyoxyethylene alkyl phenyl ether sulfuric acid, dialkyl sulfosuccinate butanedioic acid, stearic acid, oleic acid, uncle's Octylphenoxy ethyoxyl polyethoxy ethyl sulfuric acid etc. can be enumerated as the anionic surfactant of not containing metal, for example ammonium salt can be.
As the nonionic surfactant that does not contain metal, general majority is to have glycol chain as hydrophilic radical, and does not contain metal.Can enumerate for example polyoxyethylene lauryl ether, NONIN HS 240, polyoxyethylene oil base phenyl ether, polyoxyethylene nonylplenyl ether, oxirane propylene oxide block copolymer, uncle's Octylphenoxy ethyl polyethoxy ethanol, Nonylphenoxy ethyl polyethoxy ethanol etc.
And then, can enumerate for example lauryl trimethyl ammonium chloride as the cationic surfactant that does not contain metal, OTAC, hexadecyltrimethylammonium chloride, two (octadecyl) alkyl dimethyl ammonium chloride, alkyl benzyl dimethyl ammonium chloride, lauryl betaine, octadecyl betaine, lauryl dimethylamine oxide, lauryl carboxymethyl hydroxyethyl imidazoles betaine, coconut amine acetate, octadecane amine acetate, alkylamine guanidine radicals APEO (alkylamine-guanidine polyoxyethanol), alkyl methyl pyridinium chloride etc.These dispersants can be selected more than a kind or 2 kinds.
When polymerization organic filler (B), the water soluble polymer that uses in order to improve polymerization stability, storage stability etc. can comprise, also can not comprise the above-mentioned water-soluble resin that contains amide groups (A).
In the manufacturing process of semiconductor device, water-soluble resin does not preferably contain metal.As the water soluble polymer that does not contain metal, can enumerate for example water-soluble polymers such as polyvinyl alcohol, modified polyvinylalcohol, PVP, (methyl) acrylic acid (being total to) polymer, poly-(methyl) acrylamide (being total to) polymer, ethylene glycol.
Polymerization initiator when organic filler (B) is synthetic without limits, preferred water dissolubility radical initiator.Persulfates, 4 such as special initiator system of ammonium persulfate, 4 '-azo two water-soluble azo class initators such as (4-cyanopentanoic acids).Particularly preferred polymerization initiator is not for containing the initator of metal in the manufacturing process of semiconductor device.
Can enumerate for example hydrogen peroxide as the polymerization initiator that does not contain metal, ammonium persulfate, azo dicyano valeric acid, 2,2 '-azo two (2-amidine propane) dihydrochloride, 2,2 '-azo two [2-(N-phenyl amidino groups) propane] dihydrochloride, 2,2 '-azo two 2-[N-(4-chlorphenyl) amidino groups] and propane } dihydrochloride, 2,2 '-azo two 2-[N-(4-hydroxy phenyl) amidino groups] and propane } dihydrochloride, 2,2 '-azo two [2-(N-benzyl amidino groups) propane] dihydrochloride, 2,2 '-azo two [2-(N-pi-allyl amidino groups) propane] dihydrochloride, 2,2 '-azo two 2-[N-(2-hydroxyethyl) amidino groups] and propane } dihydrochloride, azodiisobutyronitrile, 2,2 '-azo two { 2-methyl-N-[1,1-two (hydroxymethyl)-2-hydroxyethyl] propionamide }, 2,2 '-azo two { 2-methyl-N-[1,1-two (hydroxymethyl) ethyl] propionamide }, 2,2 '-azo two [2-methyl-N-[2-hydroxyethyl] propionamide], 2, azo-compounds such as 2 '-azo two (isobutyramide) dihydrate; Organic peroxides such as cumene hydroperoxide, TBHP, benzoyl peroxide, tert-butyl hydroperoxide-2 ethyl hexanoic acid ester, tert butyl peroxy benzoate, lauroyl peroxide.Can select more than a kind or 2 kinds of above-mentioned initator.
Initator is preferably water-soluble, more preferably ammonium persulfate, azo dicyano valeric acid, 2,2 '-azo two (2-amidine propane) dihydrochloride.Total weight with the monomer that carries out (being total to) polymerization is a benchmark, and the use amount of initator is generally 0.1～5 weight %.
Polymerization temperature when organic filler (B) is synthetic but is considered manufacturing time and monomer to the conversion ratio (reactivity) of copolymer etc. without limits, and is preferably synthetic 30～95 ℃ of scopes, preferred especially 50～85 ℃.
In addition, make stability, when organic filler (B) polymerization, also can use as the EDTA of pH conditioning agent and metal ion sealer or its salt etc. in order to improve.After copolymer emulsion forms, can carry out pH with nertralizer commonly used such as ammonia (water) and NaOH and regulate, more preferably the nertralizer of metalline not.Can enumerate ammonia (water), various amines etc. as this nertralizer.
In the present invention, the serve as reasons situation of the particle that copolymer resins with the vitrifying point more than 25 ℃ constitutes of the particularly preferred mode of organic resin (B) because when forming grinding-material for the inhibition effect excellence of depression.In this constituted, the water-soluble resin (A) that contains amide groups can be the water-soluble copolymer resins that contains amide groups.Below carry out specific description at this mode.Here, vitrifying point is meant calculated value among the present invention.
(copolymer resins) with the vitrifying point more than 25 ℃
Aspect obtaining high grinding rate, composition when suppress grinding on liner changes, the calculated value of the copolymer resins preferred glass point with the vitrifying point more than 25 ℃ that the present invention relates to is more than 25 ℃, more preferably more than 40 ℃ below 200 ℃.
Copolymer resins with the vitrifying point more than 25 ℃ can have the functional group that can catch metal ion.Can improve the grinding quality thus.
Particularly, be preferably organic resin (B) and have the functional group that to catch metal ion, and the water-soluble resin (A) with amide groups is the water-soluble copolymer resins of vinyl monomer with amide groups, both coexistences.By being formed on the structure that there is the water-soluble copolymer resins of the vinyl monomer with amide groups in the housing department (skin section) that has the functional group that can catch metal ion, has the copolymer resins of the vitrifying point more than 25 ℃, can more effectively obtain high grinding rate and high difference of height (section is poor) elimination property.
The functional group that can catch metal ion can be for for example being selected from least a in the group of being made up of carboxyl, amide groups, sulfonic group, phosphate, cyano group, carbonyl, hydroxyl.In addition, can form anionic functional group, the high neutral functional groups of electronegativity such as hydroxyl, cyano group, carbonyl, acetoacetyl as the preferred carboxyl of the functional group that can catch metal ion, sulfonic group, phosphoric acid etc.
The copolymer resins with the vitrifying point more than 25 ℃ that the present invention relates to can wait by known aqueous solution polymerization, emulsion polymerisation, dispersin polymerization and make, but is not limited to these.
(computational methods of the vitrifying point (Tg) of the copolymer resins of formation organic filler (B))
Polymerization the vitrifying point (Tg) of copolymer resins of multiple monomer can calculate by Fox (Fox) equation and obtain.
At this, fox equation is the formula that calculates the Tg of copolymer at each monomer that forms copolymer, based on the Tg of the homopolymers of this monomer, its details is documented in Bulletin of the AmericanPhysical Society, Series 2, the 1st volume, No. 3, in 123 pages (1956).
The Tg that estimates the various unsaturated monomers that the Tg of copolymer uses by fox equation for example can adopt the numerical value of putting down in writing in 168～169 pages of " coating is crossed the threshold with synthetic resin for new peak molecular library, the 7th volume " (Bei Gang work, meeting of macromolecule publication).In addition, by using computational science software " Cheops ver.4 " (Million Zillion Software Inc.), can calculate the Tg of the homopolymers of monomer.
Quality with whole monomers is a benchmark, as forming of the monomer that constitutes the particle that forms by copolymer resins, for example has monomer 1～80 weight portion of the functional group that can catch metal ion and the vitrifying point calculated value of homopolymers is the copolymer resins that vinyl monomer 20～99 weight portions more than 25 ℃ obtain for polymerization.Thus, can keep higher grinding rate, reduce depression.
Content 5～60 weight portions more preferably with monomer of the functional group that can catch metal ion.
As the monomer that uses in the present invention, can enumerate unsaturated dibasic acid or their monoesters classes such as unsaturated monoacid, itaconic acid such as acrylic acid with the functional group that can catch metal ion; Sodium styrene sulfonate etc. contain the monomer of sulfonic acid; Acrylonitrile etc. contain the monomer of cyano group; Acetoacetyl oxygen ethyl propylene acid esters etc. contains the monomer of ketone group etc.These monomers can use separately, also can make up more than 2 kinds and use.
Wherein preferred especially acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid, maleic acid, allyl sulphonic acid, methallyl sulfonic acid, 2-methacryloxyethyl phosphate ester acid, acetoacetyl oxygen ethyl (methyl) acrylate, acetoacetyl oxygen-butyl (methyl) acrylate.
As the Tg of the homopolymers that uses in the present invention is vinyl monomer more than 25 ℃, can enumerate hydrophobic vinyl monomers such as styrene, methyl methacrylate, isobornyl acrylate, isobornyl methacrylate, cyclohexyl methacrylate, EMA, butyl methacrylate etc. (methyl) alkyl acrylate; 2-hydroxyethyl methacrylates etc. contain the vinyl monomer of hydroxyl; Glycidyl methacrylate etc. contain the vinyl monomer of glycidyl etc.In addition, also can enumerate acrylonitrile, acrylamide, Methacrylamide, acrylic acid, methacrylic acid, benzyl methacrylate, vinylacetate etc.
Raw material as the copolymer resins that forms organic filler (B) can use the bridging property vinyl monomer as required; As this monomer can illustration methylene two (methyl) acrylamide, divinylbenzene, contain two (methyl) acrylate of polyglycol chain etc.
In addition, the bridging property vinyl monomer can be the monomer that contains 2 above vinyl.
(the water-soluble copolymer resins that contains amide groups)
Grinding-material slurry of the present invention is by comprising the above-mentioned copolymer resins with the vitrifying point more than 25 ℃ as organic resin (B), comprise the water-soluble resin (A) that the water-soluble copolymer resins conduct with amide groups contains amide groups simultaneously, can obtain higher grinding rate.The water-soluble copolymer resins that contains amide groups for example contains the copolymer resins that the vinyl monomer of amide groups obtains for polymerization.
Water-soluble copolymer resins is that the content of this copolymer resins is that the light transmission rate (use wavelength 400nm, UV/VIS/NIR spectrometer JASCO V-570) of the aqueous solution of 10 weight portions is at the high copolymer resins of the water solubility more than 85%.As the special preferable methyl acrylamide of the compound that contains amide groups.
In this constitutes, quality with whole monomers is a benchmark, the water-soluble copolymer resins that contains amide groups is that polymerization 50～99 weight portions contain the vinyl monomer of amide groups and the copolymer resins that 1～50 weight portion vinyl monomer in addition obtains, and it can be for water-soluble.Thus, can keep higher grinding rate, and reduce depression.
From more positively carrying out metal and chemical reaction with water-soluble copolymer resins of amide groups, more positively realize the angle consideration of the grinding rate of expectation, containing ratio with copolymer resins of amide groups is more than the 1 weight % in the grinding-material slurry preferably, more preferably more than the 3 weight %.
In addition, reduce, realize that the angle of sufficient grinding rate is considered, have below the preferred 20 weight % of containing ratio of copolymer resins of amide groups, be preferably especially below the 10 weight % from suppressing the slurry viscosity flowability that causes that rises.
(copolymer resins particle and the complex form that contains the water-soluble copolymer resins of amide groups)
When the water-soluble resin that contains amide groups (A) is the situation of copolymer resins particle for water-soluble copolymer resins and the organic filler (B) that contains amide groups, the complex morphological that housing department (skin section) chemistry by being formed on the copolymer resins particle or a physical absorption part contain the water-soluble copolymer resins of amide groups can improve the pressure dependency of grinding rate.
At this, contain the water-soluble copolymer resins of amide groups and the compound particle that the copolymer resins particle forms, be particle diameter (d1) by dynamic light scattering determination greater than the particle diameter (d2) of the determination of transmission electron microscopy by can not observing water-soluble resin, can analyze indirectly to periphery and have resin particle with the high layer (bed thickness d1-d2) of copolymerization resin particle compatibility at the copolymer resins particle.
At this moment, can be coated with by polymerization in the housing department of the particle that copolymer resins constituted and/or skin section and contain the copolymer resins that the vinyl monomer of amide groups obtains with the functional group that can catch metal ion.Here, housing department is meant the housing parts (core) of particle inside, and skin section is meant the zone of the near surface of particle.At this, the vinyl monomer that contains amide groups can be (methyl) acrylamide.
Containing composite resin particles that the water-soluble copolymer resins of amide groups and copolymer resins particle form can obtain by for example containing the water-soluble copolymer resins of amide groups or mix after the polymerization respectively at particle that polymerization copolymer resins in the presence of the water-soluble copolymer resins that contains amide groups is constituted or in polymerization in the presence of the resin particle.
In addition, when obtaining copolymer resins, also can use thio-alcohols such as uncle's lauryl mercaptan, n-dodecyl mercaptan as required, alcohols such as isopropyl alcohol are as molecular weight regulator.
In semiconductor fabrication process, do not contain metal ingredient improving as preferred copolymer resins aspect the reliability of the metal wiring of grinding charge, in order not contained the copolymer resins of metal, can make by using dispersant, other additives such as monomer, polymerization initiator, the water soluble polymer that adds as required and surfactant of not containing metal.
Can enumerate for example hydrogen peroxide, ammonium persulfate as the polymerization initiator that does not contain metal, organic peroxides such as cumene hydroperoxide, TBHP, benzoyl peroxide, azo dicyano valeric acid, 2, azo-compounds such as 2 '-azo two (amino two propane of 2-) dicarboxylate etc. can select to use more than a kind or 2 kinds of these initators.
Initator is preferably water-soluble, more preferably ammonium persulfate, azo dicyano valeric acid, 2,2 '-azo two (amino two propane of 2-) dicarboxylate.
Gross mass with the monomer that carries out (being total to) polymerization is a benchmark, and the use amount of initator is generally 0.1～5 quality %.
By making the water-soluble resin (A) that contains amide groups for containing the water-soluble copolymer resins of amide groups, making organic resin (B) is the copolymer resins particle, can provide the composition in the time of can suppressing to grind to change, fully reduce etching, form the higher grinding-material slurry of imbedding pattern of reliability.In addition, change, can demonstrate high grinding rate, suppress the generation of cut, depression, abrasion significantly by the composition that suppresses on the grinding pad.
And, compare with the slurry of the etching inhibitor that contains metals such as insoluble complex formation agent or polyacrylic acid, the grinding residue on the distribution (grinding residue) is few, reduces cut, abrasion significantly, etching suppresses the effect height, can reduce the generation in the hole, low-lying area (depression) of metal wiring portion.
In grinding-material slurry of the present invention,, can contain the following above organic filler (B) of the following 10 weight % of the water-soluble resin that contains amide groups (A), 90 weight % of the above 90 weight % of 10 weight % with respect to all resins composition.
Containing the water-soluble resin that contains amide groups (A) of 10 weight %～90 weight % with respect to all resins composition, is being preferred mode grinding aspect the quality.In addition, consider, be preferably more than the 10 weight % with respect to the water-soluble resin that contains amide groups (A) solid component content of all resins solid constituent, more preferably more than the 30 weight % from the angle of accelerating grinding rate.In addition, consider, be preferably 90 weight % with respect to the water-soluble resin that contains amide groups (A) solid component content of all resins solid constituent, more preferably below the 70 weight % from the angle that more effectively suppresses abrasion.
In addition, consider, be preferably more than the 10 weight % with respect to organic filler (B) solid component content of all resins solid constituent, more preferably more than the 30 weight % from the angle that improves grinding rate.In addition, consider, be preferably below the 90 weight % with respect to organic filler (B) solid component content of all resins solid constituent, more preferably below the 70 weight % from the angle of stablizing grinding rate.
In grinding-material slurry of the present invention, also can add various additives.This additive can be before polymerization, in the polymerization, use after the polymerization.
For example can enumerate pH conditioning agent, chelating agent, pigment, wetting agent, antistatic agent, antioxidant, anticorrisive agent, ultra-violet absorber, light stabilizer, fluorescent whitening agent, colouring agent, penetrant, blowing agent, release agent, defoamer, make infusion, fluidity amendment, tackifier etc. as additive, but be not limited to these.
Grinding-material of the present invention contains above-mentioned grinding-material slurry as neccessary composition.
In addition, in grinding-material of the present invention, can add all cpds.Can enumerate water-soluble complex as this compound and form materials such as water soluble polymer, surfactant such as nitrogen-containing heterocycle compound such as compound, various oxidant, BTA, quinaldinic acid and polyacrylic acid, polyvinyl alcohol, polyethylene glycol, glucose, these materials can separately or make up 2 kinds with on add.About its addition, kind, just be not particularly limited as long as can realize purpose of the present invention.
For example, grinding-material of the present invention contains above-mentioned grinding-material slurry, oxidant, can form the compound and the corrosion inhibitor of complex with metal.
In addition, grinding-material of the present invention also can contain compound and the water that above-mentioned grinding-material is starched, can be formed complex with metal.Thus, can more stably control grinding rate.
Can be specially by abrasive metal with the metal that metal forms in the compound of complex.
Can be specially the water soluble compound that can form complex with the compound that metal forms complex with metal.
Consider that from the angle of grinding stabilisation grinding-material of the present invention can further contain oxidant.
Grinding-material of the present invention comprises the water soluble compound that can form complex with metal, and it is to be selected from least a in the group of being made up of carboxylic acids, amine, amino acids and ammonia, comprises oxidant, and it can be a hydrogen peroxide.Thus, can more positively take into account high grinding rate and low depression.
The all resins composition for example is more than the 1 weight % below the 15 weight % with respect to the content of all grinding-materials.Thus, can further improve grinding rate.
(complex formation compound)
As compound (complex formation compound) the preferred water soluble compound that can form complex, particularly, can enumerate carboxylic acids such as acetic acid, oxalic acid, malic acid, tartaric acid, butanedioic acid, citric acid in order to improve grinding rate with metal; Amines such as methylamine, dimethylamine, triethylamine, ethamine, diethylamine, triethylamine; Amino acidses such as glycine, aspartic acid, glutamic acid, cysteine; Ketones such as pentanedione; Imidazoles etc. contain N (nitrogen) cyclic compound; Ammonia etc.Preferably enumerate oxalic acid, malic acid, ethamine.
In addition, when grinding-material slurry of the present invention comprises the above-mentioned copolymer resins with the vitrifying point more than 25 ℃ as organic resin (B), comprise water-soluble copolymer resins simultaneously when containing the water-soluble resin (A) of amide groups with amide groups, preferably enumerate carboxylic acids, amine, amino acids, ammonia, more preferably enumerate oxalic acid, malonic acid, tartaric acid, glycine.
Aspect the etching inhibition, can contain 0.5～5 weight % in slurry with the compound that is formed complex by abrasive metal is preferred mode.
Can with formed the content of the compound (complex formation compound) of complex with respect to all grinding-materials by abrasive metal, consider from the angle of bringing into play its effect fully, more positively realizing the grinding rate of expectation, be preferably more than the 0.1 weight %, more preferably more than the 0.5 weight %.
Complex in the grinding-material forms the content of compound, from suppress and formed complex by abrasive metal, more effectively suppress to grind being considered outside the object superfluously by the angle of the depression of abrasive metal stripping, be preferably below the 10 weight %, more preferably below the 5 weight %.
In addition, in order to protect, can add nitrogen-containing heterocycle compounds such as BTA, quinaldinic acid on a small quantity in the grinding-material by lapped face.Consider that from the angle of bringing into play effect fully, positively obtaining the desired protection effect its content in grinding-material is preferably more than the 0.1 weight %, more preferably more than the 0.2 weight %.And; be accompanied by and formed the significantly reduced angle of grinding rate that the firm complex with defencive function brings by abrasive metal and consider from control; the content of the nitrogen-containing heterocycle compound in the grinding agent is preferably below the 1 weight %, more preferably below the 0.5 weight %.
(oxidant)
Can use hydrogen peroxide, ammonium persulfate etc. as oxidant, preferably use hydrogen peroxide.From the chemical reaction that carries out metal and resin, positively the angle that realizes the grinding rate of expectation considers that the containing ratio of oxidant in slurry is preferably more than the 0.1 weight %, more preferably more than the 0.5 weight %.In addition, from suppressing to hinder the angle of lapping process to consider that the containing ratio of oxidant is preferably below the 15 weight %, more preferably below the 5 weight % owing to the passivityization of the oxide-film that generates in the metal surface.
(pH)
Grinding-material of the present invention when pH more than 7 during the scope below 11, be preferred mode from grinding the quality aspect.And pH is to be preferred mode aspect the minimizing abrasion below 9 more than 7.
Consider that from the angle that more positively suppresses metal stripping, more effectively inhibition depression the pH of grinding-material of the present invention is preferably more than 5, more preferably more than 7.When the semiconducting insulation film that becomes the maximal end point that metal film grinds and metal wiring are present in when going up with one side, consider that from more effectively suppressing dielectric film angle dissolved or that decomposed partly the pH of grinding-material is preferably below 11, more preferably below 9.
In addition, when grinding-material slurry of the present invention comprises the above-mentioned copolymer resins with the vitrifying point more than 25 ℃ as organic resin (B), comprise water-soluble copolymer resins with amide groups simultaneously when containing the water-soluble resin (A) of amide groups, the pH of grinding-material is preferably more than 7.Thus, can more positively suppress the carrying out of corrosion of metals and the stripping of metal ion, thereby can suppress more fully to cave in and the formation of defective such as slit.At this, slit is the interface portion at copper layer and barrier metal layer, because the promotion of corrosion reaction, causes the copper ion stripping and the hole, low-lying area of the shape of slit that generates.
At this moment, the pH of grinding-material is preferably below 11, more preferably below 9.Thus, can further suppress to become the semiconducting insulation film of the maximal end point that metal film grinds and metal wiring is present in one side and goes up and the dissolving or the locality of the dielectric film that causes are decomposed.
In this constitutes, consider that from the angle of the complex of the water-soluble resin that contains amide groups (A) that stably forms anionic property and organic filler (B) pH that grinding-material is starched is preferably more than 8 below 10.
The material that is used to regulate the pH of this grinding-material is not particularly limited, and can enumerate amines such as ammonia, triethylamine, diethylamine, ethamine, trimethylamine, dimethylamine, methylamine, triethanolamine, diethanol amine, monoethanolamine as the alkaline matter that does not contain metal; Mineral-type such as NaOH, KOH; Alkylammonium salt such as Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide etc.
In addition, can enumerate mineral-type such as hydrochloric acid, nitric acid as acidic materials, organic acids such as acetic acid, oxalic acid, citric acid.These pH conditioning agents can double as be the water soluble compound that can become metal ligands shown in above-mentioned, also can be the water soluble compound that can form complex with metal shown in above-mentioned.And these materials can make up more than 2 kinds and use.
(manufacture method of grinding-material slurry)
As the manufacture method of grinding-material of the present invention slurry can enumerate the method for mixing behind for example synthetic respectively water-soluble resin (A) that contains amide groups and the organic filler (B), contain the water-soluble resin of amide groups (A) in the presence of polymerization organic filler (B) method, in the presence of organic filler (B) method of synthesizing water-solubility resin (A).Wherein, consider from the dispersed aspect of organic filler (B), preferably contain the water-soluble resin of amide groups (A) in the presence of the method for emulsion polymerisation organic filler (B).
(manufacture method of grinding-material)
Can make grinding-material by adding grinding-material slurry, water, complex formation compound, pH conditioning agent etc. lentamente.This manufacture method is not particularly limited, but preferably adds the aqueous solution that the complex of regulating pH forms compound in the grinding-material slurry of regulating pH, fully mixes.Subsequently, add oxidant lentamente, further mix.
After regulating final pH and concentration, remove by filter insoluble matter and agglutination body, form grinding-material with filter paper.This grinding-material is specially the CMP grinding-material.
In addition, when the water-soluble resin that contains amide groups (A) be the situation of copolymer resins particle for water-soluble copolymer resins, the organic resin (B) that contains amide groups, can make grinding-material by adding water-soluble copolymer resins particle with the functional group that can catch metal ion and amide groups, water, complex formation compound, pH conditioning agent etc. lentamente.
Manufacture method is not particularly limited, and preferably little by little mixes the aqueous solution, copolymer resins particle that the complex of regulating pH respectively forms compound.Subsequently, regulate final pH and concentration after, remove insoluble matter and agglutination body, form grinding-material.
(other, additive)
Additive can be before the polymerization of copolymer resins, in the polymerization, any stage after the polymerization uses.
For example can enumerate corrosion inhibitor, wetting agent, antistatic agent, antioxidant, anticorrisive agent, ultra-violet absorber, light stabilizer, fluorescent whitening agent, colouring agent, penetrant, blowing agent, release agent, defoamer, make infusion, foam inhibitor, fluidity amendment, tackifier etc. as additive, in semiconductor technology, can suit to select not contain the additive of metal.
Can separately or make up as corrosion inhibitor and to add aromatic amino acids such as nitrogen-containing heterocycle compounds such as BTA, quinaldinic acid, quinolinic acid, phenylalanine more than 2 kinds.
In addition, can be separately or make up the halide that interpolation more than 2 kinds contains chlorine, fluorine, iodine as grinding promoter.
As long as the addition of various additives, kind can realize that purpose of the present invention just is not particularly limited.
According to grinding-material slurry of the present invention, can when guaranteeing good grinding rate, suppress the damage of bottom, thereby for example the distribution in the semiconductor device manufacturing forms in the technology and can grind under the condition of not damaging metal wirings such as dielectric film surface or tungsten, aluminium, copper, makes its planarization.And, can provide to show high grinding rate, suppress the grinding-material slurry of the generation of cut, abrasion significantly.
The present invention also comprises following mode.
(1-1) a kind of grinding-material slurry (grinding-material emulsion) is characterized in that, comprise the resin (A) that contains amide groups and emulsion polymerisation more than a kind vinyl monomer and the resin (B) that obtains.
(1-2) the grinding-material slurry of above-mentioned (1-1) record is characterized in that, mix the resin (A) that contains amide groups and emulsion polymerisation more than a kind vinyl monomer and the resin (B) that obtains and forming.
(1-3) the grinding-material slurry of above-mentioned (1-1) record is characterized in that, resin (B) for contain the resin of amide groups (A) in the presence of the resin that obtains of the vinyl monomer of emulsion polymerisation more than a kind.
(1-4) the grinding-material slurry of above-mentioned (1-1) record is characterized in that, the resin that the resin (A) that contains amide groups obtains for polymerization in the presence of the resin (B) that obtains at the vinyl monomer of emulsion polymerisation more than a kind.
(1-5) grinding-material of any record in above-mentioned (1-1) to (1-4) slurry is characterized in that, contains the resin (A) below the 90 weight % more than the 10 weight % with respect to all resins composition.
(1-6) a kind of grinding-material (grinding-material slurry) is characterized in that, contain any record in above-mentioned (1-1) to (1-5) grinding-material slurry, can with the compound and the water that are formed complex by abrasive metal.
(1-7) grinding-material of above-mentioned (1-6) record is characterized in that, all resins composition contains in grinding-material more than the 1 weight % below the 15 weight %.
(1-8) above-mentioned (1-6) or (1-7) grinding-material of record is characterized in that, above-mentioned can containing in grinding-material more than the 0.5 weight % below the 5 weight % with the compound that is formed complex by abrasive metal.
(1-9) grinding-material of any record in above-mentioned (1-6) to (1-8) is characterized in that, the pH of above-mentioned grinding-material is more than 7 below 9.
(1-10) grinding-material of any record in above-mentioned (1-6) to (1-9) is characterized in that, also contains oxidant.
(2-1) a kind of grinding-material slurry (metal grinding slurry) is characterized in that, comprises the water-soluble copolymer resins (A) that contains amide groups and is the particle (B) that the copolymer resins more than 25 ℃ constitutes by vitrifying point.
(2-2) the grinding-material slurry of above-mentioned (2-1) record is characterized in that (2-1) particle (B) that is made of copolymer resins of middle record has the functional group that can catch metal ion.
(2-3) the grinding-material slurry of above-mentioned (2-2) record is characterized in that, (2-2) in the functional group that can catch metal ion of record be selected from least a in carboxyl, amide groups, sulfonic group, phosphate, cyano group, carbonyl, the hydroxyl.
(2-4) the grinding-material slurry of above-mentioned (2-1) record, it is characterized in that, the particle (B) that is made of copolymer resins is made of the copolymer resins with the functional group that can catch metal ion, and water-soluble copolymer resins (A) contains the copolymer resins that the vinyl monomer of amide groups obtains for polymerization.
(2-5) the grinding-material slurry of above-mentioned (2-4) record, it is characterized in that, for the particle that constitutes by copolymer resins (B) with the functional group that can catch metal ion, housing department and/or skin section coating contain the water-soluble copolymer resins (A) that the vinyl monomer of amide groups obtains by polymerization.
(2-6) above-mentioned (2-4) or (2-5) the grinding-material slurry of record is characterized in that, (2-4) or the vinyl monomer that contains amide groups of record (2-5) be (methyl) acrylamide.
(2-7) grinding-material of any record in above-mentioned (2-1) to (2-6) slurry is characterized in that, further contains oxidant, can form water soluble compound, the corrosion inhibitor of complex with metal.
Embodiment
Specifically describe the present invention by the following examples, but the present invention is not limited to these embodiment.
Here, umber among the embodiment and % are not having all to represent weight portion and weight % under the specially appointed situation.
The molecular weight of the water-soluble copolymer resins (A) that contains amide groups that obtains in following embodiment in addition, is all in 5000～500000 scope.
Used the evaluation of the grinding-material of grinding-material slurry to be undertaken by following method.
1. grinding rate
Grinding-material: contain the grinding-material slurry in embodiment and the comparative example
Grinding charge: on the substrate of silicon wafer lamination the plating of Ta film 300 dusts of heat oxide film 5000 dusts/form by sputtering method/form by the CVD method with 8 inches silicon wafers of copper film 15000 dusts of copper crystal seed film 1500 dusts/form by plating method
Lapping device: Applied materials company makes MIRRA3400
Grinding pad: NITTA HASS company makes IC1400XY グ Le one Block
Grind load: 2.0psi
Milling time: 1min
Grinding-material quantity delivered: 200cc/min
Disk revolution: 87rpm
Substrate side revolution: 83rpm
1) grinding rate calculates
To grinding charge carry out that ultra-pure water cleans and ultrasonic waves for cleaning after, drying is measured the thickness that grinds front and back by the sheet impedance measuring that utilizes 4 terminal detectors.Variable quantity and milling time by thickness calculate average grinding rate.
2) blemish
To the grinding charge after grinding carry out that ultra-pure water cleans and drying after, utilize differential interference microscope times to observe the surface with multiplication factor * 2500.Here, have that the lip-deep damage of length is judged as cut more than 0.1 micron.
Zero: damage, cut 5 are sentenced down
*: damage, cut surpass 5 places
2. abraded quantity is measured
The mensuration of abraded quantity is carried out by the following method.After grinding, form section S EM (scanning electron microscope) photo of groove of 100 microns of distribution width, 10 microns of the distribution width of wafer (SEMATECH#854) by pattern, from Ta film and SiO with above-mentioned grinding condition
2The shape of film confirms to have or not the generation of abrasion.
Part or all disappearance of film: have abrasion (*)
Film is disappearance not: do not have abrasion (zero)
3. storage stability evaluation
Under atmospheric pressure, room temperature, left standstill the grinding-material slurry 6 hours.Subsequently, the state of visual observations grinding-material slurry.
Zero: do not generate supernatant, precipitation
*: generated supernatant, precipitation
(Production Example 1 that contains the water-soluble resin (A) of amide groups)
In the detachable flask that has mixer, returned cold radiator cooler, add 200 weight portion distilled water, behind nitrogen replacement, be warming up to 80 ℃.After then adding 2.0 parts of ammonium persulfates, while stirring with adding the following vinyl monomer of forming and the mixture of water in 2 hours continuously, slaking 2 hours under same temperature then finishes polymerization.Obtain solid constituent and be the aqueous solution of 20.0% the water-soluble resin that contains amide groups (A-1).
65.0 parts of Methacrylamides
10.0 parts of methacrylic acids
20.0 parts of 2-hydroxyethyl methacrylates
5.0 parts of methyl acrylates
200.0 parts of distilled water
By being the molecular weight that the GPC-MALLS method of benchmark is measured the water-soluble resin that contains amide groups (A-1) of gained with goods name: PULLULAN (manufacturing of Shodex company), weight average molecular weight Mw is 39720 as a result.
(embodiment 1)
In the detachable flask that has mixer, returned cold radiator cooler, add 360 weight portion distilled water, behind nitrogen replacement, be warming up to 80 ℃.After then adding 2.0 parts of ammonium persulfates, add the following vinyl monomer emulsion of forming continuously with 3 hours, and then kept 3 hours, finish polymerization.Obtaining solid constituent and be 20.0% copolymer resins is organic filler (B-1).The particle diameter of the organic filler that obtains (B-1) is 154nm.Here, in present embodiment and following embodiment, do not having under the situation about specifying, the particle diameter of organic filler (B) is to be obtained by dynamic light scattering method, and with number average bead diameter as particle diameter.
Therein with (A): (B)=copolymer resins that 1: 9 mixed had before obtained promptly contains the water-soluble resin (A-1) of amide groups, makes grinding-material slurry (1).
(vinyl monomer emulsion)
95.0 parts of n-butyl acrylates
5.0 parts of methacrylic acids
0.1 part of Texapon Special
40.0 parts of distilled water
(embodiment 2)
In the aqueous solution of 1167 parts of resins that before obtained (A-1), add 360 parts of solid constituents adjustings and use distilled water, carry out the nitrogen displacement once more, be warming up to 80 ℃ simultaneously.After then adding 1.0 parts of ammonium persulfates, add the following vinyl monomer emulsion of forming continuously with 3 hours, and then kept 3 hours, finish polymerization.Obtain solid constituent and be 20.0% grinding-material slurry (2).The particle diameter of the organic filler that obtains (B-1) is 150nm.
(vinyl monomer emulsion)
55.0 parts of styrene
40.0 parts of 2-EHAs
5.0 parts in acrylic acid
0.1 part of Texapon Special
40.0 parts of distilled water
(embodiment 3)
Oxalic acid aqueous solution is adjusted to pH8.3 with ammonia.Abundant grinding-material slurry (1), pure water, 30% hydrogen peroxide, the BTA that mixes this solution, is adjusted to the embodiment 1 of pH8.3 with ammonia made the grinding-material of grinding-material with emulsion 5.0wt%, hydrogen peroxide 2.0wt%, oxalic acid 1.0wt%, BTA 0.018wt%, pH8.3.
The result who estimates nonferromagnetic substance by above-mentioned method is, can grind with stable speed, also do not have blemish even milling time is long, confirms that thus the physical loads of this grinding-material when grinding is stable, can not make grinding charge produce cut.The results are shown in the table 1.
In addition, observe the particle diameter of the particle in the grinding-material of measuring present embodiment by dynamic light scattering method and transmission electron microscope (TEM).Particle diameter d1 by dynamic light scattering determination is 154nm, and the particle diameter d2 that is obtained by tem observation is 110nm.
By this result can infer indirectly the water-soluble resin (A) that contains amide groups exist and be coated on resin particle (B) around.
(embodiment 4)
Except the grinding-material slurry (1) with embodiment 1 is replaced into the grinding-material slurry (2) of embodiment 2, carry out operation similarly to Example 3.Grinding the results are shown in the table 1.
(comparative example 1)
Except the grinding-material slurry (1) with embodiment 1 is replaced into commercially available cataloid (Japan chemistry society makes PL-1), carry out similarly to Example 3 operation, evaluation.The results are shown in the table 1.
(comparative example 2)
Except the grinding-material slurry (1) with embodiment 1 is replaced into commercially available aluminium oxide (the Japanese ア エ ロ ジ Le manufacturing AEROXIDE AluC of society), carry out similarly to Example 3 operation, evaluation.The results are shown in the table 1.
(embodiment 5)
Present embodiment relates to that in the presence of organic filler (B) polymerization contains the water-soluble resin (A) of amide groups and the grinding-material slurry that obtains.
In the detachable flask that has mixer, returned cold radiator cooler, add 360 weight portion distilled water, behind nitrogen replacement, be warming up to 80 ℃.After then adding 2.0 parts of azo dicyano valeric acids, add the following vinyl monomer emulsion of forming continuously with 3 hours, and then kept 3 hours, finish polymerization.Obtaining solid constituent and be 20.0% copolymer resins is organic filler (B-2).The particle diameter of the organic filler that obtains (B-2) is 191nm.
(vinyl monomer emulsion)
77.0 parts of styrene
20.0 parts of acrylonitrile
3.0 parts of methacrylic acids
0.1 part of Texapon Special
40.0 parts of distilled water
The aqueous solution to 500 parts of organic fillers that before obtained (B-2) carries out the nitrogen displacement once more, is warming up to 80 ℃ simultaneously.After then adding 2.0 parts of ammonium persulfates, while stirring with adding the following vinyl monomer of forming and the mixture of water in 2 hours continuously, slaking 2 hours under same temperature then finishes polymerization.Obtain solid constituent and be 20.0% grinding-material slurry (3).
89.5 parts of Methacrylamides
5.0 parts of methacrylic acids
5.0 parts of methyl methacrylates
0.5 part of methylene diacrylamine
400.0 parts of distilled water
The grinding-material slurry (3) that use obtains replaces the grinding-material slurry (1) of embodiment 1, carries out operation similarly to Example 3.Grinding the results are shown in the table 1.
(embodiment 6)
Present embodiment is the embodiment that has changed the containing ratio of water-soluble resin that contains amide groups (A) among the embodiment 1 and organic filler (B).
In embodiment 1, with (A): (B)=4: 6 mixed contains the water-soluble resin (A) and the organic filler (B) of amide groups, makes grinding-material slurry (4), carries out operation similarly to Example 3.The results are shown in the table 1.
(embodiment 7)
Present embodiment is to have changed the embodiment that can form the compound of complex in embodiment 3.
Except the oxalic acid with embodiment 3 is replaced into malic acid, the grinding-material slurry (2) that the grinding-material of embodiment 3 slurry (1) is replaced into embodiment 2 carries out operation similarly to Example 3 in addition.The results are shown in the table 1.
(embodiment 8)
Present embodiment is the example that has changed the oxidant of embodiment 7.
Except the oxidant of embodiment 7 is replaced into the ammonium persulfate by hydrogen peroxide, carry out operation similarly to Example 7.The results are shown in the table 1.
(comparative example 3)
This comparative example is that grinding-material is starched the example that only comprises the water-soluble resin (A) that contains amide groups and do not comprise organic filler (B).
In embodiment 1, with (A): (B)=10: 0 mixed contains the water-soluble resin (A) and the organic filler (B) of amide groups, makes grinding-material slurry (5), carries out operation similarly to Example 3.The results are shown in the table 1.
(comparative example 4)
This comparative example is that grinding-material is starched the example that only comprises organic filler (B) and do not comprise the water-soluble resin (A) that contains amide groups.
In embodiment 1, with (A): (B)=0: 10 mixed contains the water-soluble resin (A) and the organic filler (B) of amide groups, makes grinding-material slurry (6), carries out operation similarly to Example 3.The results are shown in the table 1.
Table 1
As shown in Table 1, the grinding-material of embodiment 3～8 inhibition effect excellence of when keeping grinding rate, denuding.
And then, in following embodiment and comparative example, carry out the evaluation of grinding-material slurry by the following method.
1. grinding rate
Grinding-material: comprise the grinding-material slurry in embodiment and the comparative example
Grinding charge: on the substrate of silicon wafer lamination the plating of Ta film 300 dusts of heat oxide film 5000 dusts/form by sputtering method/form by the CVD method with 8 inches silicon wafers of copper film 15000 dusts of copper crystal seed film 1500 dusts/form by plating method, be formed with the silicon wafer (SEMATECH#854) of Wiring pattern
Lapping device: MAT company makes MAT-ARW-681M
Grinding pad: NITTA HASS company makes IC-1000/suba400
Grind load: 3.0psi
Milling time: 1min
Grinding-material quantity delivered: 200cc/min
Disk revolution: 90rpm
Substrate side revolution: 90rpm
2. grinding rate calculates
Behind ultra-pure water cleaning and the ultrasonic waves for cleaning grinding charge, carry out drying, measure the thickness that grinds front and back by the sheet impedance measuring that utilizes 4 terminal detectors.
Variable quantity and milling time by thickness calculate average grinding rate.
3. depression is measured
Use the grinding-material of each embodiment and comparative example, after grinding under the above-mentioned grinding condition is formed with the wafer (SEMATECH#854) of Wiring pattern, the concave depth of deciding the copper wiring groove central part in 10 microns zones of distribution width by contact pin type difference of height instrumentation.
Milling time surpasses until the copper of finishing the part that does not form groove grinds 50% of the required time, implements overmastication.
4. etching is measured
Impregnating metal copper coin in the grinding-material 70cc that has added hydrogen peroxide 2.0%, BTA 0.04%, Schweinfurt green (II) 0.08% (20 * 20 * 1mm), with 1000rpm agitation grinding liquid, and kept 10 minutes.Calculate etching speed by the weight change before and after the dipping.
(Production Example 2 that contains the water-soluble resin (A) of amide groups)
In the present embodiment, contain the copolymer resins (A-2) of amide groups as the water-soluble resin (A) that contains amide groups in order to the below manufactured.
In the detachable flask that has mixer, returned cold radiator cooler, add 200 weight portion distilled water, behind nitrogen replacement, be warming up to 75 ℃.After then adding 2.0 parts of ammonium persulfates, while stirring with the mixture that added acrylamide 99 weight portions, methacrylic acid 1 weight portion and distilled water 200 weight portions in 2 hours continuously, slaking 2 hours under same temperature then finishes polymerization, obtains containing the copolymer resins (A-2) of amide groups.
(embodiment 9)
In the detachable flask that has mixer, returned cold radiator cooler, add the copolymer resins that contains amide groups (A-2) that 260 weight portion distilled water and 100 weight portions synthesize in Production Example 2, behind nitrogen replacement, be warming up to 80 ℃.After then adding 2.0 parts of ammonium persulfates, while stirring with the vinyl monomer and the distillation water emulsion of the composition that in above-mentioned flask, added table 2 record in 4 hours continuously, and then kept 4 hours, finish polymerization, obtain containing copolymer resins (A-2) and be the grinding-material slurry of the particle (B-3) that constitutes of the copolymer resins more than 25 ℃ by vitrifying point as organic filler (B).
The particle diameter of the organic filler that obtains here, (B-3) is 188nm.
(embodiment 10～16)
Except the vinyl monomer that uses the composition (weight ratio) of record in table 2 or the table 3 in embodiment 9 is made organic filler (B), obtain the grinding-material slurry similarly to Example 9.Tg calculated value as for copolymer resins, be to use computational science software Cheops ver.4 (Million Zillion SoftwareInc.) to calculate the Tg of the homopolymers of vinyl monomer, and then use fox equation to obtain the Tg calculated value of the copolymer resins of table 1 record.
In present embodiment and later embodiment, when calculating Tg, use the Tg of following value as the homopolymers of each monomer.
Methyl methacrylate 377K
Styrene 376K
Acrylonitrile 422K
Butyl methacrylate 287K
Butyl acrylate 242K
Methacrylic acid 417K
Ethyl acrylate 262K
Acetoacetyl oxygen methacrylate 324K
The particle diameter of the organic filler (B) that obtains among the embodiment 10～13 in addition, is as described below respectively.
Embodiment 10:160nm
Embodiment 11:110nm
Embodiment 12:159nm
Embodiment 13:239nm
Table 2
| Embodiment 9 | Embodiment 10 | Embodiment 11 | Embodiment 12 | |
| Methyl methacrylate | 90 | 80 | 80 | |
| Styrene | 65 | |||
| Methacrylic acid | 10 | 10 | 10 | 10 |
| Acrylonitrile | 25 | |||
| Butyl acrylate | 10 | |||
| Acetoacetoxyethyl methacrylate | 10 | |||
| The Tg calculated value (℃) | 108 | 117 | 101 | 87 |
Table 3
| Embodiment 13 | Embodiment 14 | Embodiment 15 | Embodiment 16 | |
| Ethyl acrylate | 80 | 100 | ||
| Butyl acrylate | 65 | |||
| Butyl methacrylate | 75 | |||
| Methacrylic acid | 250 | 15 | 35 | |
| Styrene | 5 | |||
| The Tg calculated value (℃) | 38 | 9.0 | -11 | -11 |
(embodiment 17,18)
In the detachable flask that has mixer, returned cold radiator cooler, add 360 weight portion distilled water, behind nitrogen replacement, be warming up to 80 ℃.After then adding 2.0 parts of ammonium persulfates,, and then kept 4 hours, finish polymerization while stirring with the vinyl monomer and the distillation water emulsion of the composition (weight ratio) that in above-mentioned flask, added table 4 record in 4 hours continuously.
The particle diameter of the organic filler that obtains in each embodiment (B) is as described below respectively.
Embodiment 17:167nm
Embodiment 18:153nm
The copolymer resins that mixes gained with 1: 1 weight ratio with mixer is an organic resin (B) and by the synthetic copolymer resins that contains amide groups (A-2) of embodiment 9.
Table 4
| Embodiment 17 | Embodiment 18 | |
| Methyl methacrylate | 90 | |
| Styrene | 65 | |
| Methacrylic acid | 10 | 10 |
| Acrylonitrile | 25 | |
| The Tg calculated value (℃) | 108 | 117 |
(embodiment 19～28, comparative example 5)
Utilize following method to make grinding-material.
Compound (complex formation agent) by ammonia neutralization can formation complex, being added drop-wise to the copolymer resins A and the B that contain by embodiment 9～18 manufacturings adds up in the slurry of 10 weight portions (solid constituent conversion), mix, before just will grinding, add hydrogen peroxide (2%) and corrosion inhibitor BTA (0.04%).
In addition, in comparative example 1, except not containing copolymer resins A and B, similarly make grinding-material with embodiment 19～28.
Composition, proportioning and the pH of the grinding-material in table 5～7 in each embodiment of expression and the comparative example.And, the evaluation result of these grinding-materials of expression in table 8.
Table 5
| Embodiment 19 | Embodiment 20 | Embodiment 21 | Embodiment 22 | Embodiment 23 | |
| Copolymer resins | Embodiment 9 | Embodiment 10 | Embodiment 11 | Embodiment 12 | Embodiment 13 |
| Copolymer resins concentration | 5％ | 5％ | 5％ | 5％ | 5％ |
| Complex forms agent | Oxalic acid | Malonic acid | Glycine | Malonic acid | Glycine |
| Complex forms agent concentration | 1.0％ | 2.0％ | 1.0％ | 1.0％ | 0.9％ |
| The pH of grinding-material | 8.0 | 7.8 | 8.3 | 8.0 | 7.5 |
Table 6
| Embodiment 24 | Embodiment 25 | |
| Copolymer resins | Embodiment 17 | Embodiment 18 |
| Copolymer resins concentration | 5％ | 5％ |
| Complex forms agent | Oxalic acid | Malonic acid |
| Complex forms agent concentration | 1.0％ | 2.0％ |
| The pH of grinding-material | 8.0 | 7.8 |
Table 7
| Comparative example 5 | Embodiment 26 | Embodiment 27 | Embodiment 28 | |
| Copolymer resins | Do not have | Embodiment 14 | Embodiment 15 | Embodiment 16 |
| Copolymer resins concentration | 5％ | 5％ | 5％ | 5％ |
| Complex forms agent | Oxalic acid | Oxalic acid | Glycine | Malonic acid |
| Complex forms agent concentration | 1.0％ | 1.0％ | 1.0％ | 2.0％ |
| The pH of grinding-material | 8.0 | 7.8 | 8.3 | 8.0 |
Table 8
As shown in Table 8, the grinding-material of embodiment 19～28 is being excellent aspect the inhibition effect of keeping and denuding of grinding rate and the balance that suppresses effect that caves in.
Claims (13)
1. a grinding-material is characterized in that, comprises the water-soluble resin (A) and the organic filler (B) that contain amide groups,
The particle that described organic filler (B) obtains for the vinyl monomer of polymerization more than a kind in the presence of the described water-soluble resin (A) that contains amide groups,
The pH of this grinding-material is more than 7 below 9, and,
With respect to all resins composition, contain the following described water-soluble resin (A) that contains amide groups of the above 90 weight % of 10 weight %, contain the above described organic filler (B) of the following 10 weight % of 90 weight %.
2. a grinding-material is characterized in that, comprises the water-soluble resin (A) and the organic filler (B) that contain amide groups,
The resin that the described water-soluble resin (A) that contains amide groups obtains for polymerization in the presence of the described organic filler (B) that obtains at the vinyl monomer of polymerization more than a kind,
The pH of this grinding-material is more than 7 below 9, and,
With respect to all resins composition, contain the following described water-soluble resin (A) that contains amide groups of the above 90 weight % of 10 weight %, contain the above described organic filler (B) of the following 10 weight % of 90 weight %.
3. grinding-material according to claim 1 and 2, it is characterized in that, the described water-soluble resin (A) of amide groups that contains is for containing the water-soluble copolymer resins of amide groups, the particle of described organic filler (B) for being made of the copolymer resins of vitrifying point more than 25 ℃.
4. grinding-material according to claim 3 is characterized in that, the described copolymer resins of vitrifying point more than 25 ℃ has the functional group that can catch metal ion.
5. grinding-material according to claim 4 is characterized in that, the described functional group that can catch metal ion is selected from least a in the group of being made up of carboxyl, amide groups, sulfonic group, phosphate, cyano group, carbonyl, hydroxyl.
6. grinding-material according to claim 4 is characterized in that, contains the copolymer resins that the described water-soluble copolymer resins of amide groups obtains for the vinyl monomer that contains amide groups by polymerization.
7. grinding-material according to claim 6, it is characterized in that, the housing department and/or the skin section of the particle that constitutes by described copolymer resins with the described functional group that can catch metal ion, the described copolymer resins institute coating that is contained by polymerization that the vinyl monomer of amide groups obtains.
8. grinding-material according to claim 6 is characterized in that, the described vinyl monomer that contains amide groups is (methyl) acrylamide.
9. a grinding-material is characterized in that, contains claim 1 or 2 described grinding-materials, oxidant, can form the compound and the corrosion inhibitor of complex with metal.
10. a grinding-material is characterized in that, contains claim 1 or 2 described grinding-materials, can form the compound and the water of complex with metal.
11. grinding-material according to claim 10 is characterized in that, also contains oxidant.
12. grinding-material according to claim 9 is characterized in that, described can to form the compound of the complex content all with respect to this grinding-material with metal be more than the 0.5 weight % below the 5 weight %.
13. grinding-material according to claim 9 is characterized in that, all resins composition content all with respect to this grinding-material is more than the 1 weight % below the 15 weight %.
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| JP2005116475 | 2005-04-14 | ||
| JP116475/2005 | 2005-04-14 | ||
| JP057117/2006 | 2006-03-03 |
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