TW571361B - Polishing agent and method for polishing a substrate - Google Patents

Abstract

A polishing agent and polishing method suitable to perform a chemical mechanical polishing (CMP) process for planarizing the surface of the substrate of semiconductor element manufacturing are proposed. The polishing agent contains particle and a medium in which at least a part of the particles is dispersed, wherein the particle is at least one of (1) a cerium compound selected from cerium oxide, cerium, halide and cerium sulfide, having a density of 3 to 6 g/cm<3> and an average particle diameter of a secondary particle of 1 to 300 nm, and (2) metallic hydride of 4 valences. The polishing method, in which this polishing agent is used, actively utilizes the chemical activity of the particle in the polishing agent, while minimizing the mechanical effects, so as to minimize the polishing defects caused by the particle while polishing speed is increased.

Description

571361 V. Description of the invention (1) [Technical Field] The present invention relates to an abrasive suitable for semiconductor device manufacturing technology and a polishing method for polishing a substrate using the abrasive. [Technical Background] In the current ULSI semiconductor device manufacturing process, research and development of a high-density, miniaturized processing technology are being developed. One of the CMP (Chemical Mechanical Polishing) technologies is required in the process of semiconductor device manufacturing, such as the planarization of interlayer insulation films, the formation of shallow trench element separation, the formation of plugs, and the formation of embedded metal wiring. Technology. In the past, in the manufacturing process of semiconductor devices, inorganic insulating film layers such as silicon oxide insulating films formed by plasma CVD, low-pressure CVD, and the like were used as abrasive grains of planarized chemical mechanical abrasives. (S i 0 0 — particles of osmium oxide (Ce 0 0. Lithium dioxide, sulphur dioxide, sulphur, sulphur, sulphur, sulphur, sulphur, sulphur, sulphur, sulphur, sulphur, sulphur). Thermal separation in two directions: search. In the second collection: fate ;: research = Line: the disadvantage of slower production. Zengsuo M TT has the greatest characteristics of grinding speed 'monoxide oxide bar 1, + abrasives i 1 The second example is osmium oxide. Oxidation grinding high grinding speed. Gasification radon, etc. This is not possible with gold-based silicon-based abrasives, and will result in chemical interactions with chemically active properties. # = Chemical action of chemical agents and mechanical removal of particles High grinding speed. Compared with silicon oxide particles or aluminum oxide particles,

313423.ptd 571361 5. Description of the invention (2) The degree is low, so it is less likely to cause damage to the polished surface, so it is quite effective for mirror polishing. Hafnium oxide abrasives are used, for example, for polishing glass surfaces. Applying these characteristics, hafnium oxide abrasives are widely used as CMP abrasives for semiconductor insulating films. This technique is disclosed in, for example, Japanese Patent Laid-Open No. 9-2 70 4 02. In recent years, with the multi-layering and high-definition of semiconductor devices, it has been required to further improve the yield and production of semiconductor devices. Therefore, a higher speed polishing is also desired for the CMP process using an abrasive without polishing. However, if the rubidium oxide abrasive for glass surface polishing is directly used for polishing semiconductor insulating films, the particle size of the primary particles is large. Therefore, if a sufficiently fast polishing speed is used for polishing, it will appear on the surface of the insulating film. Abrasive damage was visually observed. When the size of the primary particles becomes smaller, although the polishing damage is less likely to occur, the polishing rate is reduced. In the case of thorium oxide, the chemical action and the mechanical removal of particles are used for processing. If there is mechanical removal of particles, grinding will occur. Therefore, in the method using holmium oxide to further reduce the abrasion damage, for example, reducing the surface state of abrasive particles, such as abrasive particles, and the like, the program improvement method such as the improvement of the number of plate rotations, and the like can increase the polishing speed. Reduced problems, reduced lift and abrasive damage. In the future, in the evolution of high definition, in the CMP process of improving the semiconductor, the grinding loss is reduced to the desired grinding speed and brightness or density, and the abrasive particles are selected once; or the grinding pressure or solidification is reduced. However, in any case, it is difficult to take into account the improvement in polishing speed. ^ Due to the multilayering of semiconductor devices and the yield of bulk devices, it is necessary to

571361 V. Description of the invention (3) There is no abrasive damage recently, it is not easy, and in the polishing speed of the film, the pH caused by the abrasive is re-researched, the situation of dispersing, and the dispersion of the agent is stabilized by visual identification degree. Considering that the particles form an oxygen layer, it can be used in both grinding and grinding methods, as well as providing additional changes that can be made to the silicon oxide film to reduce precipitation or inhibit dispersibility. [Summary of the invention The damage of the present inventor is focused on and can only study the ratio of the pH to the grinding speed to disperse the caustic precipitation surface. The rate of grinding and oxidation is greater. As the degree of grinding and dispersion decreases, the invention siliconizes the silicon insulation. The grinding speed is a kind of abrasive used for agglomeration and diazotized silicon film agglomeration, and is characterized by the use of particle size grinding. In order to separate the shallow trench elements, the polishing speed of the silicon insulating film is higher than that of the silicon nitride insulating abrasive. In addition, there is a problem that the change is low during polishing or storage time. The particle size of the abrasive particles in the agent is unstable and changes may cause precipitation or coagulation. This kind of grinding is because the particle size of the dispersed particles is small and impossible, so it is difficult to numerically evaluate the dispersion stability. The film and other abrasives are raised and ground, and the grinding performance is good, and can provide a grinding agent, which is based on the grinding surface and chemical reaction layer in the grinding agent, and the grinding damage is reduced Substrate polishing method. It is used to grind over time and place of production by suppressing pH. In addition, it has a large speed ratio. The particles can be dispersed well and easily detected by various optical methods. Chemical action of particles and make mechanical action as possible

Page 10 571361 V. Description of the invention (4) The grinding can be made smaller, and the present invention is completed after intensive research. The abrasive of the first aspect of the present invention contains particles and a medium that disperses at least a part of the particles; the particles are selected from the group consisting of hafnium oxide, hafnium halide, and hafnium sulfide, and have a density of 3 to 6 g / cm3 At least one of them is a halide or a tetravalent metal hydroxide having an average particle diameter of secondary particles of 1 to 300 nm. In particular, the specific surface area of the particles is preferably 50 m 2 / g or more, and the average particle diameter of the primary particles is preferably 50 nm or less. Here, when the particles belong to a tetravalent metal hafnium oxide, the average particle diameter of the secondary particles is preferably 300 nm or less, the particle density is preferably 3 to 6 g / cm 3 and the average particle size of the secondary particles is The diameter is preferably 1 to 300 nm, and the particles are preferably at least one of a rare earth metal hydroxide and a hydroxide hydroxide. The rare earth metal hydroxide is preferably a rhenium hydroxide. The particles are preferably A tetravalent metal hydroxide obtained by mixing a tetravalent metal salt with an alkaline liquid phase. Furthermore, the pH of the abrasive is preferably 3 or more and 9 or less, and the medium of the abrasive is preferably water; the abrasive preferably contains a pH stabilizer, a dispersant, and a surface treatment agent to be polished. Wherein, the above-mentioned pH stabilizer is formed of more than one constituent component, and the pK a value of at least one of the constituent components is preferably within 1.0 unit of the abrasive p Η. The dispersant is preferably selected from a water-soluble anionic dispersant, a water-soluble cationic dispersant, a water-soluble nonionic dispersant, and a water-soluble amphoteric dispersant. It is preferable that the above-mentioned polished surface treatment agent contains at least one of molecular structure

313423.ptd Page 11 571361 V. Description of the invention (5) | Compounds with an asymmetric electron atom ^ © 工 々 &quot; ^ i Compounds containing at least one of nitrogen | atom or oxygen atom in the structure of the substance or molecule . Furthermore, the abrasive silicon oxide is awkward (the ratio of the film polishing speed is preferably 5 or more, and the edge film polishing speed is insulated from the nitrided sand. Also, when the abrasive contains the above-mentioned particles 0.2% by weight, the wavelength The light transmittance of the light is preferably above 10%, and the difference between the light transmittance at a wavelength of 500 to 700,000 after standing for 24 hours relative to the 7 abrasive after the modulation I &quot; The knife is preferably less than 20%. Furthermore, the conductivity of the abrasive is preferably 30 mS / cm or less, and the particles preferably have a positive z potential. A second aspect of the present invention relates to a method using the above-mentioned first In the same state | any: a polishing agent to polish the substrate. I In particular, I dare to use a polishing pad with a Shore (sh 0 re) D hardness of 50 or more to polish the substrate; the substrate is preferably a semiconductor device The substrate in the manufacturing process; it is best to polish the silicon oxide film formed on the substrate. Furthermore, while supplying the abrasive to the polishing pad on the polishing fixed plate, at least the substrate on which the silicon oxide insulating film is formed is polished. Surface and polishing pad for relative movement and polishing, especially, it is better to insulate silicon oxide The grinding speed is set to 200 to 200 Onm / min, and polishing is performed using an abrasive containing tetravalent metal and mouse oxide particles. According to the polishing method of the abrasive and the substrate of the present invention as described above, The high-speed grinding can be performed on the polished surface such as the oxide stone insulation film, etc. In addition, the polishing speed of the silicon oxide insulation film is set to be sufficiently higher than the polishing speed of the nitride stone insulation film, and can be selectively selected. Grinding silicon oxide insulating film 1 and 571361 5. Description of the invention (6) It can make the management of procedures such as separation between shallow trench elements easier. In addition, abrasives with better dispersion of particles can be obtained, and abrasives can be numerically evaluated. Dispersion stability, and can use various optical methods to detect and control the end point of polishing, particle concentration, particle size, etc. [Best Embodiment of the Invention] The particles contained in the abrasive of the present invention are (1) Self-oxidizing decoration, chemical conversion and vulcanization decoration, particles with a density of 3 g / cm and 6 g / cm, and the average particle diameter of the secondary particles above 1 nm and below 300 nm ; 2) Use of tetravalent metal hydroxide particles; any of the particles (1) and (2) above may be used, or both may be used in combination. (1) The rhenium compound of the present invention is based on erbium oxide From the viewpoint of obtaining a practical polishing rate, one or more of hafnium hafnium, hafnium sulfide, and hafnium sulfide are preferred. Hafnium oxide is used for semiconductor polishing, and therefore, the content ratio of alkali metals and i in the hafnium compound It is preferably less than 1 ppm. The method for producing (2) tetravalent metal hydroxide in the present invention may be a method of mixing a tetravalent metal salt with an alkali solution. This method is, for example, rare earth science (title) (Adachi) Yin also edited, Chemistry Fans) as explained on pages 304 to 305. The tetravalent metal salt is preferably, for example, M (S04) 2, M (NH4) 2 (N03) 6, page (Off 4) (804) 4 (where page represents a rare earth element), 21 ^ (804) 2 · 4 Η 20. In particular, a chemically active Ce salt is preferred. The test solution can use ammonia, alkali hydroxide, sodium hydroxide, preferably ammonia. The particulate tetravalent metal hydroxide synthesized by the above method can remove metal impurities after washing. The metal hydroxide can be washed by centrifugation, etc.

313423.ptd Page 13 571361 Five solids, description of the invention (7) Method of liquid separation, etc. Oxidation: It is best to use at least one of the rare earth ... It is a lice emulsion and hydrogen pupae. The gaseous metal lice gas is preferably hydrogen and oxygen. The slurry can be prepared by dispersing from at least _ ^ \ tetravalent metal hydroxide particles in the particles of the π μon, or the tritium compound particles by washing according to the above. (S 丨 ^ ^. Take all of them), except for using a general mixer to perform a square homogenizer, an ultrasonic disperser, a ball mill, etc. in a liquid state to make the metal hydroxide or rhenium compound particles. Other than 'the abrasive of the present invention can still be used', the above-mentioned slurry containing at least a part of the particles can be directly used, and the above-mentioned slurry containing the spider can also be used, ^ p 4 A, dispersant, and the surface to be polished Addition of treatment agent, uk preparation

卞, 1 笠 笠 力 力 八 埼 ΡίΙ Stabilizers, inhibitors and other abrasives. ^ Can be added after adding W to the media towel or particles of X abrasive. The average surface area of a person ’s particles is 佶 r 丨, and D is called the specific surface area of h particles ”), and the value is ten spoons (the following is more than 50 m 2 / g. The forest is below 500 m 2 / g. "Left" γπλ 9 is more preferably 80 m V g to 50 m 2 / g, more preferably 100 m 2 / g to 3 50 m 2 / g, especially for L mains and π丨 Tian, L is more ideal between 150 m2 / g and 250 m Vg. Specific surface area = BET method of rat adsorption (for example: made by Ganda Krom Co., Ltd. ("Osawa") "Original name is European Si Bing Li bite, Qi Likou, ^ ^ ^ addicted to-, day 丨 / Supu (Osawa), or the product name Ou Desu Kela said (day.) Into the lamp to test the summer. Here, the measurement sample is in The pretreatment is performed at 500 ° C. In addition, the average particle diameter of the secondary particles of the above particles in the abrasive (hereinafter referred to as "average particle diameter of the secondary particles") is preferably 300. ·

571361

V. Description of the invention (8) The following. Among them, it is more preferably 2 to 200 nm, more preferably 10 to 2000 nm, and even more preferably 50 to 150 nm. Especially in the case of (1) osmium compound particles, the average particle diameter of the secondary particles must be in the range of 1 to 300 nm. If it is lower than 1 n in, the polishing rate tends to decrease. Since the particles in the abrasive require chemical interaction between the wave Friend and the film to be polished, if the specific surface area is less than 50m2 / g, the contact area with the film to be polished will be reduced, and the polishing rate will be reduced. When the average particle diameter of the secondary particles is larger than 30 nm, the contact area between the secondary particles and the film to be polished is also reduced ', and the polishing rate is reduced. In the present invention, the so-called primary particles are particles corresponding to the smallest unit of crystals surrounded by the grain boundaries, which are confirmed by observation under a powder state using, for example, a transmission electron microscope (TEM). The term "secondary particles" refers to agglomerates formed by the primary particles. In the present invention, the particle size measurement of the di-human particles is performed by a photon correlation method. For example, you can use the device name (transliteration) made by Marupon: Qian Desai 300 00HS, or the device name (transliteration) made by Gulda: Gulda N4SD for measurement. The average primary particle diameter of the particles is preferably 50 ° or less, of which 0.1 to 50 nm is more preferable, 1 to 30 nm is more preferable, and 3 to 10 nm is more preferable. _ ^ &amp; In the present invention, 'Take a transmission electron microscope (TEM) picture, when two bevel lines are lost—secondary particles (crystals), the smallest difference between this interval is up to _ ^ Also, the short diameter is set, and the value of the largest part is set as the long diameter. The witch ruler and the ten mean value of the short diameter and the long diameter are set as the crystal size. 100 crystal inches were measured and the arithmetic mean was set as the average particle diameter of the primary particles.

Page 571361: Hair: Description ⑼ When it is larger than 50nm, the probability of occurrence of micro-damages will increase into the average particle size of the particles, and the slope of the grinding speed will be increased. On the contrary, if it is less than 0 · 1n $ 向 / 3ϊ "b, 6g / cm3 or less, among which the particle density is preferably 3 wide. In particular, the size of the gadolinium compound is 4g / cm3 or more, and 5g / cm3 or less must be 3g / cm2. Up, 6g / Cm 'down. If the density of the sclerotin is less than 3g / cni 埘, the effect of the particles on the film to be polished will be reduced, and there is a tendency to reduce the polishing speed. On the contrary, if the density is greater than 6g / cm%, it will be difficult The labor density that suppresses abrasive damage. The density of the particles is measured using a gas displacement method (eg, Ganda Krom High Yield (transliteration), the product name is super-nose gage 1 0 0 0 (transliteration)). The pH is preferably 3 or more and 9 or less, and more preferably 5 or 8 or more, and more preferably 5 or more and 7 or less. If the pH is less than 3, the chemical force will be small, and Reduce the polishing rate. Conversely, if the pH is greater than 9, the secondary particle size will increase and the polishing rate will be reduced. In addition to water, the medium used as the dispersion medium of the particles may be selected from the following groups: for example, methanol, ethanol, propanol, 2-propanol, 2-propanol-propanol, Allyl alcohol, ethylene cyanohydrin, butanol, 2-monobutanol (S)-(+)-2-butanol, 2-methyl-1-propanol, third butanol, perfluorosecond butanol Alcohol, tertiary pentanol, 1,2-ethylene glycol, I2-propanediol, I3-propanediol, 1,3-butanediol, 2,3-butanediol, 1,5-pentanediol, 2-butene-1 4-diol, 2-methyl-2,4 ^ diol, glycerol, 2-ethyl-2 (via methylamine) -1,3-propanediol, 1,2,6 -Alcohols such as hexanediol; dioxane, trioxane

313423.ptd Page 16 571361 V. Description of the Invention (Also) alkane, tetrahydrofuran, diethylene glycol diethyl ether, 2-methoxyethanol, 2, 2- (dimethoxy) ethanol, 2-isopropoxy Ethanol, 2-butoxyethanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, furfuryl alcohol, tetrahydrofurfuryl alcohol, ethylene glycol, diethylene glycol, diethylene glycol mono Methyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, triethylene glycol, triethylene glycol monomethyl ether, tetraethylene glycol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, Ethers such as tripropylene glycol monomethyl ether, polyethylene glycol, diacetone alcohol, 2-methoxyethyl acetate, 2-ethoxyethyl acetate, diethylene glycol monoethyl ether acetate; acetone, methyl ethyl ketone, ethyl酮 Ketones such as acetone, cyclohexanone, etc. Among them, water, methanol, ethanol, 2-propanol, tetrahydrofuran, ethylene glycol, propylene glycol, and methyl ethyl ketone are preferred, and water is particularly preferred from the viewpoint of obtaining a high polishing rate. Moreover, the medium is preferably 1, 0 0 0 to 1, 0 0 0, 0 0 0 parts by weight, especially 1 0, 0 0 to 1 0 0, 0 0 0, with respect to 100 parts by weight of the particles. More preferably by weight. Among the pH stabilizers contained in the abrasive of the present invention, for example, a mixture of a carboxylic acid and a salt thereof, a mixture of phosphoric acid and a salt thereof, a mixture of boric acid and a salt thereof, and a mixture of ammonia and a salt thereof may be appropriately selected and used. Know the commonly used pH buffers. The preferred use condition is that the P Η stabilizer is composed of one or more constituent components, and at least one of the constituent components has a pKa value of less than 1.0 unit of the abrasive pH. For example, when the pH of the abrasive is adjusted from 5.0 to 6.0, phosphoric acid, acetic acid, propionic acid, malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, and fumaric acid can be suitably used. Adipic acid, stearic acid citric acid, ethylenediamine, pyridine, 2-aminopyridine, 3-aminopyridine, xanthine nucleoside, toluene

313423.ptd Page 17 571361 V. Description of the invention (11) Amine, picolinic acid, histidine, pulsedazine, N-methylpiperazine, 2-bis (2-hydroxyethyl) amino-2- ( (Hydroxymethyl) -1,3-propanediol, uric acid, etc., and mixtures thereof. If the value of p K a deviates from the polishing agent p. By 1.0 unit, during long-term storage, Η will easily rise and the polishing rate will decrease. The value of p K a is preferably within 0.5 units of the abrasive p Η, and more preferably within 0.2 units. The abrasive of the present invention preferably contains a dispersant. The dispersant acts on the particles in the abrasive as long as it is a compound that reduces precipitation or maintains dispersibility. By including a dispersant in the abrasive, it is possible to suppress the polishing speed or the flatness of the surface to be polished, and to suppress the occurrence of polishing damage. The dispersant is preferably selected from a water-soluble anionic dispersant, a water-soluble nonionic dispersant, a water-soluble cationic dispersant, and a water-soluble amphoteric dispersant. A dispersant containing at least one of these two types of dispersants can also be used. Agent. Examples of the water-soluble anionic dispersant include triethanolamine lauryl sulfate, ammonium lauryl sulfate, and triethanolamine sulfate. In addition, an anionic water-soluble polymer described later can also be used. Examples of water-soluble nonionic dispersants include polyethylene oxide lauryl ether, polyethylene oxide cetyl ether, polyethylene oxide stearyl ether, polyethylene oxide oleyl ether, and polyethylene oxide advanced Alcohol ether, polyethylene oxide octyl phenyl ether, polyethylene oxide nonyl phenyl ether, polyethylene oxide alkyl ether, polyethylene oxide derivatives, polyethylene oxide sorbitan mono Lauric acid ester, polyethylene oxide sorbitan monohexadecyl ester, polyethylene oxide sorbitan monostearate, polyethylene oxide sorbitan tristearate Polyethylene oxide sorbitol

313423.ptd Page 18 571361 V. Description of the invention (12) -------Anhydride monooleate, polyepoxide ^ ethylene oxide bissorbitan = sorbitan trioleate, four Oleic acid polyalcohol monostearate, poly ^ 1 ^ water glycol monolaurate, polyethylene glycol, polyethylene oxide alkyl ^ alcohol early = stearate, polyethylene glycol monooleic acid Alkanolamine and the like. Among them: Ethylene oxide hardened ramie oil and alkyl are preferred. ^ Polyethylene oxide alkylamines such as permanent ethylene oxide and octylamine. Water-soluble cationic octaamine acetates. Examples of scorching clams are coconut amine acetate, stearin, water-soluble amphoteric dispersant, and lauryl dimethylamine bis, for example, lauryl betaine, stearyl sweet saccharine betaine, and the like. Emulsions, 2-alkyl-N, partial methyl-N, and B dispersing agents can be selected from Shi Zhiwu, Zhongzhong eight or more. In the addition of these dispersants, in terms of the relationship between dispersive fish anti-phase #f 于 # J Π, precipitation, and abrasive damage, it is 100 parts by weight with respect to the particles. Ν ιν π 17. The best cut is 〇 · Ο 1 to 1, 〇 Ο Ο part by weight, in which U 〇 _ 1 to 〇〇 will be νν 丄. Here, h is better, especially from 1 to 1 0 0 parts by weight of the dispersant. Πηηζ,, Π Λ Λ is preferably 100 to 5, 0 0 0, ΟΟΟ, in which 1, 0 0 0 to 5 0 0, 〇〇〇 Rabbit Du greedy Badandian ν · Especially 10, 0 0 to 10 0, 0 0 0 is more ideal. If the molecular weight of the right dispersant is less than 100, when k is less than 100, when grinding the oxidized stone film or gasification, the method is to obtain a sufficient grinding speed; otherwise, if the dispersant is larger than 50 in the knife 〇 ， 〇〇〇, the viscosity will increase, reducing the storage stability of the abrasive. The abrasive of the present invention preferably contains a surface-treating agent. Here, the term "surface-polished agent" means that as long as it has a surface capable of contacting the surface to be polished,

313423.ptd Page 19 571361 V. Description of the invention (13) Existing oxy group, an atom or structure compound that forms a hydrogen bond is sufficient. The polishing surface treating agent is preferably a compound containing at least one atom having an asymmetric electron in the molecular structure or a compound containing at least one of a nitrogen atom and an oxygen atom in the molecular structure. This can increase, for example, the ratio of the polishing speed of the silicon oxide film to the polishing speed of the silicon nitride insulating film, and is suitable for separation between shallow trench elements. Specifically, for example, polyvinylacetal, polyvinyl formal, polyvinyl butyral, polyvinylpyrrolidone, polyvinylpyrrolidone-metramine, polyvinyl (5-methyl- 2-pyrrolidone), polyvinyl (2-pyridinone), polyvinyl (3,3,5, -trimethyl-2-pyrrolidone), poly (N-vinylpyridine), poly (N-alkane 3-vinylpyridine), poly (N-alkyl-4-vinylpyridine), poly (N-vinyl-3, 6-dibromocarbazole), polyvinyl benzophenone, polyvinyl benzene Ethyl ketone, poly (4-vinylpyridine), poly (4- / 3-hydroxyethylpyridine), poly (2-vinylpyridine), poly (2- / 3-vinylpyridine), poly ( 4-ethylidene sigma), poly (4-ethylidene sigma), poly (4-ethylpyridine phosphonium salt), poly (α-methylstyrene-c0-4-vinylpyridine) Samarium hydrochloride), poly (U_ (3-continuene) -2-vinylpyridine, betaine, co-p-potassium p-styrene sulfonate), poly (N-vinylimidazole), poly (4-vinyl Imidazole), poly (5-vinylimidazole), poly (0-vinyl-4-methyloxazolidinone), Vinylacetamide, polyvinylacetamide, polyvinylethylacetamide, polyvinylisobutylamide, polyvinylmethylbenzylamine, polyvinylmethylpropionamine Amine, polyvinylacetophenamine, polyvinylethylpropylamine, poly (meth) acrylic acid, poly (fluorenyl) acrylic acid derivative, poly (meth) acrylic acid ammonium salt, polyvinyl alcohol, polyethylene Alcohol derivatives, polyacryl, poly

313423.ptd Page 20 571361 V. Description of the invention (14) Acrylonitrile, polyvinyl acetate, poly (vinyl acetate-co-methyl methacrylate), poly (vinyl acetate-co-vinyl acrylate), Poly (vinyl acetate-co- [i-pyrrolidine), poly (vinyl acetate-C0-acetonitrile), poly (vinyl acetate-c 0-N, N-di-di-propyl cyanide), poly (acetic acid Polymer compounds such as vinyl ester-c 0-N, N-diallylamine) and poly (vinyl acetate-co-ethylene). In addition, the surface-treating agent is anionic, and one or more of them can be used which contain free -COOM group, phenolic -OH, -S03M group, -0 S03H group, -P04M2 group, -PO 3M group. Organic compounds (wherein M refers to Η, ΝΗ 4, or an alkali metal atom) (hereinafter referred to as "anionic additive"). Examples of such anionic additives are shown below. For example: formic acid, acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, heptanoic acid, caprylic acid, nonanoic acid, capric acid, undecylic acid, lauric acid, tridecyl acid, tetradecanoic acid, fifteen courtyards Acid, palmitic acid, heptadecanoic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, cyclohexanecarboxylic acid, phenylacetic acid, benzoic acid, o-toluic acid, m-toluic acid, p-toluic acid, O-methoxybenzoic acid, m-methoxybenzoic acid, p-methoxybenzoic acid, acrylic acid, fluoracrylic acid, crotonic acid, pentenoic acid, hexenoic acid, heptenoic acid, octenic acid, nonanoic acid, Decenoic acid, undecylenic acid, dodecane dicarboxylic acid, tridecenoic acid, tetradecanoic acid, pentadecenoic acid, hexadecanoic acid, heptaenoic acid, isobutyric acid, Isovaleric acid, cinnamic acid, quinalic acid, niacin, 1-naphthoic acid, 2-naphthoic acid, picolinic acid, vinylacetic acid, phenylacetic acid, phenoxyacetic acid, 2-pyranocarboxylic acid , Mercaptoacetic acid, propionic acid acetate, oxalic acid, malonic acid, broken acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1,9-nonanecarboxylic acid,

313423.ptd Page 21 571361 V. Description of the invention (15) 1,1 0 -sebacenedicarboxylic acid, 1,1 1 -H-carbanedicarboxylic acid, 1,12 -dodecanedicarboxylic acid , 1,1 3 -tridecanedicarboxylic acid, 1,1 4 -tetradecanedicarboxylic acid, 1,1 5 -pentadecanedicarboxylic acid, 1,1 6 -hexadecanedicarboxylic acid Carboxylic acid, maleic acid, fumaric acid, itaconic acid, maleic acid, methyl fumaric acid, quinolinic acid, quinic acid, naphthalenedicarboxylic acid, phthalic acid, isophthalic acid Phthalic acid, terephthalic acid, glycolic acid, lactic acid, 3-hydroxypropionic acid, 2-hydroxybutyric acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, 3-hydroxyvaleric acid, 5-hydroxyvaleric acid, Aconitic acid, ascorbic acetylene dicarboxylic acid, acetate succinic acid, quinic acid, kynuria, salicylic acid, acetic acid, salicylic acid, acetic acid, malic acid, acetic acid-oxopentyl Diacid a-phenylpropanoic acid, α-phenyllactic acid, anthraquinonecarboxylic acid, anthracenecarboxylic acid, isoohexanoic acid, isomerized camphoric acid, isocrotonic acid, 2-ethyl-2-hydroxybutyric acid, ethyl Malonic acid, ethoxyacetic acid, oxaloacetic acid, oxydiacetic acid, 2-oxosuccinic acid Decompose camphoric acid, citric acid, acetic acid, glycidic acid, glyceric acid, glucuronic acid, gluconic acid, keto acid, cyclobutyl formic acid, cyclohexyl dicarboxylic acid, diphenylacetic acid, di-〇- Phenyl tartaric acid, dimethyl succinic acid, dimethoxyphthalic acid, hydroxymalonic acid, tannin acid, thiophene acid, isopentenyl-2 -acid, 1,2-dihydroxy-1, 1,2-ethanetricarboxylic acid, tetrahydroxysuccinic acid, tetramethylsuccinic acid, 2oxobutyrolactone, dehydroacetic acid, rheonic acid, 2-phenyl-3-hydroxypropionic acid, 4-hydroxyl -3-methoxybenzaldehyde, butyrolactone-cold-carboxylic acid, hydroxyisophthalic acid, hydroxycinnamic acid, hydroxynaphthoic acid, o-hydroxyphenylacetic acid, m-hydroxyphenylacetic acid, p-hydroxyphenylacetic acid, 3 -Hydroxy-3 -phenylpropionic acid, trimethylacetic acid, pyrimidinedicarboxylic acid, pyrimidinetricarboxylic acid, pyruvate, α-phenylcinnamic acid, phenylglycidyl acid, phenylsuccinic acid, phenyl vinegar

313423.ptd Page 22 571361 V. Description of the invention (16) Acids, phenyllactic acid, propionic acid, 1,4-hexadienoic acid, 2,4-adiadienedioic acid, 2 -decanedioic acid, 3 protic acid ,; Forkylmalonic acid, diphenylglycolic acid, pyromellitic acid, 1,2-benzenediacetic acid, benzoic acid, benzoic acid, benzoic acid, benzoic acid, phenylacetic acid, 0-phenylfluorenyl Lactic acid, 3-benzylacetic acid, gallic acid, meso-oxalic acid, 5-methylisophthalic acid, 2-methylcrotonic acid, α-fluorenylcinnamic acid, methylsuccinic acid, formazan Malonic acid, 2-Methylbutyric acid, o-Methoxycinnamic acid, p-methoxycinnamic acid, mercaptosuccinic acid, fluorenylacetic acid, 0-propanol, lactic acid, malic acid, ketonic acid, leucine Acid, rose palmitic acid, rose acid, α-oxoglutarate, L-ascorbic acid, iduronic acid, galacturonic acid, gluconic acid, pyroglutamic acid, ethylenediaminetetraacetic acid, cyanide Triacetic acid, aspartic acid, glutamic acid, etc. In addition, for example: phenol, ortho-cresol, m-cresol, p-cresol, o-chlorophenol, m-chlorophenol, p-phenol, o-aminophenol, m-aminobenzene, p-aminobenzene, ortho-sulphone , M-Zophenylbenzene, p-Zophenylphenanthrene, o-nitrophenol, 2,4-dinitrophenol, 2,4,6-trinitrophenol, phosphobenzene, resorcinol, hydroquinone And other phenols. In addition, for example: sulfonic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, heptanoic acid, octanoic acid, nonanoic acid, capric acid, undecyl Acid, dodecylbenzene acid, dodecylbenzene acid, tetradecylbenzene acid, pentacarbonene acid, hexadecylbenzenesulfonic acid, heptacarbonate acid, ten Eight-carbon burning base acid, benzoic acid, naphthalene acid, toluene acid, acetoacetic acid, acetophenic acid S, and anthracene acid, etc. In addition, one or more of the protons of the main chain such as carboxylic acid, sulfonic acid, etc., may be thin with F, Cl, Br, I, OH, CN, NO, or

313423.ptd Page 23 571361 V. Description of the invention (17) Derivatives substituted with radicals. In addition, N-Si-based amino acids such as N-fluorenyl-N-methylacetic acid, N-fluorenyl-N-methyl-0-alanine, and N-Sf-based glutamic acid can also be suitably used. ; Polyethylene glycol alkylene carboxylic acid, halogenated peptides, alkylphenyl sulfonic acid, linear alkylbenzene benzoic acid, alkylnaphthyl carboxylic acid, naphthalene formic acid polycondensate, melamine sulfonic acid Acid formaldehyde polycondensate, dialkyl sulfosuccinate, alkyl sulfosuccinate, polyethylene oxide alkyl sulfosuccinic acid, alkyl sulfoacetic acid, α-olefinsulfonic acid, N-fluorenylmethyl Taurine, dimethyl-5-ruthenium isophthalate, sulfonated oil, higher alcohol sulfate, second higher alcohol sulfate, polyethylene oxide alkyl ether sulfate, second Alcohol ethoxy sulfonate, polyethylene oxide alkyl phenyl ether sulfate, monoglyceryl phenyl ester, fatty acid alcohol amine sulfate, polyethylene oxide alkyl ether phosphoric acid, polyethylene oxide alkyl benzene Ether Phosphoric Acid, Acid Filler, etc. It may also be a water-soluble polymer such as polymaleic acid, polyaspartic acid, carboxymethyl cellulose, or alginic acid, or a derivative thereof. These anionic additives can be used as they are, and they can also be used as salts of alkali metals such as Na and K, and salts such as ammonia. Among the above-mentioned to-be-polished surface treating agents, polyvinyl alcohols and their derivatives, polyvinyl alcohol-based copolymers and their derivatives are preferably selected. In particular, it is preferable to use polyvinyl alcohol or a derivative of polyvinyl alcohol. Further, it is preferable to use any one containing vinyl alcohol (A), vinyl acetate, vinyl formal, vinyl acetal, vinyl amine, vinyl isobutyl ether, and vinyl pyrrolidone (B). A polyvinyl alcohol-based copolymer as a constituent. In addition, polyvinyl alcohol and polyvinyl pyrrolidone are preferably used.

313423.ptd Page 24 571361 V. Description of the invention (18) One or more kinds of surface treatment agents can be added. There is no particular limitation on the amount of the surface-treating agent to be polished, but in terms of the dispersibility of the particles in the abrasive and the relationship with the prevention of precipitation, it is preferable to be 〇 · 〇1 with respect to 100 parts by weight of the particles. It is preferably 1,000 parts by weight, and more preferably 1 to 300 parts by weight, and more preferably 10 to 1,000 parts by weight. Furthermore, when the surface-treating agent to be polished belongs to a polymer compound, its molecular weight is preferably from 1,000 to 5,000,000, among which it is from 1,000 to 50,000. It is better to use 10, 0 to 100, 0 0, and more preferably. When the molecular weight of the surface-treating agent is less than 100, it will not be possible to obtain sufficient polishing speed when polishing silicon oxide films or silicon nitride films; on the contrary, when the molecular weight of the surface-treating agent exceeds 5,000, At 0, 00, the viscosity will increase and the storage stability of the abrasive will decrease. Furthermore, the polishing agent of the present invention, regarding the light transmittance at a wavelength of 500 to 700 nm and the time-varying difference between the light transmittance, preferably meet at least one of the following two conditions . The first condition is that when the abrasive contains the above-mentioned particles in an amount of 0.2% by weight, the light transmittance of a ground length of 500 nm is 10% or more. Here, it is better to be above 0, and more than 30% is more ideal. The light transmittance at a wavelength of 500 to 700 ° oblique to the condition-based abrasive is 20% or less immediately after the abrasive is prepared. Here, the numerical value after standing for 24 hours is different. If the upper # #The stomach is taken below 10%, but below 5%, it is more reasonable. ^ The above-mentioned bismuth, which is left to stand for 24 hours, &amp; eight ^ Qualitative decline depends on it. At 20%, dispersion is likely to decrease. For example, a certain grinding ^ t ^. Rate is 22 3% immediately after modulation, and / fan at 9ίΛ5〇〇η_light penetration • d / ° and 24.7% after standing for 24 hours

571361 V. Description of the invention (19), the difference is 2.4%. The light transmittance of the abrasive is measured using light having a wavelength of 5000 to 700 nm. For example, it can be measured using a spectrophotometer U-34 100 manufactured by Hitachi. In addition, when the abrasive contains more than 2% by weight of particles, if the light transmittance is 10% or more, the light transmittance will be 10% or more even in the case of 0.2% by weight. . In order to obtain an abrasive that meets the aforementioned light transmittance, for example, the following treatments can be performed: adding a dispersant to the abrasive, or performing ultrasonic dispersion treatment on the abrasive, preferably more than two times, or using a degree of 1 // m Sieve filter to filter and other ways. Abrasives having a light transmittance of less than 10% and abrasives having a light transmittance greater than the above difference cause particles to be more easily precipitated and difficult to handle. In addition, the probability of abrasion damage will increase. Furthermore, if the light transmittance is low, various optical detection and controllability (detection of the end point of polishing, control, detection of particle concentration in abrasives, etc.) will deteriorate. The conductivity of the abrasive is preferably 30 mS / cm or less. In general, it is difficult to set the conductivity to 0, but it is preferably in the range of 0.001 to 10 mS / cm, and more preferably in the range of 0.001 to 3 mS / Cra. The conductivity can be measured using, for example, a model CM-20 made by Toa Electronics Co., Ltd. and a measuring device. When the conductivity exceeds 30 ^ / cm, the ratio of particles that are easier to aggregate and precipitate will also become higher. In order to obtain an abrasive having a conductivity of 30 mS / cm or less, for example, in the process of mixing a tetravalent metal salt of a metal hydroxide particle with an alkaline solution, 'make or mix the tetrakid metal salt in the / t dipped solution with a wave or mix The p of the liquid is not too high.

313423.ptd Page 26 571361 V. Description of the invention (20) The Z potential of the particles dispersed in the abrasive is preferably positive. There is no particular limitation, but if it is less than about 80mV, it can be charged with 2 potentials. It is better to perform above 1 OmV, especially above 20 mV. ~ Interest potential can be used, for example, laser Doppler measurement system (such as Marupon ^ think. ^ (Transliteration), device name: Qian Desaiza- 3 0 0 HS (Transliteration)) When the manufacturing level of Erxing is below 0mV, the grinding speed will decrease. This is due to 2 stiffness. 2 the reason why the particle chemical interaction becomes smaller. In addition, the absolute value of the Z potential in the f agent is better because the particles are less likely to agglomerate and precipitate, so the dispersibility is better. When ★ is large, the bit becomes positive. For example, the pH of the abrasive can be set to 2 and 2 of the particles. ^ The potential point is the polishing method of the present invention, which is characterized in that the substrate is polished by using j, +, and a polishing agent. The substrate is preferably a substrate made of a semiconductor element or a semiconductor substrate. In addition, it is desirable to grind the oxide scale formed on the substrate. The substrate can be formed using a circuit board and wiring patterns. The substrate conductor base on which the silicon oxide film or the silicon oxide film and the silicon nitride film is formed on a semi-conducting semi-conducting plate such as a body substrate, a semiconductor substrate at the stage where circuit elements are formed, and the like is formed on the substrate while supplying a polishing agent . The silicon film or silicon nitride film can eliminate four vaporizations on the surface of the silicon oxide film. The entire surface of the substrate forms a smooth surface without damage. Hereinafter, the method of polishing the substrate of the present invention will be described with reference to the case of a semiconductor substrate using a fossil evening film in the shape 2 ', but it is not limited to this. As a polishing device, a general polishing device having a holder for holding a semiconductor substrate, and a polishing fixed plate such as a motor with a variable rotation number attached to a polishing pad (polishing cloth) can be used.

571361 V. Description of the invention (21), Fig. ^ Is a model diagram showing an example of an embodiment of the present invention using a CMP device. The device structure of FIG. 1 is attached to the polishing pad 17 on the polishing fixed plate 丨 8 and the abrasive agent 16 of the present invention containing particles and media is supplied from the abrasive supply mechanism 15 to the polishing pad. The polishing pad on the plate 8 is placed on top: In addition, the semiconductor substrate 13 on which the silicon oxide insulating film 14 is formed is attached to the $ 2 round bracket 11 and fixed with the holder 丨 2. The surface to be polished = emulsified silicon insulating film 14 is brought into contact with the polishing pad 17, and the surface to be polished is moved relative to, specifically, the wafer holder 11 and the polishing gourd 18 are rotated. , And the structure of CMP polishing. In general, the polishing pad i 7 on the grinding fixing plate 18 can be made of a non-woven fabric, a polyurethane, a porous fluororesin, or the like, and is not particularly limited. In this case, it is preferable to perform groove processing for the retained abrasive 6 on the polishing pad. The polishing bars 1 Ϊ 2 are particularly limited, but the rotation speed of the polishing fixed disk is preferably set to a low rotation speed of 100 rpm or less which prevents the conductive substrate 13 from flying out. Grinding the semiconductor substrate 13 with the oxide surface of the oxidized stone insulation film 14 on the second grinding surface ^ Pressing pressure (processing load), preferably in the range of 10 kpa to 1 j 〇 2 ^ 2 kf / cm 2). In order to meet the polishing speed, the uniformity in the surface to be polished is 2 ° J, and the flatness is 20kPa to 50kPa (204 to 510gf / cm2). The most reasonable principle is °. During the polishing, a polishing agent supply mechanism such as a pump is used. 15 麻 2 ^ 塾 1 7 Continuously supplies the abrasive 16 of the present invention. Although this supply mechanism and the supply μ are particularly limited, it is best to always cover the surface of the polishing pad with an abrasive. The hardness of the polishing pad of the polishing substrate is preferably greater than 50 Shore D hardness. Fortunately, Shore D hardness is preferably 55 to 99, especially 60 to 95.

313423.ptd

P.28 571361 Jade, invention description (22) is ideal. If the hardness of the polishing pad is lower than 50, the mechanical effect of the pad will be reduced, and the polishing speed will be reduced. Conversely, if the Shore D hardness does not reach the value of 100 or more above the definition and is too hard, the surface to be polished may be damaged. The Shore D hardness of the pad can be measured with a Shore D hardness tester (for example: Aska (Transliteration) Rubber Hardness Tester Type D manufactured by a polymer meter) It may be any of a foam and a non-foam such as a cloth or a non-woven fabric. The material of the polishing pad can be polyurethane, acrylic, polyester, acrylic-ester copolymer, polytetrakis ethylene, polypropylene, polyethylene, poly 4-methylpentene, cellulose, etc. Polyamide, Polyamide, Polyamide and Polyamide, Polyamide and Polyamide: Polymers, Stupid Resin 'Polystyrene, Polycarbonate, Epoxy Resin and Other Resin' It is best to form small 1 "large bumps on the surface of the pad and also perform various groove processing

When the surface of the polishing pad is uneven, the convex portion 25_, especially 100 &quot; m2 or more, and the area of 0.25mm is preferably 0.2, which is more than 0.25, which will result in a more ideal polishing speed. If u m, it will be difficult to produce minute unevenness. / J,

The height of the small protrusions on the uneven surface should preferably be less than 10%. If the high-yield 1-height difference J] exceeds 10%, in the polishing, there will be micro-protrusions that are not connected and poor (1σ / average high-grinding), resulting in polishing characteristics: small mechanical protrusions on the substrate The average height is preferably above 1 // m in person u UM and below 2 0 0 // m

571361 V. Description of Invention (23). If it is more than 200 &quot; m or more, the abrasive liquid will flow excessively, and the speed will be two. Conversely, if the township is less than ^ _ Xiao, the grinding surface and the micro surface will adsorb, which hinders smooth grinding. The shape of the minute protrusions can be raised from the upper corner 3, the cone, the corner post, the hemisphere, and the like, and is not particularly limited. Further columns: ', the average distance between dogs is preferably more than 3〇 # m and i〇〇〇 # _ j = 2, the interval between the protrusion and the protrusion will be too narrow, and the blocking of n right wear debris 1 phenomenon. Conversely, if it is greater than 10. 2 The number of micro-protrusions that are in contact with the polishing surface will be reduced, and the polishing method and the J: micro-protrusion pad manufacturing method will be reduced, such as the embossing roller method: = shape method, replication method, etc. Among these, ′ is preferably a copying method using photo-hardening = ::: mold. • The photocurable resin composition used for the layer is not particularly limited. Sui Shuyue said pad. ί ΐ Γ When the polishing pad is formed into a strip, it is best to use a curved (wavy) shape of the polishing pad. For example, there is biaxially drawn polyethylene terephthalate. Hardening copies small protrusions from a mold and / or a photocurable resin layer is formed on the surface. 3 =. Use a polishing pad with a Shore D hardness of 50 or more for polishing. Polishing of conductive substrates such as oxidized oxide films can also be applied to the polishing of metal films such as copper and aluminum formed on a semi-conductor. Grinding t:::: f method is the best-while supplying the abrasive to the ground (for example, oxygen two dagger: film two so that at least the oxide stone is formed, the insulating film is polished, silicon nitride film, etc.) In addition to the semiconductor substrate system: touch: relative motion and polishing. In addition to relative motion and grinding fixed disk, you can also rotate or shake the bracket and carry out

571361 V. Description of the invention (24) Grinding. In addition, for example, there are grinding methods that make stealing seven a X, X, .. ^, 丨 the original solid disk into the planet rotation, or make the W-shaped polishing pad toward the mouth ^ ^ ^ ^ ^ ^ Early in the length direction—the grinding method of linear movement in the direction #. In addition, Tuo Muquan u, ^ ^ m ^ gave up any sorrow in consolidating, turning doubts, or shaking. The polishing method, 0 e, 孩 孩 -r 袒 ΠΓ, must be carried out on the polishing pad and the substrate: mobile 刖 ... can be appropriately selected according to the film or polishing device to be polished 0 = = such polishing Method 'It is best to polish the silicon oxide insulating film at a polishing rate of 200 nm / rain at 200 nm / min or less. In particular, it is preferable to perform such grinding using an abrasive using particles of a tetravalent metal hydroxide. Furthermore, since the surface state of the polishing pad is often maintained in the same state and polishing is performed ', it is best to add a polishing pad coating procedure before performing CMP substrate polishing. For example, a trowel with diamond particles (UreSSer) is used to grind with a liquid containing at least water. For the actual polishing procedure, it is best to add a substrate consisting of the following procedure (1) Brushing particles and other foreign matter on the substrate after polishing; (2) Changing the abrasive to water (3) Spin drying to remove water from the surface of the substrate. Figures 2 (a) to ((0) are schematic cross-sectional views of a polished substrate of a semiconductor substrate to which the present invention is applicable. Figure 2 (a) shows a section where grooves are formed on a stone substrate, (b) In the trench of (a), the step of embedding the oxide stone film and the step of 'C 糸 grinding (b) the oxide stone film to separate the elements are shown.

313423.ptd Page 31 571361 V. Description of the invention (25) — -----------. | For example, in the ditch rod of the silicon substrate 1 in Fig. 2 (a), the second picture of ^ As shown in (b), in the case where the silicon oxide film is buried at the shape point T (the shallow trenches of the plate 1 are separated, the silicon-based protrusions of the milk-shixi film 3 and the silicon nitride film 2 are ground to the bottom The silicon nitride oxide is three layers of silicon oxide, which is recessed in the element separation portion t, so that only the buried silicon nitride and the nitrided silicon nitride film (C) as the termination layer remain (C). At this time, the oxygen limit is larger. "" The greater the speed ratio, the grinding is the same. When using this private a0 | Shixi insulation film for grinding, the ratio of the oxidation speed 22 == the polishing speed of the fossil night insulation film and the nitride I is best at 5. The speed is 11 times higher than the silicon nitride film and not more than 300. In particular, the name μ is better, and the polishing speed ratio is preferably 15 or more and 300 or less. For example, when the abrasive is in the middle of people When the above-mentioned polished surface treatment agent is present in the sex PZ region, the | position will be η 〃, and the siliconized silicon film will be negatively charged, and the electrical film of the silicon nitride film will be ::: by the polished surface treatment agent Selectively adsorbed on the rate of nitrogen nitride,: f effectively terminates the film function, and obtains the above-mentioned better abrasive particles. When the abrasive contains a dispersant, it will be adsorbed on the abrasive. The three-dimensional stabilization effect can improve the dispersion stability. I produces more when I = = I use the abrasive for the separation of shallow trenches, and also requires the grinding process, damage and damage. In addition, it can also be used for flat metal wiring. Ground Impact &amp; Silicon Oxide Insulation Layer% Mill 'Forms Shallow Trench Separation on Shixi Substrate Then, the silicon oxide insulating film on the "formation * formed thereon, and the inscription wiring formed thereon" is again planarized. The planarization is performed on page 32 of 571361. V. Description of the invention (26)-Oxidation A second layer of aluminum wiring is formed on the silicon insulating film layer. After the silicon oxide insulating film is formed again in this wiring room and the wiring, the above polishing method is used to eliminate the unevenness on the surface of the insulating film, so that the semiconductor substrate can be made. A smooth surface is formed on the entire surface. By repeating this procedure a predetermined number of times, a semiconductor element having a desired number of layers can be obtained. Methods for manufacturing an inorganic insulating film to which the present invention can be applied include, for example, a low-pressure CVD method and a plasma CVD method, etc. The formation of the silicon oxide insulating film by low-pressure CVD method uses a single silane: S i 乍 is a Si light source, using oxygen: 0 as an oxygen source. It is implemented at a low temperature below 40 ° C. This si H rO2 system is paid for the oxidation reaction. In order to achieve high-temperature reflow surface planarization, when doping scales: P, SiHfOrPH 熹 reaction gas is preferred. Plasma CVD method has Under thermal equilibrium, the advantage that high-temperature chemical reactions can be performed at low temperatures. In the plasma generation method, there are two types of capacity-combination and induction-combination. The reaction gas can be S i S for S i light source. A SiHrN2O-based gas with N2O as an oxygen source, and a TEOS-〇2-based gas (TEOS-plasma CVD method) using tetraethoxysilane (τ £ 〇s) as a Si source. The substrate temperature is preferably in the range of 250 ° C to 400 ° C, and the reaction pressure is preferably in the range of 67 to 400 ° C. In this way, in the oxide oxide insulating film, it is also possible to dope the structure and stone. Similarly, the formation of the nitride nitride insulating film by the low-pressure CVD method is based on the use of silicon dichloride ... Si Η β 1 拃 as the Si source and ammonia: NH 拃 as the nitrogen source. This Si H 1 plant N Η bombardment oxidation reaction 'is at 900. It was obtained at a high temperature of 〇. Plasma CVD methods include, for example, SiHrN radon gas using SiH 拃 as the si source and NΗ 拃 as the nitrogen source. The substrate temperature is preferably in the range of 300 to 400 ° C. The abrasive and the grinding method of the present invention are not only suitable for forming semiconductors

571361 V. Description of the invention (27) ^ _ Silicon oxide film or silicon nitride film on the body substrate, in addition, it can also be applied to the silicon oxide film formed on the wiring board and wiring, glass, nitride second insulation Optical glass such as film, reticle, lens, gadolinium, inorganic conductive machine film such as IT0, optical integrated circuit composed of glass and crystalline material, optical switching element, optical waveguide, fiber end face, scintillator and other optical units Crystal, solid laser single crystal, blue sapphire substrate for LED, SiC, GaP,

Polishing of semiconductor crystals such as GaAs, glass substrates for magnetic disks, magnetic heads, etc. Furthermore, the abrasive and polishing method of the present invention can also be applied to a metal film. [Examples] Next, the present invention will be described using examples. However, the present invention is not limited to these examples. Example 1 (Preparation of Abrasive) 4 300 g of Ce (NHD-(N 0 D was dissolved in pure water). Next, in this solution, 240 g of ammonia water ( 25% aqueous solution), thereby obtaining a suspension containing 160 g of ytterbium hydroxide (yellow-white). The obtained ytterbium hydroxide suspension was subjected to solid-liquid separation by centrifugation (400 0 r pm '5 minutes). After removing the liquid, new pure water is added. Centrifugation is performed again under the above conditions, and this operation is repeated four times for washing. The specific surface area of the obtained particles is measured by the BET method, and the result is 20 0m2 / g. After mixing 160g of particles with 1584g of pure water, and performing ultrasonic dispersion, it is filtered with a sieve of 1 / m to obtain a solid j-% abrasive. Use Photon correlation method was used to measure the particle size of the particles of this abrasive. As a result, the average particle size of the primary particles was i 7 〇

313423.ptd Page 34 571361 V. Description of the invention (28) pH is 5.40 (grinding of the insulating film layer) On the bracket of the polishing device attached with the adsorption pad for substrate mounting 'installation using TEOS-plasma A 0 2 0 0 mm silicon wafer with a silicon oxide insulating film formed by a CVD method. Mount the insulating film with the insulating film face down on the holder on a fixed disk of a 0,600 mm polishing device attached with a porous urethane resin pad, and set the processing load to 30 kPa (3 0 6gf / cm2). While the above-mentioned abrasive (solid content: 1% by weight) was dripped on the fixed plate at a speed of 200 c c / m η, the fixed plate and the wafer were rotated at 50 rpm for 2 minutes to polish the insulating film. The polished wafer was sufficiently washed with pure water, and then dried. A light interference film thickness measuring device was used to measure the film thickness change before and after polishing. As a result, the polished silicon oxide insulating film was 800 nm (polishing speed: 400 nm / mi η). In addition, when the surface of the insulating film was observed with an optical microscope, no clear abrasive damage was observed. f Example 2 (Preparation of Abrasive) 4 3 g of CeUD 2 (n03) was dissolved in 7300 g of pure water. Next, 24 g of ammonia water (25% aqueous solution) was mixed and stirred in this solution to obtain a suspension containing about 16 g of rhenium hydroxide (yellow-white). Centrifugation (^ 0 0 0… 1 &quot; 1, 5 minutes) was used to perform solid-liquid separation of the obtained thorium hydroxide suspension, and after the liquid was removed, new pure water was added again. Secondly, a dispersion liquid is formed by irradiating a shoal wave. The full p 7 — ~ Jiao Yue ^, 1Qn 2 / Jue and the particle density of 4.7 g / cm3, than the table ^ m g. The particle concentration in the dispersion was adjusted to 丨 0 weight, and the pH was adjusted to 6.0 to obtain a hemp festival. Using this abrasive stock solution,

Page 35 571361 V. Description of the invention (29) When the photon correlation method is used to measure the thousand-average particle size of the secondary particle at a thickness of 100 nm, the result is (grinding of the insulating film layer). Grinding, drying, and washing, two: application: 1, change the oxidation, as a result, the film after this grinding and then grinding, the monthly rate of film grinding: 715run / min). In addition, the silicon insulating film is 1 430 nm (when the surface of the insulating film is studied, the surface of the insulating film is observed from R to Ming, and the% oxidation is observed with an optical microscope. Example 3 is a clear abrasive damage. (Production of abrasives) will be 43 0g of Ce (NH4) 2 (N03) is decomposed in pure water of 50000§. In this solution, 240g of ammonia water (25% aqueous solution) is stirred together to obtain ^ about 60g of hydroxide黄 (yellow-white) suspension. A dispersion was then formed in the same manner as in Example 2 ^. The obtained particle density was 4.2 g / cm3, and the specific surface area was 240 m2 / g. The particle concentration in the dispersion was adjusted to i 〇wt%, the pH was adjusted to 7.3 to obtain an abrasive. Using this abrasive stock solution, the average particle diameter of the secondary particles was measured by the photon correlation method, and the result was 230 nm (the thickness of the insulating film layer). Polishing) Using the polishing agent obtained as described above, the silicon oxide insulating film was polished, dried, and cleaned as in Example 2, and was polished to 80 2 nm (polishing rate: 401 nm / min). No definite abrasion damage was observed on the surface of the silicon oxide insulation. Example 4

313423.ptd Page 36 571361 V. Description of the Invention (30) (Making of Abrasives) Ce (NH4) 2 (N03) of 4 0g is decomposed into 7300 g of pure water. Next, 240 g of ammonia water (25% aqueous solution) was mixed and stirred in this solution; and suspensions each having about 160 g of thorium hydroxide (yellow-white) were obtained. Thereafter, a dispersion liquid was formed in the same manner as in Example 2. The obtained particle density was 4.5 g / cm3, and the product was 200 m2 / g. The particle concentration in the dispersion was adjusted to 〇wt. The pH was adjusted to 4 · 9 to obtain an abrasive. The average particle size of the secondary particles measured by the photon correlation method was 170 nm. (Polishing of the insulating film layer) Using the polishing agent obtained as described above, the edge film was polished, washed, and dried as in Example 2. The oxygen-cut insulating film was ground at 2560 nm (polishing rate: 28 Qnm / min). In addition, no definite abrasive damage was observed on the surface of the oxygen-cut insulating film. Example 5 (Production of Abrasives) 4300g of Ce (NH4) 2 (n〇3) was dissolved in 7300g of pure foreigner ^ == solution, and 240g of ammonia (25% water-soluble) In addition, a suspension containing about 60 g of hydroxide decoration (yellow-white) was obtained. ^ And the payment (400 rpm, 5 minutes) was used to suspend the obtained rhenium hydroxide. Remove the liquid and add new pure water. Once again, I know the solid-liquid separation for the heart, and repeat the Ph Ph condition to perform a check of 1 li. This is done four times and the hydroxide in the suspension obtained by washing The average pure a 4 particle size after washing is 5 nm. The specific surface area measured by the ㈣τ method is: 结: measured ZU0m2 / g.

313423.ptd Page 37 571361 V. Description of the invention (31) After mixing 1600 g of rhenium hydroxide particles with 1 5 8 4 g of pure water, ultrasonic dispersion treatment is performed, and then a 1V m sieve is used for Filter to obtain an abrasive. When the average particle diameter of the secondary particles of this abrasive was measured by a photon correlation method, it was 170 nm. And, of abrasives? 11 is 5.4. (Polishing of the insulating film layer) As in Example 1, a light interference film was used. As a result, 400 nm / min was measured. 0 It was not observed that the above-mentioned abrasive (solid content: 1% by weight) was used to insulate the silicon oxide. The film is polished, washed, and dried to measure the thickness change of the film before and after polishing. The polished silicon oxide insulating film is 800 nm (except for the polishing speed, the optical film is used to observe the abrasive damage when the surface of the insulating film is polished. Example 6 (Production of Abrasives) Dissolve 5 (^ of 〇6 (44) 2 (别 3) in 100〇 of pure water. Next in this solution: 1 mix and stir at a pH of about 6 Ammonia (2 5% aqueous solution) was used to obtain a δ thallium hydroxide suspension. The obtained thorium hydroxide suspension was subjected to solid-liquid separation by centrifugation (400 μm, 5 minutes), and the liquid was removed. And add new pure water. Repeat this operation three more times to wash / continue the average particle size (average crystallite size) of primary particles of the hydroxide hydroxide particles in the suspension obtained after washing. The latter is 3.5 nm. The specific surface area is measured by the BET method. S is 2 2 0m2 / g. After adjusting the concentration of thorium hydroxide particles to 0.2% with water, ammonia water (25% aqueous solution) is added to adjust the pH to 6, and then ultrasonic dispersion treatment is performed, and 1 // m sieve filter to obtain the abrasive. Photon

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Page 38 571361 V. Description of the invention (32) When the average particle diameter of the secondary particles of this abrasive is measured by the relevant method, the result is $ 10 Onm 〇 (grinding of the insulating film layer) In addition to using the above abrasive, and fixing the disk The silicon oxide insulating film was polished, washed, and dried in the same manner as in Example 1 except that the wafer was rotated at 75 rpm for 2 minutes. A light interference film thickness measuring device was used to measure the change in film thickness before and after polishing. As a result, the polished stone oxide insulating film was reduced by 1 0 4 0 n m (polishing speed ·· 5 2 0 n m / m i η). In addition, when the surface of the insulating film was observed with an optical microscope, no definite abrasive damage was observed. Compound A Example 7 (Production of Abrasives) 43 (^ of 〇6 (leg 4) 2 (瘩 3) was decomposed into pure water of 7 3 0 0§. Six were mixed in this solution, and agitated 24 0g ammonia water ( 25% aqueous solution), to obtain 1 / Og of bromide hydroxide (yellowish white). The obtained rhenium hydroxide suspension was subjected to solid-liquid separation by centrifugation (4,000 rpm '5 minutes). The liquid was removed, After: add new pure water, and then perform centrifugation under the above conditions, and weight: perform this operation four times and then wash. The specific surface of the obtained particles is the same as that measured by the Beta method. The result is 200. mVg. Adjust the pH to 5 · 4β 4 = 2: ΐ: Add the commercially available acid '' ㈣ 过 net ;;, and; after the bulk treatment, reuse]] „„ 卞At ten times the average size of the branches, the Wu rabbits __. And the abrasives stored at room temperature for four months, three.

571361 V. Description of the invention (33) (Grinding of insulating film layer) Using the above-mentioned abrasive (solid content: 1% by weight), as in Example 1, the oxide oxide insulating film is polished, washed, and dried. A light interference film thickness measuring device was used to measure the change in film thickness before and after polishing. As a result, the thickness change of the silicon oxide insulating film after this grinding was 800 nm (polishing speed: 40 nm / min). In addition, when the surface of the insulating film after polishing was observed with an optical microscope, no definite polishing damage was observed. Example 8 (Preparation of Abrasive) After mixing 16 g of the particles obtained in Example 7 with pure water 1 440 g, the pH was adjusted to 5.4 using a commercially available ammonia water. Then, after performing ultrasonic dispersion treatment, it was filtered through a 1 # m sieve to obtain an abrasive. The specific surface area of the particles measured as in Example 7 was 2000 m7g, and the average particle diameter of the secondary particles was 200 nm. After the abrasive was stored at room temperature for four months, the abrasive pH was reduced to 4.5. After the silicon oxide insulating film was polished in the same manner as in Example 7, the thickness of the silicon oxide insulating film changed to 600 nm (polishing rate: 300 nm / min). In addition, when the surface of the insulating film after polishing was observed with an optical microscope, no definite polishing damage was observed. Example 9 (Preparation of Abrasive) 4 300 g of Ce (NH4) 2 (N03) was disintegrated in 7300 g of pure water. Next, 240 g of ammonia water (25% aqueous solution) was mixed and stirred in this solution to obtain a suspension containing 160 g of thorium hydroxide. The obtained thorium hydroxide suspension was subjected to solid-liquid separation by centrifugation (4,000 rpm, $ minutes), and then removed.

571361 V. Description of the invention (34) --- Add new pure water to the liquid, then perform centrifugal separation under the above conditions, repeat this operation three times, and then wash. The specific surface area of the particles in the rhenium hydroxide suspension obtained after the washing was 200 m 2 / g as measured by the BET method. ,,mouth …,

After mixing 16 g of the particles in the rat's gadolinium oxide suspension particles, polyethylene oxide octylamine (number average molecular weight about 10,000), 1.5 g, and pure water 1 440 g, the mixture was performed. Ultrasonic dispersion. Then, malic acid was added and the pH was adjusted to 5.4 using a commercially available ^. After ultrasonic dispersion was performed, it was filtered with a second sieve to obtain an abrasive. When the average particle diameter of the secondary particles of this abrasive was measured by a photon correlation method, the result was 1 15 nm. (Polishing of the insulating film layer) The silicon oxide insulating film was polished, washed, and dried in the same manner as in Example 1 using the above-mentioned abrasive (solid content: 1% by weight). A light interference type film thickness measuring device was used to measure the film thickness change before and after polishing. As a result, the silicon oxide insulating film thus polished reduced the film thickness by 760 nm (polishing speed: 38 nm / ^ in). In addition, when the surface of the polished silicon oxide insulating film was observed with an optical microscope, no definite polishing damage was observed. ,, (production of abrasives)

= 43〇§ (^ (关 4) 2 (1 ^ 〇3) is painless in 7300〇§ pure water. Secondly, 1 ^ t is mixed and stirred with 240 g ammonia water (25% aqueous solution), And obtain a suspension containing bell) of g / oxygen / dagger. Use centrifugal separation (40000 r Pm, 5 minutes 2: after the solid hydroxide solution obtained by the rhenium hydroxide suspension is removed, remove the liquid ”4. Add new pure water, then perform the centrifugal separation under the above conditions, and then repeat

571361 V. Description of the invention (35) After performing this operation three times, wash it. After washing, the specific surface area of the particles in the decorative suspension was emulsified by using Bet * \ So oxygen at 200 m 2 / g. Li, Kou Hefeng mixed 6g particles of lice oxidized pupae suspension particles, 6g of polyvinyl alcohol (number molecular weight about 60,000, gelation degree 96%), and pure water H4〇 to mix it L Shi Λ ultrasonic dispersion. Then, a commercially available ammonia solution was used to adjust & to. &Amp; ... After dispersing / 亍 超 亍 波, it was filtered through a 1 #m sieve to obtain an abrasive. When the average particle diameter of this "is measured by a photon correlation method, the result is 170 nm. Renzi (grinding of the insulating film layer) Using the above-mentioned abrasive (solid content: i% by weight), a film thickness measuring device was used to measure before and after polishing. As the thickness of the silicon oxide insulating film has been changed, the thickness of the polished silicon oxide insulating film is reduced by 800 nm (Research,?, Σ, ◊, 240 nm / min). A 200-mm nitride nitride wafer was formed and polished in the same manner, and the thickness of the 0,20 nm film (polishing speed: film thickness / Shi Xiyu insulation "will reduce the film and silicon nitride insulation film. The polishing speed ratio was 40%. 2 Observation of the polished silicon oxide insulating film using a silicon insulating micromirror _ No clear polishing damage was observed using an optical display. 1. The surface of the silicon insulating film, Example 1 1 (Making of abrasive) In addition to using polyvinylpyrrolidone (number \ g / knife amount about 20,000) 6g

571361 V. Description of the invention (36) To replace polyvinyl alcohol, and add 1.5 g of polyethylene oxide octylamine (number average molecular weight about 10, 0 0 0) in addition to the rest and Examples 丨. Similarly, an abrasive was prepared. The specific surface area of the particles in this abrasive was 220 m 2 / g, and the average particle diameter of the secondary particles was 125 nm. Using this abrasive, as in Example 10, the silicon oxide film formed on the surface of the silicon wafer by the TEOS-CVD method and the silicon nitride insulating film produced by the low-pressure CVD method were polished. . After 2 minutes of polishing, the silicon oxide insulating film was polished at 76 nm (polishing speed: 380 nm), and the silicon nitride insulating film was polished at 22 nm (polishing speed: 11 nm). No definite abrasion damage was observed on the surface of the silicon nitride insulating film. AA Example 12 (Preparation of Abrasive) 200 g of Ce (NH4) 2 (N03) was decomposed into i8 kg of pure water. Next, ammonia water (25% aqueous solution) was mixed and stirred in this solution to obtain a suspension containing hydrogen and oxygen = tritium. After centrifugal separation (4,000 rpm, 5 minutes), all the obtained rhenium hydroxide suspensions were subjected to solid-liquid separation, the liquid was removed, and pure water was added. Repeat this operation twice more. The specific surface area of the rhenium hydroxide particles in the suspension obtained after washing was measured by the bet method, and the result was 190 m V g. The concentration of thorium hydroxide particles was adjusted to ^ 3% with water and subjected to ultrasonic dispersion treatment, and then filtered through a sieve of m to obtain an abrasive. The average particle size of the secondary particles of this abrasive was measured by a photon correlation method, and the result was 105 nm. Also, the light transmittance of this abrasive is at a wavelength of 500 nm, 600 nm,

Page 43 571361 V. Description of the invention (37) 7 0 0 n m, respectively 22.3%, 49.5%, 68_5%. In addition, the light transmittance after standing for 2 hours at the wavelengths of 500 nm, 600 nm, and 700 nm was 24.7%, 5.39%, and 73 · 7% (the difference was 2. · 4%, 4.4%, 5.2%). (Polishing of the insulating film layer) The oxide oxide insulating film was polished, washed, and dried in the same manner as in Example 1 except that the above-mentioned abrasive was used and the fixed disk and the wafer were rotated at 75 rpm for 2 minutes. The light interference type film thickness measurement device I was used to measure the film thickness change before and after polishing. As a result, the polished oxide stone insulation film was reduced by 8 40 n m (polishing speed: 4 2 0 n m / m i η). In addition, when the surface of the insulating film was observed with an optical microscope, no sharp abrasion was observed. EXAMPLES (Production of Abrasives) 11% of 0 (6) (Dragon 4) (2003) was dissolved in 181% of pure water. Next, ammonia solution (25% aqueous solution) was mixed and stirred in this solution to obtain a suspension containing aerobium oxide. Centrifugal separation (400 rpm, 5 minutes) was used to perform solid-liquid separation of the plutonium hydroxide suspension, and then the liquid was removed and pure water was added. This washing operation was repeated three more times. 'The specific surface area of the rhenium hydroxide particles in the suspension obtained after washing was measured by the B E T method, and the result was 180 m 2 / g. The concentration of aerobium aerobic oxide particles was adjusted to 0.2% with water and subjected to ultrasonic dispersion treatment, and then filtered through a 1 # m sieve to obtain an abrasive. When the average particle diameter of the secondary particles of this abrasive was measured by the photon correlation method, the result was 21Onm °

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571361 V. Description of the invention (38) And the light transmittance of this abrasive is 14.4%, 32.7%, 48.1% at the wavelengths of 500nm, 600nm, and 00nm, respectively. In addition, the light transmittance after standing for 24 hours at the wavelengths of 500 nm, 600 nm, and 70 nm was 波长 24.1%, 47.9%, and 65.2% (the differences were 9.7%, 15.2%, and 17.1%). (Polishing of insulating film layer) ^ The insulating film was polished, washed, and dried in the same manner as in Example 12 except that the above-mentioned abrasive was used. Light interference film thickness \ Berry device is used to measure the film thickness change before and after grinding. As a result, after grinding

The reduction of the silicon oxide insulating film is 800 nm (grinding speed: 400 nm / min). At this time, the surface of the insulating film was observed with an optical microscope, and a clear abrasive damage was observed. … (Manufacturing of abrasives), 100 g of Ce (NH4) 2 (N03), etc., are disintegrated in 18k g of pure water. Secondly, in this article, the ammonia solution (2 5% aqueous solution) is mixed and stirred, and the pH is adjusted to a suspension of 5 · 5, 5 八 f with gas oxidation. After centrifugal separation (4 0 0 0 rpm), the obtained oxynitride suspension was subjected to solid-liquid separation to 'remove Sogoji' Taiga's new pure water. This operation was repeated twice more. After washing / 7 &gt; [于 県 系, '

The specific surface f of the gadolinium oxide gadolinium oxide in the main r # heart ocean liquid was measured by BET method, and the result was 180 mVg. f 9 U / f is adjusted by water to have a concentration of rhenium hydroxide particles of 0.2%, ammonia water U 5% water-soluble pan w ^), and adjusted to a pH of 5.5, and then subjected to ultrasonic dispersion treatment. !! The 1 V m sieve was filtered to obtain an abrasive. By using the Euqian correlation method, the results are as follows: 3: When the average particle diameter of the secondary particles of this abrasive is

571361 V. Description of the invention (39) The result is 1 3 Onm. 5mS / cm。 For this abrasive, the model CM-20 type measuring device 'made by Toa Electronics Co., Ltd. was used to measure its conductivity to 0.5 mS / cm. The name of the device manufactured (transliterated) by Marupon using laser Doppler measurement: Qian Desaiza-3 0 0 0 H S (transliteration) 'to measure the z potential of thorium hydroxide particles. The result was 35 mV. Moreover, no phenomenon of aggregation or precipitation was found. (Polishing of the insulating film layer) The silicon oxide insulating film was polished, washed, and dried in the same manner as in Example 1 except that the above-mentioned abrasive was used and the fixed disk and the wafer were rotated at 75 rpm for 2 minutes. A light interference type film thickness measuring device was used to measure the change in film thickness before and after rubbing. As a result, the polished oxide oxide insulating film was reduced by 880 nm (polishing speed: 440 nm / min). In addition, when the surface of the insulating film was observed with an optical microscope, no definite abrasion damage was observed. tExample 15 (Preparation of Abrasive) 〇6 (关 4) 2 (^ 3) of 55§ was decomposed in pure water of 〇1 ^. Next, ammonia water (25 ° / ◦ aqueous solution) was added to the solution, and the pH was adjusted to 5.5, to obtain a suspension containing 21 g of rhenium hydroxide. After centrifugal separation (400 r Pm, 5 minutes), the obtained gadolinium dysprosium oxide suspension was subjected to solid-liquid separation, and then the liquid was removed and new pure water was added. Repeat this operation three more times. The specific surface area of the particles in the rhenium hydroxide suspension obtained after washing was 2000 m V g as a result of measurement by a BET method. To this thorium hydroxide suspension (thorium hydroxide concentration of about 0.2% by weight), ammonia water (25% aqueous solution) was added to prepare ρΗ5β 5 and then ultrasonic was performed.

313423.ptd Page 46 571361 V. Description of the invention (40) Dispersing treatment ’Then use a 1 # m sieve to perform tears and abrasives. ^ When obtained, the secondary particle of this abrasive was measured by photon correlation method. The result was 100 nm. Average grain also (grinding of insulating film layer) In addition to using the above-mentioned abrasives and Shore D hardness 6 9 non-private, metallurgy &amp; a / dagger X | &gt; w acetic acid brewing polishing pad, and the fixed disk and crystal The circle was rotated at 75 rpm for 2 minutes, and the rest was ground, washed, and dried in the same manner as in Example 1. A light interference film thickness measuring device was used to measure the change in film thickness before and after polishing. As a result, the polished silicon oxide insulating film was reduced by 850 nm (polishing speed: 42 5 nm / min). In addition, when the surface of the insulating film was observed with an optical microscope, no definite abrasive damage was observed. Comparative Example 1 (Production of Abrasive) 2 kg of europium carbonate hydrate was sintered at 800 ° C to obtain europium oxide. Rhenium oxide is mixed with pure water, and crushed and dispersed by a ball mill. It was then filtered through a 1 // m sieve to obtain a dispersion. The particle density was 7.0 g / cm3 and the specific surface area was 280 m2 / g. The particle concentration in the dispersion was adjusted to 1.0 reset%, and ρ Η was adjusted to 9 · 1 to obtain an abrasive. The average particle size of the secondary particles measured by the photon correlation method using this abrasive stock solution was 200 nm. In addition, the same measurements as in Examples 12 and 13 were performed, and as a result, the light transmittance of this abrasive was independent of the wavelength and was almost 0%. In addition, as in Example 14, the measured electrical conductivity was 3 1 mS / cm, and the Z-electricity of the hafnium oxide was -50mV.

3l3423.ptd Page 47 571361 V. Description of the invention (41) (Grinding of the insulating film layer) The silicon oxide insulating film was polished, washed, and dried in the same manner as in Example 2 using the abrasive prepared by the above method. . Although the silicon oxide insulating film was polished for 3 8 2 n m (polishing speed: 191 nm / min), polishing damage due to grinding was observed. Comparative Example 2 (Preparation of Abrasive) 2 kg of europium carbonate hydrate was sintered at 350 ° C to obtain europium oxide. Rhenium oxide is mixed with pure water, and crushed and dispersed by a ball mill. It is then filtered through a 1 // m sieve to obtain an abrasive. The particle density was 7.0 g / cm3, and the specific surface area was 200 m2 / g. The particle concentration in the dispersion was adjusted to 1.0% by weight, and ΘΗ was adjusted to 7.9 to obtain an abrasive. The average particle size of the secondary particles measured by the photon correlation method was 3 2 0 n m. (Polishing of insulating film layer) The polishing agent prepared in the above manner was used in the same manner as in Example 2 to polish, wash, and dry the silicon oxide insulating film. Although the silicon oxide insulating film was polished for 10 6 n m (polishing speed: 5 3 n m / m i η), polishing damage due to polishing was observed. [Industrial Applicability] As mentioned above, the polishing method of the abrasive and the substrate of the present invention can be applied to the planarization process of the substrate surface of the CMP, and is particularly suitable for the planarization process of the interlayer insulating film and the separation of shallow trench elements. Aspects of the formation process.

313423.ptd Page 48 571361 Brief description of the drawings [Simplified description of the drawings] Fig. 1 is a schematic diagram of an example of an embodiment of the present invention using a CMP device. FIG. 2 is a schematic cross-sectional view of an example of a semiconductor substrate polishing procedure to which the present invention can be applied; (a) is a stage of forming a trench on a silicon substrate; (b) is a stage of embedding a silicon oxide film in the trench of (a) ; (C) is a stage of polishing the silicon oxide film of (b) to separate the components. [Description of component symbols] 1 silicon substrate 2 silicon nitride film 3 silicon oxide film 11 wafer holder 12 holder 13 semiconductor substrate 14 silicon oxide insulating film 1 5 abrasive supply mechanism 16 abrasive 17 polishing pad 1 8 polishing fixed disk

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Claims (1)

571361 Case No. 91102980 Amendment Year // September 1. Application scope: An abrasive, which contains particles, and at least J part of the particles is a dispersed medium therein, which is characterized in that the particles are selected from osmium oxide, osmium halide and sulfur钸, at least one of the #compound and the tetravalent metal hydroxide having a density of 3 to 6g / cm 3 and a secondary particle formed by agglomeration of the primary particles of the above particles with an average particle diameter of 1 to 300 nm By. 2. The abrasive according to item 1 of the patent application scope, wherein the specific surface area of the particles is 50 m 2 / g or more. 3. The abrasive according to item 1 of the patent application scope, wherein the average particle diameter of the primary particles is 50 nm or less. 4. The abrasive according to item 1 of the patent application scope, wherein the particles are tetravalent metal oxides, and the average particle diameter of the secondary particles is 300 nm or less. 5. For the abrasive of item 7 of the scope of the application, wherein the particles are tetravalent metal oxides, the density of the particles is 3 to 6 g / c in 3, and the average particle diameter of the secondary particles is 1 To 300 nm. 6. The abrasive according to item 1 of the patent application scope, wherein the particles are at least one of a rare earth metal hydroxide and a hydroxide. 7. The abrasive according to item 6 of the patent application scope, wherein the rare earth metal rat oxide is oxynitride. 8. The abrasive according to item 1 of the patent application scope, wherein the particles are a tetravalent metal hydroxide obtained by mixing a tetravalent metal salt with an alkaline liquid phase. 9. As for the abrasive in the scope of the patent application, the pH is above 3 and below ί. 10. The abrasive according to item 1 of the patent application scope, wherein the medium is water. 313423 Rev. ptc Page 1 2003.11.03.051 571361 ^ _Case No. 91102980 &quot; Yue Xi Yue Amendment_ VI. Patent Application Scope 1 1. For example, the abrasive in the patent application No. 1 contains a pH stabilizer. 1 2. The abrasive according to item 11 of the scope of patent application, wherein the pH stabilizer is formed of more than one constituent component, and the pKa value of at least one of the constituent components is in the unit of 1 · 0 of the abrasive pH. Within. 1 3. The abrasive according to item 1 of the patent application scope, which contains a dispersant. 14. The abrasive according to item 13 of the patent application range, wherein the dispersant is selected from water-soluble anionic dispersants, water-soluble cationic dispersants, water-soluble non-ionic dispersants, and water-soluble amphoteric dispersants. 1 5. The abrasive according to item 1 of the scope of patent application, which contains a surface treatment agent to be polished. 16. The abrasive according to item 15 of the scope of patent application, wherein the surface-treated agent to be polished is a compound having at least one atom having an asymmetric electron in the molecular structure, or at least a nitrogen atom or an oxygen atom in the molecular structure. One of the compounds. 17. The abrasive according to item 1 of the scope of patent application, wherein the ratio of the polishing speed of the silicon oxide insulating film to the polishing speed of the silicon nitride insulating film is 5 or more. 18. The abrasive according to item 1 of the scope of patent application, wherein when the particles contain 0.2% by weight, the light transmittance of light having a wavelength of 500 nm is 10 ° / 0 or more. 19. The abrasive according to item 1 of the scope of patent application, wherein the difference between the light transmittance at a wavelength of 500 to 700 nm after standing for 24 hours is 20 compared to the prepared abrasive. %the following. 20. The abrasive according to item 1 of the scope of patent application, wherein the conductivity is below 30 in S / cm. Revised 313423.ptc Page 2 2003 · 11. 03. 052 571361 _ Case No. 9Π02980 Amended March 3 fz _ 6. Application for patent scope 2 1. For the abrasive of the first scope of patent application, the particles have Positive Z potential. 2 2. A method of polishing a substrate, which is characterized in that the substrate is polished by using the abrasive of any one of the scope of claims 1 to 21. 2 3. The method for polishing a substrate according to item 22 of the scope of patent application, wherein the substrate is polished using a polishing pad having a Shore D hardness of 50 or more. 24. The method for polishing a substrate according to item 22 of the scope of patent application, wherein the substrate is a substrate in a semiconductor device manufacturing process. 25. The method for polishing a substrate according to item 22 of the scope of patent application, wherein the silicon oxide film formed on the substrate is polished. 2 6. The method for polishing a substrate according to item 22 of the scope of patent application, wherein, while supplying the polishing agent to the polishing pad on the polishing fixed plate, at the same time, the surface to be polished and the substrate on which the silicon oxide insulating film is formed are polished. The pads are polished by relative movement. 27. The method for polishing a substrate according to item 26 of the scope of patent application, wherein the polishing speed of the silicon oxide insulating film is set to not less than 200 nm / min and not more than 2000 nm / mi η, and the use of The abrasive containing the tetravalent metal hydroxide particles is ground. 313423 Revision.ptc Page 3 2003.11.03.053