TW200838997A - Polishing liquid - Google Patents

Abstract

An object of the present invention is to provide a polishing liquid that uses a solid abrasive grain used for a barrier CMP that polishes a barrier layer including a barrier metal material, whereby an excellent polishing velocity can be achieved, and a polishing velocity for an insulating film can be controlled arbitrarily. There is provided a polishing liquid for polishing a barrier layer of a semiconductor integrated circuit, the polishing liquid including a colloidal silica having a surface that exhibits a positive ξ potential, a compound including a carboxyl group, an erosion suppressing agent, and a surfactant, the polishing liquid having a pH of 2.5 to 5.0.

Description

200838997 IX. OBJECTS OF THE INVENTION: TECHNICAL FIELD The present invention relates to a honing fluid used in a manufacturing step of a semiconductor device, and more particularly to flattening of a wiring step of a semiconductor device, which is suitable for use in planarization of a wiring step of a semiconductor device A honing fluid that is mainly honed by a barrier layer composed of barrier metal materials. [Prior Art] In the development of a semiconductor device represented by a semiconductor integrated circuit (hereinafter referred to as LSI), miniaturization and high speed have been demanded in recent years due to the miniaturization and stratification of wiring. Densification and high integration. Various techniques such as Chemical Mechanical Polishing (hereinafter referred to as CMP) have been used as the technology for use therein. In the case where the surface of the film to be processed such as the interlayer insulating film is flattened, the formation of a plug, and the formation of a buried metal wiring are required, the CMP is performing the smoothing of the substrate or the excess metal at the time of wiring formation. Removal of the film or removal of excess barrier layers on the insulating film. The general method of ® CMP is to attach a honing pad to a circular honing plate (p 1 ate η ) to immerse the immersion pad with the honing liquid and press the substrate surface (wafer )) On the mat, the honing disc and the substrate are both rotated in a state where a predetermined pressure (honing pressure) is applied from the inner surface thereof, and the surface of the substrate is flattened by mechanical friction generated. When a semiconductor device such as an LSI is manufactured, a plurality of fine wirings are formed, and in the respective layers, when a metal wiring such as Cu is formed, diffusion of the wiring material into the interlayer insulating film is prevented, or adhesion of the wiring material is improved 200838997. The purpose of 'pre-formed Ta or Ding & ^ [, Ding Bu 1 ^ 1 \ [etc. In order to form the respective wiring layers, first, the metal film CMP (hereinafter referred to as a metal film CMP) for removing the excess wiring material that has been mounted by plating or the like is continuously performed in a step or a plurality of stages, and then, the removal is performed. C Μ P (hereinafter, referred to as barrier metal CMP) of the barrier metal material (barrier metal) exposed on the surface. However, by the metal film CMP, it is a problem that the concave twisting of the so-called wiring portion is excessively honed or the corrosion is further caused. In order to reduce the concave twisting and honing, in the barrier metal CMP performed after the metal film C Μ , the honing speed of the metal wiring portion and the honing speed of the metal portion of the barrier are being sought to finally form a concave twisting. A wiring layer with less variation such as honing or corrosion. In other words, in the barrier metal C Μ , when the honing speed of the barrier metal or the interlayer insulating film is relatively small compared to the metal wiring material, a concave twisting or the like is performed due to rapid honing of the wiring portion, or As a result of the corrosion, it is desirable that the damper speed of the barrier metal or the insulating film layer is moderately large. In addition to the advantages of improving the processing ability of the barrier metal CMP, in practice, concave twisting and honing are mostly caused by the metal film CMP. For the foregoing reasons, it is also desirable to seek to relatively improve the barrier metal or the insulating film layer. The aspect of honing speed. A honing solution for metals for CMP, generally comprising cerium particles (eg, alumina, ceria) and an oxidizing agent (eg, hydrogen peroxide, persulfuric acid). The basic mechanism is believed to be the oxidation of the metal surface by an oxidizing agent and the removal of the oxide film by honing. However, when such a honing liquid containing solid cerium particles is used for CMP, 200838997, in addition to honing damage (scratch), more than necessary to honing the honing surface (thinning), The phenomenon of bending and honing the metal surface on the disk (concave twisting and dishing), exceeding the insulation necessary to honing the metal wiring, and the phenomenon of bending a plurality of wiring metal faces on the disk (corruption) Touch (erosion) and so on. Further, by using a honing liquid containing solid cerium particles, in order to remove the honing liquid remaining on the semiconductor surface after honing, the usual washing step is complicated, and further, after the washing is performed, In the liquid (waste liquid), there is a problem that the cost surface of the solid ruthenium or the like must be settled and separated. For the honing liquid containing these solid cerium particles, various investigations as follows are being carried out. For example, a CMP honing agent and a honing method for the purpose of high-speed honing which does not cause honing damage (for example, refer to Japanese Laid-Open Patent Publication No. 2003-17746), and improve the detergency in CMP. The honing composition and the honing method (for example, refer to Japanese Laid-Open Patent Publication No. 2003-1-4543-5), and the honing composition for preventing the entanglement of the honing granules (for example, refer to β-opening 2 0 0 0 - 8 4 8 3 2 Bulletin.). However, even in the honing liquid as described above, there is a technique of realizing a high honing speed when the barrier layer is not obtained, and arbitrarily controlling the honing speed of the interlayer insulating film. [Patent Document 1] Japanese Laid-Open Patent Publication No. JP-A-2003-147 A honing agent which is a honing liquid for solid granules used in dam CMP which is used for damaging a barrier layer composed of a barrier metal material, and which has excellent honing speed for the barrier layer and can be arbitrarily controlled Honing speed of the insulating film. As a result of intensive research, the inventors have found that the above problems can be solved by using the following honing liquid to achieve the problem. The honing liquid of the present invention is used for honing a barrier layer of a semiconductor integrated circuit, and is characterized by comprising a colloidal cerium oxide having a positive zeta potential on the surface, a compound having a carboxyl group, a uranium inhibitor, And a surfactant, a honing solution having a pH of 2.5 to 5.0. [Embodiment] In the present invention, the surfactant is preferably a compound represented by the following general formula (1). R-SCV General formula (1) In the general formula (1), R represents a hydrocarbon group. Further, in the present invention, the surfactant is preferably a compound represented by the following general formula (2). R4 R3 - N - R1 General formula (2) R2 In the general formula (2), R1 to R4 each independently represent a hydrocarbon group having a carbon number. However, R 1 to R 4 are not completely the same hydrocarbon group. 200838997 In the present invention, the colloidal ceria having a positive zeta potential on the surface is a cation. The colloidal ceria adsorbed on the kneading surface of the biochemical sigma is preferable, and the cationic compound is in the following general formula ( 3) The compound represented by the compound represented by the following general formula (4) is preferably a compound having a polyimine structure. R5 R5—N^R5 General formula (3) R5

In the general formula (3), in the general formula (3), R5 represents an identical hydrocarbon group having a carbon number of 丨1 to 18. Further, in the general formula (4), R6 and R7 each independently represent a hydrocarbon group. E 任意 Any integer other than 1 or more. In the present invention, the compound which preferably has a carboxyl group is a compound represented by the following general formula (5), and it is preferred that the compound represented by the general formula (5) is selected from the group consisting of 2-furancarboxylic acid, 2,5- At least one of the group consisting of furan dicarboxylic acid, 3-furancarboxylic acid, tetrahydrofurancarboxylic acid, diglycolic acid, methoxyacetic acid, methoxyphenylacetic acid, and phenoxyacetic acid. 200838997 R8—〇—R9—COOH General Formula (5) In the general formula (5), R 8 and R 9 each independently represent a hydrocarbon group. Further, it is preferred that the uranium inhibitor of the present invention is selected from the group consisting of 1,2,3-benzotriazole, 5,6-dimethyl-1,2,3-benzotriazole, 1-( 1,2-dicarboxyethyl)benzotriazole, 1-[N,N-bis(hydroxyethyl)aminemethyl]benzotriazole, and 1-(hydroxymethyl)benzotriazole At least one compound in the group. The mechanism of the effects in the present invention is considered as follows. #即' The film type used as the interlayer insulating film (for example, BD (black diamond) or the like) achieves a low dielectric constant by substituting a hydroxyl group bonded to Si to form a hydrocarbon group. The interlayer insulating film is compared with an insulating film of an unsubstituted monomer (for example, TEOS (tetraethoxysilane or the like: a CAP layer used for the upper portion of the interlayer insulating film, etc.), and has a so-called inclusion amount in the film. The amount of hydrocarbon groups contained therein. From this, the interlayer insulating film is relatively unsubstituted, and has the characteristics of (1) high hydrophobicity and (2) positively charged surface. ® The basis of these conditions, namely, adding a surfactant When the hydrophobic portion of the active agent is adsorbed on the surface of the interlayer insulating film, it is more likely to become a form in which the hydrophilic group of the surfactant concentrates on the surface thereof. Therefore, it is considered that the interlayer insulating film surface is used in the case of using an anionic surfactant. The change to an anionic property, in the case of using a cationic surfactant, the surface of the interlayer insulating film is changed to be cationic. Therefore, as in the present invention, it is considered that the use of positive ZETTA ( Γ ) potential colloidal cerium oxide (honing particles), when anionic -10-200838997 surfactant is used, honing particles and interlayer insulating film electrostatically adsorbed 'effectively enhance honing speed Further, when a cationic surfactant is used, the honing particles and the interlayer insulating film are electrostatically repelled, and the honing speed can be effectively suppressed. According to the present invention, it is possible to provide an excellent honing speed for the barrier layer, and The honing speed of the insulating film can be arbitrarily controlled. Hereinafter, a specific aspect of the present invention will be described. The honing fluid of the present invention is a honing fluid for damaging the barrier layer of the semiconductor integrated circuit, and is characterized by (A) a surface exhibiting a positive zeta potential of colloidal cerium oxide, (B) a compound having a carboxyl group, (C) a rotatory inhibitor, and (D) a surfactant as an essential component, and having a pH of 2.5 to 5.0, and further When necessary, the components of the honing liquid of the present invention may be used singly or in combination of two or more. In the present invention, the "honing fluid" is not only used. Yu Yao The honing liquid (that is, the honing liquid diluted as necessary) also means the concentrate of the honing liquid. The so-called concentrated liquid or concentrated honing liquid means that the preparation is used in comparison with honing. The sizing liquid having a high solute concentration in the grinding liquid is used for honing when it is used for honing, and is diluted with water or an aqueous solution, etc. The dilution ratio is generally 1 to 20 times the volume. In the present specification, the term "concentration _" The "concentrated liquid" is used for the conventional expression indicating the meaning of "high concentration" and "high concentration liquid" in the use state, and is used in a manner different from the general term meaning of the physical concentration operation such as evaporation. The components constituting the honing liquid of the present invention will be described in detail. -11- 200838997 [(A) Colloidal cerium oxide exhibiting a positive f potential on the surface] The honing fluid of the present invention contains (A) a surface exhibiting a positive zeta potential Colloidal cerium oxide is used as at least a part of the cerium particles. In the case of the colloidal cerium oxide, if the surface exhibits a positive zeta potential, it is not particularly limited, and a colloidal cerium oxide whose cationic compound is adsorbed on the surface is preferred. Therefore, in the case of modifying or modifying the colloidal cerium oxide on the surface, it is preferred to contain colloidal cerium which is decomposed by hydrolysis of alkoxy decane without containing an impurity such as an alkali metal inside the particles. Further, colloidal cerium oxide produced by a method of removing alkali from an aqueous citric acid solution may be used, and in this case, the alkali metal remaining inside the particles is slowly eluted, and there is concern that the honing performance is affected. . From such a viewpoint, it is preferred to use a hydrolyzed alkoxydecane as a raw material. The particle size of the colloidal cerium oxide to be used as a raw material is appropriately selected depending on the purpose of use of the granules, but is generally about 10 to 200 nm. First, it is explained that (A) the surface shows positive (potential colloidal ceria one of the 'cationic compounds adsorbed on the surface of the colloidal ceria. The cationic compound used therein is never hindered to other films. From the viewpoint of honing performance, a compound represented by the following general formula (3) or a compound having a polyimine structure represented by the following general formula (4) is preferred. a compound represented by the formula (3) and a compound having a polyimine structure represented by the following general formula (4): 200838997 R5 R5 - N - R5 - general formula (3) R5 In the above general formula (3) 'R5 denotes a hydrocarbon group having the same carbon number i to 18. The hydrocarbon group represented by R5 includes an alkyl group, an aryl group, a phenyl group, etc., and a linear one which is particularly preferably a carbon number of 1 to 5. Specific examples of the compound represented by the general formula (3) include tetramethylammonium, tetraethylammonium, tetrapropylammonium, tetrabutylammonium, tetraammonium, and the like.

FT n In the above general formula (4), R6 and R7 each independently represent a hydrocarbon group, and preferably a hydrocarbon group having 1 to 10 carbon atoms. R6 is preferably a divalent hydrocarbon group having 1 to 10 carbon atoms, for example, an alkylene group having 1 to 1 carbon atom. R7 represents a monovalent hydrocarbon group having 1 to 10 carbon atoms, for example, an alkyl group having 1 to 10 carbon atoms, a aryl group or a fluorenylphenyl group. The hydrocarbon group represented by R6 and R7 may further have a substituent, and examples of the substituent which may be introduced include an alkyl group, a hydroxyl group, a carboxyl group and the like. In the above general formula (4), η is an arbitrary integer of 1 or more. -13- 200838997 That is, a polymer having a polyimine structure represented by the general formula (4), wherein the above structural unit is n-bonded, and has a weight of about 100 to 20,000, since it is from colloidal cerium oxide ( Therefore, the η ' showing the number of repetitions in the general formula (4) is determined from the substituents of the structural unit and the above-mentioned preferred weight average molecular weight as the compound. (4) Examples of the polyimine structure represented by excipients include, for example, polyethylenimine, polyallylamine, etc. In order to adsorb the cationic compound as described above on the surface of the gel, only the above compound may be mixed with Colloidal cerium oxide whereby a cationic compound having the above-described configuration is attached to a colloidal cerium oxide having a slightly negative charge to obtain a colloidal cerium oxide having a surface potential of (A). Among them, in the present invention, The Γ霄® measuring machine for measuring the surface of (A) colloidal cerium oxide by means of, for example, electrophoresis method, can be used for DT-l2 〇0 (the surface display of (A) in the honing liquid of the Japanese Luft public invention Positive zeta potential It is the same as the honing liquid used for honing (the honing liquid after dilution in the case of dilution of the aqueous solution. The following honing liquid at the time of honing) has the same meaning. The mass 'more than 15% by mass or less. More preferably, it is 3% by mass or more and 12 is particularly preferably 5% by mass or more and 12% by mass or less. That is, the content of '(A) lanthanum is honed at a sufficient honing rate for the compound of the barrier layer, and the average molecular weight The structural unit of the ground particle 3 has a molecular weight, which is suitable for the specific paradigm of the quartz dioxide on the surface of the cerium, and the suction surface shows positive enthalpy, super 苜 wave vibration [bit. specific division) and the like. The colloidal dioxin, that is, water or "used in a mass ratio of 1% by mass or less, a colloidal cerium oxide point, preferably -14 to 200838997 1% by mass or more, is preferable from the viewpoint of preserving stability. It is 15 mass% or less. In the honing liquid of the present invention, it is possible to use the particles other than the colloidal cerium oxide having a positive zeta potential on the surface of (A), even if it is not impaired by the effects of the present invention, even in In this case, the content of the colloidal cerium oxide having a positive zeta potential on the surface of (A) is preferably 50% by mass or more, particularly preferably 80% by mass or more. It may also be a colloidal cerium oxide having a positive zeta potential on the surface of (A). With respect to the honing liquid of the present invention, and the cerium particles for colloidal cerium oxide having a positive zeta potential on the surface of (A), Examples thereof include molten vermiculite, cerium oxide, aluminum oxide, titanium oxide, etc. The size of the cerium particles used is equal to or higher than the colloidal cerium oxide having a positive zeta potential on the surface (A), and is preferably 2 times or less. [(B) Compound having a carboxyl group] In the honing liquid of the present invention, it is required to contain (B) The compound having a carboxyl group and having a carboxyl group is not particularly limited as long as it has at least one carboxyl group in the molecule, but from the viewpoint of the honing speed structure, it is preferred to select the following general formula (5) Further, the compound represented by the molecule is preferably i~4 in the molecule, and more preferably 1 to 2 from the viewpoint of being inexpensive to use. R8-〇-r9-COOH In the above general formula (5), R8 and R9 each independently represent a hydrocarbon group, preferably a hydrocarbon group having 1 to 10 carbon atoms. Further, as indicated by R8 and R9, 200838997 is also An oxygen atom may be contained in the chain. R8 is a monovalent hydrocarbon group, and is preferably, for example, an alkyl group having 1 to 1 carbon atom (for example, 'methyl group, cycloalkyl group, etc.) or an aryl group (for example, phenyl group, etc.). And alkoxy, aryloxy, etc. R9 is a divalent hydrocarbon group, for example, an alkylene group having a carbon number of 1 to 10 (e.g., a methylene group, a cycloalkylene group, etc.) or an extended aryl group (for example, Phenyl, etc.), oxime oxygen base, etc. The hydrocarbon group represented by R8 and R9 may further have a substituent, which can be introduced into the product Examples of the base include, for example, an alkyl group having 1 to 3 carbon atoms, an aryl group, an alkoxy group, a carboxyl group and the like. When a carboxyl group is used as a substituent, the compound has a plurality of carboxyl groups. Further, 'R8 and R9 Further, it may be bonded to each other to form a cyclic structure. Examples of the compound represented by the above general formula (5) include 2-furancarboxylic acid, 2,5-furandicarboxylic acid, 3-furancarboxylic acid, and 2-tetrahydrofuran. Carboxylic acid, diglycolic acid, methoxyacetic acid, methoxyphenylacetic acid, phenoxyacetic acid, etc., preferably 2,5-furandicarboxylic acid, 2-tetrahydrofurancarboxylic acid, oxidized diacetic acid ( Diglycolic acid), methoxyacetic acid, phenoxyacetic acid, preferably from the viewpoint of honing speed improvement, preferably 2-furancarboxylic acid, 2,5-furandicarboxylic acid, diglycolic acid ). In the honing liquid of the present invention, (B) a compound having a residue (preferably a compound represented by the general formula (5)) is preferably added in an amount relative to the mass of the honing fluid used in honing. It is 0.1% by mass or more and 5% by mass or less, more preferably 0.5% by mass or more and 2% by mass or less. That is, from the viewpoint of achieving a sufficient honing speed from the viewpoint of achieving a sufficient honing speed, it is preferably -16 to 200838997 of 0.1% by mass or more, from the viewpoint of not causing excessive concave twisting and honing. It is preferably 5% by mass or less. [(C) Corrosion inhibitor] In the honing liquid of the present invention, a corrosion inhibitor which adsorbs on the surface to be honed to form a film to suppress corrosion of the metal surface is contained. In the anti-corrosion inhibitor of the present invention, it is preferred to have three or more nitrogen atoms in the molecule and an aromatic heterocyclic compound having a condensed ring structure. In particular, "three or more nitrogen atoms" are preferably atoms constituting a condensed ring, and among these aromatic heterocyclic compounds Φ, benzotriazole is preferably used, and various substituents are introduced into the benzotriazole. derivative. The uranium inhibitor used in the present invention is exemplified by benzotriazole, 1,2,3·benzotriazole, 5,6-dimethyl-1,2,3·benzotriazole, 1 -( 1,2-dicarboxyethyl)benzotriazole, 1-[indene, bis- bis(hydroxyethyl)amine methyl]benzotriazole, 1-(hydroxymethyl)benzotriazole, etc. ' Among them, it is preferably selected from 1,2,3-benzotriazole, 5,6-dimethyl-1,2,3-benzotriazole, 1-(1,2-dicarboxyethyl)benzene And triazole, 1-[indene, bis-bis(hydroxyethyl)amine methyl]benzotriazole, and 1-(hydroxymethyl) benzotriazole. The amount of the (C) corrosion inhibitor to be added is preferably from 0. 01% by mass to more than 0.2% by mass, more preferably 0.05% by mass or more, based on the mass of the honing fluid used in the honing. 〇·2 mass% or less. In other words, the amount of the addition of the corrosion inhibitor is preferably 0. 0.001% by mass or more, and is preferably 0.2% by mass or less from the viewpoint of storage stability. [(D) Surfactant] The honing fluid of the present invention contains (D) a surfactant. -17- 200838997 In the honing liquid of the present invention, the honing speed of the insulating layer or the honing speed of the insulating layer can be controlled by adjusting the type and amount of the (D) surfactant. In particular, from the viewpoint of increasing the honing speed of the insulating layer, it is preferred that the compound represented by the following general formula (1) is preferable from the viewpoint of controlling the honing speed of the insulating layer. It is a compound represented by the following general formula (2). R to S 〇 3 · General Formula (1) In the above general formula (1), R represents a hydrocarbon group, preferably a hydrocarbon group having 6 to 20 carbon atoms. And a TO' is preferably, for example, an alkyl group having 6 to 2 carbon atoms, an aryl group (e.g., benzene _, -μ^ group, etc.), etc., and the alkyl group or aryl group may further have a substituent of an alkyl group. . Specific examples of the compound represented by the general formula (1) are exemplified by _ _ of the acid, dodecylbenzenesulfonic acid, tetradecylbenzenesulfonic acid, hexadecylbenzene acid, and decyl-naphthyl A compound such as sulfonic acid or tetradecylnaphthalenesulfonic acid. R4 ~~Ν-R1 General formula (2) R2 In the above general formula (2), R1 to R4 each independently represent a carbon number of 1 to 1 8 @ ! 4 ^鸯. However, R1 to R4 are hydrocarbon groups which are not completely the same. Examples of the hydrocarbon group represented by X R to H4 include an alkyl group, an aryl group, a benzene -18-200838997 group, and the like, and particularly preferably a linear or branched alkyl group having 1 to 20 carbon atoms. Further, two of R 1 to R4 may be bonded to each other to form a cyclic structure such as a fluorene-definite structure, a pyrrolidine structure, a hexahydropyridine structure or a pyrrole structure. Specific examples of the compound represented by the general formula (2) include, for example, lauryl trimethylammonium, lauryl triethylammonium, octadecyltrimethylammonium, hexadecyltrimethylammonium, octyltrimethylammonium, and dodecylpyridinium cation. a compound such as eleven pyridyl cation or octylpyridine cation. Examples of the anionic boundary surfactant other than the compound represented by the above general formula (1) include a carboxylate, a sulfate salt, and a phosphate salt. More specifically, in terms of a carboxylate, a soap, an N-guanidine salt, a polyepoxyethyl or polyepoxypropyl alkyl ether carboxylate, a deuterated peptide, or a sulfate salt can be preferably used. Preferably, a sulfated oil, an alkyl sulfate salt, an alkyl ether sulfate, a polyepoxyethyl or polyepoxypropyl alkyl decyl ether sulfate, an alkyl decylamine sulfate; a phosphate salt is preferably used; In the aspect, an alkyl phosphate salt, a polyepoxyethyl group or a polyepoxypropyl alkyl decyl ether phosphate can be preferably used. (D) The amount of the surfactant to be added is preferably 1 L in the honing liquid used for honing, and is preferably 0.01i~1 ()g, preferably 0.01 to 5 g, particularly preferably 0.01 to 1 g as the total amount. In other words, the amount of the surfactant added is preferably at least O.Olg, and is preferably lg or less from the viewpoint of preventing a decrease in the CMP rate. In the honing liquid of the present invention, in addition to the components (A) to (D) described above, other components may be appropriately added for the purpose. The addition component 0 -19-200838997 [Oxidant] The honing liquid of the present invention is preferably a compound (oxidizing agent) containing a metal which can oxidize the object to be honed. Examples of the oxidizing agent include hydrogen peroxide, peroxide, nitrate, iodate, periodate, hypochlorite, chlorite, chlorate, perchlorate, persulfate, and heavy chromium. Acid salt, permanganate, ozone water, and silver (II) salt, iron (III) salt, and particularly preferably hydrogen peroxide. In terms of iron (III) salt, it is preferably used in addition to inorganic iron (III) salts such as iron (III) nitrate, iron (III) chloride, iron (III) sulfate, and iron (III) bromide. An organic complex salt of iron (III). The amount of the oxidizing agent added can be adjusted in accordance with the amount of concave twisting in the initial stage of the barrier CMP. In the case where the amount of concave twisting in the initial stage of the barrier CMP is large*, that is, when the wiring material is not much desired in the barrier CMP, it is desirable to increase the amount of the oxidant and to offset the amount of the honing in the concave shape. In the case where it is small enough and the wiring material is to be honed at a high speed, it is desirable to add a large amount of the oxidizing agent. Therefore, it is desirable to change the amount of the oxidizing agent to be added to the honing state in the initial stage of the barrier CMP. Therefore, in 1 L of the honing liquid used for honing, it is preferably O.Olmol to 1 mol. , particularly preferably 0.05 mol ~ 〇. 6 mol. [pH Adjusting Agent] The honing liquid of the present invention requires a range of p Η 2 · 5 to 5.0, preferably p Η 3 · 0 to 4.5. By controlling the 硏 液 in the range, the honing speed adjustment of the interlayer insulating film can be performed more remarkably. In order to adjust the pH to the above preferred range, a base/acid or a buffer is used. The honing liquid system p 本 of the present invention exhibits an excellent effect in this range. -20- 200838997. In terms of alkali/acid or buffer, organic ammonium hydroxide such as ammonia, ammonium hydroxide and tetramethylammonium hydroxide; preferably, such as diethanolamine, triethanolamine or triisopropanolamine, may be mentioned. Non-metal alkaline agents such as alkanolamines; alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, and lithium hydroxide; inorganic acids such as nitric acid, sulfuric acid, and phosphoric acid; carbonates such as sodium carbonate a phosphate such as trisodium phosphate; a borate, a tetraborate, a hydroxybenzoate or the like. Particularly preferred aspects of the test are ammonium hydroxide, potassium hydroxide, lithium hydroxide and tetramethylammonium hydroxide. In terms of the amount of the alkali/acid or the buffer to be added, if the above-mentioned electrical conductivity is 下, if the pH is maintained in a preferred range, it is used in 1 L of the honing liquid used for honing. Preferably, it is O.O00lmol~l.Omol, more preferably 0.003 mol~〇.5mol 〇[chelating agent] The honing liquid of the present invention is preferably necessary for reducing the adverse effects of mixed polyvalent metal ions and the like. It contains a chelating agent (ie, a hard water softener). The chelating agent is a general hard water softening agent which is a calcium or magnesium precipitation preventing agent or a compound thereof, and examples thereof include nitrogen triacetic acid, diethylene triamine pentaethane acid, ethylenediaminetetraacetic acid, N, N, N-trimethylene phosphonic acid, ethylenediamine-N, N, N', N'-tetramethylene phosphonic acid, trans cyclohexanediaminetetraacetic acid, hydrazine, 2 • diamine propane tetraacetic acid, glycol Ether diamine tetraacetic acid, ethylenediamine orthohydroxyphenylacetic acid, ethylenediamine disuccinic acid (SS body), N-(2-carboxyaliphatic)-L-aspartic acid, /3-alanine Diacetic acid, 2-phosphino-1,2,4-tricarboxylic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, N,N,-bis(2-hydroxybenzyl)ethylenediamine- N,N,-diacetic acid, 1,2-dihydroxybenzene-4,6-disulfonic acid and the like. The chelating agent may be used in combination of two or more kinds as necessary. -21 - 200838997 The amount of the integrator added may be a sufficient amount for blocking the metal ion of the polyvalent metal ion or the like to be mixed, for example, in 1 L of the honing liquid used for honing, 0.0003 mol is added. 〜η , uu / m ο 1 ° The honing fluid of the present invention is generally present between the wiring composed of copper metal and/or copper alloy and the interlayer insulating film 'suitable for the barrier metal material for copper diffusion The damaging of the barrier layer. [Bound Metal Material] The material constituting the barrier layer of the honing liquid honing object of the present invention is generally a low-resistance metal material, particularly preferably TiN, Tiw, Ta, TaN, W, WN, of which Ta, TaN. [Interlayer insulating film] The interlayer insulating film to be honed by the honing liquid of the present invention has a dielectric constant of about 3 · 5 to 2 · 0 in addition to the interlayer insulating film which is usually used, such as TEOS. An interlayer insulating film of a dielectric material (for example, an organic polymer system, a SiOC system, an SiOF system, or the like, generally, simply referred to as an L〇w_k film). Specifically, 'materials for the formation of low dielectric interlayer insulating films' are HSG-R7 (Hitachi Chemical Industry) and black diamonds in the Si〇C system (BLACK DIAMOND (AppUed)

Materials, Inc)) and so on. [Wiring metal material] «In the middle of the month of the month, the honing system for the honing is applied to a semiconductor device such as LSI (iarge scaie integration), preferably having copper metal and / or wiring made of copper alloy. In particular, the raw material of the wiring is preferably a copper alloy. Further, it is preferable to use a copper alloy containing silver in the copper alloy. In addition, the content of silver contained in the copper alloy is preferably 40% by mass or less, particularly preferably 1% by mass or less, more preferably 1% by mass or less, and copper in the range of 0.0000 1 to 0.1% by mass. The best effect is achieved in the alloy. [Thickness of Wiring] In the present invention, in the case where the object to be honed is applied to, for example, a DRAM (dynamic random access memory) device series, half pitch It is preferable to have a wiring of 0.1 5 // m or less, preferably 〇. 1 〇# m or less, more preferably 〇. 〇8 // m or less. Further, when the honed body is applied to, for example, an MPU (micro processing unit) device series, it is preferable to have a wiring of 0.12/zm or less, preferably 〇·〇9 /zm or less. Good is 0.07 // m or less. The honing liquid of the present invention described above exerts particularly excellent effects on the honed body having such wiring. [Horse method] ® The honing liquid of the present invention has a concentration of 1%, which is a concentrated liquid, and is added to water or an aqueous solution to be used as a use liquid when used; 2) The components are prepared in the form of an aqueous solution described in the following items, and Mixing them, and mixing them with water to become a use liquid; 3. Modulation as a use liquid. A honing liquid according to the honing method using the honing liquid of the present invention can also be applied. The honing method is a method for supplying a honing liquid to a honing pad on a honing plate, and contacting the honed surface of the honed body to move the honing surface and the honing pad -23-200838997 . For the device for grinding 1 grinding, a fixing clip having a honed body having a honed surface (for example, a wafer forming a film of a conductive material, etc.) can be used (with a changeable slewing) The number of motors, etc.) is the general honing device for honing the plate. In terms of honing, a general non-woven fabric, a foamed polyurethane, a porous fluororesin, or the like can be used, and it is not particularly limited. Further, although the honing condition is not p艮', the slewing speed of the 硏_ fixing plate is preferably a low rotation of 20 rpm or less when the honing body does not fly out. The pressing pressure of the honing pad having the honed surface of the honed surface (the 磨10 is 磨10) is preferably 0.68 to 3 4.5 KPa, and the uniformity in the surface of the honed body in order to satisfy the honing speed and The flatness of the pattern is more preferably 3.4 〇~2 (K 7 KP a. When honing is done, the honing liquid is continuously supplied to the honing pad by a pump or the like. The honing system after honing is sufficient in the running water. After washing, it is dried by dropping a water droplet adhering to the object to be honed by a spin dryer or the like. In the present invention, as in the method of the above 1, when the concentrate is diluted, an aqueous solution shown below can be used. The aqueous solution is at least one or more kinds of water containing at least one of an oxidizing agent, an organic acid, an additive, and a surfactant, and a component contained in the aqueous solution and a component contained in the diluted concentrated liquid are 硏. The composition of the honing liquid (use liquid) used in the grinding. Therefore, when the concentrate is diluted with an aqueous solution, the concentrated concentrate can be prepared by mixing the insoluble components in the form of an aqueous solution. As added Or the aqueous solution is mixed with the concentrate in a method of mixing the mixture of the supply of the concentrated honing liquid with the supply water or the aqueous solution of the -24-200838997, and the mixture is supplied to the mixed dilution honing liquid. The method of honing the pad. The mixing of the concentrate with water or an aqueous solution may be carried out by a method of applying a pressure through a narrow passage to collide with the mixed liquid, and repeating a liquid which is divided and shunted in the pipe to block the filling of the gas pipe or the like. A method generally performed by a method of reflowing a flow, a method of providing a blade for rotating a power in a pipe, etc. The supply speed of the honing liquid is preferably 10 to 1 000 ml/min, and is honed in order to satisfy the honing speed. The uniformity and the flatness of the pattern are more preferably I 170 to 800 ml/min. Further, as a method of diluting the concentrated liquid by water or an aqueous solution or the like, the piping and the supply water for supplying the honing liquid are separately provided. Or the piping of the aqueous solution, which is separately supplied with a predetermined amount of liquid on the honing pad, and the method of mixing and honing the honing pad with the relative movement of the honed surface. Used in a container, from the addition and mixing of the quantitative concentrate and water or aqueous solution, the method of 'supplying the mixed honing liquid to the honing pad and honing. 'Other honing methods, there is a distinction 硏All the components contained in the grinding fluid are at least two constituent components. When they are used, they are diluted with water or an aqueous solution to be supplied to the honing pad on the honing plate to be in contact with the surface to be honed and to be honed. A honing method that moves relative to the honing pad. For example, an oxidizing agent is used as a constituent (A), and an organic acid, an additive, a surfactant, and water are used as a constituent (B), and water can be used when using them. The aqueous solution is diluted with the component (A) and the component (B). The additive having low solubility is composed of two components (A) and (B), for example, an oxidizing agent, an additive, and a surfactant. -25- 200838997 (A ), using organic acids, additives, surfactants, and water as constituents (B), adding water or an aqueous solution when using them, and diluting the constituents (A) and constituting components (B) . In the case of the above-described example, it is necessary to supply three types of pipes, which are the component (A), the component (B), and the water or the aqueous solution, and to mix and mix the three types of pipes to be supplied to the honing pad. In the case where the piping is mixed and mixed in the piping, in combination, the other piping may be combined with the other types of piping. Specifically, it is a method of mixing water or an aqueous solution by mixing a constituent component containing an additive of a poorly soluble solution and other constituent components, and extending the mixing route to ensure a dissolution time. The other mixing method directly guides the three types of pipes to the honing pad as described above, and mixes the three types of components by a relative movement of the honing pad and the surface to be honed, or by mixing the three components in one container. A method of supplying the diluted honing liquid to the honing pad. In the above honing method, one component containing an oxidizing agent is 40 ° C or less, and other components are heated from room temperature to 100 ° C, and one component and other components are mixed. When the water is added or the aqueous solution is diluted, the liquid temperature can be made 40 ° C or less. This method is a preferred method for increasing the solubility of a raw material having a low solute solution solubility by utilizing a phenomenon in which the temperature is high and the solubility is high. In the case where the raw material dissolved by heating the above-mentioned other constituent components from room temperature to 100 ° C falls, the temperature is lowered and precipitated in the solution. Therefore, when other components in a low temperature state are used, it is necessary to heat in advance to dissolve. The raw materials precipitated. Among them, means for transporting a liquid which has been heated and dissolving other constituents of the raw material -26 - 200838997; and means for transferring the liquid, heating the tube, and dissolving after stirring the liquid containing the precipitate. There is a concern that the temperature of the other constituent component that has been heated or one of the constituent components including the oxidizing agent is increased to 40 ° C or higher and the oxidizing agent is decomposed 'mixing the heated other constituent component and one constituent component containing the oxidizing agent. In the case of 40 ° C or less, it is preferable to carry out. Therefore, in the present invention, the honing liquid component may be divided into two or more components to be supplied to the honed surface. In this case, it is preferably divided into a component containing an oxide compound and a component containing an organic acid. Further, the honing liquid may be a concentrate and be different from the dilution water to be supplied to the surface to be honed. In the present invention, when the method of dividing the honing liquid component into two or more components to be supplied to the honed surface is applied, the supply amount indicates the total amount of supply from each pipe. [Cushion] The honing pad for honing which is suitable for the honing method of the present invention may be a non-foaming structural pad or a foamed structural pad. The former uses a hard ^ synthetic resin block such as a plastic sheet. Further, the latter is a further independent foam (dry foaming system), a continuous foam (wet foaming system), and a two-layer composite (layered system), and particularly preferably a two-layer composite (layered system). . Foaming is uniform or non-uniform. Further, it may be a granule which is generally used for honing (for example, cerium oxide, cerium oxide, aluminum oxide, resin, etc.). Further, the individual hardness may be either soft or hard, and in the laminated system, it is preferred to use different hardnesses in each layer. In terms of material, it is preferably non-woven fabric, artificial leather, polyamide, -27 - 200838997 polyurethane, polyester, polycarbonate, and the like. Further, it is also possible to perform processing such as lattice grooves/holes/concentric grooves/spiral grooves on the surface in contact with the surface to be honed. [Wafer] The wafer to be honed by the CMP object in the honing liquid of the present invention preferably has a diameter of 200 mm or more, particularly preferably 300 mm or more. When it is 3 00 mm or more, the effects of the present invention are remarkably exhibited. [Mulching device] The device that can perform the honing using the honing liquid of the present invention is not particularly limited, and examples thereof include Mirra Mesa CMP, Reflexion CMP (Applied Material Co., Ltd.), FREX 200, and FREX 305 (荏原株式会社). , NPS 3 3 0 1 , NPS2301 (Dawning Company), A-FP-310A, A-FP-210A (Tokyo Precision), 2 3 00 TERES ( Lam Research), Momentum (Speedfam IPEC), etc. [Examples] Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited thereto. [Example 1] A honing liquid having the composition shown below was prepared to carry out a honing experiment. <Composition (1) > (A) Colloidal cerium oxide showing a positive zeta potential on the surface

(1) Colloidal cerium oxide (PL3 slurry, manufactured by Fuso Chemical Industry Co., Ltd.) 200g/L

(2) Cationic compound: tetrabutylammonium nitrate (TBA) lg/L

(B) Compound having a carboxyl group: diglycolic acid 15 g/L (manufactured by Wako Pure Chemical Industries, Ltd.) -28- 200838997

(c) Corrosion inhibitor: benzotriazole (BTA) 0.5g/L

(D) Surfactant: undecylbenzenesulfonic acid 0.03g/L

Adding the total amount of pure water to 1 0 0 m L pH (adjusted with ammonia water and nitric acid) 3.5 <Measurement of Γ (ZETTA) potential> The surface of (A) contained in the obtained honing liquid was measured by the following conditions. The zeta potential of the surface of the colloidal cerium oxide at the potential. This result confirmed that the zeta (ZETTA) potential was 12 mV and showed positive enthalpy. In the (ZETTA) potential®, the honing liquid of Example 1 was measured in a non-concentrated form by DT-1200 manufactured by Luft Corporation of Japan. (Evaluation method) The apparatus "LGP-612" manufactured by Lapmaster Co., Ltd. was used as a honing machine. The apparatus was supplied with the slurry under the following conditions while honing various wafer films shown below: • Number of chuck revolutions: 64 rpm • Number of revolutions of the honing pad: 65 rpm • Honing pressure: 13.79 kPa • Honing pad: Rodel IC1400 XY-K-Pad manufactured by Nitta Co., Ltd. • Supply rate of honing liquid: 200 ml/min (Evaluation of honing speed: object to be honed) The object to be honed (Ta, TEOS, BD) is used on a Si substrate. The 8 吋 wafer of the film is used as a honing object. (Corrosion evaluation: honing object) The TEOS (tetraethoxy decane) substrate is patterned by a lithography step and a reactive ion etching step to form a width 〇 ·〇9~1〇〇Μ m, depth-2 9 - 200838997 6 0 Onm wiring trench and connection hole'. Further, a Ta film with a thickness of 20 nm is formed by a sputtering method, followed by sputtering. After forming a copper film having a thickness of 50 nm, a total thickness of 1 0 0 〇 n is formed by electroplating. The 8 吋 wafer of the copper film of m is used as a target for honing. <honing speed> The honing speed is measured by Ta (barrier layer), TE 0 S (insulating film), and BD (low dielectric) before and after CMP. The film thickness of the electric insulating film is obtained by the following formula: honing speed (A/min) 2 (thickness (film) thickness before honing - thickness of layer (film) after honing) / 硏The results obtained by the grinding time are shown in Table 1. <Corrosion Evaluation> For the pattern wafer which was fully exposed to Ta of the barrier metal material, the honing liquid of Example 1 was used for honing for 60 seconds, using a stylus type differential meter ^ Dektak V320Si (manufactured by VeeC Corporation) was used to measure the corrosion of the line and the space portion (line 9 // m, interval 1 / zm). [Examples 2 to 4 5 and Comparative Examples 1 to 1 0] The composition (1) was a honing liquid prepared in the compositions described in the following Tables 1 to 6, and honing experiments were carried out under the same honing conditions as in Example 。. The results are shown in Tables 1 to 6. -30 - 200838997 Corrosion (nm) 〇〇C0 oo Csl un <NI 5 CO CN CNl v〇CNl VO Csl BD Honing speed (nm/min) 〇\DS 〇v〇 v 〇csi v〇VO OO vo os TEOS honing speed (nm/min) υη o un o S o 〇ooo to CN Ta honing speed (nm/min) Ο wn 〇〇oo un V〇o V〇CN o 〇 CO un cn cn CO CO CO m cn wo CO m CO VO CO to CO CO v〇cn (D) component (content) O) such as ω 2 DBS (〇.〇3g/L) -i PQ m H 〇HBS ( 0.03g/L) DNS (〇.〇3g/L) TNS (0.03g/L) 壊oo 'Sb ω 2 DBS (0.03g/L) ^ W) PQ m H p HBS (〇.〇3g/L) DNS (〇.〇3g/L) TNS (〇.〇3g/L) 壊(C) component (content) BTA (lg/L) BTA (lg/L) BTA (lg/L) BTA (lg/L) BTA (lg/L) BTA (lg/L); BTA (lg/L) BTA (lg/L) BTA (lg/L) BTA (lg/L) BTA (lg/L) BTA (lg/L) BTA (lg/L) BTA (lg/L) (B) Ingredients (content) 贰 贰 glycolic acid (15g / L) - condensed glycolic acid (15g / L) - condensed glycolic acid (15g / L)贰glycolic acid (15g/L) - condensed glycolic acid i (15g / L) - condensed glycolic acid (15g / L) 1 - condensed glycolic acid (15g / L) 2, 54I futless dicarboxylic acid (15g /L) 2,5-furandicarboxylic acid (15g / L) 2,5-furandicarboxylic acid (15g / L) 2,5-furandicarboxylic acid (15g / L) 2,5-furandicarboxylic acid (15g/L) 2,5-furandicarboxylic acid (15g/L) 2,5 -furan dicarboxylic acid (15g/L) < zeta potential (mV) r-H o Csl cn ii CO 1 H o CN CO 〇o CNl cationic compound (content) TBA (lg/L) TBA (lg/L TBA (lg/L) TBA (lg/L) TBA (lg/L) TBA dg/L) ! TBA (lg/L) TMA (lg/L) < ^ S 'So H c < 3 S ' Sb TMA (lg/L) TMA (lg/L) < 2s TMA (lg/L) Colloidal cerium oxide (content) 2 δ 3 S Ph 3 iW m □ s 2 S 2 S Ph 13⁄4 κη ~13⁄4 uo PL3H (5 mass%) PL3H (5 mass%) PL3H (5 mass%) PL3H (5 mass%) PL3H (5 mass%) PL3H (5 mass%) PL3H (5 mass%) Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative Example 1 Example 7 Example 8 Example 9 Example 10 Example 11 Example 12 Comparative Example 2 200838997 Corrosion (nm) m CNl oo CO OQ csi CN CO CNl oo CO VO C〇BD honing speed 1 (nm/min) § VO VO o to ' oo o different S oo cs to vo csl TEOS honing speed (nm/min) υη oo Οί 〇v〇CN oo VO 〇o Ta 硏Grinding speed (nm/min) CS cn v〇ο v〇VO 〇CN cn wo 〇〇CO un CO CO cn CO CO m CO VO cn CO to CO cn un cn CO CO ( D) Ingredients (content) « S DBS (0.03g/L) TBS (0_03g/L) HBS (〇.〇3g/L) DNS (0,03g/L) TNS (〇.〇3g/L) Destroy oo ' Ϊο PQ S DBS (〇.〇3g/L) TBS 1 (〇.〇3g/L) HBS (0.03g/L) DNS (〇.〇3g/L) TNS (0,03g/L) 壊(C) Composition (content) ΒΤΑ (lg/L) BTA (lg/L) BTA (lg/L) BTA (lg/L) BTA (lg/L) BTA (lg/L) BTA (lg/L) BTA (lg/ L) BTA (lg/L) BTA (lg/L) BTA (lg/L) BTA (lg/L) BTA (lg/L) BTA (lg/L) (B) Component (content) 2-tetrahydrofurancarboxylic acid (15g/L) 2-tetrahydrofurancarboxylic acid (15g/L) 2-tetrahydrofurancarboxylic acid (15g/L) 2-tetrahydrofurancarboxylic acid (15g/L) 2-tetrahydrofurancarboxylic acid (15g/L) 2-tetrahydrofurancarboxylic acid (15g/L) 2-tetrahydrofurancarboxylic acid (15g/L) methoxyacetic acid (15g/L) methoxyacetic acid (15g/L) methoxyacetic acid (15g/L) methoxyacetic acid (15g/L Methoxyacetic acid (15g/L) methoxyacetic acid (15g/L) methoxyacetic acid (15g/L) Φ zeta potential (mV) Csl iio τ—< o CSJ oo 〇\ VO cation compound (Content) TEA (lg/L) TEA (lg/L) TEA (lg/L) One TEA (lg/L) One TEA (lg/L) ^ TEA (lg/L) I TEA (lg/L) PEI (〇.〇3g/L) PEI (〇.〇3g/ L) PEI (〇.〇3g/L) PEI (0_03g/L) PEI (〇.〇3g/L) PEI (〇.〇3g/L) PEI (〇.〇3g/L) Colloidal cerium oxide ( Content) PL3 (5 mass%) PL3 (5 mass%) PL3 (5 mass%) PL3 (5 mass%) PL3 (5 mass%) PL3 (5 mass%) PL3 (5 mass%) i PL3 (5 mass%) PL3 (5 mass%) PL3 (5 mass%) PL3 (5 mass%) PL3 (5 mass%) PL3 (5 mass%/〇) PL3 (5 mass%) Example 13 Example 14 Example 15 Example 16 Example 17 Example 18 j Comparative Example 3 Example 19 Example 20 Example 21 Example 22 Example 23 Example 24 Comparative Example 4 200838997

Corrosion (nm) CN1 OO CNI VO CM Csl csl BD Honing speed (nm/min) \〇8 〇OO VO Ο m TEOS honing speed (nm/min) 〇o Ο 〇ο Ta honing speed (nm/min 〇〇CO CO CO m CO CO cn (D) Component (content) ζΠ ^ PQ 2 DBS (0.03g/L) TBS (〇*〇3g/L) HBS (〇,〇3g/L) DNS (0.03g /L) TNS (〇.〇3g/L) (C) Component (content) BTA (lg/L) BTA (lg/L) BTA (lg/L) BTA (lg/L) BTA (lg/L) BTA (lg/L) BTA (lg/L) (B) Ingredients (content) Phenoxyacetic acid (15g/L) Phenoxyacetic acid (15g/L) Phenoxyacetic acid (15g/L) Phenoxyacetic acid ( 15g/L) phenoxyacetic acid (15g/L) phenoxyacetic acid hydrazine 5g/L) phenoxyacetic acid (15g/L) (A 戚 bifurcation potential (mV) OO r- mc 〇 cationic compound (content PPI (〇.〇3g/L) PPI (0.03g/L) PPI (〇.〇3g/L) PPI (〇.〇3g/L) 1 PPI (〇.〇3g/L) PPI (〇.〇 3g/L) PPI (〇.〇3g/L) Colloidal cerium oxide (content) PL3H (5 mass%) PL3H (5 mass%) PL3H (5 mass%) PL3H (5 mass%) PL3H (5 mass% PL3H (5 mass%) PL3H (5 mass%) Example 25 Example 26 Example 27 Example 28 Example 29 Example 30 Comparative Example 5 200838997 Corrosion (nm) CSI v〇CN1 CNl BD Honing speed (nm/min) 〇oo ο csi wn C<I ο TEOS honing speed (nm/min) 〇OQ CN o O CN Ta Honing speed (nm/min) 〇Ο VO o νη o CO CO CO VO CO cn CO cn cn (D) Component (content) LTM (0.03g/L) LTE (0.03g/L) CL · W) QS 壊1 LTM (0.03g/L) LTE (0.03g/L) CL· QS 壊(C) component (content) BTA (lg/L) BTA (lg/L) BTA (lg/L) BTA (U/L) BTA (lg/L) BTA (lg/L) BTA (lg/L) BTA (lg/L) (B) Ingredients (content) Monohydric glutamic acid (15g/L) Acid (15g / L) - condensed glycolic acid (15g / L) | a condensed glycolic acid (15g / L) 2,5-furandicarboxylic acid (15g / L) 2,5-furandicarboxylic acid (15g /L) 2,5-furandicarboxylic acid (15g / L) 2,5-furandicarboxylic acid (15g / L) (A) component zeta potential (mV) csi cn CSJ CSI CO inch CO csi cationic compound ( Content) TBA (1r/l) TBA (1r/l) ! TBA (lg/L) TBA _(WL)_ TMA (lg/L) TMA (lg/L) TMA (lg/L) TMA (lg/L ) Colloidal cerium oxide (content) | PL3 (5 mass%) PL3 (5 mass%) PL3 (5 mass%) PL3 (5 mass) ) PL3H (5 mass%) PL3H (5 mass%) PL3H (5 mass%) PL3H (5 mass%) of Example 31 Example 32 Example 33 Comparative Example 634 Example 35 Example 36 Comparative Example 7 200 838 997

Corrosion (nm) csl CN CN BD Honing speed (lim/min) CSI oo 〇ν〇CO TEOS Honing speed (nm/min) VO o JO OO VO oo Ta Honing speed (nm/min) CO o VO o To CO VO co yn cn cn cn to CO un cn cn (D) component (content) LTM (〇.〇3g/L) LTE (〇.〇3g/L) Ph QS 壊LTM (〇.〇3g/L) LTE (〇.〇3g/L) Ρμ bJD QS 壊(C) component (content) BTA (lg/L) BTA (lg/L) BTA (lg/L) BTA (lg/L) BTA (lg/L) BTA (lg/L) BTA (lg/L) BTA (lg/L) (B) Component (content) 2-tetrahydrofurancarboxylic acid (15g/L) 2-tetrahydrofurancarboxylic acid (15g/L) 2-tetrahydrofurancarboxylic acid (15g/L) 2-tetrahydrofurancarboxylic acid (15g/L) methoxyacetic acid (15g/L) methoxyacetic acid (15g/L) methoxyacetic acid (15g/L) methoxyacetic acid (15g/L (A) Component zeta potential (mV) cn to csi CNl 5 Cationic compound (content) TEA (ML)_ TEA (lg/L) TEA (lg/L) TEA _(ig^L)_ PEI (〇. 〇3g/L) PEI (0.03g/L) PEI (〇.〇3g/L) PEI (〇-〇3g/L) Colloidal cerium oxide (content) PL3 (5 mass%) PL3 (5 mass%) PL3 (5 mass%) | PL3 (5 mass%) PL3H (5 mass%) PL3H (5 mass%) PL3H (5 mass%) PL3H (5 mass%) Example 37 Example 38 i Example 39 Comparative Example 8 Example 40 Example 41 Example 42 Comparative Example 9 200838997

Corrosion (nm) CN Csl BD Honing speed (nm/min) o Ο TEOS honing speed (nm/min) 〇o υο VD ο Ta honing speed (nm/min) cn Ο CO v〇cn cn οό (D )Ingredients (content) _1 LTM (〇.〇3g/L) LIE (0.03g/L) DP (0.03g/L) * (C) Component (content) _1 BTA (lg/L) BTA (lg/L) BTA (lg/L) ι- ΒΤΑ (lg/L) (B) Ingredients (content) Phenoxyacetic acid i (15g/L) Phenoxyacetic acid (15g/L) Phenoxyacetic acid (15g/L) + Phenoxyacetic acid (15g/L) (A) Component zeta potential (mV) _1 cs CO CN CN CO CO Cationic compound (content) PPI (〇.〇3g/L) PPI (0.03g/L) TEA (0.03 g/L) 1 TEA ! (〇.〇3g/L) Colloidal cerium oxide (content) PL3 (5 mass%) PL3 (5 mass%) PL3 (5 mass%) PL3 i (5 mass%) Example 43 Example 44 Example 45 Comparative Example 10 200838997 Details of the compounds referred to in Tables 1 to 6 above are explained below. TBA: tetrabutylammonium nitrate [(2) cationic compound] TMA: tetramethylammonium nitrate [(2) cationic compound] TEA · tetraethylammonium nitrate [. (2) cationic compound] PEI : poly-extension Amine (weight average molecular weight 20 〇〇) [cationic compound] Ρ > 1: polyethylenimine (weight average molecular weight 3000) [(2) cationic twin compound] _ BTA : 1,2,3-benzotriene Azole [(C) component] BS··undecylbenzenesulfonic acid [(D) component] DBS: dodecylbenzenesulfonic acid [(D) component] TBS: tetradecylbenzenesulfonic acid [(D) component] HBS: hexadecylbenzenesulfonic acid [(D) component] DNS: dodecylnaphthalenesulfonic acid [(D) component] TNS: tetradecylnaphthalenesulfonic acid [(D) component] LTM: lauryl nitrate trimethylammonium [ (D) component: LTE: lauryl nitrate triethylammonium [(D) component] DP: dodecyl nitrate cation cation [(D) component] Further, it is described in the colloidal ceria PL3 of Tables 1 to 6, and The PL3H system is also manufactured by Fuso Chemical Industry Co., Ltd., and its primary particle size and shape are as follows. PL3: 35 nm (--thin particle size), cocoon-shaped (shape) PL3H: 35 nm (--thickness), aggregate (shape) According to Tables 1-3, Example 1 is used. In the case of the honing liquid of 30 to -37-200838997, it was found that the T a honing speed was high, and compared with the comparative examples 1 to 5, the aging speed of the low dielectric constant insulating film (BD) was high. Therefore, the honing liquids of the first to third embodiments are very fast in the honing speed of the insulating film having a low dielectric constant, so that it is known that the film composition of the wafer including the specific dielectric ratio is low in the desired amount. The dielectric film of the dielectric is very useful. Further, in the performance of the rot after honing, any of Examples 1 to 30 and Comparative Examples 1 to 5 were flawless. According to Tables 4 to 6, in the case of using the honing liquid of Examples 3 1 to 4 5 , it was found that the Ta honing speed was high, and compared with Comparative Examples 6 to 10, the dielectric film having a low dielectric constant (BD) ) The honing speed is low. Therefore, in the honing liquids of Examples 3 to 45, since the honing speed of the insulating film having a low dielectric constant is very slow, it is known that the film is composed of a film containing a specific dielectric constant, and the low dielectric is not honed. The case of an electric insulating film (for example, a case where the end of the honing is to be terminated on the surface of the insulating film having a low dielectric constant) is very useful. Further, the corrosion performance after honing was not problematic in any of Examples 3 to 4 5 and Comparative Examples 6 to 1 . As apparent from the above, according to the present invention, the honing speed is increased by adjusting the composition of the honing liquid, and the honing speed of the insulating film having a low dielectric constant can be arbitrarily controlled. [Simple description of the map]

_>fnT hot. [Main component symbol description] 4rrr. No 0 -38 -

Claims (1)

200838997 X. Patent application scope: 1 · A honing fluid, which is used for honing the barrier layer of a semiconductor integrated circuit, characterized by comprising a colloidal silica having a positive zeta potential on the surface, having a carboxyl group The compound, the uranium inhibitor, and the surfactant, and the pH is 2.5 to 5.0. 2. The honing liquid according to claim 1, wherein the surfactant is a compound represented by the following general formula (1), R-scv, as in general formula (1) [in general formula (1), R Represents a hydrocarbon group]. 3. The honing liquid according to claim 1, wherein the surfactant is a compound represented by the following general formula (2): R4 R3 - N - R1 General formula (2) R2 [In the general formula (2), R1 to R4 each independently represent a hydrocarbon group having 1 to 18 carbon atoms; however, R1 to R4 are not completely the same hydrocarbon group]. 4. The honing liquid according to the first aspect of the invention, wherein the colloidal cerium oxide whose surface exhibits a positive zeta potential is a compound represented by the following general formula (3), or has a general formula (4): Colloidal cerium oxide adsorbed on the surface of a cationic compound of polyimine structure-39- 200838997 R5 R5 fs|—R5 _ General formula (3 ) R5 - (4) [In the general formula (3), R5 represents a completely identical hydrocarbon group having 1 to 18 carbon atoms; and in the general formula (4), R6 and R7 each independently represent a hydrocarbon group, and n represents 1 or more. Any integer]. 5. The honing liquid according to item 1 of the patent application, wherein the compound having a carboxyl group is a compound represented by the following general formula (5): R8~-〇--R9-COOH General formula (5) [General formula (5) In the formula, R8 and R9 each independently represent a hydrocarbon group]. 6. The honing liquid according to claim 5, wherein the compound represented by the general formula (5) is selected from the group consisting of 2-furancarboxylic acid, 2,5-furandicarboxylic acid, 3-furancarboxylic acid, 2 At least one selected from the group consisting of tetrahydrofurancarboxylic acid, diglycolic acid, methoxyacetic acid, methoxyphenylacetic acid, and phenoxyacetic acid. 7. The honing fluid according to any one of claims 1 to 6, wherein the -40-200838997 corrosion inhibitor is selected from the group consisting of 1,2,3-benzotriazole, 5,6-di-benzene And triazole, 1-(1,2-dicarboxyethyl)benzotriazole, (ethyl)aminomethyl]benzotriazole, and at least one of 1-(hydroxymethyl group) Compound 1-[Ν,Ν-bisbenzotriazole -41 - 200838997 VII. Designation of representative representatives: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: iffi 〇 8. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: