CN101440259B - Metal polishing solution and polishing method - Google Patents
Metal polishing solution and polishing method Download PDFInfo
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- CN101440259B CN101440259B CN2008101869292A CN200810186929A CN101440259B CN 101440259 B CN101440259 B CN 101440259B CN 2008101869292 A CN2008101869292 A CN 2008101869292A CN 200810186929 A CN200810186929 A CN 200810186929A CN 101440259 B CN101440259 B CN 101440259B
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Abstract
The invention provides an abrasive liquid for a metal and abrading method. The abrasive liquid for a metal comprises (1) an oxidizing agent for a metal, (2) a dissolving agent for an oxidized metal, (3) a first protecting film-forming agent such as an amino acid or an azole which adsorbs physically on the surface of the metal and/or forms a chemical bond, to thereby form a protecting film, (4) a second protecting film-forming agent such as polyacrylic acid, polyamido acid or a salt thereof which assists the first protecting film-forming agent in forming a protecting film and (5) water.
Description
The application is that international application no is PCT/JP99/04694, and national applications number is: 99812776.0, and the applying date is on August 31st, 1999, invention and created name is: the dividing an application of the application for a patent for invention of metal polishing slurry and Ginding process.
Technical field
The invention relates in the grinding in the distribution forming process of semiconductor device metal polishing slurry that is particularly suitable for using and Ginding process.
Background technology
In recent years, follow highly integrated, the high performance of semiconductor integrated circuit (below, be called LSI), developing new Micrometer-Nanometer Processing Technology.Cmp (below, be called CMP) method also is wherein a kind of, is in the LSI manufacture process, the particularly planarization of the interlayer dielectric in multilayer wired forming process, metallic plug form, imbed distribution form in the frequent technology of using.This technology, for example open in No. 4944836 communique of United States Patent (USP).
In addition, in order to make the LSI high performance, just attempting utilizing copper alloy recently as wiring material.But copper alloy is difficult to be utilized in the dry corrosion method of frequently using in the formation of aluminium alloy distribution in the past and carries out microfabrication.Therefore; Mainly be employed on the dielectric film that is pre-formed ditch and pile up copper alloy thin films and imbed; To utilize CMP to remove the copper alloy thin films beyond the ditch portion, form so-called Damascus wave pattern (damascen) method of imbedding distribution. this technology is for example opened in the flat 2-278822 communique open the spy.
The conventional method of the CMP of metal is that fixed abrasive pad is gone up on the grinding chassis (pressure nog plate) in circle; Flood grinding pad with metal polishing slurry; Compress the face of the metal film that forms matrix, make with the state of the pressure that applies regulation (below, be called grinding pressure) from its inside and grind the chassis rotation; Utilize the mechanical friction of the protuberance of lapping liquid and metal film, remove the method for the metal film of protuberance.
The metal polishing slurry that in CMP, uses generally is made up of oxidant and solid abrasive particles, as required, can also add oxidized metal dissolving agent, diaphragm formation agent.Be considered at first make the metallic film surface oxidation, utilize solid abrasive particles to grind off the fundamental mechanism of this oxide layer through oxidation.The oxide layer of the metal surface of recess not too contacts grinding pad, does not reach the effect of utilizing solid abrasive particles to grind off, therefore along with the carrying out of CMP, removes the metal level of protuberance, makes the matrix surface planarization.About this details, described 3460～3464 pages of Journal of eletrochemical society magazine the 138th volume No. 11 (distribution in 1991).
If utilize the particle of the metal oxide that solid abrasive particles grinds off to be dissolved in the lapping liquid through oxidized metal dissolving agent.Just increase the effect of utilizing solid abrasive particles to grind off.But the oxide layer of the metallic film surface of recess is also dissolved (below, be called corrosion); When metallic film surface was exposed, because oxidant makes the further oxidation of metallic film surface, and it was when carrying out repeatedly; Also carried out the corrosion of the metal film of recess, therefore the impaired worry of planarization effect has just been arranged.In order to prevent that the planarization effect from suffering damage, add diaphragm again and form agent.The effect balance that reaches oxidized metal dissolving agent and diaphragm formation agent is very important, and the particulate efficiency of the oxide layer that hope that the oxide layer of metallic film surface not too is corroded, grinds off grinding rate dissolved well, that utilize CMP is big.
Like this, form the effect that agent increases chemical reaction with diaphragm, when improving the CMP speed grinding rate of CMP generation (promptly by), also obtain lowering the effect of the damage of the layer on surface of metal that causes by CMP through adding oxidized metal dissolving agent.
But; The metal polishing slurry that contains solid abrasive particles in the past in use; When utilizing the imbedding distribution and form of CMP, the problem below producing: each takes place to identical corrosion in the surperficial middle body of the metal wiring that (1) is imbedded, and the low-lying phenomenon (below be called hollow bent) as plate appearance takes place; (2) take place to hinder (scratch) from the grinding of solid abrasive particles; (3) the clean process that is used to remove the solid abrasive particles that remains in the matrix surface after the grinding is complicated; And (4) result from the cost of solid abrasive particles itself or the cost raising of liquid waste processing etc.
For suppress hollow bent or grind in the burn into of copper alloy form the high LSI distribution of reliability, advocate the method for using the metal polishing slurry that contains the oxidized metal dissolving agent that constitutes by amion acetic acid such as glycine or sulfamic acid and BTA (below be called BTA).This technology is for example opened in the flat 8-83780 communique on the books the spy.
But it is very high that the diaphragm of BTA forms effect, thereby corrosion rate not only, and grinding rate also reduces significantly.Therefore, hope in metal polishing slurry, to use and fully reduce corrosion rate, and do not reduce the diaphragm formation agent of CMP speed.
Disclosure of an invention
Fully reduce corrosion rate though the present invention provides, keep high CMP speed, and can form the metal polishing slurry of imbedding figure and the Ginding process of the high metal film of reliability.
Metal polishing slurry of the present invention contains the oxidant, oxidized metal dissolving agent, the 1st diaphragm that are useful on the oxidized metal and forms agent, forms agent different formation agent of the 2nd diaphragm and water with the 1st diaphragm.
It is that the diaphragm that forms diaphragm in the metal surface forms agent that diaphragm forms agent.
Form agent as the 1st diaphragm, preferably be selected from nitrogen-containing compound and salt thereof such as ammonia, alkylamine, amino acid, imines, azoles, and at least a in mercaptan, glucose and the cellulose.It is the compound that forms diaphragm through absorption and/or the chemical key of formation at metallic film surface physics that these the 1st diaphragms form agent.
Form agent as the 2nd diaphragm, preferably be selected from least a in alcohol (compound that promptly has alcohol hydroxyl group), phenol (compound that promptly has phenol property hydroxyl), ester, ether, polysaccharide, amino-acid salt, polycarboxylic acids and salt, ethylene-based polymer, sulfonic acid and salt thereof, aromatic amine, acid amides, azo-compound and the molybdenum compound.These the 2nd diaphragms form agent, are that auxiliary the 1st diaphragm forms the compound that agent forms diaphragm.
Preferably be selected from least a in hydrogen peroxide, nitric acid, periodic acid potassium, hypochlorous acid and the Ozone Water as oxidant.
As oxidized metal dissolving agent, preferably be selected from least a in organic acid, organic acid ammonium salt and the sulfuric acid.
The present invention provides; When the 2nd diaphragm in not containing diaphragm formation agent forms agent; Make corrosion rate be suppressed at the interpolation concentration A of necessary the 1st diaphragm formation of the effect agent below the 10nm/min with respect to performance; Form agent through adding the 2nd diaphragm, the 1st diaphragm that contains the low concentration that is lower than above-mentioned concentration forms agent, can show the metal polishing slurry that makes corrosion rate be suppressed at the effect below the 10nm/min.That is, in the case, it is in order to make corrosion rate be suppressed at the compound that necessary the 1st diaphragm below the 10nm/min forms the addition minimizing of agent that the 2nd diaphragm forms agent.
Ginding process of the present invention is a Ginding process of in the metal polishing slurry of the invention described above, removing the metal film on grinding charge surface through grinding.For the metal film of removing object, copper, copper alloy, Cu oxide, copper alloy oxide etc. are suitable.Therefore; The present invention provides; Use above-mentioned metal polishing slurry, contain the process of the metal film that the stacked film that is selected from least a metal level in copper, copper alloy, Cu oxide and the copper alloy oxide constitutes, remove the Ginding process of at least a portion of metal film through grinding.
The present invention provides, and forms agent through different the 1st and the 2nd diaphragms of combinatorial property, has both kept CMP speed, fully reduces the lapping liquid of corrosion rate again and uses the Ginding process of this lapping liquid.The 1st diaphragm forms agent can use the compound that generates chelating coordination thing with copper easily, for example uses ethylenediamine tetra-acetic acid, BTA etc.It is extremely strong that their metal surface protection film forms effect, and for example in metal polishing slurry, if contain 0.5 weight % when above, much less tin-copper alloy film is corroded, and CMP also loses.
In contrast, the inventor finds, forms the 2nd different diaphragm of agent with the 1st diaphragm and forms agent through using simultaneously, reduces also to be suppressed to abundant low corrosion rate when the 1st diaphragm forms the interpolation concentration of agent.And know, under the situation of using such lapping liquid,, also can obtain the not too low such optkmal characteristics of CMP speed even corrosion rate is low.In addition also find, form agent and the 2nd diaphragm formation agent through using the 1st diaphragm simultaneously, in lapping liquid, do not contain under the prerequisite of solid abrasive particles, the grinding under the CMP of practicality speed becomes possibility.Think that this is because with to grind off effect by in the past solid abrasive particles fricative opposite, found to be ground off by the fricative of grinding pad.
Knew already,,, just can obtain best planarization effect if can be suppressed at below the 10nm/min as the value of the corrosion rate that should suppress.If the reduction of CMP speed is the scope that can allow; That hope is the lower person of corrosion rate; If can be suppressed at below the 5nm/min; Even, for example carry out about 50% superfluous CMP (carry out CMP remove metal film 1.5 times CMP between in case of necessity), hollow song also rests on unquestioned degree.And then if corrosion rate can be suppressed at below the 1nm/min, even carry out the superfluous CMP more than 100%, hollow song does not become problem yet.
Corrosion rate in this manual; Be that grinding charge is immersed in the lapping liquid; 25 ℃ of liquid temperature; The speed that the metal film on grinding charge when mixing speed 100r/min stirs surface (copper film that utilizes sputter to form) is corroded, and be poor from the convert thickness of metal film obtained before and after the dipping of resistance value, the speed of obtaining divided by the thickness of metal film difference with dip time.
In addition, CMP speed (being cmp speed) is at grinding pressure 210g/cm
2, grinding charge and grinding chassis the condition of 25 ℃ of relative velocity 36m/min, liquid temperature under; Grind the metal film (copper film that utilizes sputter to form) on grinding charge surface; Poor from the convert thickness of metal film obtain before and after the dipping of resistance value, as to obtain divided by the film thickness difference with processing time speed.
According to the present invention, different with only with the lapping liquid of the 1st diaphragm formation agent, do not relying under the strong mechanical friction condition that produces by solid abrasive particles, utilize friction can realize cmp planarizationization more than the soft grinding pad of above-mentioned friction.
And then the present invention provides, and uses metal polishing slurry of the present invention, grinds on the surface has the matrix of recess to form. filling contains the Ginding process of the matrix of copper, copper alloy metal films such as (copper/chromium etc.).If use lapping liquid of the present invention that such matrix is carried out cmp (CMP), the metal film of matrix protuberance at recess kish film, thereby obtains desirable conductor fig with regard to optionally carrying out cmp.In lapping liquid of the present invention, it is also passable not contain solid abrasive particles in fact, utilizes more than the friction of the soft mechanical grinding cushion of solid abrasive particles and carries out cmp, thereby make grinding hinder rapid the attenuating.
Metal polishing slurry of the present invention forms agent, the formation agent of the 2nd diaphragm and water as necessary composition with oxidant, oxidized metal dissolving agent, the 1st diaphragm.Can not contain solid abrasive particles in fact, also can use.
Then, the concrete example that is included in each composition in the metal polishing slurry of the present invention is described.
The oxidant of metal can be enumerated hydrogen peroxide (H
2O
2), nitric acid, periodic acid potassium, hypochlorous acid, Ozone Water etc.At matrix is when comprising integrated circuit with the silicon substrate of element; Hoping does not have the pollution by generations such as alkali metal, alkaline-earth metal, halide; Thereby hope it is the oxidant that does not contain nonvolatile component; But because the composition of Ozone Water is fierce over time, in the oxidant of enumerating more than therefore, hydrogen peroxide preferably.But, be when not containing the glass substrate etc. of semiconductor element,, also to have no relations even contain the oxidant of nonvolatile component at the matrix that uses object.
Oxidized metal dissolving agent hopes it is water miscible oxidized metal dissolving agent.In the agent of water soluble oxidized dissolving metal; Can enumerate formic acid, acetate, propionic acid, butyric acid, valeric acid, 2-Methyl Butyric Acid, n-caproic acid, 3; Organic acids such as 3-acid dimethyl, 2 Ethylbutanoic acid, 4-methylvaleric acid, positive enanthic acid, 2 methyl caproic acid, caprylic acid, 2 ethyl hexanoic acid, benzoic acid, glycolic, salicylic acid, glyceric acid, oxalic acid, malonic acid, butanedioic acid, glutaric acid, adipic acid, pimelic acid, maleic acid, phthalic acid, malic acid, tartaric acid, citric acid, ammonium salt classes such as these organic acid ammonium salts or ammonium persulfate, ammonium nitrate, ammonium chloride; Inorganic acid such as sulfuric acid, chromic acid, and ammino compound etc.They can use separately, also can make up any use.
For the stacked film that contains the metal level that is made up of copper, copper alloy, Cu oxide and/or copper alloy oxide, wherein, formic acid, malonic acid, malic acid, tartaric acid, citric acid are suitable.These acid obtain with after be preferred on the balance of the 1st and the 2nd diaphragm formation agent stated.Especially, with regard to malic acid, tartaric acid, citric acid, both keeping practical CMP speed, it is preferred can suppressing the corrosion rate aspect again effectively.
Form agent as the 1st diaphragm, can enumerate ammonia; The amine of alkylamines such as dimethylamine, trimethylamine, triethylamine, propane diamine or ethylenediamine tetra-acetic acid (being designated hereinafter simply as EDTA), sodium diethyldithiocarbamate and shitosan etc.; Amion acetic acid, L-alanine, Beta-alanine, L-2-reanal, L-norvaline, L-valine, L-leucine, L-nor-leucine, L-isoleucine, the other leucine of L-, L-phenylalanine, L-proline, methyl amimoacetic acid, L-ornithine, L-lysine, taurine, L-serine, L-threonine, L-allothreonine, L-homoserine, L-tyrosine, 3; 5-two iodo-L-tyrosine, β-(3, the 4-dihydroxyphenyl)-L-alanine, L-tyrotoxin, 4-hydroxyl-L-proline, L-cysteine, L-methionine, L-ethionine, L-lanthionine, L-cystathionine, L-cystine, L-cysteic acid, L-aspartic acid, L-glutamic acid, S-(carboxymethyl)-L-cysteine, 4-reanal, L-asparagine, L-glutamine, azaserine, L-arginine, L-canavanine, L-citrulling, δ-hydroxyl-L-lysine, creatine, L-kynurenin, L-histidine, 1-methyl-L-histidine, 3-methyl-L-histidine, ergothioneine, L-tryptophan, act-C
1, amino acid such as A Baan acid (ア パ ミ Application), angiotensin I, angiotensin II and anti-papain; Dithizone, diquinoline (2,2 '-two quinoline), new diquinoline (2,9-dimethyl-1,10-phenanthroline), crust rope diquinoline (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline) and ball promonta (キ ユ ペ ラ ゾ Application) imines such as (bicyclohexanone oxalyl hydrazones); Benzimidazolyl-2 radicals-mercaptan, 2-[2-(benzothiazolyl)] propane thioic acid, 2-[2-(benzothiazolyl)] Thiobutyric acid, 2-mercaptobenzothiazole, 1; 2,3-triazole, 1,2; 4-triazole, 3-amino-1H-1; 2,4-triazole, BTA, I-hydroxybenzotriazole, 1-dihydroxypropyl BTA, 2,3-dicarboxyl propyl group BTA, 4-hydroxybenzotriazole, 4-carboxyl-1H-BTA, 4-methoxycarbonyl-1H-BTA, 4-butoxy-1H-BTA, 4-carbonyl octyloxy-1H-BTA, 5-hexyl BTA, N-(1; 2; 3-BTA quinoline base-1-methyl)-azoles such as N-(1,2,4-triazoline base-1-methyl)-2 ethyl hexylamine, tolytriazole, aphthotriazoles, two [(1-BTA quinoline base) methyl] phosphonic acids; The ninth of the ten Heavenly Stems mercaptan such as mercaptan, dodecyl mercaptans, triazine thiol, triazine two mercaptan, triazine three mercaptan; And carbohydrate such as glucose, cellulose.They can use separately, also can appropriate combination use.
Wherein, At high CMP speed and low corrosion rate and cubic plane, be good with shitosan, ethylenediamine tetra-acetic acid, L-tryptophan, ball promonta (キ ユ ペ ラ ゾ Application), triazine two mercaptan, BTA, 4-hydroxybenzotriazole, 4-carboxyl-1H-BTA butyl ester, tolytriazole and aphthotriazoles.Especially, BTA and derivative thereof are best.For benzotriazole derivatives, can enumerate above-mentioned azoles etc.
Form agent as the 2nd diaphragm; Can enumerate 1-propyl alcohol, 2-propyl alcohol, 2-propylidene-1-alcohol, allyl alcohol, ethylidene cyanhydrin, 1-butanols, 2-butanols, (S)-(+)-2-butanols, 2-methyl isophthalic acid-propyl alcohol, the tert-butyl alcohol, perfluor-tert-butyl alcohol, crotonyl alcohol, 1-amylalcohol, 2; 2-dimethyl-1-propyl alcohol, 2-methyl-2-butanols, 3-methyl isophthalic acid-butanols, sec-amyl alcohol, 1-hexanol, 4-hydroxy-4-methyl-2-amylalcohol, 4-methyl-2-amylalcohol, cyclohexanol, DL-3-hexanol, 1-enanthol, 2-Ethylhexyl Alcohol, (S)-(+)-sec-n-octyl alcohol, 1-octanol, DL-octanol, 2-hydroxy-benzyl alcohol, 2-nitrobenzyl alcohol, 3; 5-dihydroxy-benzyl alcohol, 3; 5-dinitro benzylalcohol, 3-fluoro benzylalcohol, 3-hydroxy-benzyl alcohol, 4-fluoro benzylalcohol, 4-hydroxy-benzyl alcohol, benzylalcohol, (trifluoromethyl) benzylalcohol, an aminobenzyl alcohol, m-nitrobenzyl alcohol, adjacent aminobenzyl alcohol, adjacent hydroxy-benzyl alcohol, to hydroxy-benzyl alcohol, to nitrobenzyl alcohol, 2-(to fluorophenyl) ethanol, 2-aminobenzene ethanol, 2-methoxyl group benzylalcohol, 2-methyl-3-nitro benzylalcohol, 2-xylyl alcohol, 2-nitrobenzene ethanol, 2-phenylethanol, 3,4-dimethyl benzyl alcohol, 3-methyl-2-nitrobenzyl alcohol, 3-methyl-4-nitrobenzyl alcohol, 3-xylyl alcohol, 4-fluorobenzene ethanol, 4-hydroxyl-3-methoxyl group benzylalcohol, 4-methoxyl group benzylalcohol, 4-methyl-3-nitro benzylalcohol, 5-methyl-2-nitrobenzyl alcohol, DL-α-hydroxyethylbenzene, neighbour's (trifluoromethyl) benzylalcohol, to (trifluoromethyl) benzylalcohol, equal amido phenenyl alcohol, tyrosol, to the alcohols of xylyl alcohol and sec-phenethyl alcohol etc.; Phenols such as 4-methylphenol, 4-ethyl-phenol and 4-propionitrile phenol; Esters such as glyceride, dehydration minashi sugar alcohol ester, methoxyacetic acid, ethoxyacetic acid, 3-ethoxy-propionic acid and alanine ethyl ester; Polyethylene glycol; Polypropylene glycol; Polytetramethylene glycol; Polyethylene glycol alkyl ether; The polyethylene glycol alkenyl ether; The alkyl polyethylene glycol; The alkyl polyethylene glycol alkyl ether; Alkyl polyethylene glycol alkenyl ether; The alkenyl polyethylene glycol; The alkenyl polyethylene glycol alkyl ether; Alkenyl polyethylene glycol alkenyl ether; The polypropylene glycol alkyl ether; The polypropylene glycol alkenyl ether; Alkyl polypropylene glycol; The alkyl polypropylene glycol alkyl ether; The alkyl polypropylene glycol alkenyl ether; The alkene polypropylene glycol; Ethers such as alkenyl polypropylene glycol alkyl ether and alkenyl polypropylene glycol alkenyl ether; Alginic acid, tartaric acid, carboxymethyl cellulose, coagulate polysaccharides such as polysaccharide (カ-De ラ Application) and pullulan; Amino-acid salts such as glycine ammonium salt and glycine sodium salt; Poly-aspartate, polyglutamic acid, polylysine, polymalic acid, polymethylacrylic acid, ammonium polymethacrylate salt, sodium polymethacrylate salt, polyamic acid, poly, gather itaconic acid, gather fumaric acid, gather polycarboxylic acids and salt thereof such as (to the styrene carboxylic acid), polyacrylic acid, polyacrylamide, amino polyacrylamide, ammonium polyacrylate salt, polyacrylic acid sodium salt, polyamic acid ammonium salt, polyamic acid sodium salt and metacetaldehyde acid; Ethylene-based polymers such as polyvinyl alcohol, polypropylene pyrrolidones and polyacrolein; Sulfonic acid and salt thereof such as N-methyltaurine ammonium salt, N-methyltaurine sodium salt, sulfuric acid methyl sodium salt, sulfuric acid ethyl ammonium salt, sulfuric acid butyl ammonium salt, vinyl sulfonic acid sodium salt, 1-allyl sulphonic acid sodium salt, 2-allyl sulphonic acid sodium salt, methoxy sulfonate sodium, ethoxyl methyl sulfonic acid ammonium salt, 3-ethoxycarbonyl propyl sulfonate sodium and sulfosuccinic acid sodium salt; Aniline, N, aromatic amines such as accelerine and benzyl amine; Propionamide, acrylamide, methyl urea, niacinamide, succinamide, phenylacetic acid acid amides, pyridine-4-カ Le ボ キ サ ミ De, N ', acid amides such as N-dibenzyl-L-tartaric acid acid amides and sulfanilamide (SN); 1 '; 1-azo two (cyclohexane-1-nitrile), 1 ', 1-azo two (1-acetoxyl group-1-diphenylphosphino ethane), 2 ', 2-azo two (2; 4-dimethyl-valeronitrile), 2; 2 '-azo two (4-methoxyl group-2,4-dimethyl-valeronitrile), 2, two (isobutyric acid) dimethyl esters, 2 of 2 '-azo; 2 '-azo two (isobutyronitriles), [2-(3 for 2-; 5-dibrominated pyridine radicals) azo]-5-dimethylaminobenzoic acid, 4,4 '-azo two (4-cyanopentanoic acids), 4, azo-compounds such as 4 '-azoxydianisole, azoxy methylmethane, azo group benzene, azoxy benzene, azo-dicarboxylic acid amides, diisopropyl azo-2-carboxylic acid, azo-2-carboxylic acid two (tert-butyl ester), azophenlyene, peacock green, methyl orange, Congo red and gentian violet; And molybdenum compounds such as molybdenum (VI) acid disodium dihydrate and the sour six ammonium tetrahydrates of seven molybdenums (VI) etc.These compounds can use separately, also can appropriate combination use.
Under the situation that employed matrix is a semiconductor integrated circuit with silicon substrate etc., hope the pollution that do not produce, thereby hope it is acid or its ammonium salt by alkali metal, alkaline-earth metal, halide etc.But, be under the situation of glass substrate etc. at matrix, should restriction.
Wherein, At high CMP speed and low corrosion rate and cubic plane; With 2-methyl-3-nitro benzylalcohol, polypropylene glycol, poly-aspartate, polymalic acid, polyacrylic acid, polymethylacrylic acid, ammonium polyacrylate, ammonium polymethacrylate, polyamic acid, polyamic acid ammonium, polyacrylamide, N-methyltaurine sodium, benzylamine, niacinamide, P-aminobenzene-sulfonamide, Congo red, sour six ammonium tetrahydrates of seven molybdenums (VI) is good; Especially, polyacrylic acid, polymethylacrylic acid, polyamic acid, ammonium polyacrylate, ammonium polymethacrylate, polyamic acid ammonium and polyacrylamide are best.
As the metal film that the present invention is suitable for, be to comprise at least a stacked film that is selected from copper, copper alloy, Cu oxide and the copper alloy oxide (below, these merging are called copper alloy).
In addition, CMP speed is provided is that 100nm/min is above, corrosion rate is the metal polishing slurry below the 10nm/min in the present invention.Lapping liquid with such characteristic; According to the present invention is first realization; The oxidant, oxidized metal dissolving agent and the water that contain metal cooperate with the 2nd diaphragm formation agent different with the 1st diaphragm formation agent through making up the 1st diaphragm formation agent again, just can accomplish.
Below, illustrate and form combination that agent and the 2nd diaphragm form agent with the 1st diaphragm that can use and form agent/the 2nd diaphragm as the 1st diaphragm and form agent.These combinations only are simple illustrations, and the present invention does not receive the restriction of these combinations.As required, also can use other suitable combinations.
CMP speed is more than the 100nm/min as forming, corrosion rate is the combination below the 10nm/min; For example, can enumerate ball promonta/polymalic acid, ball promonta/poly-aspartate, ball promonta/polyacrylamide, L-tryptophan/polyacrylamide, L-tryptophan/ammonium polyacrylate, L-tryptophan/polymalic acid, BTA/polyacrylamide, BTA/ammonium polyacrylate, aphthotriazoles/polymalic acid, aphthotriazoles/2-methyl-3-nitro benzylalcohol, triazine two mercaptan/poly-aspartate, triazine two mercaptan/polyacrylamide etc.
In addition; CMP speed is more than the 100nm/min as forming, corrosion rate is the combination below the 1nm/min; For example, can enumerate ball promonta/polyacrylamide, L-tryptophan/polyacrylamide, L-tryptophan/ammonium polyacrylate, BTA/polyacrylamide, BTA/ammonium polyacrylate, aphthotriazoles/polymalic acid, triazine two mercaptan/poly-aspartate, triazine two mercaptan/polyacrylamide etc.
More than CMP speed 250mm/min, the combination below the corrosion rate 10nm/min can be enumerated ball promonta/polymalic acid etc.
The use level of each composition then, is described.
The use level of oxidizer composition; Form the total amount of agent, the formation agent of the 2nd diaphragm and water with respect to oxidant, oxidized metal dissolving agent, the 1st diaphragm of 100g; Better be 0.003mol～0.7mol, be more preferably 0.03mol～0.5mol, good especially is 0.2mol～0.3mol.During less than 0.003mol, the oxidation of metal is inadequate, thereby CMP speed is low in this use level, if surpass 0.7mol, just has abradant surface to produce shaggy tendency.
The use level of oxidized metal dissolving agent composition in the present invention; Form the total amount of agent, the formation agent of the 2nd diaphragm and water with respect to oxidant, oxidized metal dissolving agent, the 1st diaphragm of 100g; Better be 0.～0.005mol; Be more preferably 0.00005mol～0.0025mol, good especially is 0.0005mol～0.0015mol.If this use level surpasses 0.005mol, exist to be difficult to the tendency that suppresses to corrode.
The 1st diaphragm forms the use level of agent; Form the total amount of agent, the formation agent of the 2nd diaphragm and water with respect to oxidant, oxidized metal dissolving agent, the 1st diaphragm of 100g; Better be 0.0001mol～0.05mol; Be more preferably 0.0003mol～0.005mol, good especially is 0.0005mol～0.0035mol.In this use level during less than 0.0001mol, exist to be difficult to the tendency that suppresses to corrode, if surpass 0.05mol, the tendency that just has CMP speed to reduce.
The 2nd diaphragm forms the use level of agent; Form the total amount of agent, the formation agent of the 2nd diaphragm and water with respect to oxidant, oxidized metal dissolving agent, the 1st diaphragm of 100g; Better be 0.001～0.3 weight %; Be more preferably 0.003 weight %～0.1 weight %, good especially is 0.01 weight %～0.08 weight %., exist in the control corrosion and can not embody the effect that forms agent and usefulness with the 1st diaphragm during in this use level less than 0.001 weight %, if surpass 0.3 weight %, the tendency that just exists CMP speed to reduce.
Though the mechanism of action of the performance of the effect in lapping liquid of the present invention and the Ginding process it be unclear that; But can infer to do,, both suppress corrosion through also forming agent with the 1st and the 2nd diaphragm; For the friction that produces by grinding pad, under not having an effect, carry out CMP again as the metal surface protection film.
Generally speaking, in CMP, particle diameter or particle size distribution or the shape that the degree of hindering exists with ... solid abrasive particles takes place to grind; The thickness that causes by grinding off of dielectric film reduce (below; Be called wearing and tearing) or the deterioration of planarization effect, also exist with ... the physical property of the particle diameter or the grinding pad of solid abrasive particles, handling metal film with BTA; When especially copper film is surperficial, think that the hollow song of metal film also exists with ... the hardness of grinding pad or the chemical property of lapping liquid.That is, hard solid abrasive particles is necessary when carrying out CMP, but the completeness (grind and hinder equivalent damage) in order to improve planarization effect or CMP face among the CMP is undesirable.Knew already that in fact the planarization effect depended on the characteristic of the grinding pad more soft than solid abrasive particles.
Like this, think that the present invention can carry out under the solid abrasive particles on this aspect of CMP not having, at the CMP of copper alloy, to use in the formation of imbedding figure of CMP of copper alloy then be that the utmost point is hoped.
The 1st diaphragm forms agent and has the effect that forms firm protective in the metal surface.For example, if when the tin-copper alloy film surface is exposed in the solution that contains BTA, because the reaction of copper (Cu) or its oxide BTA, the structure that forms with Cu (I) BTA or Cu (II) BTA is the polymer shape complex diaphragm of main framing.This diaphragm is quite firm, when use contains the metal polishing slurry of 0.5 weight %BTA, even in this lapping liquid, contain solid abrasive particles, generally also grinds hardly.
On the other hand, do not using the 1st diaphragm to form agent, when only using the 2nd diaphragm to form agent modulation metal polishing slurry separately, especially be difficult to suppress corrosion rate, the protection effect is insufficient.
Like this, the 1st diaphragm forms agent and the 2nd diaphragm forms agent, and its effect is different, and the kind that forms agent according to diaphragm forms different types of diaphragm.The present invention is based on following new knowledge, that is, use the 1st and the 2nd above-mentioned diaphragm to form agent through combination, and inhibition and the CMP speed of corrosion rate are kept existed side by side, nor need be by the strong friction of solid abrasive particles generation.
The best mode that carries out an invention
Below, according to embodiment the present invention is described.But the present invention does not receive the restriction of these embodiment.
Embodiment 1～12, comparative example 1～5
The lapping liquid modulator approach
In 0.15 parts by weight DL-malic acid (reagent is superfine), add 70 parts by weight water; And dissolving; After dissolving 0.2 parts by weight the 1st diaphragm forms the solution of agent formation in wherein being added in 0.8 parts by weight methyl alcohol, add 0.05 parts by weight the 2nd diaphragm again and form agent, (reagent is superfine to add 33.2 parts by weight aquae hydrogenii dioxidis at last; 30% aqueous solution), obtain metal polishing slurry.Form agent at the diaphragm that in each embodiment and comparative example, uses shown in the table 1.
Then, use the lapping liquid that obtains, grind grinding charge.Grinding conditions etc. as follows.
Grinding condition
Ground substrate: the silicon substrate that forms the copper film of thick 1 μ m
Grinding pad: IC1000 (ロ デ-Le corporate system)
Grinding pressure: 210g/cm
2
Matrix and the relative velocity that grinds the chassis: 36m/min
The grinding object assessment item
CMP speed:, obtain CMP speed divided by the processing time from the resistance value film thickness difference before and after the CMP obtain copper film that converts.Processing time is 1 minute.
Corrosion rate: prepare in addition to be ground the identical substrate of substrate with above-mentioned; At room temperature (25 ℃), stir (mixing speed 100r/min) on one side, in lapping liquid, flood on one side; Converse the copper layer film thickness difference before and after flooding from resistance value, obtain corrosion rate divided by dip time.Dip time is 10 minutes.
In addition, in order to estimate actual CMP characteristic, in insulating barrier, form the ditch of dark 0.5 μ m, form copper film according to known sputtering method, the silicon substrate of imbedding according to known heat treatment again uses as matrix, carries out CMP.Confirm to have or not the generation abrasion and grind wound through range estimation, observation by light microscope and the electron microscope observation of the matrix behind the CMP. its result, do not see and take place to denude and grind and hinder.The CMP speed in embodiment 1～12 and comparative example 1～5 and the evaluation result of corrosion rate are shown in Table 1.
Table 1
| The 1st diaphragm forms agent | The 2nd diaphragm forms agent | CMP speed | Corrosion rate | |
| Embodiment 1 | The ball promonta | Polymalic acid | 281 | 3.5 |
| Embodiment 2 | The ball promonta | Poly-aspartate | 234 | 1.9 |
| Embodiment 3 | The ball promonta | Polyacrylamide | 187 | 0.3 |
| Embodiment 4 | The L-tryptophan | Polyacrylamide | 219 | 0.9 |
| Embodiment 5 | The L-tryptophan | Ammonium polyacrylate | 210 | 0.7 |
| Embodiment 6 | The L-tryptophan | Polymalic acid | 252 | 2.2 |
| Embodiment 7 | BTA | Ammonium polyacrylate | 185 | 0.2 |
| Embodiment 8 | BTA | Acrylamide | 196 | 0.4 |
| Embodiment 9 | Aphthotriazoles | Polymalic acid | 203 | 0.5 |
| Embodiment 10 | Aphthotriazoles | 2-methyl-3-nitre benzyl alcohol | 212 | 1.1 |
| Embodiment 11 | Triazine two mercaptan | Poly-aspartate | 186 | 0.4 |
| Embodiment 12 | Triazine two mercaptan | Polyacrylamide | 224 | 1.0 |
| Comparative example 1 | The ball promonta | (nothing) | 255 | 15.3 |
| Comparative example 2 | The L-tryptophan | (nothing) | 287 | 10.3 |
| Comparative example 3 | BTA | (nothing) | 93 | 2.4 |
| Comparative example 4 | Aphthotriazoles | (nothing) | 72 | 2.1 |
| Comparative example 5 | Triazine two mercaptan | (nothing) | 98 | 4.8 |
Embodiment 13
In 0.15 parts by weight DL-malic acid (reagent is superfine), add 70 parts by weight water; And dissolving; Behind the solution that in wherein being added in 0.8 parts by weight methyl alcohol, dissolves 0.1 parts by weight BTA and form, add as 40% aqueous solution with 0.025 parts by weight ammonium polyacrylate, (reagent is superfine to add 33.2 parts by weight aquae hydrogenii dioxidis at last again; 30% aqueous solution); Obtain metal polishing slurry. in the present embodiment, what use as oxidized metal dissolving agent is water-soluble high organic acid DL-malic acid, and what form that agent uses as the 2nd diaphragm is water miscible ammonium polyacrylate salt.
Use this metal polishing slurry, when under the condition identical with embodiment 1, carrying out the CMP experiment, CMP speed is that 287nm/min, corrosion rate are that 3.6nm/min is good.But, about forming the matrix of ditch figure, remove the necessary CMP of the thickness time of regulation than CMP and carry out 50% CMP grinding more, the result of electron microscope observation, the hollow song of the ditch portion of wide 10 μ m (becoming the part of imbedding distribution) is about 200nm.For hollow song is suppressed at below the 100nm, need be with superfluous CMP time restriction 20%.Abrasion does not take place and grind wound.
Embodiment 14
In 0.15 parts by weight DL-malic acid (reagent is superfine), add 70 parts by weight water; And dissolving; Behind the solution that in wherein being added in 0.8 parts by weight methyl alcohol, dissolves 0.2 parts by weight BTA and form, add as 40% aqueous solution with 0.125 parts by weight ammonium polyacrylate salt, (reagent is superfine to add 33.2 parts by weight aquae hydrogenii dioxidis at last again; 30% aqueous solution), obtain metal polishing slurry.In the present embodiment, what use as oxidized metal dissolving agent is water-soluble high organic acid DL-malic acid, and what form that agent uses as the 2nd diaphragm is water miscible acrylic acid ammonium salt.
Use this metal polishing slurry, under the condition identical, carry out the CMP experiment with embodiment 1.Its result, it is high to 185nm/imn, the low result to 0.2nm/min of corrosion rate to obtain CMP speed.In addition, about in fact forming the matrix of ditch figure, also implement CMP with above-mentioned CMP condition, when looking like above-mentioned observation, even if make superfluous CMP carry out time of suitable 50%, hollow song also is below the 50nm identically, abrasion does not take place yet and grinds and hinders.
Embodiment 15
Except use DL-tartaric acid to replace modulating metal polishing slurry with embodiment 14 the DL-malic acid identically, carry out the CMP experiment with embodiment 1 identically.Its result, grinding rate is high to 194nm/min, and corrosion rate is 0.8nm/min.In addition, the matrix that forms the ditch figure identical with embodiment 13 carried out CMP after, when observing substrate, the hollow song when superfluous CMP being ground carry out suitable 50% time is about 70nm, and abrasion and grinding wound do not take place.
Embodiment 16
Except use citric acid to replace modulating metal polishing slurry with embodiment 13 the DL-malic acid identically, carry out the CMP experiment with embodiment 1 identically.Its result, grinding rate is high to 213nm/min, but corrosion rate is 4.6nm/min, poor slightly.In addition, with the observed result after the time, superfluous CMP ground of the matrix suitable 30% that forms the ditch figure identical with embodiment 13, hollow song is below about 150nm, and abrasion and grinding wound do not take place.
Comparative example 6
Except not adding the ammonium polyacrylate, modulate metal polishing slurry with embodiment 13 identically, carry out the CMP experiment with embodiment 1 identically.Its result, CMP speed is low to being less than 140nm/min, and corrosion rate is inferior to 10.3nm/min.After the superfluous CMP that the matrix that forms the ditch figure identical with embodiment 13 is carried out suitable 30% time grinds, observe the result of matrix surface, hollow song increases to 300nm. and does not observe abrasion and grind wound.
Comparative example 7
Do not use ammonium polyacrylate, and make the addition of BTA be increased to 0.2 parts by weight, in addition, modulate metal polishing slurry identically, use this metal polishing slurry to carry out testing with embodiment 1 identical CMP with embodiment 13 from 0.1 parts by weight.
Its result, corrosion rate are 2.4nm/min, are good, but CMP speed is inferior to 93nm/min.In addition, to forming the matrix of the ditch figure identical with embodiment 13, after the superfluous CMP that implements suitable 30% time grinds, the result of observation matrix surface, hollow song is about 150nm, is not the value that can fully satisfy.Corrosion rate is low, but CMP speed is also low, in CMP, needs long-time.Abrasion and scratch do not take place.
Find according to these embodiment and comparative example; Only the 1st diaphragm is formed the concentration that agent is added into regulation; Through forming agent with the 2nd diaphragm and using; Even be lower than the low concentration that the 1st diaphragm forms agent, also can reach the effect that is suppressed at the corrosion rate below the 10nm/min, and keep high CMP speed.Hence one can see that, suppress hollow bent, abrasion or grind the generation of hindering, and to form the high figure of imbedding of reliability with high CMP speed is possible.
Application possibility on the industry
As stated,, can make corrosion rate fully low according to the present invention, and can keep high CMP speed and form reliability high imbed figure.
Claims (20)
1. metal polishing slurry, it contains, and oxidant, oxidized metal dissolving agent, the 1st diaphragm form agent, the 2nd diaphragm forms agent and water,
Above-mentioned oxidant is to be selected from least a in hydrogen peroxide, nitric acid, periodic acid potassium, hypochlorous acid and the Ozone Water,
Above-mentioned oxidized metal dissolving agent is to be selected from least a in organic acid, organic acid ammonium salt and the sulfuric acid,
Above-mentioned the 1st diaphragm forms agent to be through physical absorption and/or to form chemical bond and form the compound of diaphragm in metallic film surface, and it is that auxiliary the 1st diaphragm forms the compound that agent forms diaphragm that above-mentioned the 2nd diaphragm forms agent,
It is to be selected from least a in ammonia, amine, amino acid, imines, azoles, mercaptan and the carbohydrate that above-mentioned the 1st diaphragm forms agent, and it is to be selected from least a in compound, ester, ether, polysaccharide, amino-acid salt, polycarboxylic acids, polycarboxylate, vinyl based polymer, acid amides, azo-compound and the molybdenum compound with alcohol property or phenol property hydroxyl that above-mentioned the 2nd diaphragm forms agent.
2. the described metal polishing slurry of claim 1, wherein, it is to be selected from least a in BTA and the derivative thereof that above-mentioned the 1st diaphragm forms agent.
3. the described metal polishing slurry of claim 1, wherein, it is that corrosion rate is suppressed at the compound below the 10nm/min that above-mentioned the 1st diaphragm forms agent.
4. the described metal polishing slurry of claim 1, wherein, it is to be selected from least a in polyacrylic acid, polymethylacrylic acid, polyamic acid, ammonium polyacrylate, ammonium polymethacrylate, polyamic acid ammonium and the polyacrylamide that above-mentioned the 2nd diaphragm forms agent.
5. the described metal polishing slurry of claim 1, wherein, it is the compound that the addition that makes the 1st diaphragm form agent reduces that above-mentioned the 2nd diaphragm forms agent.
6. the described metal polishing slurry of claim 1, wherein, above-mentioned oxidized metal dissolving agent is to be selected from least a in malic acid, tartaric acid, citric acid, malic acid ammonium, ammonium tartrate and the ammonium citrate.
7. the described metal polishing slurry of claim 1, the cmp speed of this lapping liquid are that 100nm/min is above, corrosion rate is below the 10nm/min.
8. the described metal polishing slurry of claim 7, wherein, above-mentioned corrosion rate is below the 1nm/min.
9. the described metal polishing slurry of claim 7, wherein, above-mentioned cmp speed is more than the 250nm/min.
10. claim 1 or 7 described metal polishing slurries, it is used for grinding any the metal at least that comprises copper, copper alloy, Cu oxide and copper alloy oxide.
11. claim 1 or 7 described metal polishing slurries, it does not contain abrasive particle in fact.
12. a Ginding process, this Ginding process are in claim 1 or 7 described metal polishing slurries, to remove the surperficial metal film of grinding charge through grinding.
13. the described Ginding process of claim 12, wherein, above-mentioned metal film comprise in copper, copper alloy, Cu oxide and the copper alloy oxide at least any.
14. the described Ginding process of claim 12; Wherein, Above-mentioned grinding charge has stack membrane from the teeth outwards; This stack membrane has any the metal level at least that comprises in copper, copper alloy, Cu oxide and the copper alloy oxide, and above-mentioned Ginding process is a method of removing at least a portion of above-mentioned metal level from above-mentioned stack membrane.
15. the described Ginding process of claim 12, wherein, above-mentioned metal polishing slurry does not contain abrasive particle in fact.
16. a Ginding process, this method are through grinding the metal film of removing the grinding charge surface in polishing liquid for metal, wherein, said metal polishing slurry contains oxidant, oxidized metal dissolving agent, the 1st diaphragm forms agent and the 2nd diaphragm forms agent,
Above-mentioned the 1st diaphragm forms agent to be through physical absorption and/or to form chemical bond and form the compound of diaphragm in metallic film surface, and it is that auxiliary the 1st diaphragm forms the compound that agent forms diaphragm that above-mentioned the 2nd diaphragm forms agent,
It is to be selected from least a in ammonia, amine, amino acid, imines, azoles, mercaptan and the carbohydrate that above-mentioned the 1st diaphragm forms agent,
Above-mentioned grinding charge has stack membrane from the teeth outwards, and this stack membrane has any the metal level at least that comprises in copper, copper alloy, Cu oxide and the copper alloy oxide.
17. the described Ginding process of claim 16, wherein, above-mentioned metal polishing slurry does not contain abrasive particle in fact.
18. the described Ginding process of claim 16, wherein, the cmp speed of above-mentioned metal polishing slurry is that 100nm/min is above, corrosion rate is below the 10nm/min.
19. the described Ginding process of claim 18, wherein, above-mentioned corrosion rate is below the 1nm/min.
20. the described Ginding process of claim 18, wherein, above-mentioned cmp speed is more than the 250nm/min.
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| JP1998-245616 | 1998-08-31 | ||
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| JP1998-351188 | 1998-12-10 | ||
| JP35118898 | 1998-12-10 |
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| CNB998127760A Division CN1204602C (en) | 1998-08-31 | 1999-08-31 | Abrasive liquid for metal and method for polishing |
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| CN101440259B true CN101440259B (en) | 2012-11-21 |
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