CN101597477A - Aqueous dispersion for chemical mechanical polishing, circuit substrate and manufacture method thereof - Google Patents
Aqueous dispersion for chemical mechanical polishing, circuit substrate and manufacture method thereof Download PDFInfo
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- CN101597477A CN101597477A CN 200910145201 CN200910145201A CN101597477A CN 101597477 A CN101597477 A CN 101597477A CN 200910145201 CN200910145201 CN 200910145201 CN 200910145201 A CN200910145201 A CN 200910145201A CN 101597477 A CN101597477 A CN 101597477A
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Abstract
The invention provides a kind of aqueous dispersion for chemical mechanical polishing, circuit substrate and manufacture method thereof.This aqueous dispersion for chemical mechanical polishing performs well in being formed on the circuit substrate that resin substrate is provided with the wiring layer of cupric or copper alloy, and the speed of grinding copper or copper alloy is very fast, and the flatness of the circuit substrate that obtains is good.Aqueous dispersion for chemical mechanical polishing of the present invention, be used to form the circuit substrate of the wiring layer that on resin substrate, is provided with cupric or copper alloy, contain: (A1) at least a kind at least a kind in organic acid and the organic acid salt, (B1) tensio-active agent and the water-soluble high-molecular compound, (C1) oxygenant and (D1) abrasive material, with respect to described aqueous dispersion for chemical mechanical polishing, the concentration M of described (A1) composition
A1The concentration M of (quality %) and described (D1) composition
D1(quality %) has following relation: M
A1/ M
D1=1～30; The pH value is 8～12.
Description
Technical field
The present invention relates to be used to make the aqueous dispersion for chemical mechanical polishing of circuit substrate, the manufacture method of using the circuit substrate of this water system dispersion, circuit substrate and Mulitilayer circuit board.
Background technology
In recent years, the miniaturization of electronic installation constantly makes progress, and for the semiconductor device that constitutes electronic installation, be used to install the circuit substrate of this semiconductor device, requires further miniaturization and multiple stratification.Mulitilayer circuit board (by the circuit substrate of multiple stratification) generally is laminated with a plurality of circuit substrates that are formed with Wiring pattern, has three-dimensional distribution structure.If Mulitilayer circuit board or circuit substrate in uneven thickness, flatness is insufficient, then can come in contact bad defective sometimes when semiconductor device is installed.Therefore, each layer circuit substrate that constitutes Mulitilayer circuit board must form as follows: make when making Mulitilayer circuit board at stacked each layer circuit substrate, do not take place concavo-convexly, crooked, make it have homogeneous thickness and have an even surface.
As one of the reason of the flatness of infringement circuit substrate, can enumerate the concavo-convex of Wiring pattern.Like this concavo-convex has generation more when making circuit substrate.Manufacture method as circuit substrate with Wiring pattern, following method is for example arranged: the surface at substrate forms and the desired corresponding recess of Wiring pattern, after this surface forms conductive layer with plating on the whole, grind the face side of substrate, only make that recess is residual a conductive layer.In such manufacture method, for plating process, the live width of Wiring pattern is thin more sometimes, and then the plated thickness of this part can become thick more; In addition, the distribution of current when producing plating because of the distribution of Wiring pattern is slightly close sometimes, because of this distribution, it is inhomogeneous that thickness can become.Therefore, the inhomogeneous grinding step that can influence the back of the plated thickness at initial stage, the result damages the flatness of circuit substrate sometimes.In addition, when forming circuit substrate by grinding, produce depression (デ イ Star シ Application グ) phenomenon sometimes, that is, the abrasive surface that is formed at the Wiring pattern of circuit substrate becomes concavity.
Above-mentioned grinding step for example grinds by moccasin (バ Off) and carries out.In patent documentation 1, disclose the Ginding process that uses the moccasin burnisher, used the tubular moccasin burnisher that forms in conjunction with hard grinding abrasive with tackiness agent.Therefore, for such Ginding process, following shortcoming is arranged: the thickness of circuit substrate is easy to generate inhomogeneous, and then the surface of conductive layer is easy to generate scar (flatness is impaired).In addition, in moccasin grinds, also proposed to use the method (for example with reference to patent documentation 2) of slurry.But this method because of being caused the grinding rate difference big by the material of abrasive surface, is not able to obtain the thickness evenness of high degree as the circuit substrate that uses, the technical level of surface yet in Mulitilayer circuit board.
Patent documentation 1: TOHKEMY 2002-134920 communique
Patent documentation 2: TOHKEMY 2003-257910 communique
Summary of the invention
When carrying out grinding step by cmp, compare with other Ginding process, flatness is good.Yet the grinding rate of cmp in the past is little.Particularly the amount of the wiring material that should remove in order to form circuit substrate is many, thereby is necessary significantly to improve the grinding rate of cmp.Like this,, not only require to improve, also require to improve grinding rate simultaneously by the flatness of abrasive surface as the performance of the aqueous dispersion for chemical mechanical polishing that is used for the cmp circuit substrate.
One of purpose of the present invention provides a kind of aqueous dispersion for chemical mechanical polishing, it performs well in being formed on the circuit substrate that resin substrate is provided with the wiring layer of cupric or copper alloy, the speed of grinding copper or copper alloy is very high, and the flatness of the circuit substrate that obtains is good.
One of purpose of the present invention provides the manufacture method of the good circuit substrate of a kind of flatness, comprises the operation of carrying out cmp, and the grinding rate in this operation is very high.
One of purpose of the present invention provides the good circuit substrate of a kind of flatness, reaches the good Mulitilayer circuit board of flatness of stacked a plurality of these circuit substrates.
The present invention finishes at least a portion that solves in the above-mentioned problem, can be in the following manner or suitable example realize.
[being suitable for example 1]
Being characterized as of a kind of mode of aqueous dispersion for chemical mechanical polishing of the present invention is used to form the circuit substrate of the wiring layer that is provided with cupric or copper alloy on resin substrate, contains:
(A1) at least a kind in organic acid and the organic acid salt,
(B1) at least a kind in tensio-active agent and the water-soluble high-molecular compound,
(C1) oxygenant and
(D1) abrasive material,
With respect to described aqueous dispersion for chemical mechanical polishing, the concentration M of described (A1) composition
A1The concentration M of (quality %) and described (D1) composition
D1(quality %) has following relation: M
A1/ M
D1=1～30;
The pH value is 8～12.
[being suitable for example 2]
In suitable example 1, further can M
A1=5～15 (quality %).
[being suitable for example 3]
In suitable example 1, described (A1) composition can be glycine.
[being suitable for example 4]
In suitable example 1, described (B1) composition can be for being selected from least a kind in Witco 1298 Soft Acid, Potassium dodecylbenzenesulfonate and the Witco 1298 Soft Acid ammonium.
[being suitable for example 5]
In suitable example 1, described (C1) composition can be hydrogen peroxide.
[being suitable for example 6]
In suitable example 1, described (D1) composition can be for being selected from least a kind in the compound particle of silicon oxide particle, calcium carbonate particles, organic polymer particle and organic-inorganic.
[being suitable for example 7]
A kind of mode of circuit substrate of the present invention is to have and use the aqueous dispersion for chemical mechanical polishing that is suitable for arbitrary example in the example 1～6 to carry out the operation of cmp.
[being suitable for example 8]
A kind of mode of circuit substrate of the present invention is, is to make with the manufacture method that is suitable for example 7.
[being suitable for example 9]
A kind of mode of Mulitilayer circuit board of the present invention is to be laminated with the circuit substrate of a plurality of suitable examples 8.
[being suitable for example 10]
Being characterized as of a kind of mode of aqueous dispersion for chemical mechanical polishing of the present invention is used to form the circuit substrate of the wiring layer that is provided with cupric or copper alloy on resin substrate, contains:
(A2) organic acid,
(B2) nitrogen-containing heterocycle compound,
(C2) oxygenant and
(D2) abrasive material,
With respect to described aqueous dispersion for chemical mechanical polishing, the concentration M of described (A2) composition
A2The concentration M of (quality %) and described (D2) composition
D2(quality %) has following relation: M
A2/ M
D2=1～20;
The pH value is 1～5.
[being suitable for example 11]
In suitable example 10, further can be M
A2=3～15 (quality %).
[being suitable for example 12]
In suitable example 10, described (A2) organic acid can be for being selected from least a kind in citric acid, glycine, oxysuccinic acid, tartrate and the oxalic acid.
[being suitable for example 13]
In suitable example 10, described (B2) nitrogen-containing heterocycle compound can be for being selected from least a kind in benzotriazole, triazole, imidazoles and the carboxyl benzotriazole.
[being suitable for example 14]
In suitable example 10, described (C2) oxygenant can be hydrogen peroxide.
[being suitable for example 15]
In suitable example 10, described (D2) abrasive material can be for being selected from least a kind in the compound particle of silicon oxide particle, calcium carbonate particles, organic polymer particle and organic-inorganic.
[being suitable for example 16]
A kind of mode of circuit substrate of the present invention is to have and use the aqueous dispersion for chemical mechanical polishing that is suitable for arbitrary example in the example 10～15 to carry out the operation of cmp.
[being suitable for example 17]
A kind of mode of circuit substrate of the present invention is, is to make with the manufacture method that is suitable for example 16.
[being suitable for example 18]
A kind of mode of Mulitilayer circuit board of the present invention is to be laminated with the circuit substrate of a plurality of suitable examples 17.
According to above-mentioned aqueous dispersion for chemical mechanical polishing, the circuit substrate that is provided with the wiring layer of cupric or copper alloy on resin substrate can be ground for the entire circuit substrate thickness evenly and have an even surface.And then according to above-mentioned aqueous dispersion for chemical mechanical polishing, the grinding rate that can greatly improve copper or copper alloy was to μ m/ minute rank.In addition, according to the manufacture method of foregoing circuit substrate, can smooth and high yield ground manufacturing circuit substrate.In addition, foregoing circuit substrate and above-mentioned Mulitilayer circuit board have homogeneous thickness on whole base plate, and have smooth surface.According to aqueous dispersion for chemical mechanical polishing of the present invention, can easily be provided at the circuit substrate or the Mulitilayer circuit board that are difficult to come in contact problem such as bad when semiconductor device etc. is installed.
Description of drawings
Fig. 1 is the sectional view of operation of the manufacture method of the medelling ground circuit substrate that shows present embodiment.
Fig. 2 is the sectional view of operation of the manufacture method of the medelling ground circuit substrate that shows present embodiment.
Fig. 3 is the sectional view of operation of the manufacture method of the medelling ground circuit substrate that shows present embodiment.
Fig. 4 is the sectional view of operation of the manufacture method of the medelling ground circuit substrate that shows present embodiment.
Fig. 5 is the sectional view that medelling ground shows the example of the circuit substrate that the manufacture method of the circuit substrate of using present embodiment is made.
Nomenclature
10... resin substrate
12... recess
20... shielded metal film
30... metallic membrane
Embodiment
Below, describe preferred implementation of the present invention in detail.Need to prove that the present invention is not limited to following embodiment, also be included in the various modified examples that to implement under the scope that does not change purport of the present invention.
1. aqueous dispersion for chemical mechanical polishing
1.1. the 1st embodiment
The aqueous dispersion for chemical mechanical polishing of the 1st embodiment contains: (A1) a kind in a kind in organic acid and the organic acid salt, (B1) tensio-active agent and the water-soluble high-molecular compound, (C1) oxygenant and (D1) abrasive material at least at least.
Below, various compositions contained in the aqueous dispersion for chemical mechanical polishing to the 1st embodiment are elaborated.Below, sometimes each material of (A1)～(D1) is omitted respectively and be recited as the composition of (A1) composition～(D1).
1.1.1. (A1) organic acid and organic acid salt
The aqueous dispersion for chemical mechanical polishing of the 1st embodiment contains at least a kind in (A1) organic acid and the organic acid salt.As one of function of (A1) composition, can enumerate that the wiring layer that can improve cupric on the resin substrate or copper alloy grinds and the function of grinding rate when using aqueous dispersion for chemical mechanical polishing.As (A1) composition that in the aqueous dispersion for chemical mechanical polishing of the 1st embodiment, uses, preferably the surface of the wiring material of the ion that is made of the wiring material element or cupric or copper alloy had the organic acid or the organic acid salt of coordination ability.As (A1) composition more preferably, the organic acid or the organic acid salt that have the chelating coordination ability.
As the organic acid that in the aqueous dispersion for chemical mechanical polishing of the 1st embodiment, uses, can enumerate tartrate, fumaric acid, oxyacetic acid, phthalandione, toxilic acid, formic acid, acetate, oxalic acid, citric acid, oxysuccinic acid, propanedioic acid, pentanedioic acid, succsinic acid, M-nitro benzoic acid, quinolinic acid, quinardinic acid, acid amides sulfuric acid etc.In addition, as the organic acid that uses among the present invention, can also the preferred amino acid that uses glycine, L-Ala, aspartic acid, L-glutamic acid, Methionin, arginine, tryptophane, die aromatischen Aminosaeuren and heterocyclic type amino acid etc.These organic acids and organic acid salt can be dissociated at least 1 proton (hydrogen ion) and pairing negatively charged ion (to と な Ru ア ニ オ Application) in aqueous dispersion for chemical mechanical polishing.In these organic acids, because the effect height that the grinding rate of aqueous dispersion for chemical mechanical polishing is improved, thereby preferred especially glycine.
As the organic acid salt that in the aqueous dispersion for chemical mechanical polishing of the 1st embodiment, uses, can enumerate above-mentioned organic acid salt.Organic acid salt can be dissociated into a pair of ion in aqueous dispersion for chemical mechanical polishing.In the organic acid salt more than divalent, the pairing positively charged ion can be 1 valency, also can be for more than 1 valency.As preferred organic acid salt in the aqueous dispersion for chemical mechanical polishing of present embodiment, for example can enumerate above-mentioned organic acid sylvite, ammonium salt and sodium salt etc.The organic acid salt that contains in the aqueous dispersion for chemical mechanical polishing as present embodiment, also comprise following salt, promptly, under above-mentioned organic acid is dissolved in state in the aqueous dispersion for chemical mechanical polishing, with from pairings such as the positively charged ion of other composition of any adding, for example ammonium ion, potassium ion, formed salt when this aqueous dispersion for chemical mechanical polishing is dry.As the concrete example of preferred organic acid salt in the aqueous dispersion for chemical mechanical polishing of present embodiment, can enumerate acid amides vitriolate of tartar, acid amides ammonium sulfate, acid amides sodium sulfate etc.
In the aqueous dispersion for chemical mechanical polishing of the 1st embodiment, can contain above-mentioned organic acid or organic acid salt separately, also can contain organic acid, organic acid salt more than 2 kinds.
The content of (A1) composition in the aqueous dispersion for chemical mechanical polishing of the 1st embodiment, as long as satisfy (A1) described later composition and (D1) relation of the amount of composition can think arbitrarily, but as (A1) composition integral body, the quality of the aqueous dispersion for chemical mechanical polishing during more preferably with respect to use is 5～15 quality %.That is, in aqueous dispersion for chemical mechanical polishing, (A1) the concentration M of composition
A1Be preferably 5～15 quality %, more preferably 7～13 quality %, preferred especially 8～12 quality %.If (A1) content of composition is less than above-mentioned scope, then can not get sufficient grinding rate sometimes, can need the plenty of time in order to finish grinding step.On the other hand, if (A1) content of composition surpasses above-mentioned scope, it is big that then chemical milling effect becomes, and the corrosion of wiring layer takes place sometimes, or impaired by the flatness of abrasive surface.
1.1.2. (B1) tensio-active agent and water-soluble high-molecular compound
The aqueous dispersion for chemical mechanical polishing of the 1st embodiment contains at least a kind in (B1) tensio-active agent and the water-soluble high-molecular compound.As one of function of (B1) composition, can enumerate and give viscosity aqueous dispersion for chemical mechanical polishing, make the nonferromagnetic substance stabilization, improve by the function of the flatness of abrasive surface.That is, the viscosity of aqueous dispersion for chemical mechanical polishing can be controlled by the content of (B1) composition.If controlled the viscosity of this aqueous dispersion for chemical mechanical polishing, then can control the nonferromagnetic substance of this aqueous dispersion for chemical mechanical polishing.
As the tensio-active agent that can in the aqueous dispersion for chemical mechanical polishing of the 1st embodiment, preferably use, can enumerate nonionic surfactant, anion surfactant or cats product.As nonionic surfactant, can exemplify out and have the triple-linked nonionic surfactant.Particularly, can enumerate alkyne diol and ethylene oxide adduct, alkynol etc.In addition, as nonionic surfactant, can enumerate silicone tensio-active agent, cyclodextrin and derivative thereof etc.As cats product, can exemplify out aliphatics amine salt and aliphatics ammonium salt etc.As anion surfactant, can exemplify out aliphatics soap, sulfuric acid and phosphate ester salt etc.
Wherein, as preferred surfactants in the aqueous dispersion for chemical mechanical polishing of present embodiment, can enumerate anion surfactant.As anion surfactant, senior sulfonic acid such as the senior organic acid of succinic acid derivatives such as preference chain alkenyl succinic acid, stearic acid, oleic acid etc. and salt thereof, alkyl benzene sulphonate (ABS), alkyl naphthalene sulfonic acid, alpha-olefin sulfonic acid and salt thereof etc.As the salt of alkenyl succinic, for example can enumerate alkenyl succinic dipotassium (trade(brand)name " LATEMULASK " can be bought by Kao Corp).As alkyl benzene sulphonate (ABS), preferred especially Witco 1298 Soft Acid.In addition, as sulfonate, preferred ammonium salt, sylvite, sodium salt.As the preferred concrete example of alkylbenzene sulfonate, can enumerate Witco 1298 Soft Acid ammonium and Potassium dodecylbenzenesulfonate.
As the water-soluble high-molecular compound that can in the aqueous dispersion for chemical mechanical polishing of the 1st embodiment, preferably use, can enumerate water-soluble high-molecular compounds such as polyvinylpyrrolidone (PVP) and polyvinyl methyl ether, polyacrylic acid (PAA), polymethyl acrylic acid, the multipolymer of vinylformic acid and methacrylic acid, polymaleic aciies etc. have carboxylic acid group's water-soluble high-molecular compound and salt thereof, polyisoprene sulfonic acid etc. has sulfonic water-soluble high-molecular compound and salt thereof, Hydroxyethyl acrylate, Natvosol, polyvinyl alcohol etc. have the water-soluble high-molecular compound of hydroxyl.
The water-soluble high-molecular compound that uses in the aqueous dispersion for chemical mechanical polishing of the 1st embodiment is during as PVP, in the weight-average molecular weight (Mw) of pressing the polyoxyethylene glycol conversion that adopts water system GPC (gel permeation chromatography) to measure, the preferred value of measuring of using surpasses 200,000 PVP.Preferably surpass 200,000 and below 1,500,000, more preferably 300,000～1,500,000, further preferred 500,000～1,200,000, preferred especially 650,000～1,100,000 PVP.If the weight-average molecular weight of PVP in above-mentioned scope, then reduces the effect height of the friction in grinding, can more stably grind copper and copper bearing wiring layer.The depression etc. that can suppress in addition, copper and copper bearing wiring layer.If weight-average molecular weight is less than above-mentioned lower limit, then above-mentioned effect is insufficient easily, thereby not preferred.In addition,, the tendency of grinding rate reduction and the tendency that causes the abrasive material cohesion are arranged then, increase owing to the agglutinative abrasive material makes the scratch on copper and the copper bearing wiring layer sometimes if weight-average molecular weight is excessive, thus not preferred.
For the aqueous dispersion for chemical mechanical polishing of the 1st embodiment,, can use independent a kind or be used in combination more than 2 kinds in above-mentioned tensio-active agent and the water-soluble polymer as (B1) composition
The content of (B1) composition in the aqueous dispersion for chemical mechanical polishing of the 1st embodiment, as (B1) composition integral body, the quality of the aqueous dispersion for chemical mechanical polishing during with respect to use, be preferably 0.01～1 quality %, more preferably 0.05～0.5 quality %, preferred especially 0.1～0.3 quality %.If (B1) content of composition is less than above-mentioned scope, then the viscosity of aqueous dispersion for chemical mechanical polishing is low excessively, thereby can not will effectively and equably be delivered to the grinding pad applied pressure by abrasive surface, the nonferromagnetic substance of this aqueous dispersion for chemical mechanical polishing is inhomogeneous in by abrasive surface, damages flatness sometimes.In addition, the viscosity of aqueous dispersion for chemical mechanical polishing, thereby aqueous dispersion for chemical mechanical polishing particularly becomes by the uneven reason of aqueous dispersion for chemical mechanical polishing amount of peripheral part in the abrasive surface sometimes just having flowed out from becoming between the substrate that grinds object and the grinding pad before the useful effect.On the other hand, if (B1) content of composition surpasses above-mentioned scope, then with respect to the flatness improved effect passivation of content, sometimes can not obtain sufficient flatness, and then grinding rate reduces sometimes, or the viscosity of this aqueous dispersion for chemical mechanical polishing becomes too high, abrasion friction heat rises, and inner evenness worsens.In addition, if (B1) content of composition surpasses above-mentioned scope, then aqueous dispersion for chemical mechanical polishing bubbles easily, thereby operability worsens sometimes.
1.1.3. (C1) oxygenant
The aqueous dispersion for chemical mechanical polishing of the 1st embodiment contains (C1) oxygenant.As one of function of (C1) oxygenant, can enumerate to improve the circuit substrate that is formed with copper and copper bearing wiring layer is ground and the function of grinding rate when using aqueous dispersion for chemical mechanical polishing.As its reason, can think that (C1) surface of oxygenant oxidation copper etc. promotes the complex reaction with the composition of aqueous dispersion for chemical mechanical polishing, thereby form fragile modified layer on the surface of copper etc., make the grinding of copper etc. easy.
(C1) oxygenant that uses in the aqueous dispersion for chemical mechanical polishing as the 1st embodiment can be enumerated the persulphate such as nitrate compound, the contour hydracid compound of perchloric acid, ammonium persulphate such as hydracid compound, nitric acid, iron nitrate of the dichromic acid compound, Potassium Iodate etc. of the permanganic acid compound, potassium bichromate etc. of organo-peroxides such as hydrogen peroxide, peracetic acid, perbenzoic acid, tertbutyl peroxide, potassium permanganate etc. and heteropolyacid etc.In these oxygenants, from oxidizing power, to considerations such as the corrodibility of resin substrate and operational eases, persulphates such as preferred hydrogen peroxide, organo-peroxide or ammonium persulphate, the preferred especially harmless hydrogen peroxide of degradation production.
(C1) oxygenate content in the aqueous dispersion for chemical mechanical polishing of the 1st embodiment, the quality of the aqueous dispersion for chemical mechanical polishing during with respect to use, be preferably 0.5～5 quality %, more preferably 1～4 quality %, preferred especially 1.5～3 quality %.If (C1) content of oxygenant is less than above-mentioned scope, then chemical result becomes insufficient sometimes, and grinding rate can descend, and needs the plenty of time in order to finish grinding step sometimes.On the other hand, if (C1) content of oxygenant surpasses above-mentioned scope, then corroded by abrasive surface sometimes and damage flatness.
1.1.4. (D1) abrasive material
The aqueous dispersion for chemical mechanical polishing of the 1st embodiment contains (D1) abrasive material.As (D1) abrasive material, can enumerate inorganic particulate, organic filler and the compound particle of organic-inorganic etc.
As inorganic particulate, can enumerate silicon oxide particle, aluminium oxide particles, Titanium particles, Zirconia particles, ceria particles, calcium carbonate particles etc.
As above-mentioned silicon oxide particle, can enumerate by in gas phase, making the pyrolysis method synthetic pyrolysis method silicon oxide of silicon chlorides etc. and oxygen and H-H reaction, be hydrolyzed condensation and the synthetic sol-gel method comes the synthetic silicon oxide by metal alkoxide, adopt the mineral colloid method of removing impurity to wait synthetic colloidal silica etc. by purifying.As silicon oxide particle, the mineral colloid method that preferred especially employing is removed impurity by purifying waits the synthetic colloidal silica.
When using silicon oxide particle as (D1) abrasive material in the aqueous dispersion for chemical mechanical polishing of the 1st embodiment, when using median size as the colloidal silica below the 200nm, flatness is good, thereby preferred.
As above-mentioned calcium carbonate particles, be preferably as follows the highly purified calcium carbonate particles that obtains: in water,, make itself and carbon dioxide reaction with behind the calcium hydroxide purifying.
As organic filler, can enumerate organic polymer particles such as polyethylene, polypropylene, poly-1-butylene, poly--olefin copolymers such as 4-methyl-1-pentene, polystyrene, styrene based copolymer, polyvinyl chloride, polyacetal, saturated polyester, polymeric amide, polycarbonate, resol, polymethylmethacrylate, (methyl) acrylic resin and acrylic copolymer.
As the compound particle of organic-inorganic, can constitute by above-mentioned organic filler and above-mentioned inorganic particulate.For the compound particle of organic-inorganic, so long as above-mentioned organic filler and inorganic particulate are formed integrally as and are not easy isolating degree get final product when the cmp operation, the kind of each particle, formation etc. are not particularly limited.As the compound particle of this organic-inorganic, can use the compound particle of for example following organic-inorganic that forms: in the presence of polymer particles such as polystyrene, polymethylmethacrylate, make polycondensations such as organoalkoxysilane, aluminium alkoxide, titanium alkoxides, on the surface at least of polymer particle, form in conjunction with polysiloxane, poly-aikyiaiurnirsoxan beta (Port リ ア Le ミ ノ キ サ Application), poly-titanoxane polycondensates such as (Port リ チ ノ キ サ Application).The polycondensate that generates can directly combine with the functional group with polymer particle, also can be situated between and wait combination by silane coupling agent.In addition, also can replace organoalkoxysilane etc. and use silicon oxide particle, aluminium oxide particles etc.At this moment, the compound particle of organic-inorganic can followingly form: as tackiness agent, make the surface of polymer particle have silicon oxide particle etc. polycondensates such as polysiloxane, poly-aikyiaiurnirsoxan beta, poly-titanoxane.They can with complexing and keeping mutually such as polysiloxane, also can be by functional group such as hydroxyl that they had Chemical bond on polymer particle.
In addition, as the compound particle of operable organic-inorganic in the aqueous dispersion for chemical mechanical polishing of the 1st embodiment, can enumerate in the water dispersion that contains organic filler with the different zeta-potential of symbol and inorganic particulate, these particles are by the compound particle of organic-inorganic of electrostatic force be combined into.The zeta-potential of organic filler mostly is negative in whole pH scope or the broad range except low pH scope, and have carboxyl by making, the organic filler of sulfonic group etc., can make organic filler more reliably with negative zeta-potential.In addition, by making organic filler, also can be formed in the organic filler that has positive zeta-potential in the particular pH range with amino etc.On the other hand, the pH dependency height of the zeta-potential of inorganic particulate, this current potential has becomes 0 iso-electric point, and before and after it, the symbol of zeta-potential reverses.Therefore, by with the combination of specific organic filler and inorganic particulate, in their zeta-potential becomes the pH scope of contrary sign, mix, just can organic filler and inorganic particulate be combined into one by electrostatic force.In addition,, also can make zeta-potential become contrary sign by changing pH subsequently even zeta-potential is a same-sign when mixing, thus organic filler and inorganic particulate is integrated.
And then, as the compound particle of above-mentioned organic-inorganic, also can use the compound particle of the following organic-inorganic that forms: with electrostatic force and compound particle as one in the presence of, make polycondensations such as organoalkoxysilane as described above, aluminium alkoxide, titanium alkoxides, on the surface at least of this particle further combined with polysiloxane etc. and the compound particle of organic-inorganic that is composited.
In above-mentioned abrasive material,, be preferably selected from least a kind in the compound particle of silicon oxide particle, calcium carbonate particles, organic polymer particle and organic-inorganic as the abrasive material that in the aqueous dispersion for chemical mechanical polishing of the 1st embodiment, uses.
The median size of (D1) abrasive material that uses among the present invention is preferably 20～500nm.This median size can be observed by laser light scattering diffraction type tester or with transmission electron microscope and be measured.If median size, then can not obtain fully big aqueous dispersion for chemical mechanical polishing of grinding rate sometimes less than 20nm.If median size surpasses 500nm, then sometimes because the precipitation of abrasive material, separation and can not easily obtain stable water system dispersion.The median size of abrasive material can be above-mentioned scope, but more preferably 30～400nm, preferred especially 40～300nm.If median size is in this scope, then grinding rate is big, and depression is fully suppressed, and is difficult to take place precipitation, the separation of particle, can obtain stable aqueous dispersion for chemical mechanical polishing.
The content of (D1) composition in the aqueous dispersion for chemical mechanical polishing of the 1st embodiment, as long as satisfy (A1) described later composition and (D1) relation of the amount of composition promptly can be arbitrarily, but the quality of the aqueous dispersion for chemical mechanical polishing during with respect to use, more preferably 0.5～5 quality %.That is, in aqueous dispersion for chemical mechanical polishing, (D1) the concentration M of composition
D10.5～5 quality % more preferably.(D1) content of composition 1～4.5 quality % more preferably, preferred especially 1.5～4 quality %.If (D1) content of composition is less than above-mentioned scope, then can not get sufficient grinding rate sometimes, need the plenty of time in order to finish grinding step sometimes.On the other hand, if the content of abrasive material surpasses above-mentioned scope, then become insufficient by the flatness of abrasive surface sometimes, cost uprises, and can not guarantee the storage stability of chemical grinding water dispersoid.1.1.5. (A1) composition of aqueous dispersion for chemical mechanical polishing and (D1) relation of the amount of composition
For the aqueous dispersion for chemical mechanical polishing of the 1st embodiment, (A1) the concentration M of composition
A1(quality %) and (D1) the concentration M of composition
D1(quality %) has M
A1/ M
D1=1～30 relation.At this, M
A1And M
D1Expression (A1) composition and (D1) concentration of composition respectively, be meant (A1) composition and (D1) quality of composition with respect to the ratio of the quality of aqueous dispersion for chemical mechanical polishing integral body.(A1) the concentration M of composition
A1(D1) the concentration M of composition
D1Ratio M
A1/ M
D1, more preferably M
A1/ M
D1=2～20, further preferred M
A1/ M
D1=3～10.If M
A1/ M
D1Ratio then has the depression of wiring layer to become big tendency less than above-mentioned scope, and is not preferred.And then, if M
A1/ M
D1Ratio is less than above-mentioned scope, and then (D1) abrasive components becomes many relatively, the mechanical mill of resin substrate is carried out excessively, as the circuit substrate of the wiring layer that on resin substrate, is provided with cupric or copper alloy of grinding charge by the abrasive surface roughen, thereby not preferred.In addition, can not obtain stable aqueous dispersion for chemical mechanical polishing sometimes.If M
A1/ M
D1Ratio surpasses above-mentioned scope, is then become insufficient by the flatness of abrasive surface sometimes.In addition, also take place sometimes the distribution corrosion of metal, thus not preferred.
1.1.6. the pH of aqueous dispersion for chemical mechanical polishing
In the aqueous dispersion for chemical mechanical polishing of the 1st embodiment, the pH value of aqueous dispersion for chemical mechanical polishing is 8～12.At this, so-called pH is meant hydrogen ion exponent, and this value can be with commercially available mensuration such as pH meter.The pH value of aqueous dispersion for chemical mechanical polishing is preferably 8.5～11.5, and more preferably 9～11.If the pH value of aqueous dispersion for chemical mechanical polishing is less than above-mentioned scope, then grinding rate descends sometimes.If the pH value of aqueous dispersion for chemical mechanical polishing surpasses above-mentioned scope, the abrasive material dissolving then takes place sometimes or by the flatness variation of abrasive surface.
The pH value of aqueous dispersion for chemical mechanical polishing with above-mentioned (A1) composition so that (D1) use level of composition change.Therefore, select the kind of each composition, or use level is changed, can be adjusted to the scope of above-mentioned pH value.In addition, according to above-mentioned (A1) composition and even (D1) kind, the use level of composition, also have the pH value and do not reach situation in the above-mentioned scope.At this moment, can in aqueous dispersion for chemical mechanical polishing, add suitable pH regulator agent etc., the pH value is adjusted in the above-mentioned scope.
1.1.7.pH conditioning agent
In the aqueous dispersion for chemical mechanical polishing of the 1st embodiment, as required can complex acid, pH regulator agent such as alkali.As one of function of pH regulator agent, be that aqueous dispersion for chemical mechanical polishing is adjusted to desired pH.Thus, aqueous dispersion for chemical mechanical polishing becomes desired pH value, can adjust the corrosion of grinding rate, improvement flatness and inhibition wiring layer.Use when the pH regulator agent can be in outside 8～12 the scope at the pH of aqueous dispersion for chemical mechanical polishing, in addition, when the pH of aqueous dispersion for chemical mechanical polishing is in 8～12 scope, also can be used for further regulating pH.
As the pH regulator agent, for example, as acid, can enumerate mineral acids such as sulfuric acid and phosphoric acid, as alkali, can enumerate alkali-metal oxyhydroxide such as sodium hydroxide, potassium hydroxide, rubidium hydroxide and cesium hydroxide, organo-alkali compound such as tetramethylammonium hydroxide, choline and ammonia etc.Bronsted lowry acids and bases bronsted lowry can cooperate separately, also can cooperate multiple.By adding the pH regulator agent, can consider to be set suitable pH by the dispersiveness of the electrochemical properties of abrasive surface, abrasive material, stability and grinding rate, make abrasive material stably to exist.Particularly preferred pH regulator agent in the aqueous dispersion for chemical mechanical polishing as present embodiment from improving the viewpoint of grinding rate, can be enumerated ammonia.
1.1.8. other additive
The aqueous dispersion for chemical mechanical polishing of the 1st embodiment except mentioned component, can also cooperate various additives as required.As other additive, can enumerate anticorrosive agent, the reduction blistered suds suppressor of slurry and the defoamer etc. of wiring material.
1.2. the 2nd embodiment
The aqueous dispersion for chemical mechanical polishing of the 2nd embodiment contains: (A2) organic acid, (B2) nitrogen-containing heterocycle compound, (C2) oxygenant and (D2) abrasive material.Below, sometimes each material of (A2)～(D2) is omitted respectively and be recited as the composition of (A2) composition～(D2).
1.2.1. (A2) organic acid
The aqueous dispersion for chemical mechanical polishing of the 2nd embodiment contains (A2) organic acid.As one of (A2) organic acid function, can enumerate that the wiring layer that can improve cupric on the resin substrate or copper alloy grinds and the function of grinding rate when using aqueous dispersion for chemical mechanical polishing.As (A2) organic acid that in the aqueous dispersion for chemical mechanical polishing of the 2nd embodiment, uses, preferably the surface of the wiring material of the ion that is made of the wiring material element or cupric or copper alloy had the organic acid of coordination ability.As (A2) organic acid more preferably, has the organic acid of chelating coordination ability.
As the organic acid that in the aqueous dispersion for chemical mechanical polishing of the 2nd embodiment, uses, can enumerate tartrate, fumaric acid, oxyacetic acid, phthalandione, toxilic acid, formic acid, acetate, oxalic acid, citric acid, oxysuccinic acid, propanedioic acid, pentanedioic acid, succsinic acid, M-nitro benzoic acid, quinolinic acid, quinardinic acid, acid amides sulfuric acid etc.In addition, as the organic acid that uses among the present invention, can also preferably use amino acid such as glycine, L-Ala, aspartic acid, L-glutamic acid, Methionin, arginine, tryptophane, die aromatischen Aminosaeuren and heterocyclic type amino acid.These organic acids can be dissociated at least 1 proton (hydrogen ion) and pairing negatively charged ion (parent ion) in aqueous dispersion for chemical mechanical polishing.In the aqueous dispersion for chemical mechanical polishing of the 2nd embodiment, can contain above-mentioned organic acid separately, also can contain the above-mentioned organic acid more than 2 kinds.In these organic acids, because the effect height that the grinding rate of aqueous dispersion for chemical mechanical polishing is improved, thereby be preferably selected from citric acid, glycine, oxysuccinic acid, tartrate and the oxalic acid at least a kind especially.
The organic acid that uses in the aqueous dispersion for chemical mechanical polishing of the 2nd embodiment, under the state in being dissolved in aqueous dispersion for chemical mechanical polishing, can with from pairings such as the positively charged ion of other composition of any adding, for example ammonium ion, potassium ions, form salt when at this moment, aqueous dispersion for chemical mechanical polishing is dry.At this moment, the pairing positively charged ion can also can be for more than 1 valency for 1 valency.
(A2) organic acid content in the aqueous dispersion for chemical mechanical polishing of the 2nd embodiment, as (A2) organic acid integral body, the quality of the aqueous dispersion for chemical mechanical polishing during with respect to use, be preferably 3～15 quality %, more preferably 3.5～12 quality %, preferred especially 4～10.5 quality %.If (A2) organic acid content is less than above-mentioned scope, then can not get sufficient grinding rate sometimes, can need the plenty of time in order to finish grinding step sometimes.On the other hand, if (A2) organic acid content surpasses above-mentioned scope, it is big that then chemical milling effect becomes, and the corrosion of wiring layer takes place sometimes, or impaired by the flatness of abrasive surface.
1.2.2. (B2) nitrogen-containing heterocycle compound
The aqueous dispersion for chemical mechanical polishing of the 2nd embodiment contains (B2) nitrogen-containing heterocycle compound.As one of function of (B2) nitrogen-containing heterocycle compound, can enumerate by forming water-fast title complex with metal such as copper, protection is by abrasive surface, thereby improves by the flatness of abrasive surface.As (B2) nitrogen-containing heterocycle compound, preferably the surface of the wiring material of the ion that is made of the wiring material element or cupric or copper alloy had the nitrogen-containing heterocycle compound of coordination ability.As (B2) nitrogen-containing heterocycle compound more preferably, has the nitrogen-containing heterocycle compound of chelating coordination ability.
Preferred (B2) nitrogen-containing heterocycle compound that uses is to contain at least 1 nitrogen in the heterogeneous ring compound as heteroatomic compound in the aqueous dispersion for chemical mechanical polishing of the 2nd embodiment.Nitrogen-containing heterocycle compound is to contain to be selected from five-membered ring with at least 1 nitrogen-atoms and at least a kind of heterocyclic organic compound in the hexa-member heterocycle.As described heterocycle, can enumerate hexa-member heterocycles such as five-membered ring such as pyrrole structure, glyoxaline structure, triazole structure and pyridine structure, pyrimidine structure, pyridazine structure, pyrazine structure.This heterocycle can form condensed ring.Particularly, can enumerate indole structure, isoindole structure, benzimidazole structure, benzotriazole structure, quinoline structure, isoquinoline 99.9 structure, quinazoline structure, cinnoline structure, phthalazines structure, quinoxaline structure, acridine structure etc.In having the heterogeneous ring compound of this spline structure, preferably has the heterogeneous ring compound of pyridine structure, quinoline structure, benzimidazole structure or benzotriazole structure.Concrete example as nitrogen-containing heterocycle compound, can enumerate aziridine, pyridine, pyrimidine, tetramethyleneimine, piperidines, pyrazine, triazine, pyrroles, imidazoles, indoles, quinoline, isoquinoline 99.9, benzisoquinoline, purine, pteridine, triazole, triazolidine, benzotriazole, carboxyl benzotriazole etc., and then, can illustration have the derivative of these skeletons.
The aqueous dispersion for chemical mechanical polishing of the 2nd embodiment can use independent a kind or be used in combination more than 2 kinds as (B2) nitrogen-containing heterocycle compound in the above-mentioned nitrogen-containing heterocycle compound.As (B2) nitrogen-containing heterocycle compound, be preferably selected from least a kind in benzotriazole, triazole, imidazoles and the carboxyl benzotriazole especially.
The content of (B2) nitrogen-containing heterocycle compound in the aqueous dispersion for chemical mechanical polishing of the 2nd embodiment, as (B2) nitrogen-containing heterocycle compound integral body, the quality of the aqueous dispersion for chemical mechanical polishing during with respect to use, be preferably 0.05～2 quality %, more preferably 0.1～1 quality %, preferred especially 0.2～0.5 quality %.If (B2) content of nitrogen-containing heterocycle compound is less than above-mentioned scope, then damage sometimes by the flatness of abrasive surface.If (B2) content of nitrogen-containing heterocycle compound surpasses above-mentioned scope, then grinding rate reduces sometimes.
1.2.3. (C2) oxygenant
The aqueous dispersion for chemical mechanical polishing of the 2nd embodiment contains (C2) oxygenant.(C2) oxygenant can use the oxygenant of explanation in above-mentioned " 1.1.3. (C1) oxygenant " item.For the function of (C2) oxygenant in the 2nd embodiment, also identical with the function of explanation in above-mentioned " 1.1.3. (C1) oxygenant " item.
(C2) oxygenate content in the aqueous dispersion for chemical mechanical polishing of the 2nd embodiment, the quality of the aqueous dispersion for chemical mechanical polishing when using is preferably 1～30 quality %, more preferably 5～20 quality %, preferred especially 5～15 quality %.If (C2) content of oxygenant is less than above-mentioned scope, then chemical result becomes insufficient sometimes, and grinding rate can descend, and needs the plenty of time in order to finish grinding step sometimes.On the other hand,, then corroded by abrasive surface sometimes and damage flatness, grinding rate also can take place sometimes descend if (C2) content of oxygenant surpasses above-mentioned scope.
1.2.4. (D2) abrasive material
The aqueous dispersion for chemical mechanical polishing of the 2nd embodiment contains (D2) abrasive material.(D2) abrasive material can use the abrasive material of explanation in above-mentioned " 1.1.4. (D1) abrasive material " item.For the function and content of (D2) abrasive material in the 2nd embodiment, also identical with the function and the content of explanation in above-mentioned " 1.1.4. (D1) abrasive material " item.
1.2.5. (A2) composition of aqueous dispersion for chemical mechanical polishing and (D2) relation of the amount of composition
For the aqueous dispersion for chemical mechanical polishing of the 2nd embodiment, (A2) the concentration M of composition
A2(quality %) and (D2) the concentration M of composition
D2(quality %) has M
A2/ M
D2=1～20 relation.At this, M
A2And M
D2Be (A2) composition and (D2) quality of composition with respect to the ratio of the quality of aqueous dispersion for chemical mechanical polishing integral body.(A2) the concentration M of composition
A2(D2) the concentration M of composition
D2Ratio M
A2/ M
D2, more preferably M
A2/ M
D2=1～10, further preferred M
A2/ M
D2=2～8.If M
A2/ M
D2Ratio then has the depression of wiring layer to become big tendency less than above-mentioned scope, and is not preferred.And then, if M
A2/ M
D2Ratio is less than above-mentioned scope, then because (D2) the relative change of abrasive components is many, the mechanical mill of resin substrate is carried out excessively, therefore as the circuit substrate of the wiring layer that on resin substrate, is provided with cupric or copper alloy of grinding charge by the abrasive surface roughen, thereby not preferred.In addition, can not obtain stable aqueous dispersion for chemical mechanical polishing sometimes.If M
A2/ M
D2Ratio surpasses above-mentioned scope, is then become insufficient by the flatness of abrasive surface sometimes.In addition, also take place sometimes the distribution corrosion of metal, thus not preferred.
1.2.6. the pH of aqueous dispersion for chemical mechanical polishing
In the aqueous dispersion for chemical mechanical polishing of the 2nd embodiment, the pH value of aqueous dispersion for chemical mechanical polishing is 1～5.At this, so-called pH is meant hydrogen ion exponent, and this value can be with commercially available mensuration such as pH meter.The pH value of aqueous dispersion for chemical mechanical polishing is preferably 1.5～4.5, and more preferably 2～4.If the pH value of aqueous dispersion for chemical mechanical polishing is less than above-mentioned scope, then sometimes by the flatness variation of abrasive surface.If the pH value of aqueous dispersion for chemical mechanical polishing surpasses above-mentioned scope, then grinding rate reduces sometimes.
The pH value of aqueous dispersion for chemical mechanical polishing with above-mentioned (A2) composition so that (D2) use level of composition change.Therefore, select the kind of each composition, or use level is changed, can be adjusted to the scope of above-mentioned pH value.In addition, according to above-mentioned (A2) composition and even (D2) kind, the use level of composition, also have the pH value and do not reach situation in the above-mentioned scope.At this moment, can in aqueous dispersion for chemical mechanical polishing, add suitable pH regulator agent etc., the pH value is adjusted in the above-mentioned scope.
1.2.7.pH conditioning agent
In the aqueous dispersion for chemical mechanical polishing of the 2nd embodiment, as required can complex acid, pH regulator agent such as alkali.The pH regulator agent can be used the pH regulator agent of explanation in above-mentioned " 1.1.7.pH conditioning agent " item.For the function of pH regulator agent in the 2nd embodiment, also identical with the function of explanation in above-mentioned " 1.1.7.pH conditioning agent " item.
1.2.8. other additive
The aqueous dispersion for chemical mechanical polishing of the 2nd embodiment except mentioned component, can also cooperate various additives as required.As other additive, can enumerate anticorrosive agent, the reduction blistered suds suppressor of slurry and the defoamer etc. of wiring material.
2. the manufacture method of circuit substrate, circuit substrate and Mulitilayer circuit board
The manufacture method of the circuit substrate of the 3rd embodiment has the operation that the aqueous dispersion for chemical mechanical polishing described in the use " 1. aqueous dispersion for chemical mechanical polishing " carries out cmp.
The cmp operation imports to above-mentioned aqueous dispersion for chemical mechanical polishing in the general chemical mechanical polishing device carries out.Below, use accompanying drawing to specify the manufacturing process of circuit substrate.Fig. 1～Fig. 5 is the sectional view of manufacturing process's example of the medelling circuit substrate 100 of representing the 3rd embodiment.Cmp operation in the manufacture method of the circuit substrate 100 of the 3rd embodiment is the operation of grinding particularly the wiring layer that is made of copper or copper alloy.
As the resin substrate 10 that in the manufacture method of the circuit substrate 100 of the 3rd embodiment, uses, as long as have insulativity, for example, can use film substrate, plastic base at the position that is formed with wiring layer, also can use glass substrate etc.Resin substrate 10 can be individual layers, also can be the duplexer that for example is formed with resin layer on the substrate of other material of silicon etc.
As shown in Figure 1, at first prepare resin substrate 10.On resin substrate 10, recess 12 is set by technology such as photoetching and etchings.Recess 12 forms accordingly with the wiring layer of circuit substrate 100.At least the mask that is provided with recess 12 sides of resin substrate 10 has electrical insulating property.
Then, as shown in Figure 2, form shielded metal film 20, make the surface of its covering resin substrate 10 and the bottom and the inner-wall surface of recess 12.Shielded metal film 20 is provided with as required.Shielded metal film 20 for example can be made of materials such as tantalum, tantalum nitrides.As the film of shielded metal film 20, can use chemical Vapor deposition process (CVD).
Then, as shown in Figure 3, pile up the distribution metal, make its surface that covers shielded metal film 20, form metallic membrane 30.Metallic membrane 30 can be made of copper or copper alloy.Metallic membrane 30 remains in the recess 12 through the cmp operation, forms the wiring layer of circuit substrate 100.As the film of metallic membrane 30, can use physical vaporous depositions (PVD) such as sputtering method, vacuum vapour deposition.
Then, as shown in Figure 4, use the aqueous dispersion for chemical mechanical polishing of present embodiment, cmp and remove the excess metal film 30 that buries outside the part of recess 12.Under the situation that is provided with shielded metal film 20, continue aforesaid method and expose up to shielded metal film 20.Behind the cmp, preferably remove the abrasive material that residues in by abrasive surface.Removing of this abrasive material can be undertaken by common purging method.
At last, as shown in Figure 5, the shielded metal film 20a that other aqueous dispersion for chemical mechanical polishing that uses the shielded metal film to use, cmp and removing are formed at outside the recess 12 and the surface of metallic membrane 30.
The cmp operation of the 3rd embodiment uses the aqueous dispersion for chemical mechanical polishing of the 1st or the 2nd embodiment to remove metallic membrane 30, thereby its grinding rate is big, and the flatness in the abrasive surface is good, and the selectivity that is difficult to cave in etc. is ground.Therefore, according to the manufacture method of the circuit substrate of the 3rd embodiment, can high yield ground make the circuit substrate 100 of flatness excellence in the face.
With the circuit substrate 100 that the manufacture method of the 3rd embodiment is made, flatness height in the face, it is also little to cave in.Therefore, circuit substrate 100 is stacked and the substrate integral body Mulitilayer circuit board that forms has homogeneous thickness, and have smooth surface.
3. embodiment and comparative example
Below, use embodiment and comparative example to further specify the present invention, but the present invention is not subjected to any qualification of these embodiment and comparative example.
3.1 estimate making with substrate
3.1.1. the flatness evaluation making of substrate
WPR-1201 varnish (JSR Corp.'s system, photosensitive insulating resin composition) is spun on the copper-clad laminated board that surface coarsening handles, and (substrate is thick, 0.6mm; Size, 10cm is square), 110 ℃ of heating 3 minutes, make the thick uniform coating of 10 μ m with hot plate.Then, use aligner (Karl Suss corporate system, " MA-100 "), Jie is by the pattern mask of pad (the パ Star De) portion of the distribution with L/S=100 μ m/100 μ m and 2mm * 2mm, and irradiation is from the ultraviolet ray of high voltage mercury lamp.Ultraviolet exposure is made as, and the exposure of wavelength 350nm is 3000～5000J/m
2Then, heat 3 minutes (PEB) with hot plate at 110 ℃, after 60 seconds, carry out 120 ℃ * 2 hour heating with convection oven 23 ℃ of immersion development with 2.38 quality % tetramethylammonium hydroxides (TMAH), formation has the insulating resin cured film of ditch pattern on copper-clad laminated board.On the insulating resin cured film that obtains, form copper seed layer by electroless plating, form the copper coating of 10 μ m then with electrochemical plating.Obtained in the ditch pattern, having imbedded the flatness evaluation substrate of copper like this.This substrate is carried out cmp, remove the outer copper of ditch pattern, can form the circuit substrate of the line of the wide conductive layer of line with the wide conductive layer of 100 μ m and 2mm.
3.1.2. the copper grinding rate evaluation making of substrate
Except the ditch pattern that does not carry out insulating resin layer forms, similarly carry out with " evaluation of 3.1.1. flatness with the making of substrate ", obtain the substrate that has copper coating of 10 μ m.
3.2. the modulation of abrasive material dispersion
3.2.1. contain the modulation of the water dispersion of pyrolysis method silicon oxide particle
With ultrasonic dispersing machine pyrolysis method silicon oxide particle (NIPPON AEROSIL corporate system, trade(brand)name " AEROSIL #90 ") 2kg is dispersed among the ion exchanged water 6.7kg, strainer with aperture 5 μ m filters, and modulation contains the water dispersion of pyrolysis method silicon oxide.
3.2.2. modulation contains the water dispersion of colloidal silica
At capacity is ammoniacal liquor 70g, ion exchanged water 40g, ethanol 175g and the tetraethoxysilane 21g that adds 25 quality % content in 2 liters the flask, the limit is stirred the limit with 180rpm and is warmed up to 60 ℃, after continuing to stir 2 hours under this temperature, cooling obtains the colloidal silica that median size is 70nm/pure dispersion.Then, on one side on one side remove pure composition adding ion exchanged water under 80 ℃ the temperature in this dispersion with vaporizer, the pure composition in the dispersion is removed in repeatedly so repeatedly operation, and the modulation solid component content is the water dispersion of 8 quality %.
3.3. (B1) modulation of the aqueous solution of composition
The aqueous solution of polyvinylpyrrolidone such as modulated, other Witco 1298 Soft Acid, alkenyl succinic dipotassium, polyvinyl alcohol and the oleic aqueous solution are by coming the described substance dissolves of specified amount synthetic in ion exchanged water.
With the N-vinyl-2-Pyrrolidone 60g of the degassing and the water 240g of the degassing capacity of packing into is in the flask of 500mL.It is warmed up to 60 ℃ in nitrogen gas stream, under the agitation condition, adds the sodium sulfite aqueous solution 0.3g of 10 quality % and the tertbutyl peroxide aqueous solution 0.3g of 10 quality %.Continue stirring down after 3 hours at 60 ℃, add the sodium sulfite aqueous solution 1.8g of 10 quality % and the tertbutyl peroxide aqueous solution 1.2g of 10 quality %, further continue to stir 3 hours.By dilute this reaction mixture with ion exchanged water, obtain the 20 quality % aqueous solution of polyvinylpyrrolidone.For at this synthetic polyvinylpyrrolidone, using the NaCl aqueous solution/acetonitrile=80/20 (vol/vol) of 0.1 mole/L is 1000000 as the weight-average molecular weight (Mw) that converts by polyoxyethylene glycol of the water system gel permeation chromatography of elutriant.In addition, the K value of obtaining with the Fikentscher method is 95.
3.4. the modulation of aqueous dispersion for chemical mechanical polishing
Be in 1 liter the polyethylene system bottle with the specified amount adding capacity of the water dispersion of record in " modulation of 3.2. abrasive material dispersion ", the compound of record and make its content that reaches separately to be put down in writing in wherein interpolation table 1 or table 2 stirs fully.Add the pH regulator agent then, making pH is the value shown in table 1 or the table 2.Then, with the strainer filtration of aperture 5 μ m, obtain the aqueous dispersion for chemical mechanical polishing of embodiment 1～18 and comparative example 1～8.
Table 1
Table 2
3.5. the grinding of substrate
Use the aqueous dispersion for chemical mechanical polishing of embodiment 1～18 and comparative example 1～8, grinding substrate that has copper film and the above-mentioned flatness evaluation substrate of in the ditch pattern, having imbedded copper that does not have Wiring pattern under the following condition.
Milling apparatus: Lapmaster LM 15
Grinding pad: IC1000 (Nitta Haas corporate system)
Carrier head load: 280hPa
Shaft collar rotation number: 90rpm
Abrasive feed rate: 100ml/ minute
The grinding rate of copper is with the calculating of following calculating formula according to the grinding result of the substrate that has copper film that does not have Wiring pattern.The grinding rate of each embodiment and comparative example is recorded in table 1 or table 2.
Grinding rate (μ m/ minute)=amount of grinding (μ m)/milling time (minute)
Amount of grinding is to be 8.9g/cm with the copper density
3, calculate with following formula.
Amount of grinding (μ m)={ (weight (g) before grinding-grinding back weight (g))/(substrate area (cm
2) * copper density (g/cm
3)) * 104
The value of grinding rate is 5 (μ m/ minutes) when above, and it is good to can be described as grinding rate.
3.6. the evaluation of depression
Accumulations such as recess there is the unnecessary film of initial stage of the thickness T (nm) of wiring material grind with grinding rate V (nm/ minute), then originally as long as T/V (minute) grinding of time promptly should reach purpose.But, in the manufacturing process of reality, in order to remove the wiring material that remains in the part beyond the recess, implement to surpass T/V (minute) over-mastication (over polish).At this moment, because the over-lapping of distribution part, thereby become the shape of concavity sometimes.The distribution shape of such concavity is become " depression ", and is from the viewpoint that meeting reduces the output of manufacture, not preferred.Therefore, in each embodiment and comparative example, adopt depression as assessment item.
The evaluation of depression is to use probe-type height plane difference meter (KLA-Tencor corporate system, model " P-10 "), carries out with substrate with above-mentioned flatness evaluation.In addition, the milling time in depression is estimated is: the value (T/V) that the grinding rate V (nm/ minute) that the unnecessary copper film of initial stage of thickness T (nm) is obtained in divided by " grinding of 3.5. substrate " obtains (minute) multiply by 1.5 and time (minute)
In the depression hurdle in the assessment item in table 1 or table 2, the amount with the calixconcavity of the fixed copper wiring of above-mentioned surfaceness instrumentation put down in writing is as depression value (μ m).In the table, " * 1 " expression distribution disappears and not measurable situation.With the 100 μ m that form on the substrate wide line and the wide line of 2mm, its depression value is recorded in the table 1 respectively for the flatness evaluation.As reference, the difference of the depression value of the line that line that 100 μ m are wide and 2mm are wide also is recorded in the table 1 in the lump.The depression value is 1.5 (μ m) when following under the situation of the wide line of 100 μ m, can be described as well, is 2.0 (μ m) when following under the situation of the wide line of 2mm, can be described as well.
3.7. storage stability
Following the carrying out of evaluation to the storage stability of the aqueous dispersion for chemical mechanical polishing of each embodiment and each comparative example: behind the modulation aqueous dispersion for chemical mechanical polishing, under normal temperature, normal pressure, leave standstill each dispersion after visual observations left standstill in 60 days.Index as the evaluation of storage stability is as follows: be evaluated as ◎ with firm modulation back does not change, that observes the small amount of precipitate thing is evaluated as zero, component separating takes place or occur being evaluated as of supernatant zone *, its result is recorded in table 1 or the table 2.
3.8. evaluation result
According to the result of table 1, for the aqueous dispersion for chemical mechanical polishing of embodiment 1～9, the grinding rate of copper all is more than 6.8 μ m/ minutes, and is very high.In addition, the depression of 100 μ m distributions is below the 1.5 μ m, and is very little, shows to have good over-mastication leeway (オ one バ one Port リ Star シ ユ マ one ジ Application).And then the depression of 2mm distribution is below the 2.2 μ m, and is very little, shows for the big distribution of width also have good over-mastication leeway.And the difference of the depression of 100 μ m lines and 2mm line is below 0.7 μ m, and Ao Xian line width dependency is little as can be known.In addition, the storage stability of the aqueous dispersion for chemical mechanical polishing of embodiment 1～9 is also good.
On the other hand, as shown in table 1, for not having M
A1/ M
D1Comparative example 1 (the M of=1～30 relation
A1/ M
D1=0.7), depression is big, for bad.In addition, for not having M
A1/ M
D1Comparative example 4 (the M of=1～30 relation
A1/ M
D1=36), because distribution disappears, depression is very big, for bad.Broken away from the comparative example 2 (pH=6.3) of the lower limit of 8～12 scope for the pH value, grinding rate is little, for bad.The comparative example 3 (pH=13.5) that has broken away from the upper limit of 8～12 scope for the pH value, depression greatly, for bad.For comparative example 1,3,4, storage stability is insufficient.
According to the result of table 2, for the aqueous dispersion for chemical mechanical polishing of embodiment 10～18, the grinding rate of copper was more than 6.6 μ m/ minutes, and is very high.In addition, the depression of 100 μ m distributions is below the 1.4 μ m, and is very little, shows to have good over-mastication leeway.And then the depression of 2mm distribution is below the 2.0 μ m, and is very little, shows for the big distribution of width also have good over-mastication leeway.And the difference of the depression of 100 μ m lines and 2mm line is below 1.0 μ m, and Ao Xian line width dependency is little as can be known.In addition, the storage stability of the aqueous dispersion for chemical mechanical polishing of embodiment 10～18 is also good.
On the other hand, as shown in table 2, for not having M
A2/ M
D2Comparative example 5 (the M of=1～20 relation
A2/ M
D2=0.5), the depression of 2mm distribution is big, for bad.In addition, for not having M
A2/ M
D2Comparative example 6 (the M of=1～20 relation
A2/ M
D2=25), the depression of 100 μ m distributions and 2mm distribution is all big, for bad.The comparative example 7 (pH=0.5) that has broken away from the lower limit of 1～5 scope for the pH value because distribution disappears, depression greatly, for bad.Broken away from the comparative example 8 (pH=5.5) of the upper limit of 1～5 scope for the pH value, grinding rate is insufficient.For comparative example 1, storage stability is also insufficient.
Show as mentioned above; the aqueous dispersion for chemical mechanical polishing of embodiment can be with the cupric that has on the high grinding rate grind resin substrate or the metallic membrane of copper alloy, and can realize guaranteeing that the inner evenness of substrate and the flatness that suppresses in the abrasive surface are inhomogeneous.
Claims (18)
1. an aqueous dispersion for chemical mechanical polishing is characterized in that, is used to form the circuit substrate of the wiring layer that is provided with cupric or copper alloy on resin substrate, contains:
(A1) at least a kind in organic acid and the organic acid salt,
(B1) at least a kind in tensio-active agent and the water-soluble high-molecular compound,
(C1) oxygenant and
(D1) abrasive material,
With respect to described aqueous dispersion for chemical mechanical polishing, the concentration M of described (A1) composition
A1Concentration M with described (D1) composition
D1Has following relation: M
A1/ M
D1=1～30, wherein, M
A1And M
D1Unit be quality %,
The pH value is 8～12.
2. aqueous dispersion for chemical mechanical polishing according to claim 1, wherein, M
A1=5～15 quality %.
3. aqueous dispersion for chemical mechanical polishing according to claim 1, wherein, described (A1) composition is a glycine.
4. aqueous dispersion for chemical mechanical polishing according to claim 1, wherein, described (B1) composition is at least a kind that is selected from Witco 1298 Soft Acid, Potassium dodecylbenzenesulfonate and the Witco 1298 Soft Acid ammonium.
5. aqueous dispersion for chemical mechanical polishing according to claim 1, wherein, described (C1) composition is a hydrogen peroxide.
6. aqueous dispersion for chemical mechanical polishing according to claim 1, wherein, described (D1) composition is at least a kind that is selected from the compound particle of silicon oxide particle, calcium carbonate particles, organic polymer particle and organic-inorganic.
7. the manufacture method of a circuit substrate is characterized in that, has to use each described aqueous dispersion for chemical mechanical polishing in the claim 1～6 to carry out the operation of cmp.
8. a circuit substrate is characterized in that, is to make with the described manufacture method of claim 7.
9. a Mulitilayer circuit board is characterized in that, is laminated with the described circuit substrate of a plurality of claims 8.
10. an aqueous dispersion for chemical mechanical polishing is characterized in that, is used to form the circuit substrate of the wiring layer that is provided with cupric or copper alloy on resin substrate, contains:
(A2) organic acid,
(B2) nitrogen-containing heterocycle compound,
(C2) oxygenant and
(D2) abrasive material,
With respect to described aqueous dispersion for chemical mechanical polishing, the concentration M of described (A2) composition
A2Concentration M with described (D2) composition
D2Has following relation: M
A2/ M
D2=1～20, wherein, M
A2And M
D2Unit be quality %,
The pH value is 1～5.
11. aqueous dispersion for chemical mechanical polishing according to claim 10, wherein, M
A2=3～15 quality %.
12. aqueous dispersion for chemical mechanical polishing according to claim 10, wherein, described (A2) organic acid is at least a kind that is selected from citric acid, glycine, oxysuccinic acid, tartrate and the oxalic acid.
13. aqueous dispersion for chemical mechanical polishing according to claim 10, wherein, described (B2) nitrogen-containing heterocycle compound is at least a kind that is selected from benzotriazole, triazole, imidazoles and the carboxyl benzotriazole.
14. aqueous dispersion for chemical mechanical polishing according to claim 10, wherein, described (C2) oxygenant is a hydrogen peroxide.
15. aqueous dispersion for chemical mechanical polishing according to claim 10, wherein, described (D2) abrasive material is at least a kind that is selected from the compound particle of silicon oxide particle, calcium carbonate particles, organic polymer particle and organic-inorganic.
16. the manufacture method of a circuit substrate is characterized in that, has to use each described aqueous dispersion for chemical mechanical polishing in the claim 10～15 to carry out the operation of cmp.
17. a circuit substrate is characterized in that, is to make with the described manufacture method of claim 16.
18. a Mulitilayer circuit board is characterized in that, is laminated with the described circuit substrate of a plurality of claims 17.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008147779 | 2008-06-05 | ||
| JP2008147779 | 2008-06-05 | ||
| JP2008155009 | 2008-06-13 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN 200910145201 Pending CN101597477A (en) | 2008-06-05 | 2009-05-27 | Aqueous dispersion for chemical mechanical polishing, circuit substrate and manufacture method thereof |
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| JP (1) | JP5459466B2 (en) |
| CN (1) | CN101597477A (en) |
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| WO2014048058A1 (en) * | 2012-09-25 | 2014-04-03 | 安集微电子（上海）有限公司 | Chemical mechanical polishing solution |
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| JP2003313542A (en) * | 2002-04-22 | 2003-11-06 | Jsr Corp | Aqueous dispersion for chemomechanical polishing use |
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| US20100230142A1 (en) * | 2007-10-23 | 2010-09-16 | Ube Industries, Ltd. | Method for manufacturing printed wiring board |
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2009
- 2009-05-07 JP JP2009112553A patent/JP5459466B2/en not_active Expired - Fee Related
- 2009-05-27 CN CN 200910145201 patent/CN101597477A/en active Pending
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Also Published As
| Publication number | Publication date |
|---|---|
| JP2010012593A (en) | 2010-01-21 |
| JP5459466B2 (en) | 2014-04-02 |
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