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CN100412153C - Process for reducing dishing and erosion during chemical mechanical planarization - Google Patents

Process for reducing dishing and erosion during chemical mechanical planarization Download PDF

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Publication number
CN100412153C
CN100412153C CNB038187892A CN03818789A CN100412153C CN 100412153 C CN100412153 C CN 100412153C CN B038187892 A CNB038187892 A CN B038187892A CN 03818789 A CN03818789 A CN 03818789A CN 100412153 C CN100412153 C CN 100412153C
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CN
China
Prior art keywords
slurry
polishing
copper
base material
abrasive
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Expired - Fee Related
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CNB038187892A
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Chinese (zh)
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CN1675327A (en
Inventor
S·D·赫尔灵
李玉琢
R·L·奥格
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PPG Industries Ohio Inc
PPG Industries Inc
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PPG Industries Inc
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02041—Cleaning
    • H01L21/02057—Cleaning during device manufacture
    • H01L21/02068—Cleaning during device manufacture during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers
    • H01L21/02074—Cleaning during device manufacture during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers the processing being a planarization of conductive layers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09G—POLISHING COMPOSITIONS; SKI WAXES
    • C09G1/00—Polishing compositions
    • C09G1/02—Polishing compositions containing abrasives or grinding agents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
    • H01L21/321—After treatment
    • H01L21/32115—Planarisation
    • H01L21/3212—Planarisation by chemical mechanical polishing [CMP]

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Mechanical Treatment Of Semiconductor (AREA)
  • Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
  • Weting (AREA)

Abstract

This invention is directed to a slurry system and process of metal removal from a substrate. This invention is useful for polishing a microelectronic device. This invention is especially useful for chemical mechanical planarization of a semiconductor wafer. The slurry system of the present invention includes a first slurry and a second slurry, wherein the first slurry has a higher abrasive concentration than the second slurry. The process of the present invention includes a first polish with the first slurry to partially remove metal from the substrate, and a second polish with the second slurry to further remove metal from the substrate.

Description

Surface depression and the abrasive method of minimizing in the chemical mechanical method complanation process
Background of the present invention
The application requires the right of priority of the u.s. patent application serial number 60/401,109 of proposition on August 5th, 2002, and this application is introduced for reference at this paper comprehensively.
General introduction of the present invention
The present invention relates to from the base material process of metal removal.The present invention can be used for polish microelectronic device.The present invention especially can be used for the chemical mechanical method complanation of semiconductor wafer.
Microelectronic device typically combines with the copper-connection thing such as semiconductor wafer and makes.These copper-connection things are inlayed (damascene) method by multistep and are made, this method by dielectric materials such as silicon-dioxide in etched trench, barrier films is mounted in the groove, form with the electro-coppering filling groove then.Generally, at the thick copper capping layer of top layout (overburden) of filling groove.This tectal application does not obtain smooth surface usually.On the contrary, in tectum, have corresponding to the low area that filling groove is arranged below with corresponding to the high zone of the spatial between groove (i.e. " step height contour structure ").
In order on microelectronic device, to arrange another interconnect level, must remove copper capping layer.Chemical mechanical method complanation (" CMP ") is the known technology that is used to remove copper capping layer.During CMP processing, remove copper capping layer from the surperficial supernatant of microelectronic device, to appear actual interconnection pattern.In typical chemical mechanical pulping polishing process, microelectronic device contacts with polishing pad.This pad rotates in the back side that power is put on microelectronic device.In polishing process, the chemical reactivity solution that contains abrasive that is commonly called " slurry " puts on this pad.Usually, the CMP polishing slurries contains abrasive substance, such as silica, and aluminum oxide, cerium dioxide or their mixture.This glossing promotes with respect to rotatablely moving of base material by this pad when slurry being offered device/polishing pad interface.Polishing lasts till by this way removes till the required film thickness degree.
Depend on the selection of abrasive and other additive, polishing slurries can be formulated into to be provided with the effective polishing of required polishing speed to metal level, makes simultaneously that the surface is imperfect, defective, corrosion and abrasion reduce to minimum.
The method of using abrasive slurry to remove copper capping layer is well known in the art.The pressure that shortcoming in these currently known methodss comprises polishing pad is compressed to the surface of base material with abrasive particles, causes the surface depression in groove and the abrasion of the pattern on base material.In the art, wish at utmost to reduce this surface depression and abrasion.Therefore, in the art for effectively removing copper capping layer, there is demand in the abrasive method that at utmost reduces interior surface depression of groove and the pattern on the base material simultaneously.
It is pointed out that the singulative that uses comprises plural object in this specification and the appended claims, unless specially and clearly be limited to single object.
For this specification sheets, unless otherwise prescribed, all numerical value of the amount of the expression composition that uses in this specification sheets and claims, reaction conditions etc. are considered in all cases and can modify by word " approximately ".Therefore, unless otherwise prescribed, all numerical parameters that provide in following specification sheets and appended claims are can be according to the approximation of the desired properties change of seeking to obtain by the present invention.At least, and be not the application of principle of equivalent of attempting to limit the scope of claims, each numerical parameter should be explained according to the numerical value of the significant figure of being reported with by using the common technology of rounding up at least.
Though setting forth the numerical range and the parameter of wide region of the present invention is approximation, the numerical value that provides in specific embodiment is as far as possible accurately reported.Yet, any numerical value contain inherently by the standard deviation that in their test determination separately, exists certain error that must cause.
Characterizing feature of the present invention is at length pointed out in the claim of a part that belongs to disclosure thing.The special object that from following detailed description and embodiment, can more fully understand these and other feature of the present invention, its service advantages and obtain by its application.
Have been found that it is desirable to, in first polishing step, remove the step height contour structure of copper capping layer, do not remove whole tectum, made for second step can be mainly used in and remove the remaining tectum that does not contain the step height contour structure relatively.
The present invention includes the slurry system that contains following component:
(a) contain and be useful on first slurry of removing the abrasive of metal from base material top; With
(b) second slurry,
Wherein said first slurry has the described abrasive of greater concn than described second slurry.
The present invention further comprises a kind of method, comprises first polishing with first slurry and polishing pad.First polishing has been removed a part of metal from base material.After first polishing finished, kish was retained on the base material.In second polishing with second slurry and polishing pad, second slurry that the enough abrasives of base material energy are less than first slurry further polishes.Second is polished to small part has removed the metal residue that is retained on the base material after first polishing.
First polishing can stop before all metals are removed from base material.When first polishing stopped, kish was retained on the base material.
In a non-limiting embodiments, metal can comprise copper, tantalum, silicon-dioxide, or their mixture.In another non-limiting embodiments, metal is a copper.
According to estimates, the use that is used for the abrasive slurry of copper removal in the first step of glossing has the proneness in the high zone that helps the step height contour structure, can hang down the remaining copper that abrasive slurry is removed by second thereby stayed.In one embodiment of the invention, second slurry can not contain abrasive.
First slurry of the present invention comprises liquid and abrasive.Be suitable for abrasive of the present invention and can comprise metal oxide.The limiting examples of metal oxide can include, but are not limited to aluminum oxide, titanium dioxide, zirconium white, germanium oxide (gennania), silicon-dioxide, cerium dioxide and their mixture.The amount that is present in the abrasive of first slurry can change significantly according to selected abrasive.In a non-limiting embodiments, abrasive can be with 0.1 to about 30.0wt%, or the amount of 0.5-12.0wt% exists.In another embodiment, abrasive can be a silica.
Various silicas and their preparation method are that those of skill in the art are known.Being suitable for silica of the present invention can select from various silicas known in the art.In a non-limiting embodiments, silica can be a precipitated silica.Various precipitated silicas and their preparation method are that those of skill in the art are known.In another non-limiting embodiments, precipitated silica can be selected from June 14 calendar year 2001 and propose, at present at described in the u.s. patent application serial number 09/882,549 and 09/882,548 of United States Patent (USP) trademark office unexamined those; Their relevant portion is introduced for reference at this paper.
In another non-limiting embodiments, abrasive slurry of the present invention comprises the silica of the aggregate with primary particle, and described primary particle has the mean diameter of at least 7 nanometers, and wherein said aggregate has the aggregate size less than 1 micron; The hydroxy radical content of at least 7 hydroxyl/square nanometers.
Silica can prepare by various methods known in the art.Generally, silica can prepare with the acid merging by the aqueous solution with soluble metal silicate.Soluble metal silicate can comprise alkalimetal silicate, is such as but not limited to water glass or potassium silicate.The acid that is fit to can comprise mineral acid, organic acid and carbonic acid gas.Silicate/wintercherry material can wear out then, and acid or alkali can be joined in silicate/wintercherry material.The gained silica granule can be separated from the liquid portion of mixture.Isolating silica can wash with water, and wet silica can carry out drying, and the exsiccant silica can use common washing known in the art, drying and isolation technique to separate from the residue of other reaction product.
In a non-limiting embodiments, be used for silica of the present invention and can carry out the particle size reduction technology.Be known in the art the various technology that the aggregate of the primary particle in the silica are broken into littler aggregate that are useful on.Limiting examples is ground including, but not limited to wet-milling and injection stream.In another non-limiting embodiments, the aggregate of the primary particle of silica can use the two jet chambers method relevant with disclosed apparatus and method in WO 00/39056 and U.S. Patent No. 5,720,551 to reduce; Their relevant portion is incorporated herein for reference.
As mentioned above, first pulp bales spotting-in grinding agent and the liquid of the present invention.In a non-limiting embodiments, first abrasive slurry can be according to the patent application serial number of declaring in United States Patent (USP) trademark office in June 14 calendar year 2001 that waits to examine 09/882, method preparation described in 549 and 09/882,548, their relevant portion is incorporated herein for reference.In another non-limiting embodiments, liquid can be water.
Except abrasive and water, slurry can comprise oxygenant and complexing agent.The existence of oxygenant in slurry can be used in the substrate metal layer is oxidized to its corresponding oxide compound, oxyhydroxide or ion.In alternative non-limiting embodiments, oxygenant can be used in titanyl is turned to titanium dioxide, and tungsten is oxidized to Tungsten oxide 99.999, and copper is oxidized to cupric oxide, and alumina is turned to aluminum oxide.The slurry that contains oxygenant can be used in polishing metal and metal mold component, including, but not limited to titanium, and titanium nitride, tantalum, tantalum nitride, copper, tungsten, tungsten nitride, aluminium, aluminium alloy, such as aluminium/copper alloy, gold, silver, platinum, ruthenium and their various mixtures and binding substances.
In first slurry of the present invention, can use various oxygenants.The oxygenant that is fit to can comprise inorganic and organo-peroxide, and the compound that contains the element of higher or highest oxidation state.The term that in this paper and claims, uses " superoxide " be meant contain at least one peroxy-radical compound (O-O-).The limiting examples that contains the compound of at least one peroxy-radical can comprise hydrogen peroxide and adducts thereof, such as urea-hydrogen peroxide and peroxocarbonate, organo-peroxide is such as benzoyl peroxide, peracetic acid, and ditertiary butyl peroxide, single persulphate (SO 5), peroxydisulfate (S 2OO), sodium peroxide and their mixture.
The limiting examples of oxygenant that contains the element of advanced oxidation attitude can comprise bromic acid, bromate, chloric acid, oxymuriate, chromic salt, acid iodide, iodate, periodic acid, periodates, perbromic acid, perbromate, perchloric acid, perchlorate, peroxyboric acid, perborate, permanganate, cerium (IV) compound is such as but not limited to ceric ammonium nitrate, and molysite is such as nitrate, vitriol, EDTA and Citrate trianion, the Tripotassium iron hexacyanide, vanadous oxide etc., and aluminium salt.
In alternative non-limiting embodiments, oxygenant can be urea-hydrogen peroxide, hydrogen peroxide, or their mixture.In another non-limiting embodiments, oxygenant can be a hydrogen peroxide.
The amount that is present in the oxygenant in first slurry can change significantly according to selected specific oxygenant.Generally, this amount should be enough to the substrate metal layer is oxidized to its corresponding oxide compound, oxyhydroxide or ion.In alternative non-limiting embodiments, oxygenant can be with 〉=0.001wt%, or 〉=0.01wt%, or≤20.0wt%, or≤17.0wt%, or≤amount of 10.0wt% exists.
Be suitable for complexing agent of the present invention and can comprise organic acid and organic alcohol acid.The organic acid limiting examples can be including, but not limited to dicarboxylic acid, tricarboxylic acid and poly carboxylic acid, glyconic acid, lactic acid, citric acid, tartrate, oxysuccinic acid, oxyacetic acid, propanedioic acid, oxalic acid, Succinic Acid, and phthalic acid.The limiting examples of organic alcohol acid can include but not limited to dicarboxyl, three carboxyls and many carboxyls alcohol acid.Other limiting examples of the complexing agent that is fit to can comprise amino acid such as glycine, Histidine, L-Ala, and aspartic acid; Nitrogenous heterocyclic carboxylic acid, such as pyridine carboxylic acid, pyridine dicarboxylic acid, quinolinic acid, 2-pyrazine carboxylic acid, quinaldine carboxylic acid and 2-quinoxaline carboxylic acid; With organic bitooth ligand such as two pyridinyl derivatives.
The amount of the complexing agent of Shi Yonging can change significantly according to the selection of complexing agent in the present invention.In non-limiting embodiments, glycine can be so that its constitutes the 0.1-5wt% of slurry, or the amount of 0.5-1wt% is as complexing agent.In another non-limiting embodiments, pyridine carboxylic acid can be so that its constitutes the 0.1-5wt% of slurry, or the amount of 0.5-1wt% is as complexing agent.
In other non-limiting embodiments, first slurry of the present invention can comprise one or more of following additive: polyvalent cation sequestrant, inhibiter, thickening material, stop compound, static etching control agent, promotor, metal halide, tensio-active agent, stablizer and metal chelator.
In another non-limiting embodiments, slurry of the present invention can comprise the polyvalent cation sequestrant.Be suitable for polyvalent cation sequestrant of the present invention and can comprise with multivalent metal cation and combining or complexing, or the cationic various compound known of chelated polyvalent metal.The limiting examples of polyvalent cation sequestrant can comprise carboxylic acid and poly carboxylic acid, amino acid, dipeptides and polyamino acid, poly-imines, phosphoric acid and polyphosphoric acid.Other limiting examples can comprise glycine; Histidine, aspartic acid, phytic acid; the hot polymerization aspartate; gamma-amino-butanic acid, Beta-alanine, altheine; the 2-aminoisobutyric acid; citric acid, N-((phosphonomethyl)) iminodiethanoic acid, poly-(dimethyl siloxane)-grafting-polyacrylic acid; 4; the 5-imidazole-2-carboxylic acid, amino three (methylene phosphonic acids), polymine; acetate; aspartic acid-phenylalanine methyl ester and 2-phosphono-1,2; 4-butane tricarboxylic acid; the cross linked polyacrylate that is purchased from B.F.Goodrich with the trade(brand)name of Carbopol, polyacrylic ester that is purchased from B.F.Goodrich with the trade(brand)name of GOOD-RITE K-700 and their mixture.In a non-limiting embodiments, can use Carbopol or GOOD-RITE K-700.
The polyvalent cation sequestrant can exist so that the copper polishing speed is enhanced with static etching, burn into tubercular corrosion, contamination and the unstable of silica dispersion or the amount that does not have excessively to increase of handling problems.In alternative non-limiting embodiments, silica type slurry comprises that its amount is higher than 0 to 5wt%, or the polyvalent cation sequestrant of 0.001-1wt% for paste compound.
In another non-limiting embodiments, slurry of the present invention can comprise anticorrosive agent or inhibiter.Be used for inhibiter of the present invention and can comprise corrosion or the static etched various known compounds that suppress copper, be such as but not limited to poly carboxylic acid, polyamino acid, amino acid, imines, pyroles (azoles), carboxylated pyroles, and mercaptan.The limiting examples of the inhibiter that is fit to comprises benzotriazole, the 4-carboxyl benzotriazole, the 5-carboxyl benzotriazole, the hot polymerization aspartate, Histidine, sulfydryl benzotriazole, phytic acid, the cross linked polyacrylate that is purchased from B.F.Goodrich with the trade(brand)name of Carbopol, polyacrylic ester that is purchased from B.F.Goodrich with the trade(brand)name of GOOD-RITE K-700 and their mixture.
In a non-limiting embodiments, phytic acid can be used for the present invention with different amounts.In another non-limiting embodiments, the amount of phytic acid can make its constitute the 0.01wt% at least of slurry, or 0.05wt% at least, or 0.05-0.1wt%, or is lower than 0.2wt%.The limiting examples that is purchased phytic acid that is fit to comprise with CDI 4302,4303 and 4304 and the trade(brand)name of CDX2128 and 2165 available from King Industries, the water soluble rust inhibitor of Incorporated.
In a non-limiting embodiments, inhibiter can be so that static etching, corrosion and tubercular corrosion be fully reduced; The copper polishing speed does not excessively reduce; With the unstable of contamination, silica dispersion, the amount existence that exceeds the quata cost or handle problems and excessively do not increase.
In one embodiment, being used for inhibiter of the present invention can form agent as passive film, and it has formed passivation layer on the surface of the base material that will polish.Inhibiter has formed passivation layer on the surface of electric substrate layer.In case formation passivation layer, passivation layer can be upset (disturbed) then, to obtain the ideal polishing speed.Inhibiter can comprise passivation layer and the compound of dissolving inhibition layer or the binding substances of compound that can promote to form metal on the surface of metal level.The passivation of substrate metal upper layer can prevent the metallic surface wet etching.This type of membrane-forming agent comprises nitrogen-containing heterocycle compound, and wherein this compound comprises that at least one has the 5 or 6 yuan heterocycles of nitrogen as the part of ring.This nitrogenous 5 and the example of 6 membered ring compounds comprise 1,2, the 3-triazole, 1,2,4-triazole, benzotriazole, benzoglyoxaline and benzothiazole and they have hydroxyl, amino, imino-, carboxyl, sulfydryl, nitro-and the derivative of alkyl-substituted radical, urea and thiocarbamide and their mixture.In one embodiment of the invention, passive film formation agent comprises benzotriazole (" BTA "), 1,2,3-triazoles, 1,2,4-triazole and their mixture.
In an alternative embodiment, what inhibiter or passive film formed that agent can account for silica type paste compound is higher than 0 to about 0.5wt%, or 0.001wt% or more at least, or 0.01wt% or more at least, or 0.1wt% or more at least, or be lower than 1wt%, or be lower than 0.5wt%, or be lower than 0.05wt%.
Forming the passivation layer of metal and dissolving on the surface of the metal level of base material suppresses layer and can be used in and at utmost reduce or prevent the metallic surface wet etching.
In another non-limiting embodiments, slurry of the present invention can comprise thickening material.The thickening material that is fit to can comprise the various known thickeners in this area.Generally, the thickening material of Shi Heing comprises and stablizes silica type slurry to lower settled material.Limiting examples can be including, but not limited to polyvinyl alcohol, polyacrylic acid, polysaccharide, Natvosol and modified hydroxyethylcellulosadsorbing, polyoxyethylene glycol, polypropylene glycol, the multipolymer of polyoxyethylene glycol and polypropylene glycol, alkylation polyoxyethylene glycol and polypropylene glycol, polymine, polyamino acid, polyacrylamide, and polyamic acid.The limiting examples of the anionic polymer that this type of is fit to can comprise the cross linked polyacrylate of buying from B.F.Goodrich with the trade(brand)name of Carbopol, the polyacrylic ester of buying from B.F.Goodrich with the trade(brand)name of GOOD-RITE K-700, KlzanAR xanthan gum polysaccharide from CP Kelco purchase, Natrosol 250MMR Natvosol from the Hercules purchase, Airvol 523 polyvinyl alcohol from Air Products purchase, with Polyox 3333 polyethylene oxides of buying from Union Carbide, or their mixture.
Thickening material can be so that subsidence rate be fully reduced, but excess stickiness is increased, but causes pumping and filtration capacity impaired, or the heat of giving birth in polishing process exists the deleterious amount of size performance.The amount of employed thickening material can change according to selected thickening material.In alternative non-limiting embodiments, thickening material can arrive 5wt% to be higher than 0, or 0.001 to 1wt% amount exists.In another non-limiting embodiments, Carbopol can exist with the amount that is lower than 0.5wt% as thickening material.
In another non-limiting embodiments, thickening material can be a shear stable.Be meant under the shearing condition of polishing the insufficient reduction of the viscosity of thickening material (for example, reduce the viscosity that is no more than before the polishing 75%) as this paper and the employed term of claims " shear stable ".
In alternative non-limiting embodiments of the present invention, as mentioned above, can be in the process of lapping of silica and/or when reducing the granularity of silica; Or after the grinding of silica and/or the particle size reduction end polyvalent cation sequestrant, inhibiter and optional thickening material are joined in the silica.
In a non-limiting embodiments of the present invention, polyvalent cation sequestrant, inhibiter and optional thickening material can be joined in the slurry.In another non-limiting embodiments, polyvalent cation sequestrant, inhibiter and/or thickening material merge under the stirring of gentleness, join in the slurry then.
In another non-limiting embodiments, slurry of the present invention can comprise at least a prevention compound.Stop compound can interact and be suppressed at the removal speed of the layer under the layer that will polish with metal level, bonding coat and/or the dielectric layer of base material.The result can make the slurry polishing substrate the first layer and can stop the second layer of polishing under the first layer basically.Be suitable for prevention compound of the present invention and can comprise all cpds known in the art, such as but be not limited to contain polar compound or the polymkeric substance of polar structure part as hydroxyl, amino, nitrogen heterocyclic ring, carboxyl, carbonyl, ethers, alkylsulfonyl or phosphono structure division.Limiting examples can comprise polyvinyl alcohol, the Polyvinylpyrolidone (PVP) class, and the polyvinylpyridine class, polyethylene oxide, glycol or polyglycol, the poly carboxylic acid derivative, such as polyacrylic acid, polymethyl acrylate.The employed term of this paper and claims " prevention basically " is meant that polishing composition or slurry have about 5: 1, or at least 10: 1, or 100: 1 the first layer and second layer polishing selectivity.Stop the selection of compound can depend on its chemical stability, with the interaction of other component of slurry, and it is to the effect of the colloidal stability of employed any abrasive particles.
In a non-limiting embodiments, abrasive can be present in the amount of 0-20.0wt% in the slurry of the present invention, and anticorrosive agent can exist with the amount of 0-1wt%, and stops compound to exist with the amount of 0-1wt%.
In another non-limiting embodiments, this slurry can comprise dispersion agent.The limiting examples of the dispersion agent that is fit to comprises poly carboxylic acid such as polyacrylic acid, cross linked polyacrylate and polymethyl acrylic acid; Phosphonic acids is such as but not limited to alkyl phosphonic acid, arylphosphonic acid, polyphosphonic acid and alkylamino phosphonic acids; Polyamino acid is such as but not limited to poly aspartic acid.
In another non-limiting embodiments, this slurry can comprise tensio-active agent.Be suitable for tensio-active agent of the present invention and can comprise positively charged ion, negatively charged ion and nonionogenic tenside.The cats product that is fit to can include but not limited to aliphatic amine and aliphatic ammonium salt.The limiting examples of anion surfactant can comprise that carboxylate salt is such as but not limited to fatty acid soaps, the alkyl ether carboxy acid salt, and the salt of alkyl and aryl sulfonic acid is such as alkyl benzene sulphonate (ABS), the salt of alkyl naphthalene sulfonic acid and alpha-olefin sulfonic acid.The limiting examples of anion surfactant can be including, but not limited to the salt of sulphonate such as the higher alcohols sulphonate, the sulphonate salt of alkyl oxide sulfonic acid and polyoxyethylene alkyl phenyl ether.In a non-limiting embodiments, anion surfactant can comprise that phosphoric acid ester is such as but not limited to the salt of alkyl phosphate and aryl phosphate ester.The limiting examples of nonionogenic tenside can be including, but not limited to ethers such as poly-ethylidene alkyl oxide, ether-ether such as the polyoxygenated ethyleneether of glyceryl ester and ester class such as glyceryl ester, and Isosorbide Dinitrate.
In a non-limiting embodiments, slurry of the present invention can comprise stablizer.The stablizer that is fit to can comprise monoacetylaniline, and tin-oxide and free radical inhibitors are such as but not limited to inorganic and the organonitrogen oxide compound.
The dispersion agent that is fit to comprises poly carboxylic acid such as polyacrylic acid, cross linked polyacrylate and polymethyl acrylic acid; Phosphonic acids is such as alkyl phosphonic acid, arylphosphonic acid, polyphosphonic acid and alkylamino phosphonic acids; Polyamino acid is such as poly aspartic acid.
In a non-limiting embodiments, oxygenant and other non-abrasive component can be blended in the aqueous medium under shearing condition, such as deionized water or distilled water, till these components fully are dissolved in the medium.Silica can be joined in the medium then.In a non-limiting embodiments, silica can be a precipitated silica.Said composition can be scattered in flowing fluid ratio such as the water then to prepare slurry of the present invention.
In the present invention, use the amount of the copper that first slurry removes in first polishing step can be, the length of polishing time and polishing condition and alter a great deal according to the composition of first slurry.In a non-limiting embodiments, first slurry can be removed and be lower than 100% copper, makes remaining copper remain.In alternative non-limiting embodiments, first slurry can be removed 10-95% from base material, or 20-90%, or the copper of 25-85%.In another non-limiting embodiments, remaining copper can exist to the form of small part with layer or film.
Copper in the first step is removed speed and can be changed significantly according to the length of the composition of first slurry, polishing time and polishing condition.In alternative non-limiting embodiments, it can be at least 2,500 that copper in the first step is removed speed, or be lower than 10,000 dusts/minute, at least 5000 dusts/minute, or be lower than 8,000 dusts/minute.
Static etch rate in first polishing step can alter a great deal.In a non-limiting embodiments, static etch rate can be the 0-20% that copper is removed speed, or 0.1-15%, or 1-10%.
In the present invention, after first polishing step finishes substantially, can in second polishing step, use second slurry.Can need not under the situation of base material and/or polishing pad cleaning first slurry, carry out with first termination of polishing of first slurry with second startup of polishing of second slurry.
The front can be used in second slurry for described various abrasives of first slurry and their preparation method.In a non-limiting embodiments, the abrasive concentration in second slurry is lower than the abrasive concentration in first slurry.In alternative non-limiting embodiments, the abrasive concentration in second slurry can be second slurry 〉=0wt%, or≤10wt%, or 〉=0.1wt%, or 〉=1wt%, or≤5wt%.
In alternative non-limiting embodiments, the front can comprise in second slurry for the described various oxygenants of first slurry, complexing agent and other optional additive.
In a non-limiting embodiments, the composition of second slurry can be identical with the composition of first slurry, and just the abrasive concentration in second slurry is lower than the abrasive concentration in first slurry.
In another non-limiting embodiments, second slurry can not contain abrasive.
Second slurry that is used for second polishing step can be used in removal and be retained in remaining copper on the base material after first polishing step with first slurry finishes.Generally, the residual abrasive of first slurry that uses in comfortable first polishing step of the abradability and come of the slurry with low abrasive concentration or abrasive-free by the relying on polishing pad copper removal of making a return journey.In a non-limiting embodiments, the copper that uses second slurry to remove remaining copper is removed the removal speed that speed can be lower than the copper that uses first slurry.In alternative non-limiting embodiments, the copper that is used to remove remaining copper is removed below 50% of removal speed that speed can be to use the copper of first slurry, or below 35%, or below 25%, or below 10%.
In second polishing step, use the static etch rate of second slurry can be lower than the static etch rate of using first slurry.In alternative non-limiting embodiments, use the static etch rate of second slurry can be to use the 0-70% of the static etch rate of first slurry, or at least 10%, or at least 20%, or be lower than 70%.
In non-limiting embodiments, slurry of the present invention can be used in the chemical mechanical method complanation (CMP) of base material such as semiconductor wafer.In this embodiment, first slurry of the present invention can be applied on the wafer substrate, and wafer can polish by the usual manner that uses polissoir known in the art and polishing pad.Being suitable for CMP equipment of the present invention can be including, but not limited to IPEC 472, Applied Materials Mirra Mesa or Reflexion, Speedfam 676, Novellus Momentum, Lam Terres and Nikon CMP SystemNPS 2301.In addition, the selection of polishing pad can comprise the IC1400 of Rodel, is stacked on the IC1000 on the SUBAIV, the FastPad of Polytex or PPG.
In a non-limiting embodiments, first slurry of the present invention can show the low polishing speed to tantalum and other bonding coat, dielectric layer or metal level simultaneously with the two-forty polish copper.Second slurry can be put on the partially polished base material then.Second slurry can show the higher polishing speed to tantalum or other bonding coat, dielectric layer or metal level simultaneously with than the low rate polish copper.According to estimates, the selection of one or more additives can be controlled required removal speed in required high or low speed polishing special metal, bonding coat or oxide skin.
When the glossing that uses slurry of the present invention finished, base material can be with deionized water or other solvent or cleaning soln washing, so that remove polishing slurries from base material.In a non-limiting embodiments, this washing process can carry out before using second slurry.When second polishing step finished, second slurry can be washed off with base material from base material with deionized water or other solvent can prepare to be used for further processing.
In two polishing steps, polishing slurries can directly put on base material with control mode in the base material polishing process, polishing pad, or the two.In a non-limiting embodiments, this slurry can put on polishing pad, and polishing pad can be against base material, and polishing pad can move with respect to base material, to finish the base material polishing.
Slurry of the present invention and method can be used in effective polishing that required polishing speed is provided, and at utmost reduce the imperfect and defective in surface simultaneously.In addition, when hope provides high material removal rate in polishing process, keep low static etch rate when at utmost reducing the surface depression that embeds feature and abrasion simultaneously, slurry of the present invention and method can be particularly useful,
Embodiment
In the experiment of copper coin dish as metal sample of 2.4 centimetres of uses, use the weight in average loss of disk to calculate copper removal speed.Weighing polishing disk before polishing.After polishing, the difference of weighing disk, and use once more between these two values calculated because the weight loss that polishing brings.Use the weight in average loss of three disks to calculate copper removal speed.By with weight in average loss divided by the average polished time (minute) the weight in average loss of calculating per minute.The density of using the area of section of disk and copper with the loss of per minute weight in average be converted into by nanometer or dust/minute removal speed.
Use Stuers LabPol-V TMPolisher comes polishing disk.Support and the rotation of polishing block inhour, and remain under the speed of 60rpm.Disk remains on the downward force of 30N (approximately 9.8psi).The slurry that is used for the disk polishing is supplied with polisher at the center of disk with fixed flow rate.All polishing experiments are used polyurethane polishing pad.
Term as used herein " polishing pad reparation " is meant the remaining slurry and the product of the polishing of removal on polishing pad.Do not have the polishing pad reparation, because the glazing effect, polishing speed reduces.Can use various recovery technique known in the art.
SUBA is used in the reparation of polishing pad TM500 pads carry out.Polishing pad reparation order is by the cleaning of 1 minute use deionized water, the conditioning of 30 seconds use hydrogen peroxide, and 1 minute washed with de-ionized water, the conditioning of 30 seconds use citric acid and 1 minute washed with de-ionized water are formed.
Using 200 millimeters copper to cover in the experiment of (blanket) wafer and figuratum wafer, wafer uses the Westech 372M rotation CMP instrument polishing with Rodel IC1400-A2.Between each wafer polishing, carry out polishing pad conditioning (outside conditioning) with deionized water and diamond grit conditioning wheel.By International SEMATECH or Montco Silicon Technologies, the copper cover wafers that Inc. obtains is as rate monitor.The figuratum wafer of SEMATECH854-006 is used for the contour structure evaluation.All chemical are ACS SILVER REAGENT.Deionized water is used for all solution.The film thickness of copper wafer and profile are by using Prometrix
Figure C0381878900171
RS-35 four probe measurement facilities are measured with the Ambios TechnologyINC.XP-2 profilometer that the stylus with 2.5 microns radius tips is housed.
Embodiment 1
Comprise the slurry (clauses and subclauses 1) of benzotriazole, glycine and hydrogen peroxide (not adding silica) and have same composition, the slurry that just changes silica concentration compares.Slurry feed speed with 60 ml/min is polished disk 3 minutes.Digital proof, the copper that contains the sample of silica is removed the copper removal speed that speed is higher than the sample that does not contain silica.The copper of polish copper disk is removed speed and is reported in table 1.As can be seen, remove speed at the copper shown in the table 1 and be not linear reduction with the increase of silica concentration.It is believed that Zheng Ming silica concentration and copper are removed concerning to the change of small part owing to the pH of sample between the speed in the present embodiment.
Table 1
Clauses and subclauses Silica (wt%) pH log[H 3O +] Hydrogen peroxide (wt%) BTA(mM) Copper is removed speed (nm/min)
1 0 5.63 3 1 207
2 1 6.47 3 1 626
3 2 6.72 3 1 499
4 3 6.84 3 1 508
5 4 6.86 3 1 379
6 5 6.79 3 1 420
7 6 6.76 3 1 462
8 7 6.75 3 1 520
9 8 6.72 3 1 545
Embodiment 2
Comprise the solution (clauses and subclauses 1) of benzotriazole, glycine and hydrogen peroxide (not adding silica) and in similar solution, have the slurry that increases progressively silica concentration and compare.Slurry feed speed with 100 ml/min is polished disk 1 minute.Similar to the embodiment of front, digital proof, the copper that contains the sample of silica is removed the copper removal speed that speed is higher than the sample that does not contain silica.The copper of polish copper disk is removed speed and is reported in table 2.As can be seen, remove speed at the copper shown in the table 2 and be not linear reduction with the increase of silica concentration.It is believed that Zheng Ming silica concentration and copper are removed concerning to the fluctuation of small part owing to the pH of sample between the speed in the present embodiment.In addition, proved that copper removes speed and reduce with the increase of flow rate of slurry.
Table 2
Clauses and subclauses Silica (wt%) pH log[H 3O +] Hydrogen peroxide (wt%) BTA(mM) Copper is removed speed (nm/min)
1 0.0 6.08 3 1 68
2 0.1 6.34 3 1 201
3 0.2 6.49 3 1 207
4 0.3 6.65 3 1 199
5 0.5 6.79 3 1 213
6 1.0 7.02 3 1 252
7 2.0 7.14 3 1 241
8 3.0 7.21 3 1 237
9 4.0 7.25 3 1 272
10 5.0 7.39 3 1 233
Embodiment 3
Slurry in the present embodiment is similar to the embodiment 2 of front, just improves concentration of hydrogen peroxide (3-5wt%), removes speed with the copper that reduces when not having silica.Comprise the solution (clauses and subclauses 1) of benzotriazole, glycine and hydrogen peroxide (not adding silica) and in similar solution, have the slurry that increases progressively silica concentration and compare.Slurry feed speed with 60 ml/min is polished disk 3 minutes.Digital proof, the copper that contains the sample of silica is removed the copper removal speed that speed is higher than the sample that does not contain silica.In addition, the result proves, the copper of slurry that only contains the silica of 1wt% is removed speed and removed speed obviously different with the copper of the slurry that contains the 8wt% silica.The copper of polish copper disk is removed speed and is reported in table 3.
Table 3
Clauses and subclauses Silica (wt%) pH log[H 3O +] Hydrogen peroxide (wt%) BTA(mM) Copper is removed speed (nm/min)
1 0 5.67 5 1 94
2 1 6.39 5 1 400
3 2 6.61 5 1 351
4 3 6.71 5 1 332
5 4 6.67 5 1 291
6 5 6.81 5 1 279
7 6 6.74 5 1 302
8 7 6.72 5 1 325
9 8 6.68 5 1 390
Embodiment 4
Slurry is in the present embodiment just regulated the pH value according to embodiment 1 preparation, makes it to keep constant.The adjusting of pH is carried out with sulfuric acid or potassium hydroxide.Each slurry comprises glycine (1wt%), benzotriazole (1 mmole), and hydrogen peroxide (3wt%).Silica concentration under various pH values is removed the influence of speed and by the slurry feed rate with 60 ml/min the polishing of copper coin dish was estimated in 1 minute to copper.The result proves that for specific silica concentration, copper is removed speed and changed with different pH levels.The result is shown in the table 4.
Table 4
Embodiment 5
Carry out the copper polishing in two stages with 200mm copper cover wafers.These wafers comprise the metal silicon chip with a laminate film layer.This lamination is included in the thermal oxide layer (5,000 on the Pure Silicon Metal ), the tantalum metal layer (250 on thermal oxide
Figure C0381878900203
) and superincumbent copper layer (15,000
Figure C0381878900204
).In all cases, wafer polished 60 seconds with the water paste (200 ml/min) that contains silica (8wt%), benzotriazole (1 mmole), glycine (1wt%) and hydrogen peroxide (3wt%) in the fs.After this polishing fs, stop slurry stream, again with deionized water or contain benzotriazole (1 mmole), glycine (1wt%) and hydrogen peroxide (3wt%), there is not the aqueous solution of silica to continue to polish.The 4psig downward force is used in all polishings, and 1psig support counterpressure and 60rpm rotating speed of table carry out.Use Prometrix RS-35 TM4 probes are measured copper and are removed speed, and conduct is reported across the mean value of 49 measurements of wafer diameter in table 5.These results prove, have removed additional copper seldom by continue the water polishing in subordinate phase.Yet, kept effective copper to remove speed in subordinate phase by polish and rely on the residual abrasive on polishing pad with the chemical solutions that does not have abrasive from the fs.
Table 5
Figure C0381878900211
Embodiment 6
Carry out the copper polishing in two stages with 200mm copper cover wafers.These wafers comprise the metal silicon chip with a laminate film layer.This lamination is included in the thermal oxide layer (5,000 on the Pure Silicon Metal
Figure C0381878900212
), the tantalum metal layer (250 on thermal oxide
Figure C0381878900213
) and superincumbent copper layer (15,000
Figure C0381878900214
).In all cases, wafer polished 60 seconds with the water paste that contains silica (11wt%), benzotriazole (1 mmole), glycine (1wt%) and hydrogen peroxide (5wt%) in the fs.After this polishing fs, stop slurry stream, again with deionized water or contain benzotriazole, glycine and hydrogen peroxide, but there is not the aqueous solution of silica to continue polishing.Chemical constitution such change the as shown in table 6 that is used for the solution that does not contain silica in stage 2.That polishing condition and liquid pH keep during two polishing stages whole is constant (downward force 4psig, rotating speed of table 70rpm, support rotating speed 68rpm, support counterpressure 0psig, flow rate of slurry 190ml/min, pH5).Use Prometrix RS-35 TM4 probes are measured copper and are removed speed, and conduct is reported across the mean value of 49 measurements of wafer diameter in table 6.These results prove, in the present embodiment, do not remove other copper effectively by continuing polishing without silica in subordinate phase.The result proves that also the copper in the stage 2 (i.e. second polishing step) is removed speed and can not changed with the removal of the copper in the stage 1 (i.e. first polishing step) rate variations.
Table 6
Figure C0381878900221
Embodiment 7
Carry out the copper polishing in two stages with 200mm copper cover wafers.These wafers comprise the metal silicon chip with a laminate film layer.This lamination is included in the thermal oxide layer (5,000 on the Pure Silicon Metal
Figure C0381878900222
), the tantalum metal layer (250 on thermal oxide ) and superincumbent copper layer (15,000
Figure C0381878900224
).In all cases, wafer polished 60 seconds with the water paste that contains silica (11wt%), benzotriazole (1mM), glycine (1wt%) and hydrogen peroxide (5wt%) in the fs.After this polishing fs, stop slurry stream, again with containing benzotriazole, glycine and hydrogen peroxide, but there is not the aqueous solution of silica to continue to polish 60 seconds.Chemical constitution such change the as shown in table 7 that is used for the solution that does not contain silica in stage 2.That polishing condition and liquid pH keep during two polishing stages whole is constant (downward force 3psig, rotating speed of table 70rpm, support rotating speed 68rpm, support counterpressure 0psig, flow rate of slurry 190ml/min, pH5).Use Prometrix RS-35 TM4 probes are measured copper and are removed speed, and conduct is reported across the mean value of 49 measurements of wafer diameter in table 7.The result proves that the copper in the stage 2 (i.e. second polishing step) is removed speed and can not changed with the removal of the copper in the stage 1 (i.e. first polishing step) rate variations.
Table 7
Figure C0381878900231
Embodiment 8
Carry out the copper polishing in two stages with 200mm copper cover wafers.These wafers comprise the metal silicon chip with a laminate film layer.This lamination is included in the thermal oxide layer (5,000 on the Pure Silicon Metal
Figure C0381878900232
), the tantalum metal layer (250 on thermal oxide
Figure C0381878900233
) and superincumbent copper layer (15,000
Figure C0381878900234
).In all cases, wafer polished 60 seconds with the water paste that contains silica (11wt%), benzotriazole (1mM), glycine (1wt%) and hydrogen peroxide (5wt%) in the fs.After this fs polishing, stop slurry stream, contain benzotriazole (3mM), glycine (1wt%) and hydrogen peroxide (8wt%) again, but do not have the aqueous solution of silica to continue polishing.That polishing condition and liquid pH keep during two polishing stages whole is constant (downward force 3psig, rotating speed of table 70rpm, support rotating speed 68rpm, support counterpressure 0psig, flow rate of slurry 190ml/min, pH5).Each wafer polishing reaches each 2 timed interval of stage.Use Prometrix RS-35 TM4 probes are measured copper and are removed speed, and conduct is reported across the mean value of 49 measurements of wafer diameter in table 8.Data presentation, polishing pad have fully kept the abrasive from stage 1 (i.e. first polishing step) polishing condition, reach at least 4 minutes thereby keep relative constant to remove speed in the stage 2 (i.e. second polishing step).
Table 8
Figure C0381878900241
Embodiment 9
SEMATECH 854 figuratum wafers are with containing silica (11wt%), hydrogen peroxide (5wt%), the slurry polishing of glycine (1wt%) and benzotriazole (1mM) 105 seconds.With containing hydrogen peroxide (8wt%), glycine (1wt%) and benzotriazole (3mM), but there is not the liquid of silica to continue other 285 seconds of polishing.Range estimation shows, being eliminated from wafer more than 95% of copper capping layer.To several characteristic structure measurement surface depression across 9 independent matrixs (die) of the diameter of wafer surface.The average surface depression value of these feature structures is described in the table 9.The result proves, when comparing with the similar polishing of using the slurry that contains abrasive in whole polishing, uses two sections polishings of the removal copper capping layer of the reactive fluid that does not contain abrasive can reduce the linear surfaces depression in the latter half.
Table 9
Figure C0381878900242
Embodiment 10
The abrasive of Shi Yonging is by the silica of surface modification with the dichlorodimethylsilane reaction in the present embodiment.SEMATECH 854 figuratum wafers are with containing surface modification silica (11wt%), hydrogen peroxide (5wt%), the slurry polishing of glycine (1wt%) and benzotriazole (1mM) 95 seconds.With containing hydrogen peroxide (8wt%), glycine (1wt%) and benzotriazole (3mM), but there is not the liquid of surface modification silica to continue other 275 seconds of polishing.Range estimation shows, being eliminated from wafer more than 95% of copper capping layer.To several characteristic structure measurement surface depression across 9 independent matrixs (die) of the diameter of wafer surface.The average surface depression value of these feature structures is described in the table 10.The result proves, when comparing with the similar polishing of using unmodified abrasive, uses surface modified abrasives can further reduce the linear surfaces depression in the fs of copper polishing.For a data presentation that 50_50 micron feature structure is obtained in the intermediary matrix (die) of wafer radius, in the second liquor finish stage surface depression of polishing after 215 seconds be after 275 seconds end value about 52%.These data show that this multi-stage method has the wide excessive polishing time limit.
Table 10
Figure C0381878900251
Embodiment 11
SEMATECH 854 figuratum wafers are with containing silica (11wt%), and hydrogen peroxide (4wt%), the water paste of glycine (1wt%) and benzotriazole (1mM) use the downward force of 4.5psig to polish 105 seconds.Continue to polish other 90 seconds with the downward force of identical water paste with 1psig.Range estimation shows, being eliminated from wafer more than 95% of copper capping layer.To several characteristic structure measurement surface depression across 3 independent matrixs (die) of the radius of wafer surface.The average surface depression value of these feature structures is described in the table 11.These results prove that wherein polishing condition only relents gradually by reducing mechanical force, but use two sections polishings of removing copper capping layer of the slurry that contains silica to produce more surface depression in whole polishing process.
Table 11 is untreated
Figure C0381878900252
Embodiment 12
The abrasive that uses in the slurry of present embodiment is by the silica of surface modification with the dichlorodimethylsilane reaction.SEMATECH 854 figuratum wafers are with containing surface modification silica (11wt%), and hydrogen peroxide (5wt%), the slurry of glycine (1wt%) and benzotriazole (1mM) use the downward force of 3.5psig to polish 90 seconds.Continue to polish other 120 seconds with the downward force of identical water paste with 1psig.Range estimation shows, being eliminated from wafer more than 95% of copper capping layer.To several characteristic structure measurement surface depression across 3 independent matrixs (die) of the radius of wafer surface.The average surface depression value of these feature structures is described in the table 12.These results prove that wherein polishing condition only relents gradually by reducing mechanical force, but use two sections polishings of removing copper capping layer of the slurry that contains silica to produce more surface depression in whole polishing process.
Table 12
The static etch rate of the slurry that in polishing embodiment, uses
Embodiment 13
With pH5 contain silica (11wt%), hydrogen peroxide (4wt%), the slurry (400ml) of glycine (1wt%) and benzotriazole (1mM) is poured glass dish (30 * 22 * 6cm) into.This slurry stirs with magnetic bar, and uses the Nuova that comes from Thermolyne Company TMHeatable agitating plate heating.Attemperation makes it to equilibrate to 23 ℃ (measuring with thermometer (10 ℃ to 100 ℃ scopes)).Stop to stir slurry.At the TR-2102 that comes from Denver Instruments TMPre-weighing 200mm copper cover wafers drops in the slurry again on the balance.After placing 20 minutes, from slurry, take out wafer, use deionized water rinsing, with the Virahol flushing, drying is weighed with same balance more again.By coming the gravimetry loss at the weight difference of weighing in advance and weighing again between the wafer.Wafer weight loss is 140mg, corresponding to 250
Figure C0381878900262
The copper thickness loss of/min.
Embodiment 14
With pH5 contain silica (11wt%), hydrogen peroxide (4wt%), the slurry (400ml) of glycine (1wt%) and benzotriazole (1mM) is poured glass dish (30 * 22 * 6cm) into.This slurry stirs with magnetic bar, and uses the Nuova that comes from Thermolyne Company TMHeatable agitating plate heating.Attemperation makes it to equilibrate to 55 ℃ (measuring with thermometer (10 ℃ to 100 ℃ scopes)).Stop to stir slurry.At the TR-2102 that comes from Denver Instruments TMPre-weighing 200mm copper cover wafers drops in the slurry again on the balance.After placing 5 minutes, from slurry, take out wafer, use deionized water rinsing, with the Virahol flushing, drying is weighed with same balance more again.By coming the gravimetry loss at the weight difference of weighing in advance and weighing again between the wafer.Wafer weight loss is 100mg, corresponding to 710
Figure C0381878900271
The copper thickness loss of/min.
Embodiment 15
With pH5 contain hydrogen peroxide (8wt%), the slurry (400ml) of glycine (1wt%) and benzotriazole (3mM) is poured glass dish (30 * 22 * 6cm) into.This slurry stirs with magnetic bar, and uses the Nuova that comes from Thermolyne Company TMHeatable agitating plate heating.Attemperation makes it to equilibrate to 23 ℃ (measuring with thermometer (10 ℃ to 100 ℃ scopes)).Stop to stir slurry.At the TR-2102 that comes from Denver Instruments TMPre-weighing 200mm copper cover wafers drops in the slurry again on the balance.After placing 20 minutes, from slurry, take out wafer, use deionized water rinsing, with the Virahol flushing, drying is weighed with same balance more again.By coming the gravimetry loss at the weight difference of weighing in advance and weighing again between the wafer.Wafer weight loss is 10mg, corresponding to 18
Figure C0381878900272
The copper thickness loss of/min.
Embodiment 16
With pH5 contain hydrogen peroxide (8wt%), the slurry (400ml) of glycine (1wt%) and benzotriazole (3mM) is poured glass dish (30 * 22 * 6cm) into.This slurry stirs with magnetic bar, and uses the Nuova that comes from Thermolyne Company TMHeatable agitating plate heating.Attemperation makes it to equilibrate to 55 ℃ (measuring with thermometer (10 ℃ to 100 ℃ scopes)).Stop to stir slurry.At the TR-2102 that comes from Denver Instruments TMPre-weighing 200mm copper cover wafers drops in the slurry again on the balance.After placing 5 minutes, from slurry, take out wafer, use deionized water rinsing, with the Virahol flushing, drying is weighed with same balance more again.By coming the gravimetry loss at the weight difference of weighing in advance and weighing again between the wafer.Wafer weight loss is 10mg, corresponding to 71
Figure C0381878900273
The copper thickness loss of/min.

Claims (26)

1. be used for removing the slurry system of metal and/or silicon-dioxide, comprise from base material:
(a) contain first slurry that abrasive and preparation are used for removing from described base material top described metal, described abrasive is the silica of dichlorodimethylsilane surface modification; With
(b) preparation is used for further removing from described base material second slurry of described metal,
Wherein said first slurry has higher abrasive concentration than described second slurry.
2. the slurry system of claim 1, wherein said metal is selected from copper, tantalum or their mixture.
3. the slurry system of claim 1, wherein said metal is a copper.
4. the slurry system of claim 1, wherein said second slurry does not contain abrasive.
5. the slurry system of claim 1, wherein said abrasive exists with the amount of the 0.1-30wt% of described first slurry.
6. the slurry system of claim 4, wherein said silica has the aggregate of primary particle, and described primary particle has the mean diameter of at least 7 nanometers, and wherein said aggregate has the aggregate size less than 1 micron; The hydroxy radical content of at least 7 hydroxyl/square nanometers.
7. the slurry system of claim 1, at least a oxygenant that further comprises of wherein said first and second slurries.
8. the slurry system of claim 7, wherein said oxygenant is selected from inorganic and organo-peroxide, bromic acid, chloric acid, nitrate, vitriol, or their mixture.
9. the slurry system of claim 7, wherein said oxygenant is selected from hydrogen peroxide, urea-hydrogen peroxide, or their mixture.
10. the slurry system of claim 1, at least a material that is selected from complexing agent, anticorrosive agent, prevention compound, polyvalent cation sequestrant, thickening material or their mixture that further comprises of wherein said first and second slurries.
11. the slurry system of claim 1, be selected from pyridine carboxylic acid at least a further the comprising of wherein said first and second slurries, pyridine dicarboxylic acid, the acid in quinolinic acid and their mixture.
12. the slurry system of claim 1, at least a polyvalent cation sequestrant and the anticorrosive agent of further comprising of wherein said first and second slurries.
13. the slurry system of claim 1, at least a polyvalent cation sequestrant that further comprises of wherein said first and second slurries, anticorrosive agent, and thickening material.
14. the slurry system of claim 1, wherein said first slurry has stayed kish on described base material.
15. the slurry system of claim 3, wherein said first slurry has stayed remaining copper on described base material.
16. the slurry system of claim 14, wherein said second slurry is from having removed described remaining copper to small part on the described base material.
17. the slurry system of claim 15, wherein said second slurry is from having removed described remaining copper to small part on the described base material.
18. be used to remove the method for copper, comprise:
(a) first slurry that will contain abrasive puts on the base material, and described abrasive is the silica of dichlorodimethylsilane surface modification;
(b) second slurry is put on the described base material,
Wherein said first slurry has the described abrasive of greater concn than described second slurry.
19. the method for claim 18, wherein said first slurry gets on except the described copper of a part from described base material, and has stayed remaining copper on described base material.
20. the method for claim 18, wherein said second slurry is from having removed described remaining copper to small part on the described base material.
21. be used for the method for polish microelectronic base material, comprise:
(a) carry out first polishing with first slurry and polishing pad, wherein said first slurry contains abrasive, and described abrasive is the silica of dichlorodimethylsilane surface modification; With
(b) carry out second polishing with second slurry and polishing pad, wherein said first slurry has the described abrasive of greater concn than described second slurry.
22. the method for claim 21, wherein said first polishing are provided for described metal and/or the silicon-dioxide removing metal and/or silicon-dioxide from described base material top and stayed lingering section at described base material.
23. the method for claim 22, wherein said second polishing is provided for from remove the metal of this lingering section on the described base material to small part.
24. the method for claim 22, wherein said metal is selected from copper and tantalum.
25. the method for claim 21, wherein said first polishing was finished before applying described second slurry.
26. the method for claim 21 further is included in the step that described first polishing is finished afterwards and washed described base material before the described second polishing beginning.
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