CN101426730A - Method for producing oxide particle, slurry, polishing agent and method for polishing substrate - Google Patents
Method for producing oxide particle, slurry, polishing agent and method for polishing substrate Download PDFInfo
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- CN101426730A CN101426730A CNA2007800141741A CN200780014174A CN101426730A CN 101426730 A CN101426730 A CN 101426730A CN A2007800141741 A CNA2007800141741 A CN A2007800141741A CN 200780014174 A CN200780014174 A CN 200780014174A CN 101426730 A CN101426730 A CN 101426730A
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Abstract
Disclosed is a method for producing oxide particles which comprises a step for obtaining a mixture by mixing a metal carbonate and an acid, a step for obtaining a metal oxide by heating the mixture, and a step for pulverizing the metal oxide. Also disclosed are a slurry obtained by dispersing the metal oxide particles produced by such a method in an aqueous medium, a polishing agent and a method for polishing a substrate. Further specifically disclosed is a polishing agent containing cerium oxide particles which are obtained by using cerium carbonate as the raw material metal carbonate and oxalic acid as the raw material acid. The method for producing oxide particles enables to quickly obtain fine particles not containing coarse particles or worn powder. A polishing agent using the thus-produced oxide particles enables to precisely polish a semiconductor surface, while maintaining an appropriate polishing rate and reducing generation of scratches.
Description
Technical field
The invention provides the Ginding process of a kind of manufacture method of oxide particle, slurry therefrom, abrasive and substrate.
Background technology
The particulate of metal oxide is used for various uses, for example, cerium oxide is used for abrasive, catalyzer, ultraviolet screening agent etc., and cobalt oxide is used for electrical condenser, varistor, secondary cell etc., nickel oxide is used for ferrite etc., and titanium oxide is used for materials such as photocatalyst, pigment.
Especially, the cerium oxide particulate is being popularized in recent years apace as the precise finiss abrasive of semiconductor integrated circuit.Usually, counting nanometer as this precise finiss to the scope of hundreds of nanometers with the median size of the cerium oxide particulate of abrasive.In order to obtain such cerium oxide particulate, the someone has proposed the whole bag of tricks.
At first, in cerium solutions such as the cerous nitrate aqueous solution, add volatile salt or bicarbonate of ammonia, obtain the precipitation of cerous carbonate.Then, with this washing of precipitate, filtration, drying, heating, thereby obtain cerium oxide.As Heating temperature, need be in order to make the cerous carbonate thermolysis more than 400 ℃.The size of the cerium oxide particles that obtains here can not be different from the size of cerous carbonate particle significantly.For example, the median size that will form with the form of the aggregate of plate crystal is that tens of microns cerous carbonate is heated to 700 ℃, and the median size of the cerium oxide that obtains thus is tens of microns, and shape also is the aggregate of tabular particle.Then, the cerium oxide that obtains is carried out dry type with airflow milling (jet millor) etc. pulverize, perhaps carry out case of wet attrition, thereby the micronize of finishing makes median size in the scope of number nanometers to hundreds of nanometers with ball mill etc.
But, with this method, pulverize needed artificial big, according to the ability of pulverizer, may residual thick cerium oxide particles.In addition, when long-time when continuing to pulverize, the parts abrasion of pulverizer have increased the abrasion powder and have sneaked into possibility in the abrasive.Thick cerium oxide particles and abrasion powder are to produce to grind the reason of hindering, thereby not preferred.
In addition, add oxalic acid in the cerium solutions such as the also oriented cerous nitrate aqueous solution, obtain the sedimentary method of Sedemesis.Because this method also is the heating Sedemesis, obtains cerium oxide, pulverizes, and realizes micronize, therefore, exists because of producing and grind the possibility of hindering with above-mentioned same reason.
In addition, also there is following method: concentration and the temperature of reaction of optimizing the cerous nitrate aqueous solution and ammonium bicarbonate aqueous solution, generate the precipitation of fine cerous carbonate, this precipitation is heated, and just can to obtain median size be the following spherical cerium oxides (opening the 2004-107186 communique with reference to the spy of Japan) of 50 nanometers thereby need not pulverize.But, with this method, keep ammonium easily because throw out is fine, therefore washing needs the time.In addition, also keep water easily because throw out is fine, so drying also needs the time.And when Heating temperature was high, some produced sintering because cerium oxide particles is fine, may generate thick cerium oxide particles.
In addition, also has following method:, obtain the precipitation of fine basic carbonate cerium by in water, heating cerous carbonate, filter, drying, be heated to more than 300 ℃, pulverize, thereby do not contained the cerium oxide particles (opening the 2005-126253 communique) of oversize particle with reference to the spy of Japan.But with this method, the operation of heating cerous carbonate needs 2～48 hours in water, and the sedimentary operation of dry basic carbonate cerium is 5～96 hours, and handling needs the time.
Summary of the invention
Like this, the cerium oxide particulate of using manufacture method in the past to obtain exists and contains the possibility of oversize particle or the possibility of sneaking into from the abrasion powder of pulverizer.In addition, also having report not contain the manufacture method of thick particle, is a difficult point but need the problem of time on making.
In view of the above problems, the invention provides the manufacture method of the oxide particle of the particulate that can not contained thick particle or abrasion powder apace.In addition, provide a kind of abrasive, described abrasive adopts this oxide particle, keeps suitable grinding rate, reduces the generation that scratches, critically grinding semiconductor surface simultaneously.
The oxide compound that discovery of the present invention obtains with direct heating carbonate is compared, and adds acid in carbonate, and when heating, the shape of oxide compound can great changes have taken place.
The present invention relates to following content.
(1) a kind of manufacture method of oxide particle is characterized in that, comprises: the carbonate of hybrid metal and acid obtain the operation of mixture; Heat the operation that described mixture obtains metal oxide; Pulverize the operation of described metal oxide.
(2) according to the manufacture method of the described oxide particle of preceding paragraph (1), wherein, the carbonate of metal is cerous carbonate.
(3) according to the manufacture method of preceding paragraph (1) or (2) described oxide particle, wherein, acid is solid at 25 ℃.
(4) according to the manufacture method of the described oxide particle of preceding paragraph (3), wherein, acid is Powdered at 25 ℃.
(5) according to the manufacture method of each described oxide particle in preceding paragraph (1)～(4), wherein, acid is organic acid.
(6) according to the manufacture method of the described oxide particle of preceding paragraph (5), wherein, organic acid is made of carbon atom, Sauerstoffatom and hydrogen atom.
(7) according to the manufacture method of preceding paragraph (5) or (6) described oxide particle, wherein, organic acid acid ionization constant pKa is than the acid ionization constant pKa of carbonic acid
1Little.
(8) according to the manufacture method of the described oxide particle of preceding paragraph (7), wherein, organic acid acid ionization constant pKa is below 6.
(9) according to the manufacture method of each described oxide particle in preceding paragraph (5)～(8), wherein, organic acid is at least a for what select from succsinic acid, propanedioic acid, citric acid, tartrate, oxysuccinic acid, oxalic acid, toxilic acid, hexanodioic acid, Whitfield's ointment, phenylformic acid, phthalic acid, oxyacetic acid, xitix, their isomer, polymkeric substance or multipolymer, polyacrylic acid, polymethyl acrylic acid.
(10) according to the manufacture method of each described oxide particle in preceding paragraph (5)～(9), wherein, the carbonate of metal is cerous carbonate, and organic acid is an oxalic acid, and the ratio of mixture of cerous carbonate and oxalic acid is: with respect to 1 mole cerous carbonate, oxalic acid is 0.5～6 mole.
(11) a kind of slurry is characterized in that, contains the resulting metal oxide particle of manufacture method by each described oxide particle in preceding paragraph (1)～(10) that is scattered in the aqueous medium.
(12) a kind of abrasive is characterized in that, containing the metal that is scattered in the aqueous medium is that cerium and acid are the resulting cerium oxide particles of manufacture method by each described oxide particle in preceding paragraph (1)～(10) of oxalic acid.
(13) a kind of abrasive is characterized in that, aqueous medium contains the particle of pulverizing cerium oxide, and the mixture of described cerium oxide heating cerous carbonate and oxalic acid obtains.
(14) according to preceding paragraph (12) or (13) described abrasive, wherein, the intermediate value of cerium oxide particle diameter is 100～2000nm.
(15) according to the described abrasive of preceding paragraph (14), wherein, the above cerium oxide particles of particle diameter 3 μ m is below the 500ppm in solid.
(16) according to each described abrasive in preceding paragraph (14) or (15), wherein, further contain dispersion agent.
(17) according to each described abrasive in preceding paragraph (14)～(16), wherein, all in the cerium oxide particles, the particle diameter of the cerium oxide particles of 99 volume % is below the 1.0 μ m.
(18) a kind of Ginding process of substrate is characterized in that, uses the substrate of each described abrasive grinding regulation in preceding paragraph (12)～(17).
(19) according to the Ginding process of the described substrate of preceding paragraph (18), wherein, the substrate of regulation is the semiconductor substrate that is formed with silicon oxide film at least.
The application's disclosure is willing to that with the spy who applies on April 21st, 2006 spy of 2006-117772 and application on June 16th, 2006 is willing to that the theme that 2006-167283 puts down in writing is associated, and their disclosure is incorporated in this.
Description of drawings
Fig. 1 is the mixture of heating cerous carbonate and succsinic acid and the electron scanning micrograph of the powder that obtains.
Fig. 2 is the mixture of heating cerous carbonate and propanedioic acid and the electron scanning micrograph of the powder that obtains.
Fig. 3 is the mixture of heating cerous carbonate and citric acid and the electron scanning micrograph of the powder that obtains.
Fig. 4 is heating cerous carbonate and tartaric mixture and the electron scanning micrograph of the powder that obtains.
Fig. 5 is the mixture of heating cerous carbonate and oxysuccinic acid and the electron scanning micrograph of the powder that obtains.
Fig. 6 is the mixture of heating cerous carbonate and oxalic acid and the electron scanning micrograph of the powder that obtains.
Fig. 7 is the mixture of heating cerous carbonate and toxilic acid and the electron scanning micrograph of the powder that obtains.
Fig. 8 is the mixture of heating cerous carbonate and hexanodioic acid and the electron scanning micrograph of the powder that obtains.
Fig. 9 is heating cerous carbonate and salicylic mixture and the electron scanning micrograph of the powder that obtains.
Figure 10 is heating cerous carbonate and benzoic mixture and the electron scanning micrograph of the powder that obtains.
Figure 11 is the mixture of heating cerous carbonate and phthalic acid and the electron scanning micrograph of the powder that obtains.
Figure 12 is the mixture of heating cerous carbonate and oxyacetic acid and the electron scanning micrograph of the powder that obtains.
Figure 13 is the mixture of heating cerous carbonate and xitix and the electron scanning micrograph of the powder that obtains.
Figure 14 is heating cerous carbonate and polyacrylic mixture and the electron scanning micrograph of the powder that obtains.
Figure 15 is the mixture of heating cerous carbonate and polymethyl acrylic acid and the electron scanning micrograph of the powder that obtains.
Figure 16 is the mixture of heating cerous carbonate, Phosbloc and propanedioic acid xitix and the electron scanning micrograph of the powder that obtains.
Figure 17 only heats cerous carbonate and the electron scanning micrograph of the powder that obtains.
Figure 18 is the mixture of heating cerous carbonate and polyoxyethylene glycol and the electron scanning micrograph of the powder that obtains.
Embodiment
Being characterized as of the manufacture method of oxide particle of the present invention comprises: the carbonate and the acid of metal are mixed the operation that obtains mixture, the operation that the described mixture of heating obtains metal oxide, the operation of pulverizing the described metal oxide that obtains.Usually, during the carbonate of a heating of metal, the carbonate thermolysis obtains the oxide compound of its metal.At this moment, carbonate and oxide compound is too not big in shape different.But when the carbonate mixing of acid and metal was heated, the carbonate of acid and metal produced chemical reaction, replaces the carbonic acid ion, generates new metal-salt, obtains the oxide compound of its metal after the thermolysis.At this moment, the shape of carbonate and oxide compound has a great difference, and oxide compound becomes the aggregate of fine particle.Therefore this oxide compound is pulverized in the short period of time easily owing to be the aggregate of fine particle, forms oxide fine particle.
The carbonate of metal of the present invention is not only the carbonate that only contains a kind of metallic element, also can be by multiple metal ion, carbonic acid ion, other positively charged ion, the double salt that negatively charged ion constitutes.When heating the mixture of these double salt and acid, replace the carbonic acid ion in the double salt composition, generate new metal-salt, obtain oxide compound after the thermolysis as the aggregate of fine particle.Because of same reason, the carbonate of metal can contain impurity.
The metal that forms carbonate can be enumerated cerium, cobalt, nickel etc.Particularly, when as described later oxide compound being used for abrasive, metal is preferably cerium.As the manufacture method of cerous carbonate, following method is for example arranged, that is, mixed carbonic acid hydrogen aqueous ammonium in the nitrate aqueous solution of the cerium of 3 valencys precipitates cerous carbonate, filters, washing obtains, and there is no particular restriction.Certainly, cerous carbonate also can contain the carbonate or the impurity of other metal.
Preferred acid of the present invention is solid at 25 ℃, is gas as tartaric acid, then Suan use or with the difficulty that just becomes mixing of the carbonate of metal, therefore not preferred.In addition, be liquid or solution state as tartaric acid, then the mixture with the carbonate of metal becomes liquid state,, need take time to need to carry out drying before obtaining oxide compound in heating.
In addition, consider that from the carbonate blended angle of easy and metal acid of the present invention is preferably Powdered.There is no particular restriction for the size of powder.
Acid of the present invention is preferably organic acid.In addition, more preferably be pulverous organic acid down at 25 ℃.When mineral acids such as nitric acid or sulfuric acid were mixed with the carbonate of metal, the chemical reaction fierceness produced carbonic acid gas tempestuously, the control difficulty, and if Heating temperature is low, then nitrate ion or sulfate ion may not break away from and residue in the oxide compound.
Organic acid among the present invention preferably is made of carbon atom, Sauerstoffatom and hydrogen atom.In addition, can contain other nitrogen-atoms or sulphur atom, be nitrate ion or sulfate ion, when Heating temperature is low, may not break away from and residue in the oxide compound but the time can become in heating.
Organic acid acid ionization constant pKa among the present invention is than the acid ionization constant pKa of the one-level of carbonic acid
1Little, that is, be preferably the organic acid stronger than carbonic acid acidity.Further preferred organic acid pKa is below 6.Organic acid is multistage when dissociating, relatively the acid ionization constant pKa of one-level
1PKa with carbonic acid
1With the acid ionization constant pKa of acid ionization constant pKa than carbonic acid
1Little organic acid mixes with the carbonate of metal and when heating, carbonic acid ion and organic acid conjugate base are substituted, and produces carbonic acid gas, generates the organic acid salt of metal.When further continuing heating, the organic acid salt thermolysis of metal, the aggregate that obtains fine particle is an oxide compound.In the present invention, acid ionization constant is with the denary logarithm value pKa of the inverse of actual acid ionization constant Ka
1Value represent.In addition, organic acid is multistage when dissociating, with the acid ionization constant pKa of one-level
1Value represent.
Organic acid among the present invention is preferably more than select from succsinic acid, propanedioic acid, citric acid, tartrate, oxysuccinic acid, oxalic acid, toxilic acid, hexanodioic acid, Whitfield's ointment, phenylformic acid, phthalic acid, oxyacetic acid, xitix, their isomer, polymkeric substance or multipolymer, polyacrylic acid, polymethyl acrylic acid at least a.These organic acids at room temperature are solid, can easily obtain powder.Be preferably oxalic acid especially owing to following reason.That is, the mixture of oxalic acid and cerous carbonate burnt till and the cerium oxide that obtains is Powdered, pulverizing process is easy.
On the other hand, when burning till the mixture of other organic acids and cerous carbonate, the cerium oxide that obtains often is bulk, the frequent spended time of pulverizing process.
In addition, because the combustion heat of oxalic acid is little, the temperature when control is heated easily.
In addition, the carbon amount of each acid number of oxalic acid is few, and the growing amount as the carbonic acid gas of global warming gas during burning is few.
As the combined amount of acid, for example, when mixing,, preferably mix the acid of the n valency of 1/n mole～12/n mole with respect to 1 mole of cerous carbonate with cerous carbonate.The combined amount of acid after a little while, reaction may not be carried out fully, the combined amount of acid for a long time, the acid that has neither part nor lot in reaction may wait and the damage heating unit in when heating burning, therefore with respect to 1 mole of cerous carbonate, preferably mixes the acid of the n valency of 3/n mole～9/n mole.
For example, the ratio of mixture of the situation of cerous carbonate and oxalic acid, with respect to 1 mole of cerous carbonate, preferred oxalic acid is 0.5～6 mole.More preferably 3～5 moles.
The carbonate of the metal among the present invention is not particularly limited with the blending means of acid, but owing to the acid according to kinds such as oxalic acid produces carbonic acid gas in mixing, therefore preferably drops into both in not airtight container, and stirring method.According to mixing time, the shape of the oxide compound of Sheng Chenging changes thereafter, but as long as the blended words will not depended on mixing time and the easy at short notice effect of pulverizing.
Heating temperature among the present invention for example in the situation of cerous carbonate, is preferably more than 350 ℃ more preferably 400 ℃～1000 ℃.
Because the oxide compound among the present invention is the aggregate of minuteness particle and pulverizing easily, so, breaking method without limits, making median size if desired is words below several microns, preferably carry out dry type and pulverize, perhaps carry out case of wet attrition by contracurrent system or ball mill by airflow milling etc.
The metal oxide particle that obtains in the present invention can be scattered in makes slurry in the aqueous medium.As the method that oxide particle is scattered in aqueous medium, except carry out dispersion treatment with common stirrer, can also use clarifixator, ultrasonic dispersing machine, wet crushing mill etc.In addition, when using dispersion agent, for example,, can use the macromolecule dispersing agent that contains ammonium acrylate as copolymer composition.
The slurry that obtains in the present invention can be used as abrasive.Especially, containing the abrasive of cerium oxide particles can be as the precise finiss abrasive of semiconductor integrated circuit.As in the semiconductor integrated circuit by grinding film, can enumerate the silicon oxide film of silicon oxide film, silicon nitride film, interpolation boron phosphorus etc.
Abrasive of the present invention preferably contains cerium oxide particles and the water that cerium oxide is pulverized, and described cerium oxide burns till the mixture of cerous carbonate and oxalic acid and obtains.
Abrasive of the present invention is preferably the composition that also contains dispersion agent outside described cerium oxide particles and water.For example, can obtain by the composition that contains the cerium oxide particles made of aforesaid method and dispersion agent is scattered in the water.
The concentration of cerium oxide particles still disperses the angle of aqueous abrasive to consider from easy processing without limits, is preferably the scope that 0.1 weight % is above, 20 weight % are following.
As dispersion agent, grind owing to be used for semiconductor element, therefore be preferably the dispersion agent that the containing ratio of basic metal such as sodium ion, potassium ion and halogen can be suppressed at below the 10ppm, macromolecule dispersing agents such as preference such as ammonium polyacrylate salt.
The addition of dispersion agent, dispersion of particles from abrasive and the angle consideration that prevents sedimentation and grind the relation of hindering (scuffing) and dispersion agent addition, with respect to cerium oxide particles 100 weight parts, be preferably the scope that 0.01 weight part is above, 5.0 weight parts are following.
The weight-average molecular weight of dispersion agent is preferably 100～50000, and more preferably 1000～10000.If the molecular weight of dispersion agent less than 100, then when grinding silicon oxide film or silicon nitride film, has the tendency that is difficult to obtain sufficient grinding rate,, then has the low tendency of storage stability of viscosity height, abrasive if the molecular weight of dispersion agent surpasses 50000.In the present invention, weight-average molecular weight is measured with gel permeation chromatography, is the value that polystyrene standard converts.
As making cerium oxide particles be scattered in method in the water, except carry out dispersion treatment with common stirrer, can use clarifixator, ultrasonic dispersing machine, wet-type ball mill etc.
The aggregate particle size of the cerium oxide particles in the abrasive of Zhi Zuoing like this, in order to keep size distribution, the particle diameter of 99 volume % of the integral body of preferred cerium oxide particles (below, be called D99) is below the 1.0 μ m.If D99 surpasses 1 μ m, scuffing then mostly occurs.If it is D99 then can reduce scuffing less than below the 0.7 μ m, therefore further preferred.
The intermediate value of the aggregate particle size of the described cerium oxide particles in the abrasive (below, be also referred to as D50), be preferably more than the 100nm, more preferably more than the 150nm.In addition, be preferably below the 2000nm, more preferably below the 500nm.If the intermediate value of offspring, then has the tendency that grinding rate reduces less than 100nm,, then have to be easy to generate on by lapped face and grind the tendency of hindering if surpass 2000nm.Intermediate value of the aggregate particle size of the cerium oxide particles in the abrasive (D50) and D99 can use light scattering method, and for example size-grade distribution meter (for example, the Mastersizer Micro Plus of Ma Erwen Instr Ltd. manufacturing) is measured.
In the present invention, the above particle content of shared particle diameter 3 μ m in weight ratio, is preferably below the 500ppm in the solid integral body in the abrasive.Like this, the effect of minimizing scuffing is obvious.The oversize particle that said described 3 μ m are above is meant in the present invention and filters the particle of catching by the strainer with aperture 3 μ m.More preferably, the above particle content of shared 3 μ m is 200ppm when following in the solid integral body, and the effect that reduces scuffing is big, further preferably, if the above particle content of the 3 μ m that occupied in the solid integral body is below the 100ppm, it is also maximum to reduce the effect that scratches.
The oversize particle content that 3 μ m are above, the particle that can be captured the strainer filtration with aperture 3 μ m carries out weight determination and tries to achieve.The content of the solid integral body in the abrasive can be in advance individually the drying and grinding agent measure.For example, with the abrasive of 10g 150 ℃ dry 1 hour down, the residue that obtains is carried out weight determination, obtain solids concn.Then, multiply by the quality of the filtering abrasive of strainer that is used for aperture 3 μ m, obtain the content in the solid integral body with described solids concn.
As the means that reduce oversize particle content, can use filtration, classification, but be not limited to this.
Abrasive of the present invention, for example, also can be prepared into a liquid formula abrasive that constitutes by additives such as cerium oxide particles, dispersion agent, polymer and water, in addition, also can be prepared into two liquid formula abrasives of the annex solution that classification constitutes for the ceria slurry that is made of cerium oxide particles, dispersion agent and water with by additive and water.No matter which kind of situation all can obtain stable properties.
When preserving,, can regulate planarization characteristics and grinding rate by the cooperation of these two liquid of any change as the two liquid formula lapping liquids that are categorized as ceria slurry and annex solution.In the situation of two liquid formulas, pipe arrangement makes these pipe arrangements interflow, promptly to measure conveying annex solution and ceria slurry arbitrarily with distinguishing independently, the method that can adopt has: the mixing nearby of supplying tubing both, be supplied in the method (hybrid mode nearby) of grinding on the chassis; In container, mix both with ratio arbitrarily in advance, then the method for Gong Geiing (hybrid mode in advance).
Abrasive of the present invention can be used to grind the Ginding process of substrate of the substrate of regulation.For example, can be used for such grinding: on one side to forming on the substrate by grinding film and abrasive cloth between supply with lapping liquid, on one side with substrate by on abrasive cloth, pressurizeing, make by relative movement between grinding film and the abrasive cloth, will be ground smooth by grinding film.
As substrate, can enumerate the substrate of the formation operation that for example relates to semiconductor device, have particularly to separate to form the substrate of on substrate, imbedding inorganic insulation layer in the operation etc. at the substrate that forms inorganic insulation layer on the semiconductor substrate in the stage that forms circuit element, at the shallow ridges element.And,, can enumerate the insulation layer that constitutes by silicon oxide film at least as being described inorganic insulation layer by grinding film.
Embodiment
Below, enumerate embodiments of the invention the present invention is carried out more specific description, but the present invention is not limited to these embodiment.In addition, the chemical substance of using in an embodiment is the reagent of Wako Pure Chemical Industries, Ltd..
Embodiment 1
The making of oxide compound
In the polyethylene container made, add cerous carbonate eight hydrate 100g and succsinic acid 52g carbonate and acid, stirring rake per minute rotation 20 is changeed, mixed 10 minutes as metal.Mixture is put into the aluminum oxide container made, heating 1 hour in air under 750 ℃, thus obtain the yellow-white powder of about 50g.Fig. 1 is the electron scanning micrograph of the powder that obtains like this.Compare with the situation of the not mixed organic acid of comparative example 1 described later, change in shape.Resolve this powder with X-ray diffraction method, confirm to be cerium oxide.
The making of oxide fine particle
The cerium oxide 40g that will obtain in the making of oxide compound, ammonium polyacrylate salt brine solution (40 quality %) 1g and deionized water 759g mix, stir after 10 minutes, pulverized 30 minutes with adverse current wet crushing mill microjet machine (manufacturing of microfluidex company).Adopt laser diffraction formula size-grade distribution meter MastersizerMicro Plus (manufacturing of Ma Erwen Instr Ltd.), measure the cerium oxide particles in the slurry that obtains, result, median size are 300nm.In addition, dry slurry is used the sem observation cerium oxide particles, does not confirm the oversize particle more than 3 microns or thinks the particle of the abrasion powder beyond the cerium oxide.
Embodiment 2
The making of oxide compound
As the carbonate and the acid of metal, use cerous carbonate eight hydrate 100g and propanedioic acid 45g, in addition, operate similarly to Example 1, obtain the powder of the yellow-white of about 50g.Fig. 2 is the electron scanning micrograph of the powder that obtains like this.Resolve this powder with X-ray diffraction method, confirm to be cerium oxide.
The making of oxide fine particle
With making slurry with embodiment 1 complete same method, result, median size are 230nm.In addition, dry slurry is used the sem observation cerium oxide particles, and the result does not confirm the oversize particle more than 3 microns or thinks the particle of the abrasion powder beyond the cerium oxide.
Embodiment 3
The making of oxide compound
Except using cerous carbonate eight hydrate 100g and citric acid 56g, operate similarly to Example 1, obtain the powder of the yellow-white of about 50g.Fig. 3 is the electron scanning micrograph of the powder that obtains like this.Resolve this powder with X-ray diffraction method, confirm as cerium oxide.
The making of oxide fine particle
With making slurry with embodiment 1 identical method, median size is 210nm.In addition, dry slurry is used the sem observation cerium oxide particles, and the result does not confirm the oversize particle more than 3 microns or thinks the particle of the abrasion powder beyond the cerium oxide.
Embodiment 4
The making of oxide compound
Except using cerous carbonate eight hydrate 100g and tartrate 65g, operate similarly to Example 1, obtain the powder of the yellow-white of about 50g.Fig. 4 is the electron scanning micrograph of the powder that obtains like this.Resolve this powder with X-ray diffraction method, confirm as cerium oxide.
The making of oxide fine particle
With making slurry with embodiment 1 identical method, median size is 230nm.In addition, dry slurry is used the sem observation cerium oxide particles, and the result does not confirm the oversize particle more than 3 microns or thinks the particle of the abrasion powder beyond the cerium oxide.
Embodiment 5
The making of oxide compound
Except using cerous carbonate eight hydrate 100g and oxysuccinic acid 58g, operate similarly to Example 1, obtain the block of the yellow-white of about 50g.Pulverize this block with mortar.Fig. 5 is the electron scanning micrograph of the powder that obtains like this.Resolve this powder with X-ray diffraction method, confirm as cerium oxide.
The making of oxide fine particle
With making slurry with embodiment 1 identical method, median size is 290nm.In addition, dry slurry is used the sem observation cerium oxide particles, and the result does not confirm the oversize particle more than 3 microns or thinks the particle of the abrasion powder beyond the cerium oxide.
Embodiment 6
The making of oxide compound
Except using cerous carbonate eight hydrate 100g and oxalic acid dihydrate 55g, operate similarly to Example 1, obtain the powder of the yellow-white of about 50g.Fig. 6 is the electron scanning micrograph of the powder that obtains like this.Resolve this powder with X-ray diffraction method, confirm as cerium oxide.
The making of oxide fine particle
With making slurry with embodiment 1 identical method, median size is 210nm.In addition, dry slurry is used the sem observation cerium oxide particles, and the result does not confirm the oversize particle more than 3 microns or thinks the particle of the abrasion powder beyond the cerium oxide.
Embodiment 7
The making of oxide compound
Except using cerous carbonate eight hydrate 100g and toxilic acid 51g, operate similarly to Example 1, obtain the powder of the yellow-white of about 50g.Fig. 7 is the electron scanning micrograph of the powder that obtains like this.Resolve this powder with X-ray diffraction method, confirm as cerium oxide.
The making of oxide fine particle
With making slurry with embodiment 1 identical method, median size is 280nm.In addition, dry slurry is used the sem observation cerium oxide particles, and the result does not confirm the oversize particle more than 3 microns or thinks the particle of the abrasion powder beyond the cerium oxide.
Embodiment 8
The making of oxide compound
Except using cerous carbonate eight hydrate 100g and hexanodioic acid 64g, operate similarly to Example 1, obtain the block of the yellow-white of about 50g.Pulverize this block with mortar.Fig. 8 is the electron scanning micrograph of the powder that obtains like this.Resolve this powder with X-ray diffraction method, confirm as cerium oxide.
The making of oxide fine particle
With making slurry with embodiment 1 identical method, median size is 280nm.In addition, dry slurry is used the sem observation cerium oxide particles, and the result does not confirm the oversize particle more than 3 microns or thinks the particle of the abrasion powder beyond the cerium oxide.
Embodiment 9
The making of oxide compound
Except using cerous carbonate eight hydrate 100g and Whitfield's ointment 60g, operate similarly to Example 1, obtain the powder of the yellow-white of about 50g.Fig. 9 is the electron scanning micrograph of the powder that obtains like this.Resolve this powder with X-ray diffraction method, confirm as cerium oxide.
The making of oxide fine particle
With making slurry with embodiment 1 identical method, median size is 250nm.In addition, dry slurry is used the sem observation cerium oxide particles, and the result does not confirm the oversize particle more than 3 microns or thinks the particle of the abrasion powder beyond the cerium oxide.
Embodiment 10
The making of oxide compound
Except using cerous carbonate eight hydrate 100g and phenylformic acid 105g, operate similarly to Example 1, obtain the powder of the yellow-white of about 50g.Figure 10 is the electron scanning micrograph of the powder that obtains like this.Resolve this powder with X-ray diffraction method, confirm as cerium oxide.
The making of oxide fine particle
With making slurry with embodiment 1 identical method, median size is 250nm.In addition, dry slurry is used the sem observation cerium oxide particles, and the result does not confirm the oversize particle more than 3 microns or thinks the particle of the abrasion powder beyond the cerium oxide.
Embodiment 11
The making of oxide compound
Except using cerous carbonate eight hydrate 100g and phthalic acid 72g, operate similarly to Example 1, obtain the powder of the yellow-white of about 50g.Figure 11 is the electron scanning micrograph of the powder that obtains like this.Resolve this powder with X-ray diffraction method, confirm as cerium oxide.
The making of oxide fine particle
With making slurry with embodiment 1 identical method, median size is 240nm.In addition, dry slurry is used the sem observation cerium oxide particles, and the result does not confirm the oversize particle more than 3 microns or thinks the particle of the abrasion powder beyond the cerium oxide.
Embodiment 12
The making of oxide compound
Except using cerous carbonate eight hydrate 100g and oxyacetic acid 33g, operate similarly to Example 1, obtain the powder of the yellow-white of about 50g.Figure 12 is the electron scanning micrograph of the powder that obtains like this.Resolve this powder with X-ray diffraction method, confirm as cerium oxide.
The making of oxide fine particle
With making slurry with embodiment 1 identical method, median size is 200nm.In addition, dry slurry is used the sem observation cerium oxide particles, and the result does not confirm the oversize particle more than 3 microns or thinks the particle of the abrasion powder beyond the cerium oxide.
Embodiment 13
The making of oxide compound
Except using cerous carbonate eight hydrate 100g and xitix 77g, operate similarly to Example 1, obtain the powder of the yellow-white of about 50g.Figure 13 is the electron scanning micrograph of the powder that obtains like this.Resolve this powder with X-ray diffraction method, confirm as cerium oxide.
The making of oxide fine particle
With making slurry with embodiment 1 identical method, median size is 280nm.In addition, dry slurry is used the sem observation cerium oxide particles, and the result does not confirm the oversize particle more than 3 microns or thinks the particle of the abrasion powder beyond the cerium oxide.
Embodiment 14
The making of oxide compound
Except the polyacrylic acid 63g that uses cerous carbonate eight hydrate 100g and molecular-weight average 25000, operate similarly to Example 1, obtain the powder of the yellow-white of about 50g.Figure 14 is the electron scanning micrograph of the powder that obtains like this.Resolve this powder with X-ray diffraction method, confirm as cerium oxide.
The making of oxide fine particle
With making slurry with embodiment 1 identical method, median size is 270nm.In addition, dry slurry is used the sem observation cerium oxide particles, and the result does not confirm the oversize particle more than 3 microns or thinks the particle of the abrasion powder beyond the cerium oxide.
Embodiment 15
The making of oxide compound
Except using cerous carbonate eight hydrate 100g and polymethyl acrylic acid 75g, operate similarly to Example 1, obtain the powder of the yellow-white of about 50g.Figure 15 is the electron scanning micrograph of the powder that obtains like this.Resolve this powder with X-ray diffraction method, confirm as cerium oxide.
The making of oxide fine particle
With making slurry with embodiment 1 identical method, median size is 290nm.In addition, dry slurry is used the sem observation cerium oxide particles, and the result does not confirm the oversize particle more than 3 microns or thinks the particle of the abrasion powder beyond the cerium oxide.
Embodiment 16
The making of oxide compound
Except using cerous carbonate eight hydrate 90g, lanthanum carbonate hydrates 10g and propanedioic acid 45g, operate similarly to Example 1, obtain the powder of the yellow-white of about 50g.Figure 16 is the electron scanning micrograph of the powder that obtains like this.Resolve this powder with X-ray diffraction method, confirm as the mixture of cerium oxide and lanthanum trioxide.
The making of oxide fine particle
With making slurry with embodiment 1 identical method, median size is 220nm.In addition, dry slurry, with sem observation cerium oxide and lanthanum trioxide particle, the result does not confirm the oversize particle more than 3 microns or thinks cerium oxide and the particle of lanthanum trioxide abrasion powder in addition.
Comparative example 1
The making of oxide compound
Except need not acid and only use the cerous carbonate eight hydrate 100g, operation similarly to Example 1 obtains the powder of the yellow-white of about 50g.Figure 17 is the electron scanning micrograph of the powder that obtains like this.Resolve this powder with X-ray diffraction method, confirm as cerium oxide.
The making of oxide fine particle
With making slurry with embodiment 1 complete same method, median size is 340nm.In addition, dry slurry is used the sem observation cerium oxide particles, and the result observes the oversize particle more than 3 microns.In addition, with other observed amorphous particle of energy dispersion X ray component analysis device analysis, the result confirms for containing iron particle.Owing to promptly use the particle before energy dispersion X ray component analysis device analysis is pulverized, also fail to confirm and contain iron particle, therefore, think that ferruginous amorphous particle is the abrasion powder that comes from beyond the cerium oxide.
Comparative example 2
The making of oxide compound
Except need not acid and use cerous carbonate eight hydrate 100g and be not the polyoxyethylene glycol 50g of molecular-weight average 400 of acid, operation similarly to Example 1 obtains the powder of the yellow-white of about 50g.Figure 18 is the electron scanning micrograph of the powder that obtains like this.Resolve this powder with X-ray diffraction method, confirm as cerium oxide.
The making of oxide fine particle
With making slurry with embodiment 1 identical method, median size is 340nm.In addition, dry slurry is used the sem observation cerium oxide particles, analyzes with energy dispersion X ray component analysis device, as a result, similarly confirm the oversize particle more than 3 microns with comparative example 1 and think the particle of the abrasion powder beyond the cerium oxide.
Embodiment 17
Commercially available cerous carbonate 6kg and oxalic acid dihydrate 3.3kg are put into the polyethylene container made that has venting hole, mixed in 5 minutes with the vibrating machine vibration.Mixture is put into the aluminum oxide container made, under 800 ℃, in air, burnt till 2 hours, obtain the yellow-white powder of 3kg.With X-ray diffraction method this powder is carried out the identification of phases, confirm to be cerium oxide.
The above-mentioned cerium oxide particles 1000g that obtains, ammonium polyacrylate salt brine solution (40 quality %) 80g and deionized water 5600g are mixed, stir after 10 minutes, carry out 30 minutes case of wet attrition with ball mill (manufacturing of ashizawa finetec company).Make the dispersion liquid that obtains standing sedimentation 20 hours at room temperature, take supernatant liquor.After filtering this supernatant liquor with the strainer of aperture 1.0 μ m, the strainer with 1.0 μ m filters again, adds deionized water, and solid component concentration is adjusted to 5%, obtains the cerium oxide abrasive that semiconductor planarization is used.
Adopt laser diffraction formula size-grade distribution meter (the MastersizerMicro Plus that Ma Erwen Instr Ltd. makes), in specific refractory power: 1.9285, light source: He-Ne laser, absorb under 0 the condition, the cerium oxide abrasive stoste that semiconductor planarization is used, the particle diameter of the cerium oxide abrasive that the semiconductor planarization that mensuration obtains is used, the result, the intermediate value of aggregate particle size (D50) is 190nm, and D99 is 0.7 μ m.
In order to investigate oversize particle content, 15 times of the cerium oxide abrasive dilution agents that the semiconductor planarization that obtains is used are with 3 μ m strainers (the cyclopore track etch thin film strainer that Whatman Inc. (US) makes) filter 23 0g.After the filtration, device for drying and filtering is at room temperature measured the quality of strainer, and the quality before and after filtering increases, and obtains the above oversize particle amount of 3 μ m.In addition, this abrasive 10g was descended dry 1 hour at 150 ℃, calculate the solids concn in the abrasive.As a result, the above oversize particle amount (mass ratio) of 3 μ m is 300ppm in solid.
In addition, the cerium oxide abrasive that above-mentioned semiconductor planarization is used dilutes 5 times with deionized water, grinds in order to following method.Grinding rate is 650nm/min, uses the observation by light microscope wafer surface, observes 20 scuffings on whole of 200mm wafer.
The grinding test method
Grind loading: 30kPa
Grinding pad: the foaming polyurethane resin (IC-1000) that Rodel company makes
Revolution: chassis 75min
-1, pad 75min
-1
Abrasive feed speed: 200mL/min
Grind object: P-TEOS film forming Si wafer (200mm)
Embodiment 18
The cerium oxide particles 1000g that will obtain in embodiment 17, ammonium polyacrylate salt brine solution (40 quality %) 80g and deionized water 5600g mix, stir after 10 minutes, carry out 30 minutes case of wet attrition with ball mill (manufacturing of ashizawafinetec company).Make the dispersion liquid that obtains standing sedimentation 100 hours at room temperature, take supernatant liquor.After filtering this supernatant liquor with the strainer of aperture 0.7 μ m, the strainer with 0.7 μ m filters again, adds deionized water, and solid component concentration is adjusted to 5%, obtains the cerium oxide abrasive that semiconductor planarization is used.
With method similarly to Example 17, the particle diameter of the cerium oxide abrasive that the semiconductor planarization that mensuration obtains is used, the result, the intermediate value of aggregate particle size (D50) is 160nm, and D99 is 0.5 μ m.
In order to investigate oversize particle content, the cerium oxide abrasive that the semiconductor planarization that obtains is used is with similarly to Example 1 method, and the oversize particle amount more than the 3 μ m is obtained in the quality increase before and after filter.As a result, the above oversize particle amount of 3 μ m is 20ppm in solid.
In addition, the cerium oxide abrasive that above-mentioned semiconductor planarization is used dilutes 5 times with deionized water, grinds with grinding test method similarly to Example 1.Grinding rate is 350nm/min, uses the observation by light microscope wafer surface, and the result observes 10 scuffings on whole of 200mm wafer.
Embodiment 19
Commercially available cerous carbonate 6kg and oxalic acid dihydrate 4.9kg are put into the polyethylene container made that has venting hole, mixed in 12 hours with the vibrating machine vibration.Mixture is put into the aluminum oxide container made, under 800 ℃, in air, burnt till 2 hours, obtain the yellow-white powder of 3kg.With X-ray diffraction method this powder is carried out the identification of phases, confirm to be cerium oxide.
The above-mentioned cerium oxide particles 1000g that obtains, ammonium polyacrylate salt brine solution (40 quality %) 80g and deionized water 5600g are mixed, stir after 10 minutes, carry out 30 minutes case of wet attrition with ball mill (manufacturing of ashizawa finetec company).Make the dispersion liquid that obtains standing sedimentation 100 hours at room temperature, take supernatant liquor.After filtering this supernatant liquor with the strainer of aperture 0.7 μ m, the strainer with 0.7 μ m filters again, adds deionized water, and solid component concentration is adjusted to 5%, obtains the cerium oxide abrasive that semiconductor planarization is used.
With method similarly to Example 17, the particle diameter of the cerium oxide abrasive that the semiconductor planarization that mensuration obtains is used, the result, the intermediate value of aggregate particle size (D50) is 160nm, and D99 is 0.5 μ m.
In order to investigate oversize particle content, the cerium oxide abrasive that the semiconductor planarization that obtains is used is with similarly to Example 17 method, and the oversize particle amount more than the 3 μ m is obtained in the quality increase before and after filter.As a result, the above oversize particle amount of 3 μ m is 20ppm in solid.
In addition, the cerium oxide abrasive that above-mentioned semiconductor planarization is used dilutes 5 times with deionized water, grinds with grinding test method similarly to Example 17.Grinding rate is 350nm/min, uses the observation by light microscope wafer surface, and the result observes 10 scuffings on whole of 200mm wafer.
Embodiment 20
Commercially available cerous carbonate 6kg and oxalic acid (anhydrous) 2.4kg are put into the polyethylene container made that has venting hole, mixed in 5 minutes with the vibrating machine vibration.Mixture is put into the aluminum oxide container made, under 800 ℃, in air, burnt till 2 hours, obtain the yellow-white powder of 3kg.With X-ray diffraction method this powder is carried out the identification of phases, confirm to be cerium oxide.
The above-mentioned cerium oxide particles 1000g that obtains, ammonium polyacrylate salt brine solution (40 quality %) 80g and deionized water 5600g are mixed, stir after 10 minutes, carry out 30 minutes case of wet attrition with ball mill (manufacturing of ashizawa finetec company).Make the dispersion liquid that obtains standing sedimentation 100 hours at room temperature, take supernatant liquor.After filtering this supernatant liquor with the strainer of aperture 0.7 μ m, the strainer with 0.7 μ m filters again, adds deionized water, and solid component concentration is adjusted to 5%, obtains the cerium oxide abrasive that semiconductor planarization is used.
With method similarly to Example 17, the particle diameter of the cerium oxide abrasive that the semiconductor planarization that mensuration obtains is used, the result, the intermediate value of aggregate particle size (D50) is 160nm, and D99 is 0.5 μ m.
In order to investigate oversize particle content, the cerium oxide abrasive that the semiconductor planarization that obtains is used is with similarly to Example 17 method, and the oversize particle amount more than the 3 μ m is obtained in the quality increase before and after filter.As a result, the above oversize particle amount of 3 μ m is 20ppm in solid.
In addition, the cerium oxide abrasive that above-mentioned semiconductor planarization is used dilutes 5 times with deionized water, grinds with grinding test method similarly to Example 17.Grinding rate is 350nm/min, uses the observation by light microscope wafer surface, and the result observes 10 scuffings on whole of 200mm wafer.
Comparative example 3
Commercially available cerous carbonate 6kg is put into the aluminum oxide container made, under 800 ℃, in air, burnt till 2 hours, obtain the powder of 3kg yellow-white.This powder is carried out the identification of phases with X-ray diffraction method, confirm to be cerium oxide.
Similarly to Example 17, the above-mentioned cerium oxide particles 1000g that obtains, ammonium polyacrylate salt brine solution (40 quality %) 80g and deionized water 5600g are mixed, stir after 10 minutes, carry out 30 minutes case of wet attrition with ball mill (manufacturing of ashizawa finetec company).Make the dispersion liquid that obtains standing sedimentation 20 hours at room temperature, take supernatant liquor.After filtering this supernatant liquor with the strainer of aperture 1.0 μ m, the strainer with 1.0 μ m filters again, adds deionized water, and solid component concentration is adjusted to 5%, obtains the cerium oxide abrasive that semiconductor planarization is used.
With method similarly to Example 17, the particle diameter of the cerium oxide abrasive that the semiconductor planarization that mensuration obtains is used, the result, the intermediate value of aggregate particle size (D50) is 190nm, and D99 is 0.7 μ m.
In order to investigate oversize particle content, the cerium oxide abrasive that the semiconductor planarization that obtains is used is with similarly to Example 17 method, and the oversize particle amount more than the 3 μ m is obtained in the quality increase before and after filter.As a result, the above oversize particle amount of 3 μ m is 500ppm in solid.
In addition, the cerium oxide abrasive that above-mentioned semiconductor planarization is used dilutes 5 times with deionized water, grinds with grinding test method similarly to Example 17.Grinding rate is 650nm/min, uses the observation by light microscope wafer surface, and the result observes 50 scuffings on whole of 200mm wafer.
Comparative example 4
Similarly to Example 18, cerium oxide particles 1000g, ammonium polyacrylate salt brine solution (the 40 quality %) 80g and the deionized water 5600g that obtain in the above-mentioned comparative example 3 are mixed, stir after 10 minutes, carry out 30 minutes case of wet attrition with ball mill (manufacturing of ashizawa finetec company).Make the dispersion liquid that obtains standing sedimentation 100 hours at room temperature, take supernatant liquor.After filtering this supernatant liquor with the strainer of aperture 0.7 μ m, the strainer with 0.7 μ m filters again, adds deionized water, and solid component concentration is adjusted to 5%, obtains the cerium oxide abrasive that semiconductor planarization is used.
With method similarly to Example 17, the particle diameter of the cerium oxide abrasive that the semiconductor planarization that mensuration obtains is used, the result, the intermediate value of aggregate particle size (D50) is 160nm, and D99 is 0.5 μ m.
In order to investigate oversize particle content, the cerium oxide abrasive that the semiconductor planarization that obtains is used is with similarly to Example 17 method, and the oversize particle amount more than the 3 μ m is obtained in the quality increase before and after filter.As a result, the above oversize particle amount of 3 μ m is 50ppm in solid.
In addition, the cerium oxide abrasive that above-mentioned semiconductor planarization is used dilutes 5 times with deionized water, grinds with grinding test method similarly to Example 17.Grinding rate is 350nm/min, uses the observation by light microscope wafer surface, and the result observes 15 scuffings on whole of 200mm wafer.
Comparative example 5
The cerium oxide particles 1000g that will obtain in comparative example 3, ammonium polyacrylate salt brine solution (40 quality %) 80g and deionized water 5600g mix, and stir after 10 minutes, carry out 2 hours case of wet attrition with ball mill (manufacturing of ashizawa finetec company).Similarly to Example 18, make the dispersion liquid that obtains standing sedimentation 100 hours at room temperature, take supernatant liquor.After filtering this supernatant liquor with the strainer of aperture 0.7 μ m, the strainer with 0.7 μ m filters again, adds deionized water, and solid component concentration is adjusted to 5%, obtains the cerium oxide abrasive that semiconductor planarization is used.
With method similarly to Example 17, the particle diameter of the cerium oxide abrasive that the semiconductor planarization that mensuration obtains is used, the result, the intermediate value of aggregate particle size (D50) is 160nm, and D99 is 0.5 μ m.
In order to investigate oversize particle content, the cerium oxide abrasive that the semiconductor planarization that obtains is used is with similarly to Example 17 method, and the oversize particle amount more than the 3 μ m is obtained in the quality increase before and after filter.As a result, the above oversize particle amount of 3 μ m is 30ppm in solid.
In addition, the cerium oxide abrasive that above-mentioned semiconductor planarization is used dilutes 5 times with deionized water, grinds with grinding test method similarly to Example 17.Grinding rate is 350nm/min, uses the observation by light microscope wafer surface, and the result observes 30 scuffings on whole of 200mm wafer.
Industrial application
By the present invention, can provide the oxygen of the particulate that can not contained rapidly oversize grain and abrasion powder The manufacture method of compound particle, and slurry therefrom. In addition, can provide a kind of grinding agent and base The Ginding process of plate, described grinding agent reduce scratching when keeping suitable grinding rate, and can The semiconductor surface that distribution is formed operation grinds to such an extent that flatness is good.
Claims (19)
1. the manufacture method of an oxide particle is characterized in that, comprises:
The carbonate and the acid of metal are mixed the operation that obtains mixture,
Heat the operation that described mixture obtains metal oxide,
Pulverize the operation of described metal oxide.
2. the manufacture method of oxide particle according to claim 1, wherein, the carbonate of metal is cerous carbonate.
3. the manufacture method of oxide particle according to claim 1 and 2, wherein, acid is solid at 25 ℃.
4. the manufacture method of oxide particle according to claim 3, wherein, acid is Powdered at 25 ℃.
5. according to the manufacture method of each described oxide particle in the claim 1～4, wherein, acid is organic acid.
6. the manufacture method of oxide particle according to claim 5, wherein, organic acid is made of carbon atom, Sauerstoffatom and hydrogen atom.
7. according to the manufacture method of claim 5 or 6 described oxide particles, wherein, organic acid acid ionization constant pKa is than the acid ionization constant pKa of carbonic acid
1Little.
8. the manufacture method of oxide particle according to claim 7, wherein, organic acid acid ionization constant pKa is below 6.
9. according to the manufacture method of each described oxide particle in the claim 5～8, wherein, organic acid is at least a for what select from succsinic acid, propanedioic acid, citric acid, tartrate, oxysuccinic acid, oxalic acid, toxilic acid, hexanodioic acid, Whitfield's ointment, phenylformic acid, phthalic acid, oxyacetic acid, xitix, their isomer, polymkeric substance or multipolymer, polyacrylic acid, polymethyl acrylic acid.
10. according to the manufacture method of each described oxide particle in the claim 5～9, wherein, the carbonate of metal is cerous carbonate, and organic acid is an oxalic acid, and the ratio of mixture of cerous carbonate and oxalic acid is: with respect to 1 mole cerous carbonate, oxalic acid is 0.5～6 mole.
11. a slurry is characterized in that, contains the resulting metal oxide particle of the manufacture method by each described oxide particle in the claim 1～10 that is scattered in the aqueous medium.
12. an abrasive is characterized in that, containing the metal that is scattered in the aqueous medium is that cerium and acid are the resulting cerium oxide particles of the manufacture method by each described oxide particle in the claim 1～10 of oxalic acid.
13. an abrasive is characterized in that, contains the particle of the cerium oxide after the pulverizing in aqueous medium, the mixture of described cerium oxide heating cerous carbonate and oxalic acid obtains.
14. according to claim 12 or 13 described abrasives, wherein, the intermediate value of cerium oxide particle diameter is 100～2000nm.
15. abrasive according to claim 14, wherein, the above cerium oxide particles of particle diameter 3 μ m is below the 500ppm in solid.
16., wherein, further contain dispersion agent according to each described abrasive in claim 14 or 15.
17. according to each described abrasive in the claim 14～16, wherein, all in the cerium oxide particles, the particle diameter of the cerium oxide particles of 99 volume % is below the 1.0 μ m.
18. the Ginding process of a substrate is characterized in that, grinds the substrate of regulation with each described abrasive in the claim 12～17.
19. the Ginding process of substrate according to claim 18, wherein, the substrate of regulation is the semiconductor substrate that is formed with silicon oxide film at least.
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| JP2006117772 | 2006-04-21 | ||
| JP117772/2006 | 2006-04-21 | ||
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110168702A (en) * | 2016-12-26 | 2019-08-23 | 福吉米株式会社 | Composition for polishing and grinding method |
| CN112041120A (en) * | 2018-04-24 | 2020-12-04 | 3M创新有限公司 | Abrasive particles comprising shaped abrasive particles having a predetermined angle of inclination |
| CN113213523A (en) * | 2021-06-29 | 2021-08-06 | 广西立之亿新材料有限公司 | Nano cerium oxide powder with high cutting efficiency and preparation method thereof |
| CN115433521A (en) * | 2022-09-21 | 2022-12-06 | 广东粤港澳大湾区黄埔材料研究院 | Cerium oxide granulation powder polishing solution and application thereof |
-
2007
- 2007-04-20 CN CNA2007800141741A patent/CN101426730A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110168702A (en) * | 2016-12-26 | 2019-08-23 | 福吉米株式会社 | Composition for polishing and grinding method |
| CN110168702B (en) * | 2016-12-26 | 2023-12-29 | 福吉米株式会社 | Polishing composition and polishing method |
| CN112041120A (en) * | 2018-04-24 | 2020-12-04 | 3M创新有限公司 | Abrasive particles comprising shaped abrasive particles having a predetermined angle of inclination |
| CN112041120B (en) * | 2018-04-24 | 2023-01-10 | 3M创新有限公司 | Abrasive article comprising shaped abrasive particles having a predetermined angle of inclination |
| CN113213523A (en) * | 2021-06-29 | 2021-08-06 | 广西立之亿新材料有限公司 | Nano cerium oxide powder with high cutting efficiency and preparation method thereof |
| CN115433521A (en) * | 2022-09-21 | 2022-12-06 | 广东粤港澳大湾区黄埔材料研究院 | Cerium oxide granulation powder polishing solution and application thereof |
| CN115433521B (en) * | 2022-09-21 | 2024-06-04 | 广州飞雪芯材有限公司 | Cerium oxide granulation powder polishing solution and application thereof |
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