WO2000039843A1 - Cmp abrasive, liquid additive for cmp abrasive and method for polishing substrate - Google Patents
Cmp abrasive, liquid additive for cmp abrasive and method for polishing substrate Download PDFInfo
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- WO2000039843A1 WO2000039843A1 PCT/JP1999/007209 JP9907209W WO0039843A1 WO 2000039843 A1 WO2000039843 A1 WO 2000039843A1 JP 9907209 W JP9907209 W JP 9907209W WO 0039843 A1 WO0039843 A1 WO 0039843A1
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- WIPO (PCT)
- Prior art keywords
- polishing
- slurry
- cmp
- dispersant
- cerium oxide
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Classifications
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
- H10P52/00—Grinding, lapping or polishing of wafers, substrates or parts of devices
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24D—TOOLS FOR GRINDING, BUFFING OR SHARPENING
- B24D3/00—Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents
- B24D3/34—Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents characterised by additives enhancing special physical properties, e.g. wear resistance, electric conductivity, self-cleaning properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
- B24B37/00—Lapping machines or devices; Accessories
- B24B37/04—Lapping machines or devices; Accessories designed for working plane surfaces
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09G—POLISHING COMPOSITIONS; SKI WAXES
- C09G1/00—Polishing compositions
- C09G1/02—Polishing compositions containing abrasives or grinding agents
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
- C09K3/1454—Abrasive powders, suspensions and pastes for polishing
- C09K3/1463—Aqueous liquid suspensions
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
- H10P95/00—Generic processes or apparatus for manufacture or treatments not covered by the other groups of this subclass
- H10P95/06—Planarisation of inorganic insulating materials
- H10P95/062—Planarisation of inorganic insulating materials involving a dielectric removal step
Definitions
- the present invention relates to a CMP polishing agent, an additive solution for a CMP polishing agent, and a substrate polishing method used in a semiconductor device manufacturing technique. More specifically, the present invention relates to a substrate surface flattening step, and more particularly, an inter-layer insulating film flattening step. The present invention relates to a CMP polishing agent used in a step of forming a shallow trench isolation, a CMP polishing additive, and a method of polishing a substrate using the CMP polishing agent.
- CMP chemical mechanical polishing
- Colloidal silica-based abrasives have been generally studied as an abrasive. Colloidal silica-based abrasives are produced by subjecting silica particles to grain growth by a method such as thermal decomposition of tetrachlorosilicic acid and adjusting the pH. However, such an abrasive has a technical problem that the polishing rate of the inorganic insulating film does not have a sufficient rate, and it is necessary to improve a low polishing rate for practical use.
- LOCOS Silicon Local Oxidation
- CMP is used to remove excess silicon oxide film deposited on the substrate.
- a stopper film having a low polishing rate is formed below the silicon oxide film. Silicon nitride or the like is used for the stopper film, and it is desirable that the polishing rate ratio between the silicon oxide film and the stopper film is large.
- the conventional colloidal silica-based abrasive has a small polishing rate ratio of about 3 between the silicon oxide film and the stopper film, and does not have practically usable characteristics for shallow trench isolation.
- cerium oxide abrasives have been used as glass surface abrasives for photomasks and lenses. Cerium oxide particles have a lower hardness than alumina particles and are less likely to scratch the polished surface, so they are useful for finishing mirror polishing.
- a cerium oxide abrasive for polishing a glass surface uses a dispersant containing a sodium salt, and thus cannot be used as it is as a semiconductor abrasive. Disclosure of the invention
- An object of the present invention is to provide a CMP polishing slurry that can polish a surface to be polished such as a silicon oxide insulating film at high speed without any damage.
- Another object of the present invention in addition to the above invention, is to polish a surface to be polished such as a silicon oxide insulating film at high speed without flaws without contaminating alkali metal such as sodium ions on the surface to be polished. It is an object of the present invention to provide a possible CMP polishing agent.
- Another object of the present invention is to provide, in addition to the above invention, a CMP polishing agent capable of increasing a ratio of a polishing rate of a silicon oxide insulating film to a polishing rate of a silicon nitride insulating film.
- Another object of the present invention is to provide a high-speed polishing of a surface to be polished such as a silicon oxide insulating film without flaws and contamination of the surface to be polished without alkali metal contamination such as sodium ions.
- An object of the present invention is to provide a CMP polishing slurry with improved storage stability of the slurry.
- Another object of the present invention in addition to the above invention, is to polish a surface to be polished such as a silicon oxide insulating film at high speed without flaws without contaminating alkali metal such as sodium ions on the surface to be polished. It is an object of the present invention to provide a CMP polishing slurry which makes a ratio of a polishing rate of a silicon oxide insulating film to a polishing rate of a silicon nitride insulating film 50 or more.
- Another object of the present invention is to improve the storage stability of the above-mentioned CMP abrasive.
- An object of the present invention is to provide an additive for a CMP polishing slurry to be used.
- Another object of the present invention is to provide a CMP polishing slurry additive liquid used for improving the flatness of a polished surface of a substrate.
- Another object of the present invention is to provide a substrate polishing method capable of polishing a surface to be polished of a substrate without scratching.
- Another object of the present invention is to enable a surface to be polished such as a silicon oxide insulating film to be polished at high speed without being damaged, and to have a ratio of a polishing rate of a silicon oxide film to a polishing rate of a silicon nitride film of 50 or more. To provide a polishing method for a substrate.
- the present invention relates to the following.
- a CMP polishing slurry comprising a cerium oxide slurry containing cerium oxide particles, a dispersant and water, and an additive liquid containing a dispersant and water.
- the content of the dispersant in the cerium oxide slurry is 0.01 to 2.0 parts by weight based on 100 parts by weight of the cerium oxide particles, and the content of the cerium oxide particles is 0.3 to 40% by weight based on the cerium oxide slurry.
- the dispersant is a polyacrylic acid ammonium salt or a polyacrylic acid amine salt (9) Additive for CMP abrasive.
- a polishing method for a substrate comprising: moving a substrate and a polishing plate while polishing a film to be polished.
- cerium oxide is obtained by oxidizing cerium compounds of carbonate, nitrate, sulfate and oxalate.
- TEOS Cerium oxide abrasives used for polishing silicon oxide films formed by CVD, etc., have large primary particle diameters and use single crystal cerium oxide particles, but they tend to have polishing scratches. is there. Therefore, the cerium oxide particles used in the present invention are not limited to the production method, but are preferably polycrystals in which single crystal particles having a size of 5 nm or more and 300 nm or less are aggregated. Further, since it is used for polishing a semiconductor chip, it is preferable that the contents of alkali metals and halogens be suppressed to 10 ppm or less in the cerium oxide particles.
- the cerium oxide powder as a method for producing the cerium oxide powder, calcination or an oxidation method using hydrogen peroxide or the like can be used.
- the firing temperature is preferably 350 ⁇ or more and 900 ⁇ or less.
- cerium carbonate is preferable. Since the cerium oxide particles produced by the above method are agglomerated, it is preferable to mechanically pulverize the particles.
- a pulverization method a dry pulverization method using a jet mill or the like and a wet pulverization method using a planetary bead mill or the like are preferable.
- the cerium oxide slurry in the present invention can be obtained, for example, by dispersing a cerium oxide particle having the above characteristics, a dispersant of cerium oxide particles in water, and water.
- the content of the cerium oxide particles is not limited, but is preferably 0.3 to 40% by weight, and more preferably 0.5 to 20% by weight from the viewpoint of easy handling of the dispersion.
- the content of cerium oxide particles in the CMP polishing slurry when the cerium oxide slurry and the additive liquid are mixed is preferably 0.01 to 10% by weight, more preferably 0.1 to 5% by weight.
- the dispersant is one selected from a polymer dispersant, a water-soluble anionic surfactant, a water-soluble nonionic surfactant, a water-soluble cationic surfactant, and a water-soluble amphoteric surfactant. Or two or more compounds are used. Since it is used for polishing a semiconductor chip, it is preferable that the content of alkali metal such as sodium ion and potassium ion, halogen and zeolite in the dispersant be suppressed to 10 ppm or less.
- polymer dispersant examples include: unsaturated polymers such as acrylic acid, methacrylic acid, and maleic acid; polymers of rubonic acid or its ammonium salts and amine salts; unsaturated carboxylic acids such as acrylic acid, methacrylic acid, and maleic acid; Alkyl acrylates such as methyl acrylate and ethyl acrylate; hydroxyalkyl acrylates such as hydroxyethyl acrylate; alkyl methacrylate such as methyl methacrylate and ethyl methacrylate; hydroxy methacrylate such as hydroxyethyl ethyl methacrylate; Copolymers with copolymerizable monomers such as alkyl, vinyl acetate and vinyl alcohol, and their ammonium salts and amine salts.
- unsaturated polymers such as acrylic acid, methacrylic acid, and maleic acid
- polymers of rubonic acid or its ammonium salts and amine salts unsaturated carboxylic acids such
- the unsaturated carboxylic acid may be converted into an ammonium salt before polymerization.
- the ratio of the unsaturated carboxylic acid in these polymers or copolymers is preferably from 1 to 100 mol%, and particularly preferably from 10 to 100 mol%.
- a polymer containing ammonium acrylate as a copolymer component, polyammonium acrylate, and polyamine acrylate are preferable.
- the weight average molecular weight of the ammonium polyacrylate or the amine salt of polyataryl acid is preferably 1,000. ⁇ : 100,000, more preferably 3,000 to 60,000, even more preferably 10,000 to 40,000. If the weight average molecular weight is less than 1,000, the cerium oxide particles tend to aggregate, and if it exceeds 100,000, the polishing rate ratio tends to decrease.
- the molecular weight distribution (weight average molecular weight and number average molecular weight) of the ammonium polyacrylate or the polyacrylamide salt is preferably 1.005 to 1.300, more preferably 1.100 to 1.250, and further preferably 1.150 to 1.200. If the molecular weight distribution is less than 1.005, the cerium oxide particles tend to aggregate, and if it exceeds 1.300, the polishing rate ratio tends to decrease.
- the weight average molecular weight and number average molecular weight used are those measured by gel permeation chromatography using a standard polystyrene calibration curve.
- Polyacrylic acid ammonium or polyacrylic acid amine salt is obtained by mixing polyacrylic acid with an equimolar amount of ammonia or amine with its propyloxyl group and allowing it to undergo a neutralization reaction.
- Those having a proportion of ammonia or amine of 10 mol% or less are particularly preferred in terms of high flatness.
- the amount of free ammonia or amine which does not form a salt can be determined by quantifying the amount of ammonia or amine in a solution obtained by adding an organic solvent and precipitating and filtering the polymer.
- water-soluble anionic surfactant examples include triethanolamine lauryl sulfate, ammonium lauryl sulfate, and polyoxyethylene alkyl ether sulfate triethanolamine.
- water-soluble nonionic surfactant examples include polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene higher alcohol ether, and polyoxyethylene.
- the cationic surfactant include coconutamine acetate, stearylamine acetate, and the like.
- water-soluble amphoteric surfactant examples include lauryl betaine, stearyl betaine, lauryl dimethylamine oxide, 2-alkyl-N-potoxymethyl-1-N-hydroxyethylimidazolinium betaine and the like.
- the amount of these dispersants added to the cerium oxide slurry is 0.01 weight per 100 parts by weight of the cerium oxide particles due to the dispersibility and prevention of sedimentation of the particles in the slurry and the relationship between the polishing scratches and the amount of the dispersant added.
- the range is preferably from 2.0 parts by weight to 2.0 parts by weight.
- the molecular weight of the high molecular weight dispersant is preferably 100 to 100,000, more preferably 100 to 50,000 as a weight average molecular weight measured by gel permeation chromatography using a standard polystyrene calibration curve. , 000 to 10,000 are more preferred. If the molecular weight of the dispersant is too small, a sufficient polishing rate cannot be obtained when polishing a silicon oxide film or a silicon nitride film, and if the molecular weight of the dispersant is too large, the viscosity increases and the cerium oxide slurry is stored. This is because the stability decreases.
- the pH of the cerium oxide slurry is preferably 6 to: 10.
- the pH is too low, the storage stability of the mixed solution of the cerium oxide slurry and the additive liquid is reduced, and polishing scratches occur when the silicon oxide film or silicon nitride film is polished, and if the pH is too high, This is because the storage stability of the liquid mixture of the cerium oxide slurry and the additive liquid is reduced, and polishing scratches occur when the silicon oxide film or the silicon nitride film is polished.
- a method of mixing and stirring aqueous ammonia is used.
- a homogenizer As a method of dispersing these cerium oxide particles in water, a homogenizer, an ultrasonic disperser, a wet pole mill, or the like can be used in addition to the dispersion treatment using a normal stirrer.
- the average particle size of the cerium oxide particles in the slurry thus produced is preferably 0.01 m to 1.0 m. If the average particle size of the polishing liquid is too small, the polishing rate will be too low, and if the average particle size is too large, the film to be polished will be easily damaged.
- the CMP polishing slurry additive liquid of the present invention contains a dispersant and water.
- a dispersing agent for dispersing the cerium oxide particles in water used in the cerium oxide slurry described above is preferably used in the cerium oxide slurry in view of the polishing rate ratio of the polished surface and high flatness. It is also preferably used in an additive solution.
- the kind of the dispersant for the cerium oxide slurry and the additive liquid may be the same or different.
- the concentration of the dispersant is preferably 1 to L0% by weight in the additive liquid. If it is less than 1% by weight, the flatness of the polished surface tends to decrease, and if it exceeds 10% by weight, the cerium oxide particles tend to aggregate.
- the CMP polishing slurry of the present invention is prepared by separately preparing a cerium oxide slurry and an additive solution, and mixing and using the two at the time of polishing.
- the cerium oxide slurry and the above-mentioned additive solution are mixed and stored, the cerium oxide slurry is added. Particles agglomerate, causing polishing flaws and causing fluctuations in the polishing rate. Therefore, this additive liquid is supplied to the polishing platen separately from the cerium oxide slurry and mixed on the polishing platen, or mixed with the cerium oxide slurry immediately before polishing and supplied to the polishing platen.
- the mixing ratio of the cerium oxide slurry and the additive liquid is not particularly limited as long as it finally reaches a target concentration.
- the amount of the dispersant used in the additive liquid relative to the cerium oxide is determined based on the dispersibility of the particles in the slurry and the prevention of sedimentation, and the relationship between the polishing scratches and the amount of the dispersant added.
- the dispersant in the additive liquid is preferably in the range of 0.001 to 2000 parts by weight, more preferably 0.01 to: L000 parts by weight, and still more preferably 0.01 to 500 parts by weight.
- the added liquid preferably has a specific gravity of 1.005 to 1.050.
- the specific gravity is more preferably 1.007 to 1.040, and still more preferably 1.010 to 1.030.
- the pH of the additive solution is preferably 4 to 8.
- the pH is more preferably 5-7, and even more preferably 6-7. If the pH is less than 4, the polishing rate tends to decrease, and if the pH exceeds 8, the flatness of the polished surface tends to decrease.
- the pH is adjusted by adding an acid or an alkali such as acetic acid or aqueous ammonia to the additive solution.
- the viscosity of the additive liquid at 25 is preferably from 1.20 to 2.50 mPa ⁇ s.
- the viscosity is more preferably 1.30 to 2.30 mPa ⁇ s, More preferably, it is 1.40 to 2.20 mPa ⁇ s. If the viscosity is less than 1.20 mPa ⁇ s, the cerium oxide particles tend to aggregate, and if the viscosity exceeds 2.50 Pa ⁇ s, the flatness of the polished surface tends to decrease.
- the above-mentioned cerium oxide slurry and the additive solution may be used as they are, but non-high-density compounds such as N, N-getylethanolamine, N, N-dimethylethanolamine, aminoethylethanolamine and the like may be used.
- the molecular additive can be added to the ceramic oxide slurry or the additive for CMP to form a CMP abrasive. These additives are preferably used so that the final concentration in the CMP abrasive is 0.001 to 20% by weight, and more preferably 0.01 to 10% by weight. preferable.
- Examples of a method for forming an inorganic insulating film using the CMP polishing slurry of the present invention include a low-pressure CVD method and a plasma CVD method.
- a silicon oxide film formed by low pressure CVD method, monosilane as a source of Si: Si, oxygen as an oxygen source: 0 2 is used.
- This Si—O 2 -based oxidation reaction can be obtained by performing the reaction at a low temperature of 400 or less. In some cases, it is heat-treated at a temperature of 1000 or less after CVD.
- Plasma CVD has the advantage that chemical reactions that require high temperatures under normal thermal equilibrium can be performed at low temperatures.
- As the reactive gas Si as Si source, SiH4 _ N 2 O-containing gas and tetraethoxysilane using N 2 O as an oxygen source (TEOS) was used in the Si source TEOS-O 2 based gas (TEOS-plasma CVD Law).
- the substrate temperature is preferably from 250 to 400, and the reaction pressure is preferably from 67 to 400 Pa.
- the silicon oxide film of the present invention may be doped with elements such as phosphorus and boron.
- dichlorosilane: SiH 2 Cl 2 is used as a Si source
- ammonia: NH 3 is used as a nitrogen source. This is obtained by performing the SiH 2 Cl 2 —NH 3 system oxidation reaction at a high temperature of 900.
- Plasma CVD method, as the reaction gas, as a Si source SiH4, SiH4- NH 3 containing gas with NHs are exemplified up as a nitrogen source.
- the substrate temperature is preferably 300 to 400.
- the semiconductor substrate that is, the circuit element A substrate in which a silicon oxide film layer or a silicon nitride film layer is formed on a semiconductor substrate such as a semiconductor substrate or a semiconductor substrate at a stage where circuit elements are formed can be used.
- the silicon oxide film layer or silicon nitride film layer formed on such a semiconductor substrate with the above-mentioned CMP polishing agent, unevenness on the surface of the silicon oxide film layer is eliminated, and the entire surface of the semiconductor substrate is smoothed. Plane. It can also be used for shallow trench isolation.
- the ratio of the polishing rate of silicon oxide film to the polishing rate of silicon nitride film, the polishing rate of silicon oxide film, and the polishing rate of silicon nitride film must be 10 or more. If this ratio is too small, the difference between the polishing rate of the silicon oxide film and the polishing rate of the silicon nitride film becomes small, and it becomes impossible to stop the polishing at a predetermined position when isolating the trench. In addition, when the ratio is 50 or more, the polishing speed of the silicon nitride film is further reduced, so that the polishing can be easily stopped, which is more suitable for shallow trench isolation.
- a polishing device As a polishing device, a general polishing device having a surface plate on which a holder for holding a semiconductor substrate and a polishing cloth (pad) are attached (a motor or the like whose rotation speed can be changed) is attached can be used.
- a polishing cloth general nonwoven fabric, foamed polyurethane, porous fluororesin, etc. can be used, and there is no particular limitation. Further, it is preferable that the polishing cloth is subjected to a groove processing for accumulating a CMP abrasive.
- the polishing conditions are not limited, but the rotation speed of the platen is preferably 200 rpm or less so that the semiconductor substrate does not jump out, and the pressure applied to the semiconductor substrate is lkgZcm 2 or less so that scratches do not occur after polishing. preferable. In order to be used for shallow trench isolation, it is necessary to minimize the occurrence of scratches during polishing.
- the slurry is continuously supplied to the polishing cloth with a pump or the like. Although the supply amount is not limited, it is preferable that the surface of the polishing pad is always covered with the slurry.
- the semiconductor substrate is preferably washed well in running water, and then dried using a spin dryer or the like to remove water droplets adhering to the semiconductor substrate.
- aluminum wiring is formed on the silicon oxide insulating film layer, and the silicon oxide insulating film is formed again between the wirings and on the wiring by the above method.
- the surface of the insulating film is eliminated by polishing using the above-mentioned CMP polishing agent to make the surface of the semiconductor substrate smooth. This By repeating the process a predetermined number of times, a semiconductor having a desired number of layers is manufactured.
- the CMP polishing slurry of the present invention can be used not only for a silicon oxide film formed on a semiconductor substrate but also for a silicon oxide film formed on a wiring board having predetermined wiring, an inorganic insulating film such as glass and silicon nitride, a photomask and a lens.
- Optical integrated circuits composed of optical glass such as prisms, inorganic conductive films such as ITO, glass, and crystalline materials' optical switching elements'Optical waveguides, optical fiber end faces, optical single crystals such as It can polish solid-state laser single crystals, blue laser sapphire substrates for LEDs, semiconductor single crystals such as SiC, GaP, and GaAS, glass substrates for magnetic disks, and magnetic heads.
- Cerium oxide powder was mixed with deionized water so as to be 10% by weight, and pulverized at 1400 rpm for 120 minutes using a horizontal wet ultrafine particle dispersion mill. The obtained polishing liquid was dried at 110 for 3 hours to obtain cerium oxide particles.
- cerium oxide particles had a primary particle diameter of 10 nm to 60 nm, which was a constituent of the polycrystal, and that the specific surface area measured by the BET method was 39.5 m 2 Zg. Was.
- 3 g of an aqueous solution of an ammonium salt of an acid copolymer (40% by weight) and 2372 g of deionized water were mixed and subjected to ultrasonic dispersion with stirring. Dispersion was performed at an ultrasonic frequency of 40 kHz and a dispersion time of 10 minutes.
- the obtained slurry was filtered through a 0.8-micron filter, and further, deionized water was added to obtain a 2% by weight cerium oxide slurry (A-1).
- the pH of the cerium oxide slurry (A-1) was 8.5. Examination of the particle size distribution of the cerium oxide slurry (A-1) using a laser diffraction type particle size distribution analyzer revealed that the average particle size was as small as 0.20 m. 95.0% of the particles had a particle size of 1.0 zm or less.
- Preparation Example 4 Preparation of cerium oxide slurry
- Oxidation was carried out in the same manner as in preparation example 3 of cerium oxide slurry except that cerium oxide slurry prepared in preparation example 2 of cerium oxide particles was used instead of cerium oxide particles prepared in preparation example 1.
- a cerium slurry (A-2) was prepared. The pH of this cerium oxide slurry (A-2) was 8.7. Examination of the particle size distribution of the cerium oxide slurry (A-2) revealed that the average particle size was as small as 0.21 m. 95.0% of the particles were 1.0 m or less.
- cerium oxide particles prepared in Example 1 A cerium oxide slurry was prepared in the same manner as in Example '1 except that the cerium oxide particles prepared in Example 1 were used. — 1) was prepared. The pH of this cerium oxide slurry (B-1) was 8.4. Examination of the particle size distribution of the cerium oxide slurry (B-1) revealed that the average particle size was as small as 0.35 m. Also, 85.5% of the particles were 1.0 m or less.
- Examples 1 to 10 and Comparative Examples 1 and 2 As shown in Table 1, a cerium oxide slurry and an additive solution were prepared to prepare a CMP polishing agent, and an insulating film was polished by the following method using a mixed solution of the cerium oxide slurry and the additive solution. The results are shown in Table 1.
- the ammonium polyacrylate used as a dispersant in Examples 6, 8, and 10 had a weight average molecular weight of 10,000, a number average molecular weight of 8,333, a molecular weight distribution of 1.2, and 4.3 mol% of free ammonia.
- the viscosity of the additive liquid used in Example 6 was 1.46 mPa's, and the specific gravity was 1.010.
- Example 2 the cerium oxide slurry and the additive liquid in Example 1 were mixed in advance, and after one day had passed, an insulating film was polished using this mixture.
- a 125 mm diameter silicon wafer with a silicon oxide film formed by a TEOS-plasma CVD method was placed on a holder with a suction pad for attaching a substrate on a surface plate on which a polishing pad made of porous urethane resin was attached. It was set with the insulating film side down, and weighted so that the polishing load was 300 g / cm 2 .
- the above-mentioned cerium oxide slurry (solid content: 2% by weight) and the additive liquid were fed onto the platen at the speed of ZSmlZmin, respectively. was rotated at 40 rpm for 2 minutes to polish the insulating film.
- the wafer was removed from the holder, washed well with running water, and further washed for 20 minutes using an ultrasonic cleaner. After washing, water droplets were removed with a spin drier and dried with a dryer of 120 X: for 10 minutes. The change in film thickness before and after polishing was measured using an optical interference film thickness measuring device, and the polishing rate was calculated.
- a silicon nitride film formed by the low-pressure CVD method was polished under the same conditions, the change in film thickness before and after polishing was measured, and the polishing rate was calculated. From the results of the film thickness measurement, it was found that the silicon oxide film formed by the TEOS-plasma CVD method and the silicon nitride film formed by the low-pressure CVD method had a uniform thickness over the entire surface of the wafer. . In addition, the surface of the insulating film was not damaged by visual observation under the light source of a mercury lamp. Pass AL-2000, Olympus Optical Co., Ltd. (trade name).
- a silicon oxide film having 20 m square and 5,000 A high protrusions formed at 100 m intervals is polished, and the dents between the protrusions when the protrusions are polished (dates) Singing) The amount was determined and the flatness was evaluated.
- Example 1 Example 2
- Example 3 Example 4
- Example 5 Example 6 Name (A-1) (A-1) (A-1) (A-1) (A-2) ( ⁇ -2) (A-1) Cerium oxide slurries Secondary particle size 10-60 10-60 10-60 10-60 10-60 10-60 10-60 10-60
- the surface to be polished such as a silicon oxide film or a silicon nitride film is contaminated with alkali metal such as sodium ions. Polishing that can be polished without scratching, and that achieves a silicon oxide film polishing rate Z silicon nitride film polishing rate ratio of 50 or more, and a substrate using these CMP polishing agents. It can be seen that a polishing method can be obtained.
- the CMP polishing slurry of the present invention is excellent in polishing a surface to be polished such as a silicon oxide film at high speed without scratching, and is a polishing method used for semiconductor device manufacturing technology, especially for a substrate for shallow trench separation. It is suitable for a polishing method.
- the CMP polishing slurry of the present invention is also excellent in that the surface to be polished is not contaminated with alkali metals such as sodium ions, and that the ratio of the polishing rate of silicon oxide film to the polishing rate of silicon nitride film can be increased.
- the CMP polishing slurry of the present invention can improve the storage stability of a cell oxide slurry, and is suitable for a polishing method used in semiconductor device manufacturing technology.
- the substrate polishing method of the present invention is excellent in polishing a surface to be polished, such as a silicon oxide film, at high speed without scratches, and is suitable for a polishing method used in semiconductor device manufacturing technology.
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
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- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
Description
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Priority Applications (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020047019184A KR100754103B1 (ko) | 1998-12-25 | 1999-12-22 | Cmp 연마제, cmp 연마제용 첨가액 및 기판의 연마방법 |
| JP2000591656A JP3649279B2 (ja) | 1998-12-25 | 1999-12-22 | 基板の研磨方法 |
| EP99961311A EP1148538A4 (en) | 1998-12-25 | 1999-12-22 | CMP ABRASIVE, LIQUID SUPPLEMENT FOR DASSEL AND SUBSTRATE POLISHING METHOD |
| US09/856,491 US6783434B1 (en) | 1998-12-25 | 1999-12-22 | CMP abrasive, liquid additive for CMP abrasive and method for polishing substrate |
| KR10-2004-7021176A KR20050006299A (ko) | 1998-12-25 | 1999-12-22 | Cmp 연마제, cmp 연마제용 첨가액 및 기판의 연마방법 |
| KR1020077004271A KR100797218B1 (ko) | 1998-12-25 | 1999-12-22 | Cmp 연마제, cmp 연마제용 첨가액 및 기판의 연마방법 |
| US11/407,196 US20060186372A1 (en) | 1998-12-25 | 2006-04-20 | CMP abrasive, liquid additive for CMP abrasive and method for polishing substrate |
| US11/407,195 US20060197054A1 (en) | 1998-12-25 | 2006-04-20 | CMP abrasive, liquid additive for CMP abrasive and method for polishing substrate |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP36835598 | 1998-12-25 | ||
| JP10/368355 | 1998-12-25 |
Related Child Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US09/856,491 A-371-Of-International US6783434B1 (en) | 1998-12-25 | 1999-12-22 | CMP abrasive, liquid additive for CMP abrasive and method for polishing substrate |
| US10/759,163 Division US20040147206A1 (en) | 1998-12-25 | 2004-01-20 | CMP abrasive, liquid additive for CMP abrasive and method for polishing substrate |
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| Publication Number | Publication Date |
|---|---|
| WO2000039843A1 true WO2000039843A1 (en) | 2000-07-06 |
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Family Applications (1)
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|---|---|---|---|
| PCT/JP1999/007209 Ceased WO2000039843A1 (en) | 1998-12-25 | 1999-12-22 | Cmp abrasive, liquid additive for cmp abrasive and method for polishing substrate |
Country Status (6)
| Country | Link |
|---|---|
| US (6) | US6783434B1 (ja) |
| EP (2) | EP1566421B1 (ja) |
| JP (1) | JP3649279B2 (ja) |
| KR (6) | KR20050006299A (ja) |
| TW (1) | TW492095B (ja) |
| WO (1) | WO2000039843A1 (ja) |
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| JP3676030B2 (ja) * | 1997-04-10 | 2005-07-27 | 株式会社東芝 | 研磨パッドのドレッシング方法及び半導体装置の製造方法 |
| JP4095731B2 (ja) * | 1998-11-09 | 2008-06-04 | 株式会社ルネサステクノロジ | 半導体装置の製造方法及び半導体装置 |
| JP3983949B2 (ja) * | 1998-12-21 | 2007-09-26 | 昭和電工株式会社 | 研磨用酸化セリウムスラリー、その製造法及び研磨方法 |
| KR20050006299A (ko) * | 1998-12-25 | 2005-01-15 | 히다치 가세고교 가부시끼가이샤 | Cmp 연마제, cmp 연마제용 첨가액 및 기판의 연마방법 |
| US6176763B1 (en) * | 1999-02-04 | 2001-01-23 | Micron Technology, Inc. | Method and apparatus for uniformly planarizing a microelectronic substrate |
| JP3805588B2 (ja) * | 1999-12-27 | 2006-08-02 | 株式会社日立製作所 | 半導体装置の製造方法 |
| US6319095B1 (en) * | 2000-03-09 | 2001-11-20 | Agere Systems Guardian Corp. | Colloidal suspension of abrasive particles containing magnesium as CMP slurry |
| US7887714B2 (en) * | 2000-12-25 | 2011-02-15 | Nissan Chemical Industries, Ltd. | Cerium oxide sol and abrasive |
| US7018560B2 (en) * | 2003-08-05 | 2006-03-28 | Rohm And Haas Electronic Materials Cmp Holdings, Inc. | Composition for polishing semiconductor layers |
| US7300480B2 (en) * | 2003-09-25 | 2007-11-27 | Rohm And Haas Electronic Materials Cmp Holdings, Inc. | High-rate barrier polishing composition |
| KR101526731B1 (ko) * | 2013-12-10 | 2015-06-05 | 동부대우전자 주식회사 | 냉장고 도어의 힌지 어셈블리 |
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- 1999-12-22 KR KR10-2004-7021176A patent/KR20050006299A/ko not_active Ceased
- 1999-12-22 KR KR1020077015887A patent/KR100851451B1/ko not_active Expired - Lifetime
- 1999-12-22 KR KR1020047019184A patent/KR100754103B1/ko not_active Expired - Lifetime
- 1999-12-22 KR KR1020077004271A patent/KR100797218B1/ko not_active Expired - Lifetime
- 1999-12-22 WO PCT/JP1999/007209 patent/WO2000039843A1/ja not_active Ceased
- 1999-12-22 US US09/856,491 patent/US6783434B1/en not_active Expired - Lifetime
- 1999-12-22 KR KR10-2001-7008089A patent/KR100475976B1/ko not_active Expired - Fee Related
- 1999-12-22 KR KR1020087002987A patent/KR100822116B1/ko not_active Expired - Lifetime
- 1999-12-22 EP EP05075862.2A patent/EP1566421B1/en not_active Expired - Lifetime
- 1999-12-22 EP EP99961311A patent/EP1148538A4/en not_active Withdrawn
- 1999-12-22 JP JP2000591656A patent/JP3649279B2/ja not_active Expired - Lifetime
- 1999-12-24 TW TW088122949A patent/TW492095B/zh not_active IP Right Cessation
-
2004
- 2004-01-20 US US10/759,163 patent/US20040147206A1/en not_active Abandoned
- 2004-11-18 US US10/990,427 patent/US7163644B2/en not_active Expired - Lifetime
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2005
- 2005-07-11 US US11/177,352 patent/US20050269295A1/en not_active Abandoned
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2006
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Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002212228A (ja) * | 2001-01-12 | 2002-07-31 | Hitachi Chem Co Ltd | ポリ(メタ)アクリル酸アミン塩水溶液及びその製造方法 |
| WO2003016424A1 (en) * | 2001-08-20 | 2003-02-27 | Samsung Corning Co., Ltd. | Polishing slurry comprising silica-coated ceria |
| JP2005529485A (ja) * | 2002-06-07 | 2005-09-29 | キャボット マイクロエレクトロニクス コーポレイション | low−k絶縁材料用のCMP組成物 |
| JP4773091B2 (ja) * | 2002-06-07 | 2011-09-14 | キャボット マイクロエレクトロニクス コーポレイション | low−k絶縁材料用のCMP組成物 |
| JP4554363B2 (ja) * | 2002-07-22 | 2010-09-29 | Agcセイミケミカル株式会社 | 半導体用研磨剤、その製造方法及び研磨方法 |
| JPWO2004010487A1 (ja) * | 2002-07-22 | 2005-11-17 | セイミケミカル株式会社 | 半導体用研磨剤、その製造方法及び研磨方法 |
| JPWO2004061925A1 (ja) * | 2002-12-31 | 2006-05-18 | 株式会社Sumco | 化学的機械研磨用スラリー組成物、これを利用した半導体素子の表面平坦化方法及びスラリー組成物の選択比制御方法 |
| JP2011151405A (ja) * | 2002-12-31 | 2011-08-04 | Sumco Corp | 半導体素子の表面平坦化方法 |
| US8168541B2 (en) | 2003-01-31 | 2012-05-01 | Hitachi Chemical Co., Ltd. | CMP polishing slurry and polishing method |
| US7838482B2 (en) * | 2003-01-31 | 2010-11-23 | Hitachi Chemical Co. Ltd. | CMP polishing compound and polishing method |
| JP2007531300A (ja) * | 2004-03-29 | 2007-11-01 | ハンファ ケミカル コーポレーション | 半導体における浅いトレンチ素子分離工程用の化学・機械的な研磨スラリー |
| WO2005123864A1 (ja) * | 2004-06-21 | 2005-12-29 | Showa Denko K.K. | 流動性研磨材ペースト及びその製造方法、用途 |
| JP2006019740A (ja) * | 2004-06-30 | 2006-01-19 | Dongjin Semichem Co Ltd | 化学的機械的研磨スラリー組成物 |
| US9293344B2 (en) | 2004-07-23 | 2016-03-22 | Hitachi Chemical Company, Ltd. | Cmp polishing slurry and method of polishing substrate |
| US7674716B2 (en) | 2004-12-29 | 2010-03-09 | Lg Chem. Ltd. | Adjuvant for chemical mechanical polishing slurry |
| WO2006071063A1 (en) * | 2004-12-29 | 2006-07-06 | Lg Chem, Ltd. | Adjuvant for chemical mechanical polishing slurry |
Also Published As
| Publication number | Publication date |
|---|---|
| US6783434B1 (en) | 2004-08-31 |
| EP1148538A1 (en) | 2001-10-24 |
| KR100797218B1 (ko) | 2008-01-23 |
| US20060186372A1 (en) | 2006-08-24 |
| KR100475976B1 (ko) | 2005-03-15 |
| KR20010108048A (ko) | 2001-12-07 |
| KR20050006299A (ko) | 2005-01-15 |
| EP1148538A4 (en) | 2009-10-21 |
| JP3649279B2 (ja) | 2005-05-18 |
| TW492095B (en) | 2002-06-21 |
| KR20070034640A (ko) | 2007-03-28 |
| KR20080016979A (ko) | 2008-02-22 |
| US20050118820A1 (en) | 2005-06-02 |
| KR100754103B1 (ko) | 2007-08-31 |
| US7163644B2 (en) | 2007-01-16 |
| US20060197054A1 (en) | 2006-09-07 |
| KR20050005499A (ko) | 2005-01-13 |
| EP1566421A2 (en) | 2005-08-24 |
| US20040147206A1 (en) | 2004-07-29 |
| KR100851451B1 (ko) | 2008-08-08 |
| US20050269295A1 (en) | 2005-12-08 |
| EP1566421B1 (en) | 2014-12-10 |
| EP1566421A3 (en) | 2009-10-21 |
| KR100822116B1 (ko) | 2008-04-15 |
| KR20070087037A (ko) | 2007-08-27 |
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