JP2008113015A - Polishing slurry and polishing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polishing slurry capable of obtaining a surface to be polished having high flatness even if the surface to be polished is made of a plurality of substances, and further capable of suppressing metal residue and scratches after polishing; and to provide a method of performing CMP (chemical mechanical polishing) using the same, in the polishing slurry and polishing method used for polishing in a process for forming wirings of a semiconductor device, and the like. <P>SOLUTION: The polishing slurry contains: one of a surfactant and an organic solvent; a metal oxide-dissolving agent; and water, wherein the polishing slurry is used for polishing the surface to be polished that has at least a conductive substance and an insulating film on a surface thereof. The metal oxide-dissolving agent contains at least one selected from organic acid, organic ester, an organic acid ammonium salt, and sulfuric acid. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a polishing liquid and a polishing method used for polishing in a wiring formation process of a semiconductor device.

  In recent years, new microfabrication techniques have been developed along with higher integration and higher performance of semiconductor integrated circuits (hereinafter referred to as LSIs). A chemical mechanical polishing (hereinafter referred to as CMP) method is one of them, and a technique frequently used in the planarization of an interlayer insulating film, the formation of a metal plug, and the formation of a buried wiring in an LSI manufacturing process, particularly a multilayer wiring forming process. It is. This technique is disclosed in Patent Document 1, for example.

  Recently, in order to improve the performance of LSIs, attempts have been made to use copper and copper alloys as conductive materials serving as wiring materials. However, copper and copper alloys are difficult to be finely processed by the dry etching method frequently used in the formation of conventional aluminum alloy wiring. Therefore, a so-called damascene method is mainly employed, in which a thin film of copper or a copper alloy is deposited and embedded on an insulating film in which a groove is formed in advance, and the thin film other than the groove is removed by CMP to form a buried wiring. ing. This technique is disclosed in Patent Document 2, for example.

  A general method of metal CMP for polishing a metal for a wiring part such as copper or a copper alloy is to apply a polishing cloth (pad) on a circular polishing surface plate (platen), and to polish the surface of the polishing cloth with a metal polishing liquid. While dipping, the surface of the substrate on which the metal film is formed is pressed against the surface of the polishing cloth, and a predetermined pressure (hereinafter referred to as polishing pressure) is applied to the metal film from the back surface of the polishing cloth, and the polishing platen is turned. The metal film on the convex portion is removed by relative mechanical friction between the polishing liquid and the convex portion of the metal film.

  The metal polishing liquid used for CMP is generally composed of an oxidizer and abrasive grains, and a metal oxide solubilizer and a protective film forming agent are further added as necessary. First, it is considered that the basic mechanism is to oxidize the surface of a metal film with an oxidizing agent and scrape the oxidized layer with abrasive grains. Since the oxide layer on the metal surface of the recess does not touch the polishing pad so much and the effect of scraping off by the abrasive grains does not reach, the metal layer of the projection is removed and the substrate surface is flattened with the progress of CMP. This detail is disclosed in Non-Patent Document 1.

  As a method for increasing the polishing rate by CMP, it is effective to add a metal oxide solubilizer. It is interpreted that if the metal oxide particles scraped off by the abrasive grains are dissolved in the polishing liquid (hereinafter referred to as etching), the effect of scraping off by the abrasive grains is increased. Although the polishing rate by CMP is improved by adding a metal oxide solubilizer, on the other hand, when the oxide layer on the metal film surface in the recess is also etched to expose the metal film surface, the metal film surface is further oxidized by the oxidant, and this is repeated. As a result, the etching of the metal film in the recesses proceeds. For this reason, a phenomenon occurs in which the central portion of the surface of the metal wiring embedded after polishing is depressed like a dish (hereinafter referred to as dishing), and the planarization effect is impaired.

  In order to prevent this, a protective film forming agent is further added. The protective film forming agent forms a protective film on the oxide layer on the surface of the metal film and prevents dissolution of the oxide layer in the polishing liquid. This protective film can be easily scraped off by abrasive grains, and it is desirable not to decrease the polishing rate by CMP.

  In order to suppress corrosion during dishing or polishing of copper or copper alloy, and to form a highly reliable LSI wiring, it contains BTA as a protective film forming agent and a metal oxide solubilizer composed of aminoacetic acid or amide sulfuric acid such as glycine A method using a polishing slurry for CMP is proposed. This technique is described in Patent Document 3, for example.

  In metal embedding formation such as damascene wiring formation such as copper or copper alloy and plug wiring formation such as tungsten, interlayer insulation is used when the polishing rate of the silicon dioxide film which is an interlayer insulating film formed other than the embedded portion is high. Thinning occurs where the thickness of the wiring is reduced with each film. As a result, since the wiring resistance increases, the silicon dioxide film must have a sufficiently low polishing rate with respect to the metal film to be polished. Therefore, in order to suppress the polishing rate of silicon dioxide by anions generated by acid dissociation, a method of making the polishing solution pH higher than pKa-0.5 has been proposed. This technique is described in Patent Document 4, for example.

  On the other hand, as a barrier conductor layer (hereinafter referred to as a barrier layer) for preventing copper diffusion into the interlayer insulating film and improving adhesion, for example, tantalum or tantalum is provided below the metal for wiring part such as copper or copper alloy. A conductor layer such as an alloy or a tantalum compound such as tantalum nitride is formed. Therefore, it is necessary to remove the exposed barrier layer by CMP except for the wiring portion in which copper or a copper alloy is embedded. However, the conductors of these barrier layers are harder than copper or copper alloy, so even if a polishing material for copper or copper alloy is combined, a sufficient polishing rate cannot be obtained, and the flatness deteriorates. There are many. In view of this, a two-step polishing method comprising a first step of polishing the wiring portion metal and a second step of polishing the barrier layer has been studied.

In the second step of polishing the barrier layer in the above-mentioned two-stage polishing method, an interlayer insulating film such as silicon dioxide or trimethylsilane which is a low-k (low dielectric constant) film is used as a starting material for planarization. In some cases, polishing of an organosilicate glass or a wholly aromatic ring-based Low-k film is required. In that case, by making the polishing rate of the barrier layer and the metal for the wiring portion and the polishing rate of the interlayer insulating film substantially equal so that the polished surface is flat when all of the interlayer insulating film is exposed, the barrier layer, A method of polishing while maintaining the flatness of the surfaces of the metal for the wiring portion and the interlayer insulating film is mentioned.
U.S. Pat. No. 4,944,836 JP-A-2-278822 Journal of Electrochemical Society, Vol. 138, Issue 11 (1991), pages 3460-3464 JP-A-8-83780 Japanese Patent Publication No. 2819196

  In order to improve the polishing rate of the interlayer insulating film to the same level as that of the barrier layer and the wiring portion metal, for example, it is conceivable to increase the grain size of the abrasive grains in the conductor polishing liquid of the barrier layer. There is a problem in that polishing flaws occur in the alloy or oxide film and cause electrical characteristics defects.

  Moreover, such an electrical characteristic defect may occur due to insufficient cleaning after polishing by CMP. On the other hand, in the CMP process, there is a problem that the copper residue on the high-density wiring part cannot be completely removed and a short circuit defect occurs.

  In view of the above problems, the present invention provides a polishing liquid having a highly flat surface to be polished. Further, it provides a polishing liquid whose interlayer insulating film has a polishing rate as high as that of the barrier layer and the metal for the wiring portion. And according to this polishing liquid, the polishing rate of the wiring portion can be adjusted without reducing the polishing rate of the barrier layer. Furthermore, metal residues and polishing scratches after polishing can be suppressed. The present invention also provides a polishing method in the manufacture of semiconductor devices and the like that are excellent in miniaturization, thinning, dimensional accuracy, electrical characteristics, reliability, and cost.

  The present invention relates to the polishing liquids (1) to (17) below.

(1) A surfactant, a metal oxide solubilizer and water are contained, and the metal oxide solubilizer is at least one selected from organic acids, organic acid esters, ammonium salts of organic acids, and sulfuric acid,
A polishing liquid which is used for polishing a surface to be polished having at least a conductive substance and an insulating film on its surface.

(2) A surfactant, a metal oxide solubilizer, and water, wherein the metal oxide solubilizer is at least one selected from organic acids, organic acid esters, ammonium salts of organic acids, and sulfuric acid,
At least a conductive material, and
Silicon-based film or organic polymer film
A polishing liquid used for polishing a surface to be polished on a surface.

(3) It contains perfluoroalkanesulfonic acid, a metal oxide solubilizer and water, and the metal oxide solubilizer is at least one selected from organic acids, organic acid esters, ammonium salts of organic acids and sulfuric acid. A characteristic polishing liquid.

(4) containing an organic solvent, a metal oxide solubilizer and water, and the metal oxide solubilizer is at least one selected from organic acids, organic acid esters, ammonium salts of organic acids and sulfuric acid,
A polishing liquid which is used for polishing a surface to be polished having at least a conductive substance and an insulating film on its surface.

(5) containing an organic solvent, a metal oxide solubilizer, and water, the metal oxide solubilizer being at least one selected from organic acids, organic acid esters, ammonium salts of organic acids, and sulfuric acid,
At least a conductive material, and
Silicon-based film or organic polymer film
A polishing liquid used for polishing a surface to be polished on a surface.

(6) The polishing liquid according to any one of (1) to (5), comprising abrasive grains.

(7) The polishing liquid according to (6), wherein the abrasive is at least one selected from silica, alumina, ceria, titania, zirconia, and germania.

(8) The polishing liquid according to (6), wherein the surface of the abrasive grains is modified with an alkyl group.

(9) The polishing liquid according to (4) or (5) above, containing 0.1 to 95% by weight of an organic solvent.

(10) The polishing liquid according to (4) or (5), wherein the organic solvent is at least one selected from glycols and derivatives thereof, alcohols, and carbonates.

(11) The polishing liquid according to (1) or (2), wherein the surfactant is at least one selected from a nonionic surfactant and an anionic surfactant.

(12) The polishing liquid according to (1) or (2), wherein the surfactant is at least one selected from perfluoroalkanesulfonic acid and derivatives thereof.

(13) The polishing liquid according to the above (1) or (2), which contains 0.00001 to 20% by weight of a surfactant.

(14) The polishing liquid according to any one of (1) to (5), comprising a metal oxidizing agent.

(15) The polishing liquid according to (14), wherein the metal oxidizing agent is at least one selected from hydrogen peroxide, nitric acid, potassium periodate, hypochlorous acid, and ozone water.

(16) The polishing liquid according to any one of (1) to (5), which contains a water-soluble polymer having a weight average molecular weight of 500 or more.

(17) The polishing liquid according to (16), wherein the water-soluble polymer is at least one selected from polysaccharides, polycarboxylic acids, polycarboxylic acid esters and salts thereof, and vinyl polymers.

  Furthermore, the present invention relates to the following polishing methods (18) to (21).

(18) An interlayer insulating film having a concave portion and a convex surface, a barrier conductor layer covering the interlayer insulating film along the surface, and a conductive material layer filling the concave portion and covering the barrier conductor layer A first polishing step of polishing the conductive material layer of the base body to expose the barrier conductor layer of the convex portion, and at least a part of the barrier conductor layer, the conductive material layer of the concave portion, and the interlayer insulating film ( A polishing method comprising: a second polishing step of exposing the convex interlayer insulating film by chemical mechanical polishing while supplying the polishing liquid according to any one of 1) to (17).

(19) The polishing method according to (18), wherein the interlayer insulating film is a silicon-based film or an organic polymer film.

(20) The polishing method according to (18), wherein the conductive material contains copper as a main component.

(21) The barrier conductor layer is a barrier layer that prevents the conductive material from diffusing into the interlayer insulating film, and includes tantalum, tantalum nitride, tantalum alloy, other tantalum compounds, titanium, titanium nitride, titanium alloy, and others. The polishing method according to (18), comprising at least one selected from the group consisting of titanium compounds, tungsten, tungsten nitride, tungsten alloys, and other tungsten compounds.

  With the polishing liquid of the present invention, a polished surface having high flatness can be obtained even if the polished surface is made of a plurality of substances. Moreover, metal residues and polishing scratches after polishing can be suppressed. Furthermore, the polishing rate of the interlayer insulating film can be increased without reducing the polishing rate of the barrier layer, and the polishing rate of the wiring portion metal can be adjusted. The polishing method of the present invention in which chemical mechanical polishing is performed using this polishing liquid is highly productive, and is excellent in miniaturization, thinning, dimensional accuracy, electrical characteristics, and production of highly reliable semiconductor devices and other electronic devices. It is suitable for.

  The first feature of the polishing liquid of the present invention is that it contains at least one of a surfactant and an organic solvent, a metal oxide solubilizer, and water. Preferably, it further contains abrasive grains and a metal oxidizing agent. Furthermore, you may contain a water-soluble polymer, a metal anticorrosive, etc. as needed.

  Surfactants are generally classified into four types: nonionic surfactants, anionic surfactants, cationic surfactants and amphoteric surfactants.

  Moreover, the surfactant in this invention can also use the fluorine-type surfactant which has a carbon- fluorine chain as a hydrophobic group. For example, perfluoroalkanesulfonic acid and its derivatives are exemplified. Perfluorooctane sulfonic acid and its derivatives are preferred. Fluorosurfactants are also classified into the same four types as described above.

  Examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene propyl perfluorooctane sulfonamide, polyoxyethylene-polyoxypropylene block polymer, polyoxyethylene glycerin fatty acid ester. , Polyoxyethylene hydrogenated castor oil, polyethylene glycol fatty acid ester, propyl-2-hydroxyethyl perfluorooctanesulfonamide, sorbitan fatty acid ester, glycerin fatty acid ester, sucrose fatty acid ester, fatty acid alkanolamide, polyoxyethylene alkylamine and the like Derivatives, and glycols such as acetylenic diol and its ethylene oxide adducts. The “polyoxyethylene” includes not only the number of added ethylene oxides (n) of 2 or more but also one added.

  Examples of the anionic surfactant include alkylbenzene sulfonate, perfluorooctane sulfonate, bis [2- (N-propylperfluorooctanesulfonylamino) ethyl] ester, alkylsulfosuccinate, alkylsulfone. Examples thereof include acid salts, alkyl ether carboxylates, alcohol sulfate esters, alkyl ether sulfate esters, alkyl phosphate esters, and the like.

  Examples of the cationic surfactant include aliphatic alkylamine salts and aliphatic quaternary ammonium salts. Examples of the amphoteric surfactant include aminocarboxylates.

  These surfactants are used alone or in combination of two or more.

  As the surfactant in the polishing liquid of the present invention, nonionic surfactants and anionic surfactants are preferable, and those containing no alkali metal are particularly preferable.

  More preferably, polyethylene glycol type nonionic surfactant, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene propyl perfluorooctanesulfonamide, glycols, glycerin fatty acid ester, sorbitan fatty acid ester, fatty acid alkanol It is at least one selected from amide, alcohol sulfate ester salt, alkyl ether sulfate ester salt, alkylbenzene sulfonate salt, and alkyl phosphate ester salt.

  Examples of the polyethylene glycol type nonionic surfactant include polyethylene glycol fatty acid esters such as polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol distearate, and polyethylene glycol monooleate.

  Although there is no restriction | limiting in particular as an organic solvent contained in the polishing liquid of this invention, The thing which can be mixed with water arbitrarily is preferable.

  For example, carbonates such as ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, and methyl ethyl carbonate; lactones such as butyrolactone and propyrolactone; ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene Glycols such as glycol; derivatives of glycols such as ethylene glycol monomethyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, triethylene glycol monomethyl ether, tripropylene glycol monomethyl ether and ethylene glycol monoethyl ether, Propylene rubber Cole monoethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monoethyl ether, tripropylene glycol monoethyl ether, ethylene glycol monopropyl ether, propylene glycol monopropyl ether, diethylene glycol monopropyl ether, dipropylene Glycol monopropyl ether, triethylene glycol monopropyl ether, tripropylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monobutyl ether, diethylene glycol monobutyl ether, dipropylene glycol monobutyl ether, triethylene glycol monobutyl ether, tripropylene Glycol monoethers such as ethylene glycol dimethyl ether, ethylene glycol dimethyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, triethylene glycol dimethyl ether, tripropylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol diethyl ether, diethylene glycol diethyl ether , Dipropylene glycol diethyl ether, triethylene glycol diethyl ether, tripropylene glycol diethyl ether, ethylene glycol dipropyl ether, propylene glycol dipropyl ether, diethylene glycol dipropyl ether, dipropylene glycol Rudipropyl ether, triethylene glycol dipropyl ether, tripropylene glycol dipropyl ether, ethylene glycol dibutyl ether, propylene glycol dibutyl ether, diethylene glycol dibutyl ether, dipropylene glycol dibutyl ether, triethylene glycol dibutyl ether, tripropylene glycol dibutyl ether, etc. Glycol diethers, etc .; ethers such as tetrahydrofuran, dioxane, dimethoxyethane, polyethylene oxide, ethylene glycol monomethyl acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate; methanol, ethanol, propanol, n-butanol, n- Pentano Le, n- hexanol, alcohols such as isopropanol; ketones such as acetone and methyl ethyl ketone; and other phenols, dimethylformamide, n- methyl pyrrolidone, ethyl acetate, ethyl lactate, sulfolane.

  A preferred organic solvent is at least one selected from glycols and derivatives thereof, alcohols, and carbonates.

  The second feature of the polishing liquid of the present invention is that it contains water and abrasive grains whose surface is modified with an alkyl group. Preferably, a metal oxide solubilizer, a metal oxidizer, an organic solvent, and a surfactant are further contained as necessary. Furthermore, you may contain a polymer, a metal anticorrosive, etc. as needed.

  The abrasive grains in the present invention may be any of inorganic abrasive grains such as silica, alumina, zirconia, ceria, titania, germania and silicon carbide, and organic abrasive grains such as polystyrene, polyacryl and polyvinyl chloride. Good. Of these, silica, alumina, zirconia, ceria, titania, and germania are preferable. In particular, dispersion stability in the polishing liquid is good, and the number of polishing scratches (scratches) generated by CMP is small. Colloidal silica and colloidal alumina of 70 nm or less are preferable, and colloidal silica and colloidal alumina having an average particle size of 40 nm or less are more preferable. The particle size can be measured, for example, with a light diffraction scattering type particle size distribution meter (for example, trade name COULTER N4 SD manufactured by COULTER Electronics). In addition, particles in which primary particles are aggregated with an average of less than 2 particles are preferable, and particles in which primary particles are aggregated with an average of less than 1.2 particles are more preferable. Furthermore, the standard deviation of the average particle size distribution is preferably 10 nm or less, and the standard deviation of the average particle size distribution is more preferably 5 nm or less. These may be used alone or in combination of two or more.

  Examples of the abrasive grains having a surface modified with an alkyl group in the second feature of the present invention include those obtained by modifying the surface of the inorganic abrasive grains or the organic abrasive grains with an alkyl group. Either inorganic abrasive particles or organic abrasive particles may be used, and preferred particles are the same as described above. The modified abrasive grains can be used alone or in combination of two or more.

  The method of modifying the abrasive grain surface with an alkyl group is not particularly limited, and examples thereof include a method of reacting a hydroxyl group present on the abrasive grain surface with an alkoxysilane having an alkyl group. The alkoxysilane having an alkyl group is not particularly limited, but monomethyltrimethoxysilane, dimethyldimethoxysilane, trimethylmonomethoxysilane, monoethyltrimethoxysilane, diethyldimethoxysilane, triethylmonomethoxysilane, monomethyltriethoxysilane, dimethyl Examples include diethoxysilane and trimethylmonoethoxysilane. The reaction method is not particularly limited, and for example, abrasive particles and alkoxysilane are reacted in a polishing liquid at room temperature, but may be heated to accelerate the reaction.

  Colloidal silica is known for its production by hydrolysis of silicon alkoxide or ion exchange of sodium silicate, and colloidal alumina is known for its production by hydrolysis of aluminum nitrate. Colloidal silica is most often used in terms of particle size controllability and alkali metal impurities by a production method by hydrolysis of silicon alkoxide. As the silicon alkoxide, TEMS (tetramethoxysilane) or TEOS (tetraethoxysilane) is generally used. In the method of hydrolyzing in an alcohol solvent, parameters affecting the particle size include the concentration of silicon alkoxide, the concentration and pH of ammonia used as a catalyst, the reaction temperature, the type (molecular weight) of the alcohol solvent, and the reaction time. By adjusting these parameters, a colloidal silica dispersion having a desired particle size and agglomeration degree can be obtained.

  The metal oxide solubilizer in the present invention is not particularly limited, but formic acid, acetic acid, propionic acid, butyric acid, valeric acid, 2-methylbutyric acid, n-hexanoic acid, 3,3-dimethylbutyric acid, 2-ethylbutyric acid, 4 -Methylpentanoic acid, n-heptanoic acid, 2-methylhexanoic acid, n-octanoic acid, 2-ethylhexanoic acid, benzoic acid, glycolic acid, salicylic acid, glyceric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, Examples thereof include organic acids such as adipic acid, pimelic acid, maleic acid, phthalic acid, malic acid, tartaric acid, citric acid, and p-toluenesulfonic acid, organic acid esters thereof, and ammonium salts of these organic acids. Further, inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid, and ammonium salts of these inorganic acids such as ammonium persulfate, ammonium nitrate, ammonium chloride and chromic acid can be mentioned. Among these, formic acid, malonic acid, malic acid, tartaric acid, and citric acid are effective in that the etching rate can be effectively suppressed while maintaining a practical CMP rate, and sulfuric acid is also effective in terms of a high CMP rate. It is suitable for a conductive material containing a metal as a main component. These may be used alone or in combination of two or more.

  A metal oxidizing agent may be added to the polishing liquid of the present invention. Examples of the metal oxidizing agent include hydrogen peroxide, nitric acid, potassium periodate, hypochlorous acid, ozone water, etc. Among them, hydrogen peroxide is particularly preferable. These may be used alone or in combination of two or more. When the substrate is a silicon substrate including an integrated circuit element, contamination by alkali metal, alkaline earth metal, halide, etc. is not desirable, so an oxidizing agent that does not contain a nonvolatile component is desirable. However, hydrogen peroxide is most suitable because ozone water has a severe compositional change over time. However, when the substrate to be applied is a glass substrate or the like that does not include a semiconductor element, an oxidizing agent that includes a nonvolatile component may be used.

  A water-soluble polymer may be added to the polishing liquid of the present invention. The weight average molecular weight of the water-soluble polymer is preferably 500 or more, more preferably 1500 or more, and particularly preferably 5000 or more. The upper limit of the weight average molecular weight is not particularly specified, but is preferably 5 million or less from the viewpoint of solubility. When the weight average molecular weight is less than 500, a high polishing rate tends not to be exhibited.

  The weight average molecular weight can be measured by gel permeation chromatography using a standard polystyrene calibration curve.

  The water-soluble polymer having a weight average molecular weight of 500 or more is not particularly limited. For example, polysaccharides such as alginic acid, pectic acid, carboxymethylcellulose, agar, curdlan and pullulan; polyaspartic acid, polyglutamic acid, polylysine, polymalic acid, Polymethacrylic acid, polyammonium methacrylate, polymethacrylic acid sodium salt, polyamic acid, polymaleic acid, polyitaconic acid, polyfumaric acid, poly (p-styrenecarboxylic acid), polyacrylic acid, polyacrylamide, aminopolyacrylamide, polyacrylic Polycarboxylic acids such as ammonium acid salt, sodium polyacrylate, polyamic acid, ammonium polyamic acid salt, sodium polyamic acid salt and polyglyoxylic acid, polycarboxylic acid esters and salts thereof; Alkenyl alcohol, vinyl polymers such as polyvinyl pyrrolidone and polyacrolein; polyethylene glycol, and the like. These may be used alone or in combination of two or more. However, when the substrate to be applied is a silicon substrate for a semiconductor integrated circuit or the like, contamination with an alkali metal, an alkaline earth metal, a halide or the like is not desirable, so an acid or an ammonium salt thereof is desirable. This is not the case when the substrate is a glass substrate or the like. Among these, pectinic acid, agar, polymalic acid, polymethacrylic acid, ammonium polyacrylate, polyacrylamide, polyvinyl alcohol and polyvinylpyrrolidone, esters thereof and ammonium salts thereof are preferable.

  Moreover, you may add a metal anticorrosive to the polishing liquid of this invention. Examples of metal anticorrosives include 2-mercaptobenzothiazole, 1,2,3-triazole, 1,2,4-triazole, 3-amino-1H-1,2,4-triazole, benzotriazole, 1-hydroxybenzo Triazole, 1-dihydroxypropylbenzotriazole, 2,3-dicarboxypropylbenzotriazole, 4-hydroxybenzotriazole, 4-carboxyl (-1H-) benzotriazole, 4-carboxyl (-1H-) benzotriazole methyl ester, 4-carboxyl (-1H-) benzotriazole butyl ester, 4-carboxyl (-1H-) benzotriazole octyl ester, 5-hexylbenzotriazole, [1,2,3-benzotriazolyl-1-methyl] [1 , 2,4-G Azolyl-1-methyl] [2-ethylhexyl] amine, tolyltriazole, naphthotriazole, bis [(1-benzotriazolyl) methyl] phosphonic acid.

  Further, pyrimidine having a pyrimidine skeleton, 1,2,4-triazolo [1,5-a] pyrimidine, 1,3,4,6,7,8-hexahydro-2H-pyrimido [1,2-a] pyrimidine 1,3-diphenyl-pyrimidine-2,4,6-trione, 1,4,5,6-tetrahydropyrimidine, 2,4,5,6-tetraaminopyrimidine sulfate, 2,4,5-trione Hydroxypyrimidine, 2,4,6-triaminopyrimidine, 2,4,6-trichloropyrimidine, 2,4,6-trimethoxypyrimidine, 2,4,6-triphenylpyrimidine, 2,4-diamino-6 Hydroxylpyrimidine, 2,4-diaminopyrimidine, 2-acetamidopyrimidine, 2-aminopyrimidine, 2-methyl-5,7-diphenyl- (1,2,4) Riazolo (1,5-a) pyrimidine, 2-methylsulfanyl-5,7-diphenyl- (1,2,4) triazolo (1,5-a) pyrimidine, 2-methylsulfanyl-5,7-diphenyl Examples include -4,7-dihydro- (1,2,4) triazolo (1,5-a) pyrimidine, 4-aminopyrazolo [3,4-d] pyrimidine and the like. These may be used alone or in combination of two or more.

  The blending amount when the surfactant is blended with the polishing liquid of the present invention is preferably 0.00001 to 20% by weight in the polishing liquid from the viewpoint of dispersibility, prevention of settling, and polishing scratches. That is, it is preferably 0.00001 to 20 g, more preferably 0.0001 to 10 g, and particularly preferably 0.0001 to 5 g with respect to 100 g of the total amount of the polishing liquid. When the blending amount is less than 0.00001 g, the wettability of the polishing liquid to the surface to be polished is low, and when it exceeds 20 g, the polishing rate tends to decrease.

  The blending amount of the organic solvent in the polishing liquid of the present invention is preferably 0.1 to 95% by weight in the polishing liquid. That is, it is preferably 0.1 to 95 g, more preferably 0.2 to 50 g, and particularly preferably 0.5 to 10 g with respect to 100 g of the total amount of the polishing liquid. If the blending amount is less than 0.1 g, a sufficient polishing rate cannot be obtained because the wettability of the polishing liquid to the substrate is low, and if it exceeds 95 g, the solubility of the polishing liquid component deteriorates, which is not preferable.

  The compounding amount when the metal oxide solubilizer is blended with the polishing liquid of the present invention is the surfactant, organic solvent, metal oxide solubilizer, water, abrasive grains, metal oxidizer and water-soluble polymer (hereinafter referred to as “polishing agent”). And 7 components) is preferably 0.001 to 20 g, more preferably 0.002 to 10 g, and particularly preferably 0.005 to 5 g with respect to 100 g of the total amount. When the blending amount is less than 0.001 g, the polishing rate is low, and when it exceeds 20 g, it is difficult to suppress etching and the polished surface tends to be rough.

  In addition, among the seven components, the blending amount of water may be the remainder, and there is no particular limitation as long as it is contained.

  When mix | blending an abrasive grain with the polishing liquid of this invention, it is preferable that the compounding quantity of an abrasive grain shall be 0.01-50g with respect to 100g of total amounts of seven components, and it is more preferable to set it as 0.02-40g. Preferably, it is particularly preferably 0.05 to 30 g. When the blending amount is less than 0.01 g, the polishing rate is low, and when it exceeds 50 g, there is a tendency that many polishing scratches are generated.

  The blending amount when the metal oxidizing agent is blended with the polishing liquid of the present invention is preferably 0 to 50 g, more preferably 0 to 20 g, more preferably 0 to 10 g with respect to 100 g of the total amount of the seven components. It is particularly preferable that When the amount exceeds 50 g, the polished surface tends to be rough.

  The blending amount when the water-soluble polymer is blended with the polishing liquid of the present invention is preferably 0 to 10 g, more preferably 0 to 5 g, and more preferably 0 to 2 g with respect to the total amount of seven components of 100 g. It is particularly preferred. If this amount exceeds 10 g, the polishing rate tends to decrease.

  When the metal anticorrosive is blended in the polishing liquid of the present invention, the blending amount is preferably 0 to 10 g, more preferably 0 to 5 g, and more preferably 0 to 2 g with respect to the total amount of seven components of 100 g. It is particularly preferred. If this amount exceeds 10 g, the polishing rate tends to be low.

  The polishing liquid of the present invention may contain a coloring agent such as a dye such as Victoria Pure Blue, a pigment such as phthalocyanine green, in addition to the various components described above.

  The polishing liquid of the present invention as described above can be used for chemical mechanical polishing (CMP) of a conductive material layer, a barrier layer, and an interlayer insulating film in a semiconductor device. In CMP under the same conditions, the conductive material layer / barrier layer / interlayer insulating film is preferably polished at a polishing rate ratio of 1 / 0.01 to 20 / 0.01 to 20. More preferably, it is 1 / 0.05-10 / 0.05-10, More preferably, it is 1 / 0.1-10 / 0.01-10.

  Examples of the conductive substance include copper, copper alloy, copper oxide, copper alloy oxide, tungsten, tungsten alloy, silver, gold, and the like, which are mainly composed of metals. Conductive substances containing copper as the main component, such as oxides and oxides of copper alloys, are preferred. As the conductive material layer, a film in which the material is formed by a known sputtering method or plating method can be used.

  Examples of the interlayer insulating film include a silicon-based film and an organic polymer film. Examples of the silicon-based coating include silica-based coatings such as silicon dioxide, fluorosilicate glass, organosilicate glass, silicon oxynitride, silsesquioxane hydride, silicon carbide, and silicon nitride. Examples of the organic polymer film include a wholly aromatic low dielectric constant interlayer insulating film. In particular, organosilicate glass is preferable. These films are formed by a CVD method, a spin coating method, a dip coating method, or a spray method.

  The barrier layer is formed to prevent diffusion of the conductive material into the insulating film and to improve the adhesion between the insulating film and the conductive material. The conductor used for the barrier layer is selected from tungsten, tungsten nitride, tungsten alloys, other tungsten compounds, titanium, titanium nitride, titanium alloys, other titanium compounds, tantalum, tantalum nitride, tantalum alloys, and other tantalum compounds. Preferably it contains more than one species. The barrier layer may be a single layer made of one kind or a laminated film of two or more kinds.

  The polishing method of the present invention comprises an interlayer insulating film having a concave portion and a convex surface, a barrier layer that covers the interlayer insulating film along the surface, and a conductive material layer that fills the concave portion and covers the barrier layer. A first polishing step for polishing the conductive material layer of the substrate having the convex portions to expose the barrier layer of the convex portion, and supplying the polishing liquid of the present invention to at least the conductive layer of the barrier layer and the concave portion. And a second polishing step for exposing the convex interlayer insulating film by chemical mechanical polishing.

  Here, in chemical mechanical polishing, the polishing surface plate and the substrate are relatively moved while supplying the polishing liquid while the substrate having the surface to be polished is pressed onto the polishing cloth (pad) of the polishing surface plate. The method of grind | polishing a to-be-polished surface is mentioned. Other methods for exposing the interlayer insulating film include a method of contacting a metal or resin brush and a method of spraying a polishing liquid at a predetermined pressure.

  As an apparatus used for polishing, for example, when polishing with a polishing cloth, it is common to have a holder that can hold a substrate to be polished and a surface plate that is connected to a motor or the like that can change the number of rotations and to which the polishing cloth is attached. A simple polishing apparatus can be used. As an abrasive cloth, a general nonwoven fabric, a polyurethane foam, a porous fluororesin, etc. can be used, and there is no restriction | limiting in particular. The polishing conditions are not limited, but the rotation speed of the surface plate is preferably a low rotation of 200 rpm or less so that the substrate does not jump out. The pressing pressure of the substrate having the surface to be polished against the polishing cloth is preferably 1 to 100 kPa, and in order to satisfy the uniformity of the CMP rate within the wafer surface and the flatness of the pattern, it is preferably 5 to 50 kPa. More preferred. During polishing, the polishing liquid is continuously supplied to the polishing cloth with a pump or the like. Although there is no restriction | limiting in this supply amount, it is preferable that the surface of polishing cloth is always covered with polishing liquid. The substrate after polishing is preferably washed in running water and then dried after removing water droplets adhering to the substrate using spin drying or the like.

  In order to perform chemical mechanical polishing with the surface state of the polishing cloth always the same, it is preferable to perform a conditioning process of the polishing cloth before polishing. For example, the polishing cloth is conditioned with a liquid containing at least water using a dresser with diamond particles. Subsequently, it is preferable to perform a chemical mechanical polishing process according to the present invention, and further add a substrate cleaning process.

  The polishing method of the present invention can be applied to the formation of a wiring layer in a semiconductor device, for example. Hereinafter, embodiments of the polishing method of the present invention will be described along with formation of a wiring layer in a semiconductor device.

  First, an interlayer insulating film such as silicon dioxide is laminated on a silicon substrate. Next, a known pattern concave portion (substrate exposed portion) is formed on the surface of the interlayer insulating film by a known means such as resist layer formation or etching to obtain an interlayer insulating film having convex portions and concave portions. On this interlayer insulating film, a barrier layer made of tantalum or the like covering the interlayer insulating film is formed along the surface irregularities by vapor deposition or CVD. Further, a metal conductive material layer such as copper covering the barrier layer is formed by vapor deposition, plating or CVD so as to fill the concave portion. The formation thickness of the interlayer insulating film, the barrier layer, and the conductive material is preferably about 0.01 to 2.0 μm, 1 to 100 nm, and 0.01 to 2.5 μm, respectively.

  Next, the conductive material layer on the surface of the semiconductor substrate is polished by CMP using, for example, a polishing liquid for the conductive material having a sufficiently high polishing rate ratio of the conductive material / barrier layer (first first material). Polishing process). Thereby, the barrier layer of the convex part on a board | substrate is exposed on the surface, and the desired conductor pattern with which the said electroconductive substance film was left in the recessed part is obtained. The obtained pattern surface can be polished as a surface to be polished for the second polishing step in the polishing method of the present invention using the polishing liquid of the present invention.

  In the second polishing step, at least the exposed conductive material of the barrier layer and the recess is formed by chemical mechanical polishing using the polishing liquid of the present invention capable of polishing the conductive material, the barrier layer, and the interlayer insulating film. To polish. The interlayer insulating film under the convex barrier layer is all exposed, the conductive material layer that becomes the wiring layer is left in the concave portion, and the desired pattern in which the cross section of the barrier layer is exposed at the boundary between the convex portion and the concave portion The polishing is finished when it is obtained. In order to ensure better flatness at the end of polishing, over polishing (for example, if the time until a desired pattern is obtained in the second polishing step is 100 seconds, in addition to this 100 second polishing) Polishing for an additional 50 seconds may be referred to as over-polishing 50%), and may be polished to a depth including a portion of the convex interlayer insulating film.

  An interlayer insulating film and a second-layer metal wiring are further formed on the metal wiring thus formed, an interlayer insulating film is formed again between and on the wiring, and then polished to obtain a semiconductor substrate. Make the surface smooth throughout. By repeating this step a predetermined number of times, a semiconductor device having a desired number of wiring layers can be manufactured.

  The polishing liquid of the present invention is not only for polishing a silicon compound film formed on a semiconductor substrate as described above, but also for an inorganic insulating film such as a silicon oxide film, glass, or silicon nitride formed on a wiring board having a predetermined wiring. Optical glass such as optical masks such as photomasks, lenses, and prisms, inorganic conductive films such as ITO, glass and crystalline materials, optical integrated circuits, optical switching elements, optical waveguides, end faces of optical fibers, scintillators, etc. It can also be used to polish crystals, solid-state laser single crystals, LED sapphire substrates for blue lasers, semiconductor single crystals such as SiC, GaP, and GaAs, glass substrates for magnetic disks, and magnetic heads.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples without departing from the technical idea of the present invention. For example, the type of polishing liquid material and the blending ratio thereof may be other than those described in this embodiment, and the composition and structure of the polishing target may be other than those described in this embodiment.

(Polishing liquid preparation method)
The materials shown in Tables 1 to 5 were mixed in respective formulations to prepare polishing liquids used in Examples 1 to 27 and Comparative Examples 1 to 4. In addition, acetylene diol was used as glycols in Tables 3 and 4, and sodium dodecylbenzenesulfonate was used as the alkylbenzene sulfonate.

(substrate)
The following substrates were prepared.

Blanket substrate (a): A silicon substrate on which organosilicate glass (thickness: 1000 nm) is formed by a CVD method.

Blanket substrate (b): A silicon substrate formed by CVD of silicon dioxide having a thickness of 1000 nm.

Blanket substrate (c): A silicon substrate on which a tantalum film having a thickness of 200 nm is formed by sputtering.

Blanket substrate (d): A silicon substrate on which a copper film having a thickness of 1600 nm is formed by sputtering.

  Preparation of pattern substrate (a): The above-mentioned organosilicate glass (thickness: 1000 nm) was formed as a interlayer insulating film on a silicon substrate by a CVD method. Grooves are formed at a depth of 800 nm on this organosilicate glass by photolithography so that wiring metal part widths of 4.5 μm and interlayer insulating film part widths of 0.5 μm are arranged alternately. A stripe pattern portion (for erosion evaluation) with a portion (non-groove portion) was produced. Separately, grooves were formed at a depth of 800 nm so that wiring metal part widths of 100 μm and interlayer insulating film part widths of 100 μm were alternately arranged, and striped pattern parts (for dishing evaluation) were formed on the surface.

Further, along this surface, a tantalum film having a thickness of 200 nm was formed as a barrier layer by sputtering. A copper film of 1.6 μm was formed as a conductive material layer on the tantalum film so as to fill all the grooves by sputtering. The projecting copper film is used as a first polishing step, and the substrate is polished and planarized by high-selectivity CMP for polishing only copper until the convex barrier layer is completely exposed on the surface to be polished ( a) was obtained (polishing time 180 seconds, maximum polishing thickness 1.6 μm)
Pattern substrate (b): produced in the same manner as the pattern substrate (a) except that silicon dioxide was used as an interlayer insulating film.

(Examples 1-27 and Comparative Examples 1-4)
Using each polishing liquid prepared above, each substrate prepared above was subjected to chemical mechanical polishing under the following polishing conditions. Moreover, it was stopped even if the etching rate of copper was immersed in each polishing liquid on the following conditions. Tables 6 to 10 show the evaluation results of polishing rate by chemical mechanical polishing, in-plane uniformity of polishing rate, copper etching rate, dishing amount, erosion amount, wiring resistance value, amount of polishing residue, and polishing scratches.

(Polishing conditions) [common to the first polishing step, which is a pretreatment of the patterned substrate, and the following polishing of each substrate]
Polishing pad: Foam polyurethane resin (IC1000 (Rodel))
Polishing pressure: 20.6 kPa (210 g / cm ² )
Relative speed between substrate and polishing surface plate: 36 m / min
(Polishing process for each substrate)
Blanket substrates (a), (b), (c), and (d) were subjected to chemical mechanical polishing for 60 seconds while supplying each polishing solution prepared above at 150 cc / min, and washed with distilled water after polishing. Processed.

  The pattern substrates (a) and (b) were subjected to chemical mechanical polishing for 90 seconds while supplying 150 cc / min of each of the polishing liquids prepared above, and washed with distilled water after polishing. The polishing of the pattern substrates (a) and (b) corresponds to the second polishing step. In about 30 seconds, the convex interlayer insulating film was all exposed to the surface to be polished, and was over-polished at the end of polishing. .

(Evaluation item)
(1) Polishing rate: Among the blanket substrates of (a) to (d) polished and washed under the above conditions, the polishing rate of organosilicate glass (a) and silicon dioxide (b) is determined by the difference in film thickness before and after polishing. Was measured using a Dainippon Screen Mfg. Co., Ltd. film thickness measuring device (product name: Lambda Ace VL-M8000LS). Further, the polishing rate of the tantalum film (c) and copper (d) was obtained by converting the film thickness difference before and after polishing from the electric resistance value.

(2) In-plane uniformity of polishing rate: (1) The standard deviation of the polishing rate was expressed as a percentage (%) with respect to the average value.

(3) Copper etching rate: The copper film thickness difference before and after immersing the blanket substrate (d) in the polishing liquid (25 ° C., stirring 100 rpm) for 60 seconds was calculated from the electrical resistance value.

(4) Flatness (amount of dishing): Striped pattern in which wiring metal (copper) part width 100 μm and interlayer insulating film part width 100 μm of pattern substrates (a) and (b) polished and washed under the above conditions are arranged alternately From the surface shape of the pattern portion (hereinafter referred to as a dishing evaluation portion), the amount of film reduction of the wiring metal portion relative to the insulating film portion was determined with a stylus type step meter.

(5) Flatness (erosion amount): a total width of 2.5 mm in which wiring metal portion widths of 4.5 μm and interlayer insulating film portion widths of 0.5 μm formed on the pattern substrates (a) and (b) are alternately arranged. The surface shape of the stripe pattern portion (hereinafter referred to as the erosion evaluation portion) is measured by a stylus type step gauge, and the amount of film reduction of the interlayer insulating film portion near the center of the pattern portion relative to the interlayer insulating film portion around the stripe pattern Asked.

(6) Wiring resistance value: In the above (4) dishing evaluation section, the wiring resistance value with a wiring length of 1 mm was measured. Further, in the above (5) erosion evaluation section, the wiring resistance value with a wiring length of 1 mm was measured.

(7) Detergency (amount of polishing residue): The amount of polishing residue remaining on the surfaces of the pattern substrates (a) and (b) was observed using an SEM and evaluated by the number per 1 cm ² .

(8) Polishing scratches: The amount of polishing scratches was measured from the pattern substrates (a) and (b) using a pattern wafer defect detection device 2138 manufactured by KLA Tencor, and evaluated by the number per 1 cm ² .

  In Comparative Examples 1 to 4, since the polishing rate of the organosilicate glass is small and the in-plane uniformity of the polishing rate is large, dishing and erosion are large and the wiring resistance value is increased. In Comparative Examples 1 to 4, the amount of polishing residue and the amount of polishing scratches are large. On the other hand, in Examples 1 to 27, the polishing rate of the organosilicate glass or silicon dioxide is large and the in-plane uniformity of the polishing rate is excellent, so that the increase in wiring resistance is small due to good dishing and erosion characteristics. Further, the amount of polishing residue and the amount of polishing scratches are small and good.

Claims (21)

A surfactant, a metal oxide solubilizer, and water, wherein the metal oxide solubilizer is at least one selected from organic acids, organic acid esters, ammonium salts of organic acids, and sulfuric acid,
A polishing liquid which is used for polishing a surface to be polished having at least a conductive substance and an insulating film on its surface. A surfactant, a metal oxide solubilizer, and water, wherein the metal oxide solubilizer is at least one selected from organic acids, organic acid esters, ammonium salts of organic acids, and sulfuric acid,
At least a conductive material, and
Silicon-based film or organic polymer film
A polishing liquid used for polishing a surface to be polished on a surface.   It contains perfluoroalkanesulfonic acid, a metal oxide solubilizer and water, and the metal oxide solubilizer is at least one selected from organic acids, organic acid esters, ammonium salts of organic acids and sulfuric acid. Polishing fluid. Containing an organic solvent, a metal oxide solubilizer and water, the metal oxide solubilizer is at least one selected from organic acids, organic acid esters, ammonium salts of organic acids and sulfuric acid,
A polishing liquid which is used for polishing a surface to be polished having at least a conductive substance and an insulating film on its surface. Containing an organic solvent, a metal oxide solubilizer and water, the metal oxide solubilizer is at least one selected from organic acids, organic acid esters, ammonium salts of organic acids and sulfuric acid,
At least a conductive material, and
Silicon-based film or organic polymer film
A polishing liquid used for polishing a surface to be polished on a surface.   The polishing liquid according to any one of claims 1 to 5, which contains abrasive grains.   The polishing liquid according to claim 6, wherein the abrasive is at least one selected from silica, alumina, ceria, titania, zirconia, and germania.   The polishing liquid according to claim 6, wherein the surface of the abrasive grains is modified with an alkyl group.   The polishing liquid according to claim 4 or 5, which contains 0.1 to 95% by weight of an organic solvent.   The polishing liquid according to claim 4 or 5, wherein the organic solvent is at least one selected from glycols and derivatives thereof, alcohols, and carbonates.   The polishing liquid according to claim 1 or 2, wherein the surfactant is at least one selected from a nonionic surfactant and an anionic surfactant.   The polishing liquid according to claim 1 or 2, wherein the surfactant is at least one selected from perfluoroalkanesulfonic acid and derivatives thereof.   The polishing liquid according to claim 1 or 2, which contains 0.00001 to 20% by weight of a surfactant.   The polishing liquid according to any one of claims 1 to 5, which contains a metal oxidizing agent.   The polishing liquid according to claim 14, wherein the metal oxidizing agent is at least one selected from hydrogen peroxide, nitric acid, potassium periodate, hypochlorous acid, and ozone water.   The polishing liquid according to any one of claims 1 to 5, comprising a water-soluble polymer having a weight average molecular weight of 500 or more.   The polishing liquid according to claim 16, wherein the water-soluble polymer is at least one selected from polysaccharides, polycarboxylic acids, polycarboxylic acid esters and salts thereof, and vinyl polymers.   A substrate having an interlayer insulating film having a concave portion and a convex surface, a barrier conductor layer covering the interlayer insulating film along the surface, and a conductive material layer filling the concave portion and covering the barrier conductor layer A first polishing step of polishing the conductive material layer to expose the barrier conductor layer of the convex portion, and at least a part of the barrier conductor layer, the conductive material layer of the concave portion, and the interlayer insulating film. A polishing method comprising: a second polishing step of exposing the interlayer insulating film of the convex portion by chemical mechanical polishing while supplying the polishing liquid according to any one of items 1 to 17.   19. The polishing method according to claim 18, wherein the interlayer insulating film is a silicon film or an organic polymer film.   The polishing method according to claim 18, wherein the conductive substance contains copper as a main component.   The barrier conductor layer is a barrier layer that prevents the conductive material from diffusing into the interlayer insulating film, and includes tantalum, tantalum nitride, tantalum alloy, other tantalum compounds, titanium, titanium nitride, titanium alloy, and other titanium compounds. The polishing method according to claim 18, comprising at least one selected from tungsten, tungsten nitride, tungsten alloy, and other tungsten compounds.