TW200815571A - Polishing composition and polishing method - Google Patents

Abstract

The present invention provides a polishing composition used, in a method for manufacturing a semiconductor device, to chemically mechanically polish the insulation film of a body to be polished that includes embedded wiring, via a barrier metal layer, on an insulation film having an organic siloxane structure and a relative dielectric constant of 3.0 or less, the polishing composition comprising colloidal silica particles, a benzotriazole compound and a primary amino alcohol represented by the following formula (I): NH2-R1-OH and having a pH within the range of 7 to 10; and a polishing method using the polishing composition. In formula (I), R1 represents an aliphatic hydrocarbon group or an aromatic hydrocarbon group.

Description

[Technical Field] The present invention relates to a honing method and a honing composition for chemical mechanical planarization of a semiconductor device during honing processing. [Prior Art] In the development of a semiconductor device including a semiconductor integrated circuit (hereinafter referred to as LSI), in order to reduce the size and speed of the semiconductor device, it has been required to increase the density and thickness of the wiring in recent years. Integrated. In the LSI interlayer insulating film, in order to increase the speed of the LSI, a material having a low capacitance ratio with a small wiring capacity is required. In the past, the SiO 2 was used as the interlayer insulating film material of the semiconductor device, and the permittivity was about 3.8 to 4.2. However, as the line width becomes narrow, the permittivity of the interlayer insulating film material must also become low. For example, a component having a line width of 13 〇 nm must be a material having a permittivity of about 2 · 5 to 3.0. As a material of a low permittivity insulating film (hereinafter referred to as a Low_k film) for forming an interlayer insulating film, a SiOC-based material (for example, SiOC containing a plurality of Si-C or Si-H bonds), an organic compound such as MSQ, and the like are known. Inorganic composite materials. Specifically, as a material for forming an insulating film having a permittivity, there are an OSiO-based HSG-R7 (Hitachi Chemical Industry Co., Ltd.), a BLACKDIA M〇ND (Applied Materials, lnc), etc., and these Low-k films are fine for LSI. Flattening is a necessary requirement. In the method of flattening a Low-k film, a flattening method using a cMP technique, that is, a method of honing using cerium oxide particles as honing particles, is disclosed in Japanese Laid-Open Patent Publication No. Hei. No. Hei. Here, CMP is an abbreviation for Chemical Mechanical Polishing, which is usually applied to a circular honing plate (platen platen) and immersed in the surface of the honing pad with a honing composition. The surface of the pad and the substrate (wafer wafer) is post-applied to apply a predetermined pressure (honing pressure) from the inside of the substrate to rotate both the honing plate and the substrate, and the surface of the honed surface is flattened by mechanical friction. Chemical. However, the honing method using the cerium oxide particles as the honing granules is slow, and the insulating film between the metal wirings is necessary to be honed, and it is easy to cause the disk-shaped concave portions to be formed on the surface of the plurality of wiring metal surfaces (corrosion) Erosion 〇 With the progress of LSI miniaturization and stratification, in order to increase the speed of LSI, it is necessary to reduce the capacitance of the interlayer insulating film to reduce the capacity between wirings. However, in the past, the flattening of the Low-k film took a long time and corrosion occurred. The present invention has been made in view of the above problems of the prior art, and has achieved the following objects. In other words, the present invention provides a low-density insulating film (Low-K film) which is formed by using a material having a permittivity of 3.0 or less for honing, and has a high honing speed and a composition for honing which can suppress corrosion and use. The honing method of the honing composition is aimed at. SUMMARY OF THE INVENTION In view of the above circumstances, the inventors of the present invention conducted a drill collar and found that the above problem can be solved by a honing method using a composition for honing having a specific composition, and thus the present invention has been completed. That is, the present invention has been achieved by the following means. &lt;ι&gt; A composition for honing, which is a honing composition for chemical mechanical honing of an insulating film of a honed body, comprising colloidal cerium oxide particles, benzene, in a method of manufacturing a semiconductor device And a triazole compound and a first-order amino alcohol represented by the following formula (I), and having a pH of from 7 to 10, wherein the honing system is included in an insulating film permeation barrier having a permittivity of 3 or less having an organic decane structure Buried wiring of metal layer, NH2-R1-OH Formula (I) [In the formula (I), Ri represents an aliphatic hydrocarbon group or an aromatic hydrocarbon group]. <2> The honing composition according to the above <1>, wherein the concentration of the colloidal cerium oxide particles is 〜 5 to 15% by mass. &lt;3&gt; The honing composition according to the above &lt;1&gt; or &lt;2&gt;, wherein the benzotriazole compound is selected from the group consisting of 1,2,3-benzotriazole and 5,6-dimethyl -1,2,3-benzotriazole, 1-(1,2-dicarboxyethyl)benzotriazole, 1-[N,N-bis(hydroxyethyl)aminomethyl]benzotriene One or more compounds of azole and 1-(hydroxymethyl)benzotriazole. &lt;4&gt; A honing method characterized in that a honing composition is supplied to a honing pad on a honing plate, and the honing pad is brought into contact with an insulating film of the honing body to make the enamel A grinding method in which the grinding disc rotates to make a relative movement to the contact surface, and the insulating film is the insulating film of the above-mentioned honed body, and the honing composition is as in the first item of the patent application scope. The composition of 200815571 is used to form an insulating film having a permittivity of 3.0 or less in an organic siloxane structure and is buried in a barrier metal layer. &lt;5&gt; The honing method according to the above <4>, wherein the load when the honing pad is brought into contact with the insulating film of the honed body is 〇·69 to 21.6 KPa. &lt;6&gt; The honing method according to the above <4>, wherein when the honing composition is supplied to the honing pad on the honing plate, the supply flow rate is 0.03 5 to 0.6 Oml/min • cm 2 ° [Effects] According to the present invention, it is possible to provide a honing composition which has a high honing rate and can suppress corrosion when an insulating film (Low-K film) having a low permittivity formed by a material having a permittivity of 3.0 or less is used for honing; And a honing method using the honing composition. [Embodiment] [Best Mode for Carrying Out the Invention] The composition for honing of the present invention is a low-k having a permittivity of 3.0 or less in an organic germanium oxide structure, which is used for transmission of a semiconductor device in a semiconductor device. When the film is formed into a buried wiring, the composition for honing for chemical mechanical honing is characterized by containing colloidal cerium oxide particles, a benzotriazole compound, and a first-order amino alcohol represented by the following formula (I), pH It is a range of 7 to 10. NH2-Ri-〇H Formula (I) [In the formula (I), R! represents a hydrocarbon group or an aromatic ring. Hereinafter, the constituent elements of the honing composition of the present invention will be described in order. [Low permittivity insulating film] The insulating film of the present invention has a low permittivity insulating film (hereinafter referred to as "Low_K film of the present invention" having a permittivity of an organic siloxane structure of 200815571 3 or less. As a material for forming the above-described low-permittivity insulating film, a material capable of forming an insulating film having a permittivity of 3.0 or less in the organic siloxane structure can be used, and is not particularly limited.

Specifically, it is preferably an organic-inorganic composite material such as SiOC having an organic siloxane structure of the formula (II) (for example, SiOC containing a plurality of Si-c or Si-H bonds) or MSQ.

In the above formula (II), R2 represents a hydrogen atom, a hydrocarbon group or OR4, and R3 represents a hydrocarbon group or hydrazine R5. R4 and R5 each independently represent a hydrocarbon group. In the above formula (II), examples of the hydrocarbon group represented by R2 to R5 include an aliphatic hydrocarbon group or an aromatic hydrocarbon group.

Specific examples of the material for forming the above-mentioned low-permittivity insulating film include HSG-R7 (Hitachi Chemical Co., Ltd.: 2.8), BLACKDIAMOND (Applied Materials, Inc: 2.4-3.0), and p-MTES. Development: 3.2), Coral (Novellus Systems 5 Inc: 2.4-2.7), Aurora (Japan AMS: 2.7), and MSQ series, OCDT-9 (Tokyo Chemical Industry: 2.7), LKD-T200 (JSR: 2) ·5-2·7), HOSP (Honey well Electronic Materials: 2.5), HSG-RZ25 (Hitachi Chemical Industry: 2.5), OCLT-31 (Tokyo Chemical Industry Co., Ltd.: 2.3), LKD-T400 (JSR system: 2.0) -2.2), HSG-6211X (Industrial Chemical Co., Ltd.: 200815571 2.1), ALCAP-S (Asahi Kasei Industrial Co., Ltd.: 1.8-2.3), OCLT-77 (Tokyo Chemical Industry Co., Ltd.: 1.9-2.2), HSG-6211X ( Hitachi Chemical Industrial Co., Ltd.: 2_4), 811 &amp;&amp;&amp; 61: (^61 (manufactured by Shinkan Steel Co., Ltd.: 1.1-1.4), etc., is not limited to these. The material for forming the above low-permittivity insulating film may be separately used. One type may be used, and a plurality of types may be used. Further, the materials may be in the form of fine pores. The method for forming the insulating film in the present invention may be plasma CVD or Therefore, in the present invention, the permittivity of the low permittivity insulating film must be 3.0 or less, and the lower is preferably, particularly preferably 1.8 to 2.8. When the above permittivity is in the range of 1 · 8 to 2 · 8 The effect of the present invention is preferably in terms of significant corrosion inhibition and honing speed improvement. In the present invention, the permittivity of the solid film can be measured by a mercury probe, and the permittivity of the insulating film provided with the wiring can be borrowed. It is measured by a precision 42 84 A LCR meter. The measurement of the permittivity in the present invention is carried out by using these methods. Conventionally, the conventional electric conductor material is a material having a permittivity of about 3.8 to 4.2. As the line width becomes narrow, The permittivity of the interlayer insulating film material must also be low. For example, a component with a line width of 130 nm must be a material having a permittivity of about 2.5 to 3.0. For a material with a low permittivity, the capacitance is usually about 2.0 to 2.5. The component having a line width of 90 nm has a dielectric constant of less than 2.4. From this viewpoint, the composition for honing of the present invention is preferably an element using a wiring strip which is finer than 130 nm. [Material for honing] -10- 200815571 Composition of honing of the present invention The product is characterized by containing (a) colloidal dioxide@particles, (b) a benzotriazole compound, and (c) a tertiary amino alcohol represented by the above formula (I). Colloidal cerium oxide particles The honing composition used in the present invention contains colloidal oxidized chopped particles as a constituent component. Contains colloidal cerium oxide particles as honing particles. The method for producing the colloidal ceria particles may be, for example, a bismuth alkoxide compound such as Si(OC2H5)4, Si(sec-OC4H9)4, Si(OCH3)4, or Si(OC4H9)4. It is obtained by solification, gelation and hydrolysis. The particle size distribution of such colloidal cerium oxide particles is very steep. The average particle diameter of the colloidal cerium oxide particles in the present invention means a particle size cumulative curve (degree distribution curve) indicating a relationship between the particle diameter of the colloidal cerium oxide particles and the cumulative number of the particles having the particle diameter. In the case, the cumulative degree is 50% of the particle size. The average particle diameter of the above colloidal ceria particles indicates the average particle diameter determined by the particle size distribution obtained by the dynamic light scattering method. For the measurement apparatus for obtaining the above-described particle size distribution, for example, LB-500 manufactured by Horiba, Ltd. can be used. The colloidal ceria particles contained have an average particle diameter of preferably 5 to 60 nm, more preferably 5 to 30 nm. From the viewpoint of achieving a sufficient honing work speed, particles having an average particle diameter of 5 nm or more are preferred. Further, in order to prevent excessive frictional heat from occurring during the honing process, the average particle diameter is preferably 6 Onm or less. The concentration of the colloidal cerium oxide particles of the honing particles in the total mass of the honing composition is preferably from 0.5 to 15% by mass, more preferably from 1 to 1% by mass. When the honing processing speed is achieved by -11-200815571, the concentration is preferably 0.5% by mass or more. Further, in the case where no excessive friction heat is generated during the honing process, the concentration is preferably 10% by mass or less. Further, the composition for honing of the present invention may be used as it is, or may be used in a diluted form, but in the case where the honing composition is diluted and used, the concentration of the honing particles in the boring composition diluent is used. The preferred range is the same as the preferred range of honing particle concentration in the composition. [Benzotriazole compound] The composition for honing of the present invention contains a benzotriazole compound. In the present invention, as the benzotriazole compound, it is preferably selected from the group consisting of 1,2,3-benzotriazole (BTA) and 5,6-dimethyl-1,2,3-benzotriazole ( DBTA), 1-(1,2-dicarboxyethyl)benzotriazole (DCEBTA), 1-[N,N-bis(hydroxyethyl)aminomethyl]benzotriazole (HE ABTA) and One or more compounds of 1-(hydroxymethyl)benzotriazole (HMBTA). Among the above, a more preferable benzotriazine compound is exemplified by 5,6-dimethylcarbonyl-1,2,3-benzotriazole (DBTA), 1-(1,2-dicarboxyethyl)benzene. And triazole (DCEBTA), 1-[N,N-bis(hydroxyethyl)aminomethyl]benzotriazole (HEABTA), 1-(hydroxymethyl)benzotriazole (hmbTA). The benzotriazole compound used in the present invention may be used singly or in combination of two or more. The concentration of the benzotriazole compound in the honing composition is not particularly limited, but is preferably 0.01% by mass. The above-mentioned, 〇·2 temporary amount % or less, more preferably 0.05% by mass or more and 0.2% by mass or less. [First-Oriented Amino Alcohol] -12- 200815571 The composition for honing of the present invention contains a compound represented by the formula (I). NH2-Ri-〇H Formula (I) [In the formula (I), Ri represents an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The aliphatic hydrocarbon group represented by Ri in the above formula (1) may, for example, be an aliphatic chain or a cyclic hydrocarbon group having 1 to 15 carbon atoms, and preferably an aliphatic chain having 2 to 10 carbon atoms. Or a cyclic hydrocarbon group. The aliphatic chain hydrocarbon group may, for example, be an alkylene group having 1 to 15 carbon atoms (preferably 1 to 12, more preferably 2 to 8), and these may be an alkyl group, a hydroxyl group, an amine group, a carboxyl group or the like. Replace it. Examples of the aliphatic cyclic hydrocarbon group include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclodecane, cyclodecane, dicyclohexyl, indole cyclohexyl, Norbornane. The divalent aromatic hydrocarbon group represented by the above formula (I) may be a divalent hydrocarbon group other than the two hydrogen atoms constituting any carbon atom of the aromatic hydrocarbon. Examples of the aromatic hydrocarbons include benzene, naphthalene and anthracene. These divalent aromatic hydrocarbon groups may be substituted with an alkyl group, a hydroxyl group, an amine group, a carboxyl group or the like. Preferred specific examples of the above primary amino alcohol are shown in Table 1 below. However, the present invention is not limited by the above. -13 - 200815571 [Table π

Ri A-1 CH2CH2 A-2 ch2ch2ch2 A-3 GH2CH2CH2GH2 A-4 CH2CH2CH2CH2CH2 A-5 ,,: .'-V..V . : * :· Ph (phenylene: 〇-) A-6 Ph Phenyl: in-) A -7 Ph (phenylene: p-) A-8 HNCH2CH2 &quot; A- 9 eH2GH2HNCH2CH2 A-10] A-11 ch(ch2ch2oh)ch2ch2 A-12 G(GH2CH20H)2CH2CH2 A- 1 3 gh(ch2gh2ch2oh)gh2gh2gh2 A-14 C(CH2CH2CH20H)2CH2CH2CH2

The one-stage amino alcohol used in the present invention may be a commercially available product or may be synthesized. The one-stage amino alcohol which can be used in the present invention may be used singly or in combination of two or more. Further, the concentration of the primary amino alcohol in the honing composition is not particularly limited, but is preferably from 0. 01 to 10% by mass, more preferably from 0 to 01% to 10% by mass. ·1 to 5 mass%. [pH] The composition for honing of the present invention must be in the range of pH 7.0 to 1 Torr. The honing composition of the present invention exhibits an excellent effect of improving the honing speed and corrosion inhibition by setting the pH within this range. Further, the pH of the honing composition of the present invention is preferably from 8 to 0 to 10, particularly preferably from 8.5 to 10, from the viewpoint of increasing the honing speed and the corrosion inhibition. In the present invention, in order to satirize the above pH to a range of 7.0 to 10, a base, an acid or a buffer may be used. The base, the acid or the buffering agent is preferably a non-metal such as an organic ammonium hydroxide such as ammonia, ammonium hydroxide or tetramethylammonium hydroxide, or an alkanolamine such as diethanolamine, triethanolamine or triisopropanolamine. Alkaline agent; 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; phosphates such as trisodium phosphate; borate, tetraboric acid And hydroxybenzoic acid. Examples of the particularly preferable alkaline agent include ammonium hydroxide, potassium hydroxide, lithium hydroxide, and tetramethylammonium hydroxide. The amount of the base, the acid or the buffer to be added is preferably such that the pH of the honing composition is maintained in the range of 7.0 to 10, and in the case of honing, 1 L of the honing composition is preferably 0.0. 0 0 1 m ο 1 to 1. 0 m ο 1, more preferably 0.0 03 mol to 0.5 mol 〇g [oxidizing agent] The honing composition of the present invention preferably contains a compound which can oxidize the metal for honing (oxidizing agent) ). Examples of the oxidizing agent include hydrogen peroxide, peroxide, nitrate, iodate, periodate, hypochlorite, chlorite, chlorate, perchlorate, persulfate, and chromite. The acid salt, permanganate, aqueous ozone solution, silver (II) salt and iron (III) salt, of which hydrogen peroxide is preferably used. Iron (ΠΙ) salt, preferably using inorganic iron (III) salts such as iron (III) nitrate, iron (III) chloride, iron (III) sulfate, iron (III) bromide, and iron (III) There is a 200815571 machine complex. The amount of the oxidizing agent to be added is preferably from 0.1 mol% to 1 mol, particularly preferably from 0.05 mol to 0.6 mol, per 1 L of the honing composition. [Organic Acid] In the present invention, the composition for honing is more preferably an organic acid. The organic acid referred to herein is a compound different from the oxidizing agent structure for oxidizing a metal, and may not be an acid containing the function as the oxidizing agent. The acid system here has a function of promoting oxidation, pH adjustment, and acting as a buffer. The organic acid in the present invention can be appropriately selected from the following groups. Namely, 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, positive 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, adipic acid, Pimelic acid, maleic acid, terephthalic acid, malic acid, tartaric acid, citric acid, lactic acid, glycine acid, imine diacetic acid and the ammonium or alkali gold thereof; salts such as salts; sulfuric acid, nitric acid, Ammonia, ammonium salts, or mixtures of these, and the like. Among these, for a laminated film containing at least one metal layer selected from the group consisting of copper, a copper alloy, and an oxide of copper or a copper alloy, formic acid, malonic acid, malic acid, tartaric acid, citric acid, and glycine Amine acid and imine diacetic acid are suitable. The organic acid in the present invention is preferably an amino acid. The amino acid, preferably water-soluble, is more preferably selected from the group consisting of the following. That is, for example, it is desirable to contain at least one of the following: glycine, L-propylamine-16-200815571 acid, β-alanine, L-2-aminobutyric acid, L•valeric acid, L•proline, L_proline, L-hexylamine, L-isoleucine, L-isolylamine, phenylpropene Fe: Is:, L-脯fe: acid, muscle|fed acid, l-uranium Acid, L _ trimethylglycine, taurine, L-serine, L-threonine, L. bethreonine, L-homouric acid, L-tyrosine, 3,5 _Diiodo-L-tyrosine, Bu (3, dihydroxyphenyl)_l_ alanine, L-thyroxine, 4-hydroxyproline, L-cysteine, L-methionine, L - ethionine, L-lanine thiamine, L-cystathionine, cysteine, L-cysteine, L-aspartic acid, L-glutamate, s_ (carboxyl -L-cysteine, 4-aminobutyric acid, L_aspartate, cysteine glycine, diazoacetate, L · arginine, L · concanavalin Acid, L-citrulline, δ-trans-L-trimethylglycine, creatine, kynuric acid, histidine, 1-methyl-L-histidine, 3-methyl -L · histidine, ergothione, L _ tryptophan, discharge Su C 1, celery amine (&amp;? 111 Shu 116), rather a protein hypertension, hypertensive and anti-protein rather II enzymes papain amino acids and the like. Among these, from the viewpoint of maintaining the practical C MP speed and suppressing the effect of the etching rate, malic acid, tartaric acid, citric acid, glycine, and glycolic acid are particularly preferable. The amount of the organic acid to be added is preferably from 0.001 mol to 0.5 mol, more preferably from 0.005 mol to 0.3 mol, particularly preferably from 0.01 mol to 0.1 mol, per 1 L of the honing composition at the time of honing. In other words, the amount of the organic acid to be added is preferably 〇5 mol or less from the viewpoint of suppressing etching, and is preferably 5 mol or more in order to obtain sufficient effects. [Clamping agent] The composition for honing of the present invention preferably contains a chelating agent as needed in order to reduce the adverse effects of the mixed polyvalent metal from 200815571. The chelating agent may be a commonly used hard water softening agent and a related compound as a precipitating agent for calcium and magnesium, and examples thereof include nitrile triacetic acid, diethylenetriamine pentaacetic acid, ethylenediaminetetraacetic acid, n, n, n-. Trimethylene phosphate, ethylenediamine-N,N,N',N'-tetramethylenesulfate, anticyclohexanediaminetetraacetic acid, 1,2,diaminopropanetetraacetic acid, glycol ether diamine Tetraacetic acid, ethylenediamine o-hydroxyphenylacetic acid, ethylenediamine disuccinic acid (SS-isomer), N-(2-carboxylic acid ethyl)^-L-aspartic acid, β-alanine II Acetic acid, 2-phosphobutane-1,2,4-tricarboxylic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, N,N'-bis(2-hydroxybenzyl)ethylenediamine- N,N'-diacetic acid, and 1,2-dihydroxybenzene-4,6.disulfonic acid. [Haw grinding method] The honing method of the present invention is to supply the honing composition to the honing pad on the honing plate, and to make the honing pad contact the insulating film of the honing body while making the honing pad The honing plate rotates to make a relative movement of the contact surface of the honing plate and the contact surface of the insulating film to perform a honing method, wherein the ρ insulating film is a barrier metal layer and has an organic argon gas. The insulating film having a permittivity of 3 to 0 or less of the alkane structure forms the insulating film of the above-mentioned honed body in which the wiring is buried, and the honing composition is the honing composition of the present invention. According to the above configuration, it is possible to provide a honing method in which a low-permittivity insulating film (Low-K film) formed of a material having a permittivity of 3.0 or less has a high honing speed and can suppress corrosion. In the honing method of the present invention, the low-permittivity insulating film (Low-K film) formed of the material having a permittivity of 3.0 or less is the same as the insulating film described in the honing composition item of the present invention. The preferred example is also the same as -18-200815571. Further, the honing composition used in the honing method of the present invention is the same as the above-described honing composition of the present invention, and preferred examples are also the same. The composition for honing of the present invention is: 1. A concentrated liquid which is diluted with water or an aqueous solution to form a use liquid at the time of use; 2. Each component is separately prepared into an aqueous solution as described below, and mixed. And depending on the case, it is diluted with water to form a use liquid; 3. The case of using a liquid. The honing composition of the present invention can be suitably used in the honing agent composition of the present invention. The honing method is to supply the honing composition to the honing pad on the honing plate, so that the honing pad is in contact with the honed surface of the honed body, so that the honed surface is opposite to the honing pad. The method of exercise. For the honing device, a holder having a honed body (for example, a wafer forming a film of a conductive material, etc.) having a honed surface, and a honing plate attached to the honing pad may be used. (Also, it has a motor φ that can change the number of revolutions, etc.). Specific examples of the above honing device include Mirra Mesa CMP, Reflexion CMP, FREX 200, FREX 300 (荏原制所), NPS3 3 0 1 , NP S 2 3 0 1 (Nikon ), A-FP-310A, A-FP-210A (Tokyo Precision), 23 00 TERES (ram research), Momentum (SpeedfamlPEC), and the like. As the honing pad, a non-woven fabric, a foamed polyurethane, a porous fluororesin or the like can be usually used without particular limitation. Details will be described later. Further, the honing condition is not particularly limited, but the rotational speed of the honing plate -19-200815571 is preferably a low rotation of 200 rpm or less in a form in which the honing body does not fly out. The pressure of the honed body having the honed surface (the honed film) attached to the honing pad is preferably 0.68 to 34.5 KPa, more preferably 0.69 to 21.6 KPa; and the honing body is required to satisfy the honing speed. In-plane uniformity and pattern flatness, particularly preferably 3.40 to 20.7 KP a. In the case of the honing pad, the honing pad is continuously supplied by a pump or the like. After the honing system after the honing is well washed in the running water, the water droplets adhering to the honed body are smashed and dried using a rotary dryer or the like. In the present invention, as described in the above 1., the aqueous solution shown below can be used when the concentrate is diluted. In the aqueous solution, at least one or more kinds of water selected from the group consisting of an oxidizing agent, a primary amino alcohol, an additive, and a surfactant are prepared in advance, and the liquid system in which the concentrated solution is diluted with the aqueous solution satisfies the composition for honing (use liquid) An aqueous solution and a concentrate of the conditions described in the above. g Thus, in the case where the concentrate is diluted with an aqueous solution, since the less soluble component can be added as an aqueous solution later, a more concentrated concentrate can be prepared. Further, a method in which water or an aqueous solution is added to a concentrate to be diluted is a method in which a pipe for supplying a concentrate composed of a concentrated honing composition and a pipe for supplying water or an aqueous solution are mixed and mixed on the way, and mixed. The use liquid for diluting the honing composition is supplied to the honing pad. The mixture of the concentrated liquid and the water or the aqueous solution may be a method in which the liquids are mixed with each other through a narrow passage in a state of applying pressure; the glass tube is filled with a 塡-20-200815571, and the liquid flow is repeatedly subjected to split separation. A method of joining, a method of providing a power-rotating vane in a pipe, and the like. The supply speed of the honing composition is preferably 10 to l 〇〇〇 ml/min, and in order to satisfy the honing speed of the honing surface uniformity and the pattern flatness, it is more preferably 170 to 800 ml/mino. The supply flow rate of the grinding composition is such that the flow rate of the honing composition of the honing pad per minute is specified in relation to the flow area (wafer area) of the honing surface of the honed body by the honing process. The supply flow rate of the honing composition is preferably 〇·〇3 5 to 0.60 m 1 /min·cm 2 . Thereby, the honing surface uniformity and pattern flatness of the honing speed can be satisfied. Further, by diluting the concentrate with water or an aqueous solution or the like, the honing method is a pipe in which a pipe for supplying a concentrate and a pipe for supplying water or an aqueous solution are separately provided, and a predetermined amount of liquid is supplied therefrom to the honing pad, and one side The method of mixing and honing with the relative movement of the honing pad and the surface to be honed. Further, a method in which the mixed honing composition is supplied to the honing pad by immersing a predetermined amount of the concentrated liquid in a container with water or a water p solution may be used. Further, in other honing methods, there is a structuring component which contains at least two components which should be contained in the honing composition, and the diluted solution which is diluted with water or an aqueous solution at the time of use is supplied to the honing pad on the honing plate. A method of making a contact with the surface to be honed to make the honed surface and the honing pad move relative to each other. For example, an oxidizing agent is used as a constituent component (A): a -amino alcohol, an additive, a surfactant, and water as a constituent (B), which can be used as a component (A) in water or an aqueous solution at the time of use. Component (B) is diluted to use -21 - 200815571. Further, two kinds of components (A) and (B) of the additive having low solubility are respectively used (for example, an oxidizing agent, an additive, and a surfactant as a constituent component (A), and a primary amino alcohol, an additive, a surfactant, and When water is used as the component (B)), the component (A) and the component (B) are diluted and used by adding water or an aqueous solution. In these cases, the colloidal cerium oxide particles (honing particles) in the present invention are preferably contained in the constituent component (A). In the case of the above example, it is necessary to supply the three components of the component (A) and the component (B) ^ to the water or the aqueous solution. The dilution and mixing system combines the three pipes into one for the honing. A method in which the mat is piped and mixed in the pipe. In this case, two pipes may be combined and then combined with another pipe. Specifically, a method in which a constituent component containing a less soluble additive is mixed with other constituent components, a mixing passage is lengthened to secure a dissolution time, and then a pipe of water or an aqueous solution is combined is used. In other mixing methods, the three pipes as described above are directly guided to the 硏_brading pad, mixed by the relative movement of the honing pad and the surface to be honed, or three components are mixed in one container. A method of supplying a honing composition from the diluted honing pad to the honing pad. In the honing method, one of the constituent components containing the oxidizing agent is kept at 4 (TC or less, and the other constituent components are heated from room temperature in a range of 1 ° C, and when one type of constituent component and other constituent components are mixed, or added When water or an aqueous solution is diluted, the liquid temperature may be changed to 40 ° C or less. This method is a preferred method for improving the solubility of a raw material having a low solubility of the honing composition by utilizing a phenomenon that the solubility is high when the temperature is high. * -22- 200815571 The raw material which dissolves in the range of 100 °c from room temperature and dissolves the above-mentioned other constituent components is precipitated in the solution when the temperature is lowered. Therefore, when other components in a low temperature state are used, the supply is performed. Before the honing pad, it is necessary to heat the precipitated material to dissolve it. Therefore, it is possible to heat and transport the other components in which the raw material is dissolved. Since the temperature of the constituent component containing the oxidizing agent is heated to 40. When the temperature is above °c, the oxidizing agent may be decomposed. Therefore, when mixing other constituent components and one constituent component containing an oxidizing agent, the temperature of the mixed liquid is preferably 40 ° C or lower. As described above, in the present invention, the honing composition may be separated into two or more parts and supplied to the honed surface. In this case, the oxide-containing component and the primary amino group-containing component are preferably. Further, the honing composition may be used as a concentrate to supply the dilution water and the concentrate to the surface to be honed. In the present invention, the composition for honing is separated into two or more portions. In the case of the method of supplying the surface to be honed, the supply amount of the honing composition is expressed by the total amount of supply from each pipe. [Mat] A honing honing method suitable for the honing method of the present invention The mat may be a non-foamed structural mat or a foamed structural mat. The former may be used as a mat for a hard synthetic resin bulk material such as a plastic sheet. Further, the latter is further an independent foam (dry type) Three types of foaming system, continuous foam (wet foaming system), and two-layer composite (layered system), particularly preferably two-layer composite (layered system). Foaming may be uniform or uneven. Furthermore, it is generally possible to contain abrasive grains for honing (for example) Such as argon, 矽-2 3 - 200815571 oxygen, aluminum oxide, resin, etc.) Further, although the hardness may be either soft or hard, it is preferred to use different hardnesses in each layer of the laminate. The material is preferably a non-woven fabric, an artificial leather, a polyamide, a polyurethane, a polyester, a polycarbonate, etc. Further, regarding a surface in contact with the surface to be honed, a groove can be formed Processing of a pit, a concentric groove, or a thread groove. [Wafer] The wafer to be honed by the CMP for the honing composition of the present invention preferably has a diameter of 200 mm or more, and particularly preferably 300 mm. When the above is more than 300 mm, the effects of the present invention can be remarkably exhibited. [Examples] The present invention will be described in more detail by way of the following examples, but the invention is not limited thereto. [Example 1] Preparation of composition for honing _ The following components were mixed to prepare a composition for honing. &lt;Composition&gt;

L〇g/L 14g/L 0.5g/L 30g/L 9.5 lOOOmL • Hydrogen peroxide (oxidizing agent) • A-1 : Aminoethanol (1 grade amino alcohol, and light pure bismuth industrial (stock) system) • 1H -benzotriazole (BTA: aromatic ring compound) • Colloidal ceria particles (PL-3, primary particle size 15 nm, degree of binding 4, secondary particle size 40 nm) • pH (adjusted with ammonia and sulfuric acid) • Pure Total amount of water added - 24 - 200815571 &lt;Examples 2 to 2 0 and Comparative Examples 1 to 2&gt; In the preparation of the composition for honing of Example 1, 'except for the primary amino alcohol and the benzotriazole compound, The composition for honing was prepared in the same manner as in Example 1 except that the amount of addition and the honing speed were changed as described in Table 2. The honing test and the evaluation were carried out using the apparatus "LGP-612" manufactured by Lapmaster Co., Ltd. as a honing device, and the honing composition (slurry) obtained as described above was supplied under the following conditions. Round the membrane and measure the difference in time. Specifically, while the honing composition is supplied to the honing pad of the honing plate of the honing device, the substrate (the honed body) is pressed against the honing pad to make the honing plate and the honing plate The substrate is relatively moved, and a copper film (conductor film), a Ta film (barrier metal film), a BDI (insulating film), or the like is honed. - Honing target _ honed body (substrate): The solid of the honing speed BD was calculated, and each of the 8 吋 wafers prepared by the following film corrosion evaluation was used. On the 8 吋矽 wafer, an insulating film is formed by sputtering in the order of tetraethoxy decane (TEOS), tantalum carbide (SIC), black diamond (BDI), and tantalum oxide film (SiOx). The photo-etching step and the reactive ion etching step form a pattern to form a wiring trench and a connection hole having a width of 0·09 to 1 ΟΟμπι and a depth of 45 nm. Further, a Ta film (Ta barrier layer) having a thickness of 25 nm was formed by a sputtering method. A copper film (Cu-Seed) having a thickness of 10 Onm was formed by sputtering, and a copper film having a total thickness of 10 nm was formed by a plating method of -25-200815571 to form an 8-inch wafer. - Honing conditions · Honing pad: Model IC-1400 (K-grv) + (A21) manufactured by Rohm and Haas Co., Ltd. • Platform rotation number: 64 rpm • Number of head rotation: 65 rpm (processing line speed = 1.0 m/s • Honing pressure · · l.Opsi (about 6.9KPa) • Slurry supply speed: 200ml / min - evaluation method - (1) Insulating film honing speed Honing speed is the film thickness of BDI insulating film before and after CMP The difference is calculated from the electric resistance 値 and is obtained by the following equation. The film thickness difference measurement was carried out using F20 manufactured by Filmetalix Co., Ltd. Honing speed (A / min) == (thickness of BDI before honing - thickness of BDI after honing) / honing time (2) Corrosion of pattern wafer after honing of Ta barrier film, with stylus type step Dektak V320Si (manufactured by Veeco Co., Ltd.) was used to measure the corrosion of the line and space portion (line 9 μm, space 1 μm) (step: A). -26- 200815571 [Table 2]

Grade 1 amino alcohol benzotriazole compound, other additives pH composition of the honing composition BDI honing rate (A / min) Corrosion (A) Example 1 A-K1.4) ΒΤΑ (0.5) 9.5 400 200 Example 2 Α_2(1·4) DBTA(0.5) 10 360 250 Example 3 Al(1.4) DBTA(0.5) 350 220 Dodecylbenzenesulfonic acid (0.03) 8.5 Example 4 Α-3(1.4) BTA( 0.5) 9.5 420 Dodecylbenzenesulfonic acid (0.03) 200 Example 5 Α-4(1·4) ΗΕΑΒΤΑ(0·5) 8.5 390 190 Example 6 Α-1(1·4) DCEBTA(0.5) 9 380 150 Example 7 HMBTA (0.5) 450 170 Α-1 (1.4) Dodecylbenzenesulfonic acid (0·03) 10 Example 8 Α-6 (1.5) DCEBTA (0.5) 9.5 440 190 Example 9 Α- 7(1.5) BTA(0.5) 9 360 190 Example 10 Α-3(1.4) HMBTA(0.5) 10 380 170 Example 11 Α-8(1·5) DCEBTA(0.5) 9.5 390 210 Example 12 Α· 9(1·5) DBTA(0.5) 9.5 410 190 Example 13; Α-10(1.8) BTA(0.5) 10 420 200 Example 14 Α-11(1_8) DCEBTA(0.5) 8.5 370 260 Example 15 Α -9(1.5) BTA(0.5) 9.5 420 200 Example 16 HEABTA(0.5) 9.5 380 240 Α-12(1·8) DBTA(0.5) 10 Example 17 Α-13(1·8) BTA(0.5) 9.5 360 200 implementation 18 Α-14(1·8) BTA(0.5) 8,5 420 200 Example 19 DBTA(0.5) 350 190 Α-14(1.8) Dodecylbenzenesulfonic acid (0.03) 10 ΒΤΑ(0·5) Example 20 Α-1 (1.4) HEABTA (0.5) 9.5 400 150 Dodecylbenzenesulfonic acid (0.03) Comparative Example 1 Glycine (1·4) BTA (0.5) 6.5 20 560 Comparative Example 2 Lactic acid (1.3) ΒΤΑ (0·5) 9 450 '600 -27- 200815571 &lt;About abbreviated &gt; 1,2,3-benzotriazole (BTA) 5,6-dimethyl-1,2,3-benzotriene哩(〇8丁八) 1-(1,2-dicarboxyethyl)benzotriazole (1:) (^3丁丁1-[N,N-bis(hydroxyethyl)aminomethyl; ]Benzatriazole (heabta) 1-(hydroxymethyl)benzotriazole (HMBTA) From Table 2, it can be seen that Examples 1 to 20 can achieve high 硏® grinding speed and high flattening under low pressure conditions. On the other hand, in Comparative Examples 1 and 2, it was observed that the honing speed was lowered and the rot was touched, and the processing of the flattening of the cylinder could not be achieved for each component.

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Claims (1)

200815571 X. Patent application scope: 1 · A composition for honing, which is used in a manufacturing method of a semiconductor device, for honing a chemical composition for honing an insulating film of a honed body, comprising a colloidal composition a cerium oxide particle, a benzotriazole compound, and a monohydric amino alcohol represented by the following formula (I), and having a pH in the range of 7 to 10, wherein the honing system is included in a permittivity 3 having an organic decane structure The following insulating film is passed through the buried wiring of the barrier metal layer, NH2-Ri-OH Formula (I) ® [In the formula (I), I represents an aliphatic hydrocarbon group or an aromatic hydrocarbon group]. 2. The composition for honing according to the first aspect of the invention, wherein the concentration of the colloidal cerium oxide particles is from 0.5 to 15% by mass. 3. The honing composition according to claim 1 or 2, wherein the benzotriazole compound is selected from the group consisting of 1,2,3-benzotriazole, 5,6-dimethyl-1,2 , 3-benzotriazole, 1-(1,2-dicarboxyethyl)benzotriazole, 1-[indene, fluorenyl-bis(hydroxyethyl)aminomethyl]benzotriazole and 1- One or more compounds of (hydroxymethyl)benzotriazole. I. A honing method characterized in that a honing composition is supplied to a honing pad on a honing plate, and the honing pad is brought into contact with an insulating film of the honing body to make the honing The honing method is a honing method in which the aligning is performed by the relative rotation of the contact surface, the insulating film is the insulating film of the honed body, and the honing composition is honed according to the first item of the patent application. In the composition, the honing body is formed of an insulating film having a permittivity of 3.0 or less in an organic siloxane structure and buried in a barrier metal layer. 5. The honing method of claim 4, wherein the load of the honing pad is 0.69 to 21.6 KPa when it is brought into contact with the insulating film of the honing body of -2 9 - 200815571%. 6. The honing method of claim 4, wherein when the honing composition is supplied to the honing pad on the honing plate, the supply flow rate is 〇. 3 5 to 0.6 0 ml/min · cm2 〇 -30 - 200815571 VII. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: Μ 〇 j \ \\ 8. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: