TW200817498A - Polishing composition and polishing method - Google Patents

Abstract

A polishing composition which is used, in a production method of a semiconductor device, for chemically and mechanically polishing an insulating layer of a body to be polished, the insulating layer having an organosiloxane structure, a dielectric constant of 3.0 or less, and a built-in wiring via a barrier metal layer, wherein the composition has a pH of 7-10 and comprises colloidal silica particles, benzotriazole compound and a secondary or tertiary aminoalcohol represented by the following formula (I): Formula (I) wherein R1, R2 and R3 each independently represents a hydrogen atom, an aliphatic hydrocarbon group or an aromatic hydrocarbon group; the aliphatic hydrocarbon group and the aromatic hydrocarbon group may be substituted with an amino group, a hydroxy group, a carboxy group or a hydrocarbon group; at least one of R1, R2 and R3 has a hydroxy group at a terminal thereof; and at least two of R1, R2 and R3 are substituents other than a hydrogen atom.

Description

[Technical Field] The present invention relates to a honing composition and a honing method for planarizing a chemical machine, for example, during honing of a semiconductor device. [Prior Art] In the development of a semiconductor device represented by a semiconductor integrated circuit (hereinafter referred to as LSI), in order to reduce the size and speed of wiring, in recent years, with the miniaturization and lamination of wiring, high density and high density are required. Integrated. In the interlayer insulating film used for L s I, in order to increase the speed of L SI , a material having a lower dielectric constant than that having a small inter-wiring capacity is required. As the interlayer insulating film material of the semiconductor device, Si〇2 is used, and its specific dielectric constant is about 3·8 to 4·2. However, as the line width is narrowed, the specific dielectric constant of the interlayer insulating film material must also be low. For example, for a device having a line width of 〇3 〇 nm, a material having a dielectric constant of about 2.5 to 3.0 must be used. As a material for forming an insulating moon (referred to as an L 〇w - k film) having a low specific dielectric constant as an interlayer insulating film, a material of the Si Ο C system (for example, a plurality of S i ) is known. - A material of an organic-inorganic hybrid system such as C or S i - Η bonded si Ο C ), MSQ, or the like. Specifically, as a material for forming an insulating film having a low specific dielectric constant, there are HSG-R7 (Hitachi Chemical Industry Co., Ltd.), BLACKDIAMOND (Applied Material Co., Ltd.), and the like in the SlOC system. These Low-k films are required to be flattened due to the miniaturization of the LSI. As a method of flattening a Low-k film, a flattening method which does not use a CMP technique, that is, a honing method using a cerium oxide particle as a grinding 200817498 pellet, is disclosed in the patent document. Here, CMP is an abbreviation for Chemical Mechanical Polishing. Generally, a honing pad is adhered to a circular enamel platen, and the surface of the honing pad is immersed by the honing composition. The surface of the (wafer) is pressed against the pad, and the honing plate and the substrate are both rotated while a predetermined pressure (honing pressure) is applied thereto, and the honed surface is rubbed by the mechanical friction generated. The surface is flattened. However, the honing method using cerium oxide particles as the abrasive grains is slow in honing, and since the concentration of the honing particles for the honing composition used for the flattening of the Low-k film is high, the honing particles are liable to occur. Condensed. In particular, when the honing composition in which the honing particles have been condensed for a long period of time is used to planarize the Low-k film, stress concentration is caused during honing, and honing damage (scratches) is likely to occur. Therefore, it is required to suppress aggregation of particles of the honing composition for a long period of time, and to suppress scratches when flattening the l〇wk film [Patent Document 1] Special opening 2〇0 0 - 2 8 62 5 SUMMARY OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION The present invention has been made in view of the above problems of the prior art, and has achieved the following object. In other words, the object of the present invention is to provide an insulating film (Low-k film having a specific dielectric constant of 3.0 or less) having a structure of an organic siloxane having a structure in which the honing particles contained in the honing composition can be suppressed for a long period of time. In the honing, the composition for honing which can suppress the occurrence of scratches, and the honing method using the same. Means for Solving the Problems 200817498 The inventors of the present invention conducted intensive studies in view of the above-described facts, and as a result, found that the above problems can be solved by using a honing method having a composition of honing having a specific composition, and the present invention has been completed. That is, the present invention is achieved by the following means. &lt; 1 &gt; An honing composition for use in a method of manufacturing a semiconductor device for chemically mechanically honing an insulating film of a honed body having an organic siloxane structure, 3·0 The following specific dielectric constant has a buried line through the barrier metal layer. The honing composition includes colloidal vermiculite particles, a benzotriazole compound, and two or three of the following formula (I). a primary amino alcohol, and a pH in the range of 7 to 10, n formula ω R2 / / [In the above formula (I), Ri, R2, and R3 each independently represent a hydrogen atom, an aliphatic hydrocarbon group, or an aromatic hydrocarbon group, The aliphatic hydrocarbon group and the aromatic hydrocarbon group may be further substituted with an amine group, a hydroxyl group, a carboxyl group, or a hydrocarbon group; however, at least one of R1, r2, and r3 has a hydroxyl group at the terminal; and, at least 2 of R1, r2, and r3 More than one substituent other than a hydrogen atom]. The honing composition according to the above-mentioned item, wherein the concentration of the colloidal vermiculite particles is 〇 5 to 15% by mass. The honing composition according to the above-mentioned, wherein the benzotriazole compound is from 1,2,3-benzotriazole, 5,6_2. Methyl-l,2,3-benzotriazole, iO,2-dicarboxyethyl)benzotriazole, 1-[N,N-bis(hydroxyethyl) 200817498 amine methyl]benzotriazole And at least one or more compounds selected from i-(hydroxymethyl)benzotriazole. &lt; 4 &gt; A honing method for supplying the honing composition to the honing pad on the honing plate while rotating the honing plate while contacting the honing pad with the insulating film of the honing body A honing method for honing a contact surface in a relative motion, characterized in that the insulating film is formed by an insulating film having a specific dielectric constant of 3.0 or less in an organic siloxane structure and buried in a barrier metal layer The honing composition according to any one of the above-mentioned items of the above-mentioned honing body, and the honing composition according to any one of <1> to <3>. The honing method according to <4>, wherein when the honing pad is brought into contact with the insulating film of the honed body, the load (honing pressure) is 6969 kPa (0.007 kgf/cm2). The honing method as described in <4> or <5>, wherein the honing composition is supplied to the crucible platen. In the case of a sanding pad, the supply flow rate is 0.035 to 0.60 ml/min-cm2. According to the present invention, it is possible to provide agglomeration of the honing particles contained in the honing composition for a long period of time, and to have an organic siloxane. In the honing of the insulating film (Low-k film) having a specific dielectric constant of 3.0 or less, the honing composition capable of suppressing the occurrence of scratches and the honing method using the same. [Embodiment] The best embodiment of the present invention is characterized in that the composition for honing is characterized in that it is produced in a semiconductor device, and has a specific dielectric constant of 1.00 or less in an organic siloxane structure.

A honing composition for chemical mechanical honing, which comprises colloidal vermiculite particles, a benzotriazole compound, and a formula (I) below, when a low-k film is formed into a buried line via a barrier metal layer The di- or tertiary amino alcohol is shown to have a pH in the range of 7 to 10.

Formula (I)

In the above formula (1), 'R1, R2, and R3 are each independently a hydrogen atom, an aliphatic smo- or an aromatic hydrocarbon group. The aliphatic hydrocarbon group and the aromatic hydrocarbon group may further be an amine group, a trans group, a carboxyl group, or a hydrocarbon group. Replaced. However, at least one of h has a last $ and has a radical. Further, at least two or more of them are substituents other than a hydrogen atom. In the following, the constituent elements of the honing composition of the present invention [low specific dielectric constant insulating film] will be described in order. The insulating film of the present invention has a low specific ratio of a specific dielectric constant of 3.0 or less in the organic siloxane structure. An insulating film of electrical constant (hereinafter referred to as "Low-k film" as appropriate). The material used for forming the insulating film having a low specific dielectric constant can be formed by a material capable of forming an insulating film having a specific dielectric constant of 3 Å or less having an organic siloxane structure, and is not particularly limited. It is preferably an organic material such as S i Ο C having an organic shale structure (for example, SiC containing a plurality of Si-C or Si-H bonds) or MSQ. -10- 200817498 The above-mentioned organic oxime structure is exemplified by the following formula (Π).

In the above formula (II), R4 represents a hydrogen atom, a hydrocarbon group or OR6, and R5 represents a hydrocarbon group or OR7. Each of R6 and R7 independently represents a hydrocarbon group. Further, the nicotinyl group represented by R4 to R7 in the above formula (II) may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. Specific examples of the material for the formation of the insulating film having a low specific dielectric constant include, for example, HSG-R7 (Hitachi Chemical Industry: 2.8) and BLACKDIAMOND (Applied Material Corporation: 2.4-3.0). p-MTES (Hitachi Development: 3.2), Coral (Novellus Systems: 2·4-2·7), Aurora (Japan AMS: 2.7), and, as the MSQ system, 〇CDT-9 (Tokyo Yinghua) Industry: 2 · 7), LKD-T200 (JSR: 2.5-2.7), HOSP (Honeywell Electronic Materials: 2.5), HSG-RZ25 (Hitachi Chemical Industry: 2.5), OCLT-31 (Tokyo Industrial Co., Ltd.: 2.3) , LKD-T400 (JSR system: 2.0-2.2), HSG-6211X (Hitachi Chemical Co., Ltd.: 2.1), ALCAP-S (Asahi Kasei Industrial Co., Ltd.: 1.8-2.3), 〇CLT-77 (Tokyo Industrial Co., Ltd.: 1.9 -2.2), HSG-6211X (manufactured by Hitachi Chemical Co., Ltd.: 2.4), silica aerogel (manufactured by Kobelco Steel Co., Ltd.: 1.1 -1. 4), etc., but not limited thereto. The material of the insulating film capable of forming the above-mentioned low specific dielectric constant can be used singly or in combination of several types. Furthermore, such materials may be in the form of tiny voids of -11-200817498. The method of forming the insulating film in the present invention may be plasma CVD or spin coating. The dielectric constant of the insulating film having a low specific dielectric constant in the present invention must be 3 or less, and the lower the better, the more preferably 1. 8 to 2.8. When the specific dielectric constant is in the range of 1.8 to 2 · 8 , it is preferable from the viewpoint of the present invention that the occurrence of scratches is remarkably suppressed by suppressing the aggregation of the honing particles for a long period of time. . The specific dielectric constant in the present invention can be measured by a measurement method using a mercury probe for a full film system, and the specific dielectric constant of an insulating film provided with a wiring can be obtained by P recisi ο η 4 2 8 4 ALCR. Calculated. The specific dielectric constant in the present invention is such a method. At present, the general dielectric material is a material having a dielectric constant of about 3. 8 to 4 · 2. As the line width is narrowed, the specific dielectric constant must also be lower. For example, a component having a line width of 1 3 Onm requires a material having a dielectric constant of about 2.5 to 3 Å. A material referred to as a low specific dielectric constant is usually a dielectric constant of about 2 〇 〜 2.5. The element having a line width of 9 〇 nm has a specific dielectric constant of less than 24 . In the element having a line width of 9 〇 nm, the specific dielectric constant is lower than 2.4. From these points of view, the honing composition of the present invention is effective when it is used for flattening the wiring width which is thinner than the element having a line width of 130 nm. [Mechanical composition for honing] The composition for honing of the present invention is characterized by containing (a) colloidal vermiculite particles, (b) a bismuth compound, and (c) two of the above formula (〗) Or a tertiary amino alcohol. (a) Colloidal vermiculite particles 200817498

The composition for honing used in the present invention contains as a constituent component. A method for preparing colloidal vermiculite particles as honing I as the above colloidal vermiculite particles, for example, a method for hydrolyzing Si(OC2H5)4, Si(sec-OC4H9)4, Si(OC4H9)4 alkoxylation Derived from bismuth compounds. Such a particle size distribution is very steep. The particle size of the colloidal vermiculite particles in the present invention means a particle size accumulation curve (degree distribution curve) which relates to the particle diameter of the vermiculite particles and the number of particles having the particle diameter, and the particle diameter of the curve of 50% . In the particle size distribution obtained by the particle size scattering method of the colloidal vermiculite particles, the apparatus for measuring the above-mentioned particle size distribution is obtained, for example, LB-500 or the like which can be used. The average particle diameter of the colloidal vermiculite particles contained is preferably 5 to 30 nm. A particle having a sufficient honing processing speed of preferably 5 n m or more is obtained. Further, for the purpose of friction heat in the honing process, the particle diameter is preferably 60 nm or less. The concentration of the colloidal vermiculite particles of the honing particles is preferably in the range of 5 to 15% by mass, and 10% by mass in the total mass of the crucible. In order to achieve sufficient honing processing, the g degree is preferably 0.5% by mass or more. Further, for the purpose of friction heat in the honing process, the concentration is preferably 10% by mass or less. Further, the composition for honing of the present invention can be used as it is. -1 3 - colloidal vermiculite particles used to dilute the honing composition. The cumulative number of cumulative degrees showing the colloidal state by sol-gel Si(OCH3)4 and colloidal vermiculite particles is shown by the dynamic light particle size. As for the purpose of the system of the production of 5~60 nm ' for the production of the 堀 制作 ' ' ' ' 不 ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' The concentration in the honing composition diluent of 200817498 is the same as that of the composition concentrate, and the preferred range is also the same. (b) benzotriazole compound The honing composition of the present invention contains a benzotriazole compound in the present invention, and as a exemplified triazole compound, benzotriazole (BTA), 5, 6-di is preferable. Methyl-l,2,3-benzotriazole 1-(1,2-dicarboxyethyl)benzotriazole (DCEBTA), 1_[N,N_)aminemethyl]benzotriazole (HEABTA) And one or more compounds selected from 1-(hydroxymethyl) (HMBTA). Among the above, as a better benzotriazole compound, ϊ dimethyl-1,2,3-benzotriazole (DBTA), 1-(1,2-dicarboxyethazole (DCEBTA), 1 -[N,N-bis(hydroxyethyl)aminemethyl](HEABTA), 1-(hydroxymethyl)benzotriazole (HMBTA). The benzotriazole compound used in the present invention can be used alone Further, the concentration of the benzotriazole compound is preferably 0.01% by mass or more and 0.2% by mass or less, more preferably &lt; or more and 0.2% by mass or less. (Secondary or tertiary amino group) Alcohol The honing composition of the present invention contains a white amino alcohol represented by the following formula (I): The formula (1) has the same range / 5 from 1,2,3-(DBTA), _bis(hydroxyethylbenzotriazole) 0* refers to 5,6-yl)benzotribenzotriazole, and can also be limited to 2, 〇.〇5 mass% second or third

-14- 200817498 In the above formula (I), R1, R2 and R3 each independently represent a hydrogen atom, an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and the aliphatic hydrocarbon group and the aromatic hydrocarbon group may further pass an amine group, a hydroxyl group or a carboxyl group. Or a hydrocarbon group is substituted; however, at least one of R1, R2 and r3 has a hydroxyl group; and at least two or more of R1, r2 and R3 are a substituent other than a hydrogen atom. The aliphatic hydrocarbon group represented by Ri, R2, and R3 in the above formula (I) may, for example, be an aliphatic nicotinyl group having 1 to 15 carbon atoms, and preferably a carbon number of 2 to 1 Torr, more preferably a carbon number. 2 to 6. The above aliphatic hydrocarbon group may be in the form of a chain, a ring or a branch or a branch. Further, the aliphatic hydrocarbon group may be a saturated hydrocarbon group or an unsaturated hydrocarbon group (excluding an aromatic hydrocarbon group). Specific examples of the aliphatic hydrocarbon group include a methyl group, an ethyl group, a n-propyl group, and a third butyl group. The aromatic hydrocarbon group represented by R!, R2 and R3 in the above formula (I) may, for example, be a phenyl group, a naphthyl group or an anthracenyl group. When R!, R2 and R3 in the above formula (I) represent an aliphatic hydrocarbon group or an aromatic hydrocarbon group, they may further have an amine group, a hydroxyl group, a carboxyl group or a hydrocarbon group as a substituent. As such a substituent, a hydroxyl group or an amine group is preferred. Specific examples of the aliphatic hydrocarbon group or the aromatic hydrocarbon group having a substituent as described above include -CH2CH2OH, -CH2CH2CH2OH, -C(CH2OH)3, -CH2CH2NH2, -C6H4OH and the like. Further, one or more of these carbon atoms may be further substituted with a hetero atom (preferably nitrogen or oxygen). Preferable specific examples of the di- or tertiary-order amino alcohol represented by the above formula (1) include the compounds A-1 to A-1 9 shown in the following Table 1. The compounds A - 1 to A - 1 9 in the following Tables 1 - 15 to 200817498 are represented by the descriptions of R p R2 and R3 in the above formula (1). However, the di- or tertiary amino alcohols are not limited by these. 【Table 1】

Ri r2 Rs A-1 Η CH2CH2OH CH2CH20H A-2 Η ch3 CH2CH2OH A-3 Η CH2CH3 ch2ch2oh A-4 Η CH2CH2CH3 CH2CH20H A-5 Η CH2CH2NH2 CH2CH20H A-6 Η (CH3)3C ch2ch2oh A-7 Η ch2ch2ch2oh ch2ch2ch2oh A- 8 Η ch3 ch2ch2ch2oh A-9 ch2ch2oh ch2ch2oh ch2ch2oh A-10 ch3 CH2CH20H ch2ch2oh A-11 CH2CH3 ch2ch2oh CH2CH20H A-12 CH2CH2CH3 CH2CH20H CH2CH20H A-13 (CH3)3C ch2ch2oh ch2ch2oh A-14 (CH2OH)3C CH2CH20H ch2ch2oh A-15 CH2CH3 CH2CH3 ch2ch2oh A-16 CH2CH2CH3 CH2CH2CH3 ch2ch2oh A-17 ch2ch2ch2oh ch2ch2ch2oh ch2ch2ch2oh A-18 ch3 ch3 ch2ch2ch2oh A-19 H ch2ch2ch2oh ch2ch2ch2oh Specific examples of the di- or tertiary amino alcohols shown in Table 1 above (Compound A -1 to A In the case of preventing aggregation, A-1, A-7, -9, Α-10, Α11, Α12, A-13, A-14, A are preferable. -17, A-19, more preferably A - 9, A - 1 7. As the di- or tertiary-grade amino alcohol used in the present invention, a commercially available product can be used, and a synthesizer can also be used. The di- or tertiary-grade amino alcohol used in the present invention may be used singly or in the range of 2 -1 6 - 200817498 or more. Further, the concentration of the di- or tertiary-grade amino alcohol is not particularly limited, but is preferably from 0. 0 1 to 10% by mass, more preferably from the viewpoint of particle dispersibility in the composition for honing. 0.1 to 5 mass%. [PH] The composition for honing of the present invention must be in the range of pH 7.0 to 10. When the pH of the composition for honing of the present invention is in this range, the particle dispersibility of the composition for honing is excellent. Further, from the viewpoint of particle dispersibility of the composition for honing, the p Η of the honing composition of the present invention is preferably 8.0 to 1 0, and particularly preferably 8.5 to 10 0 in the present invention. In order to adjust the above pH to the range of ρΗ7·0 to 10, a base/acid or a buffer may be used. Examples of the above-mentioned test/acid or buffer include alkanolamines such as organic ammonium hydroxide, diethanolamine, triethanolamine, and triisopropanolamine such as gas, hydrogen peroxide, and tetramethylammonium hydroxide. An alkali metal hydroxide such as a non-metal alkaline agent, sodium hydroxide, potassium hydroxide or lithium hydroxide; a mineral acid such as nitric acid, sulfuric acid or pragic acid; a carbonate such as sodium carbonate; a diacid salt such as trisodium phosphate; A borate, a tetraborate, a hydroxybenzoate or the like is taken as a suitable example. Particularly preferred reagents are ammonium hydroxide, potassium hydroxide, lithium hydroxide and tetramethyl hydroxide. The amount of the alkali/acid or the buffer to be added may be an amount that can maintain pIi in the range of p Η 7 · 0 to 10 0; and when used for honing, the composition for honing is used. Preferably, it is 0.00 0 1 Moer~丨·〇莫耳, more preferably 0.003 mol to 0.5 mol. [Oxidant] 200817498 The composition for honing of the present invention preferably contains a compound (oxidizing agent) which can oxidize and honinate the metal. Examples of the oxidizing agent include hydrogen peroxide, peroxide, nitrate, iodate, periodate, hypochlorite, chlorite, chlorate, perchlorate, and persulfate. Dichromate, permanganate, ozone water, and silver (II) salts, iron (III) salts, of which hydrogen peroxide is preferably used. As the iron (III) salt, for example, an inorganic iron (III) salt using iron (III) nitrate, iron (III) chloride, iron (III) sulfate, iron (III) or the like, and iron (III) are preferably used. ) the organic wrong salt. The amount of the oxidizing agent to be added is preferably in the composition of the liter honing composition, preferably ο. ο 1 摩尔 〜 1 摩尔, more preferably 0.05 mM to 0.6 摩尔. [Cathing Agent] In the honing composition of the present invention, in order to reduce the adverse effects of the polyvalent metal ions to be mixed or the like, it is preferred to contain a chelating agent as needed. The chelating agent may, for example, be a general hard water softening agent or a similar compound of a calcium or magnesium precipitation preventing agent, and examples thereof include nitrogen triacetic acid, diethylenetriamine pentaacetic acid, ethylenediaminetetraacetic acid, and N. ,N,N-trimethylenephosphonic acid, ethylenediamine-oxime, hydrazine, hydrazine, N'. tetramethylenesulfonic acid, trans-cyclohexanediaminetetraacetic acid, 1,2-diamine Propane tetraacetic acid, glycol ether diamine tetraacetic acid, ethylenediamine o-hydroxyphenylacetic acid, ethylenediamine disuccinic acid (SS body), N-(2-residual acid ethyl)-L-day Aspartic acid, β-alanine diacetic acid, 2-phosphonium decyl j: complete-1,2,4-tridecanoic acid, 1-transethylidene-1,1-diphosphonic acid, N,N ,-bis(2-phenyl)-ethylenediamine-N,N'-diacetic acid, 1,2-dihydroxybenzene-4,6-disulfonic acid and the like. [Organic Acid] -18- 200817498 The honing liquid in the present invention may further contain an organic acid. The organic acid as used herein means a compound having a different structure for oxidizing an oxidizing agent for a metal, and does not include an acid having the function of the aforementioned oxidizing agent. The acid here has an effect of promoting oxidation, adjusting ρ 。, and a buffer. As the organic acid, those selected from the following groups are suitable. That is, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, 2-methylbutyric acid, n-hexanoic acid, 3,3-dimethylbutyric acid, 2-ethylbutyric acid, 4-methylpentane Acid, n-heptanoic acid, 2-methylhexanoic acid, n-octanoic acid, 2-ethylhexanoic acid, benzoic acid, glycolic acid, salicylic acid, glyceric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, Adipic acid, pimelic acid, maleic acid, phthalic acid, malic acid, tartaric acid, citric acid, lactic acid, salts of such ammonium or alkali metal salts, sulfuric acid, nitric acid, ammonia, ammonium salts, Or such a mixture, etc. Among these, formic acid, malonic acid, malic acid, tartaric acid, and citric acid are used for a laminated film containing at least one metal layer selected from copper, a copper alloy, and an oxide of copper or a copper alloy. More suitable. The organic acid in the present invention may, for example, be an amino acid. It is preferred that the amino acid is water-soluble, and it is more suitable from the group selected below. That is, for example, it is preferable to contain glycine, L-alanine, β-alanine, L-2-aminobutyric acid, L-protoporic acid, 1-proline, L-leucine, L. - leucine, L-isoleucine, L-aloe leucine, L-phenylalanine, L-proline, sarcosine, L-ornithine, L_lysine, Taurine, l-serine, L_threonine, L-bethuric acid, L-homoserine, tyrosine, 3,5-diiodo-L-tyrosine, β-(3, 4-dihydroxyphenyl)-L-alanine, L-thyroxine, 4-hydroxy-19- 200817498 -L-proline, L-cysteine, L-methionine, L-ethyl thiamin Acid, L-laner thioglycolic acid, L-cystathionine, L-cystamine, L-cysteine, L. aspartic acid, L-glutamic acid, S-(carboxymethyl)-L -cysteine, 4-aminobutyric acid, L-aspartate, L-glutamine, diazonium, lysine, L-cutosin, L- Citrulline, δ-hydroxy-L-lysine, creatine, L-canine urea, L-histamine, methyl-L-histidine, 3-methyl-L-histidine, ergot sulfur Cause, L-tryptophan, actinomycin C 1 , bee venom peptide, hypertension protein I, high blood pressure egg Nanjing and Hangzhou Π papaya enzymes of amino acids and the like at least one. Among these, it is particularly preferable to use malic acid, tartaric acid, citric acid, glycine, and glycolic acid from the viewpoint of maintaining a practical CMP speed while effectively suppressing the etching rate. The amount of the organic acid to be added is preferably 0.0005 mol to 〇.5 mol, more preferably 0.005 mol to 0.3 mol, more preferably 0 · 0 1 in the 1 liter honing liquid at the time of honing use. Moer ~ 0 · 1 Moh. Namely, the amount of the organic acid to be added is preferably from 5 m or less from the viewpoint of suppression of etching, and is preferably 0.0005 mol or more in terms of sufficient effects. Ik [honing method] The honing method of the present invention supplies the honing composition to the honing pad on the honing plate to rotate the honing plate while contacting the honing pad to the honing body. A honing method for honing a film while performing relative motion, characterized in that the insulating film is formed by an insulating film having a specific dielectric constant of 3.0 or less in an organic siloxane structure, and a buried wiring is formed via a barrier metal layer. The insulating film of the above-mentioned honed body, and the above-mentioned honing composition is the above-mentioned honing composition of the present invention. -20 - 200817498 With the above configuration, it is possible to suppress scratches in the honing of an insulating film (Low-k film) having a low specific dielectric constant formed using a material having a dielectric constant of 3.0 or less. The honing method that occurs. In the honing method of the present invention, the insulating film (Low-k film) having a low specific dielectric constant formed by using the material having a specific dielectric constant of 3.0 or less is used in the honing composition of the present invention. The items recorded under the item are the same, and the preferred examples are the same. The composition for honing according to the present invention is: 1. A concentrated liquid, which is diluted with water or an aqueous solution at the time of use to be a use liquid, and 2) each component is prepared in the form of an aqueous solution described in the following item, and they are prepared. Mixing, if necessary, adding water to dilute to become a use liquid, 3. As a use liquid preparation. In the honing method using the honing composition of the present invention, the honing composition in any case can also be applied. The honing method is a method in which a honing composition is supplied to a honing pad on a honing plate to bring it into contact with the honed surface of the honed body to cause relative movement between the honed surface and the honing pad. As a device used for honing, a bracket having a honed surface (for example, a wafer on which a film of a conductive material is formed) having a honed surface, and a honing pad (with a number of revolutions mounted) can be used. A general honing device for honing the pressure plate of a motor or the like that can be changed. Specific examples of the honing device include Mirra Mesa CMP, Reflexion C Μ P (application material), F RE X 2 0 0, FREX 3000 (荏原株式会社), NPS 3 3 0 1 , NPS23 0 1 (NIKON), A-FP-310A, A-FP-2 1 0 A (Tokyo Precision), 2 3 00 TERES (LAM RESEARCH), 200817498

Momentum (Speedfam IPEC) and so on. As the honing pad, a general non-woven fabric, a foamed polyurethane, a porous fluororesin or the like can be used without particular limitation. The details are as follows. Further, the honing condition is not limited, but the slewing speed of the honing plate is preferably a low rotation of 200 rpm or less which does not fly out of the honing body. The pressing pressure of the honed body with the honed surface (the honed film) on the honing pad is preferably 0.68~34.5KPa, more preferably 0.6 9~2 1.6 KP a; in order to satisfy the honing The in-plane uniformity of the honed body and the flatness of the pattern, / it is preferably 3.40 to 20.7 KP a. During the honing, the honing composition is continuously supplied to the honing pad by a pump or the like. After the honing, the honed body is sufficiently washed in the running water, and the water droplets adhering to the honed body are shaken off using a rotary dryer or the like to be dried. In the present invention, when the concentrate is diluted as in the above method, an aqueous solution shown below can be used. The aqueous solution is at least one or more water containing an oxidizing agent, a di- or tertiary amino alcohol, an additive, and a surfactant, and the component contained in the aqueous solution and the diluted concentrated solution are contained. The component of the component is used as a component of the honing composition (use liquid) used in honing. Thus, in the case where the aqueous solution is used to dilute the concentrate, the components which are not easily soluble can be blended in the form of an aqueous solution at a later stage, so that a more concentrated concentrate can be prepared. Further, as a method of diluting water or an aqueous solution to a concentrate, a pipe for supplying a concentrated liquid having a concentrated composition of the honing composition and a pipe for supplying water-22 - 200817498 or an aqueous solution are mixed and mixed in the middle, and A method of supplying a hydrating mat to a honing pad by mixing and diluting the use liquid of the honing composition. The mixture of the concentrated liquid and the water or the aqueous solution may be a method in which the liquid is collided with each other through a narrow passage under a pressure, and the filling of the glass tube or the like is repeated in the piping to repeat the liquid. A method in which the flow split separation and the joining are performed, and a method in which the blade is rotated by the power is provided in the piping. The supply flow rate of the honing composition is preferably 10 to 10 ml/min, which is the flatness of the honed surface and the flatness of the pattern satisfying the honing speed, and more preferably 170 to 800 ml/min. . Further, the supply flow rate per unit area of the honing composition is preferably 0.03 5 to 0.60 ml/cm 2 . In addition, as a method of honing the concentrated liquid by using water or an aqueous solution or the like, the piping for supplying the concentrated liquid is separately provided from the piping for supplying the water or the aqueous solution, and each of the specified amount of liquid is supplied to the honing pad. The method of honing while mixing by the relative movement of the honing pad and the surface to be honed. Further, it is also possible to use a method in which a specified amount of the concentrated liquid and water or a water solution are mixed in one container, and the mixed honing composition is supplied to the honing pad to perform honing. In addition, as another honing method, the component containing the honing composition is divided into at least two constituent components, and when they are used, water or an aqueous solution is diluted for supply to the honing pad on the honing plate, and The method of being rubbed by the honing surface to make the honed surface and the honing pad move relative to each other. For example, 'the oxidizing agent can be used as a constituent (A), and the second or third amino group 23 - 200817498 alcohol, an additive, a surfactant, and water are used as a constituent (B), when they are used as 'water or The aqueous solution is used to dilute the constituent component (A) and the constituent component (B). Further, 'the additive having low solubility is divided into two constituent components (A) and (B) ' For example, an oxidizing agent, an additive, and a surfactant are used as constituent components (A) 'A second or third amino alcohol, an additive, an interface The active agent and water are used as the component (B), and when they are used, the component (A) and the component (B) are diluted with water or an aqueous solution and used. In these cases, the colloidal vermiculite particles (abrasive grains) of the present invention are preferably contained in the constituent component (A). In the case of the above example, it is necessary to supply three components of the component (A), the component (B), and the water or the aqueous solution, and the three-component pipe is bonded to the honing pad. i is a method of mixing in the pipe, in which case two pipes may be combined and then combined with another pipe, specifically, a component containing the insoluble additive and other constituents. As a method of mixing, increasing the mixing path to ensure the dissolution time, and then combining the piping of water or an aqueous solution. As another mixing method, as described above, three pipes are directly guided to each of the honing pads, and the lining pad is mixed with the relative movement of the honed surface, or three components are mixed in one container. And then the method of supplying the diluted honing composition to the honing pad. In the above honing method, one component containing an oxidizing agent may be 40 ° C or less, and the other component may be heated from room temperature to 100 ° C to mix one component with other components. When it is diluted with water or an aqueous solution, the liquid temperature is made 40 ° C or lower. This method is a preferred method for improving the solubility of a raw material having a low solubility in a honing composition by using a phenomenon in which the solubility is high at a high temperature. Since the above-mentioned other components are heated from room temperature to 100 ° C and the dissolved raw material is precipitated in the solution when the temperature is lowered, it is necessary to preheat the other components in the low temperature state. In order to dissolve the precipitated raw materials. Here, a means for supplying the liquid to dissolve the other constituent components of the raw material, a means for stirring the liquid containing the precipitate, and feeding the liquid, and heating the pipe to dissolve the mixture may be employed. When the temperature of one component containing an oxidizing agent is raised to 40 ° C or more, the oxidizing agent is decomposed after the other components which are heated, so that the other components which are heated and one containing the oxidizing agent are contained. When the components are mixed, it is preferably formed to have a temperature of 40 ° C or less. As described above, in the present invention, the components of the honing composition may be divided into two or more parts and supplied to the honed surface. In this case, it is preferred to supply the component containing the oxide and the component containing the di- or tertiary amino alcohol. Further, the composition for honing may be used as a concentrate, and diluted water may be supplied to the surface to be honed. In the present invention, when the component for honing the composition is divided into two or more and supplied to the surface to be honed, the supply amount indicates the total amount of supply from each pipe. [Cushion] The honing pad for honing which may be applied to the honing method of the present invention may be a non-foamed structural mat or a foamed structural mat. The former is made of a rigid synthetic resin such as a plastic sheet. In addition, the latter has three independent foams (dry type - 25, 2008, 498, #, bubble type), continuous foam (wet foaming system), and two-layer composite (layered system). Complex (layered system). The foaming may be uniform or uneven -* 〇 Further, it may also contain abrasive grains generally used for honing (for example, alumina, vermiculite, oxidized, resin, etc.). Further, each of the hardnesses may be either a soft one or a hard one. In the laminated system, it is preferred to use different hardnesses in each layer. The material 'is preferably non-woven fabric, artificial leather, polyamide, polyamine, polyester, polycarbonate, or the like. Further, it is also possible to apply a lattice groove/acupoint, a concentric groove, a spiral groove, or the like to the surface in contact with the honed surface. [Wafer] The CMP target of the honing composition in the present invention, that is, the wafer to be honed, preferably has a diameter of 200 mm or more, particularly preferably 30,000 m or more. The effect of the present invention is remarkably exhibited at 300 mm or more. [Examples] The present invention will be described in more detail by the following examples, but the invention is not limited by the following: &lt;Example 1&gt; Each of the honing compositions shown below was prepared, and the evaluation of the time-lapse test of the grinding particle dispersion stability and the scratch performance was performed. (Preparation of composition for honing) The following composition was mixed to adjust the composition for grinding.

Hydrogen peroxide (oxidant) 1 〇 g / L A-1 : diethanolamine -26 - 200817498

24g/L

0.5g/L 5〇g/L (powder conversion)

lOOOOmL (Secondary Amino Alcohol, and Pure Pure Industrial Co., Ltd.) 1H-Benzotriazole (BTA: Aromatic Ring Compound) Colloidal Vermiculite Particles (PL-3, Primary Particle Size 30nm, Association Degree 2, II Sub-particle size: 60 nm)) Adding pure water to the full amount of pH (adjusted with ammonia water and sulfuric acid) (Evaluation method of honing particle dispersion stability) The adjusted slurry was observed by TURBISCAN (Turbiscan MA2000, manufactured by Hidehiro Seiki Co., Ltd.) The convergence of the body. The evaluation system transmitted the light intensity of the slurry to the next day until 180 days (in this evaluation, the smaller the change in transmitted light intensity, the better the dispersion stability of the honing particles). The evaluation criteria for honing particle dispersion stability are as follows. 〇: The change with time (change in transmitted light intensity) after half a year is 10% or less △: Change over time (change in transmitted light intensity) after half a year is less than 21% X: Change over time after half a year (transmitted light intensity) The change is 21% or more, and the 〇 and △ are judged to be practically no problem. (Method for Evaluating Scratch Performance) The BD wafer (BLACKDIAMOND, manufactured by Applied Materials, Inc.) was honed, washed with pure water, dried sequentially, and observed by an optical microscope. The evaluation criteria were used to evaluate the state of the machined surface after honing. This evaluation was carried out immediately after the liquid adjustment and after the time-test test after the 1980 time. The evaluation criteria of the scratch performance are as follows. -27- 200817498 〇: There is almost no scratching and it is good △: A small number of scratches of 1 μη or more are observed X: Most scratches of 1 μm or more are observed, and 〇 and △ are judged to be practical. The extent of the problem. &lt;Examples 2 to 2 1 &gt; In addition to the adjustment of the honing composition of Example 1, the A-1 (secondary amino alcohol) was changed to the di- or tertiary amino group described in Table 2. In the same manner as in Example 1, the evaluation of the composition for honing was carried out. However, in Examples 20 and 21, a mixture of three or three or more amino alcohols shown in Table 2 was used. &lt;Comparative Example 1 to 2&gt; Except that in Comparative Example 1, the A-1 compound (secondary amino alcohol) used in the composition adjustment for honing of Example 1 was removed, and the same procedure as in the Example was carried out. Adjustment and evaluation of the composition for honing. In the same manner as in Example 1, except that the compound (secondary amino alcohol) used for the adjustment of the honing composition of Example 1 was changed to lactic acid in Example 2, the composition for honing was adjusted. Evaluation. Fig. 1 shows changes over time in the dispersion stability of Examples 1, 9, and 15 and Comparative Examples 1 and 2. Further, Table 2 shows the evaluation results of Examples 1 to 2 1 and Examples 1 to 2. Further, in Comparative Examples 1 and 2, since the enthalpy of the composition for honing was aggregated, the evaluation of the scratch performance after the 1800 days could not be performed. The compound alcohol is compared with the two of the two materials. The comparison of the A-1 ground is divided into the abrasive grains -28 - 200817498 [Table 2] The second or tertiary amino alcohol (concentration) PH Dispersion stability evaluation scratch / energy After a liquid adjustment, 180 Example 1 Α-1 (2.4% by mass) 9.5 〇〇 Example 2 Α-2 (2.2% by mass) 10 〇〇〇_- Example 3 Α-3 (2.2% by mass 9 Δ 〇〇 _ Example 4 Α-4 (2·2% by mass) 9.5 Δ 〇〇 - Example 5 Α-5 (2·2% by mass) 8.5 〇〇〇 Example 6 Α-6 (2.4 Mass %) 9.5 Δ Δ Δ _ - Example 7 Α-7 (2.6% by mass) 10 〇〇〇 Example 8 Α-8 (2.4% by mass) 9.5 〇〇〇 Example 9 Α-9 (3.0% by mass) 9 〇〇〇 Example 10 Α-10 (2·8 mass 0 / 〇) 10 实施 Example 11 A-ll (2.8 mass%) 9.5 〇〇〇 - Example 12 Α-12 (2· 8% by mass) 9 〇〇〇Example Π·13 (3.4% by mass) 9.5 〇〇〇Example 14 Α-14 (3.4% by mass) 10 〇〇〇Example 15 Α-15(2 · 8 mass%) 9.5 Δ 〇〇 Example 16 Α-16 (3·5 mass%) 9 Δ 〇〇 Example 17 Α-17 (4·0 mass%) 10 〇〇〇_ Example 18 Α-18 (3·5 mass%) 9.5 Δ 〇Δ Example 19 Α-19 (3·5 mass%) 9.5 〇〇 〇Example 20 Α-1 (2.4% by mass) Α-9 (1.0% by mass) 9.5 〇〇〇 Example 21 Al (2.4% by mass) Α-9 (1.0 mass 0/〇) Α-17 (1 ·5 mass 0/〇) 9.5 〇〇〇Comparative example 1 Blank (blank) 9.5 X Δ - Comparative Example 2 Lactic acid (1.5% by mass) 9.5 X Δ - * "1" in the table indicates that it cannot be evaluated as known from Table 2. In Examples 1 to 2, the particle dispersibility of the composition for honing was stable over a long period of time, and good scratch performance was maintained in the honing of the BD wafer. On the other hand, in Comparative Examples 1 and 2, the dispersion stability of the composition for honing decreased with time, and the B D was rounded and squeezed due to the occurrence of scratches due to aggregation of particles. -29 200817498 BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a graph showing changes in the stability of particles in Examples 1, 9, and 15 and Comparative Examples 1 and 2 over time. [Main component symbol description] 4FR1 〇 -30-

Claims (1)

200817498 X. Patent Application Range: 1. A honing composition for use in a method of manufacturing a semiconductor device for supplying a chemically mechanically honed insulating film of an object to be honed, the insulating film having an organic decane structure a dielectric constant of 3.0 or less and an embedded line via a barrier metal layer, the honing composition comprising colloidal vermiculite particles, a benzotriazole compound, and two or three of the following formula (1) Alkaloid alcohol, and the pH is in the range of 7 to 10, N Formula (1) r2// nr3 [In the above formula (I), Ri, R2, and R3 each independently represent a hydrogen atom, an aliphatic hydrocarbon group, or an aromatic hydrocarbon group, and the aliphatic hydrocarbon group and the aromatic hydrocarbon group may further be an amine group. The hydroxyl group, the carboxyl group, or the hydrocarbon group is substituted; however, at least one of R i, R 2 and R 3 has a hydroxyl group; and at least two or more of Ri, R 2 and R 3 are a substituent other than a hydrogen atom. 2. The composition for honing according to the first aspect of the invention, wherein the concentration of the colloidal vermiculite particles is 0.5 to 15% by mass. 3. The honing composition according to claim 1 or 2, wherein the benzotriazole compound is from 1,2,3-benzotriazole, 5,6-dimethyl-1,2, 3-benzotriazole, 1-(1,2.dicarboxyethyl)benzotriazole, 1-[indene, bis(hydroxyethyl)amine methyl]benzotriazole, and 1-( At least one or more compounds selected from hydroxymethyl) benzotriazole. 4 · A honing method, which supplies the honing composition to the 200817498 honing pad on the honing plate, while the ram pad is in contact with the insulating film of the honed body, and the platen is honed to make contact The honing force of the surface for the relative movement is characterized in that the insulating film is formed of an insulating film having a constant of 3.0 or less in a structure having an organic siloxane structure, and the honed body is formed by interposing a barrier metal layer. An insulating film, and the above-mentioned honing group is a honing composition as claimed in claim i or 2 of the patent application. 5. The honing method according to item 4 of the patent application, wherein the load (honing pressure) is (0.007 kgf/cm2) to 21.6 kPa (0.22 kgf/cm2) when the insulating film of the honing honing body is brought into contact. ° 6. The honing method of claim 4, wherein when the honing material is supplied to the honing pad on the honing plate, the supply flow rate is 0.60 ml/min-cm2 〇 rotating the "method, the ratio Dielectric into the line into a mat with 0.6 9 k P a; with a composition of 0.03 5 ~ -32 -