TW200907035A - Polishing liquid - Google Patents

Abstract

The invention provides a polishing liquid for polishing a barrier layer of a semiconductor integrated circuit, the polishing liquid including a quaternary ammonium cation, a corrosion inhibitor, a nonionic surfactant and a colloidal silica and having a pH of from 2. 5 to 5. 0. According to the invention, a polishing liquid is provided that, when applied to a substrate having an insulating film including a TEOS insulation film and a Low-k film, enables polishing of the TEOS insulation film at high speed and polishing of low-strength insulating films such as the Low-k film at an effectively-restrained speed, and that also enables suppression of scratches caused by aggregation of solid abrasive grains or the like.

Description

200907035 IX. Description of the Invention: [Technical Fields of the Invention] In the flattening of the honing liquid line step used in the invention, the "LSI" is a high-density, high-density chemical system. Honing (Zhongbei IJ is called "CMP" insulating film (interlayer candidize, form a plug, and is used to perform a base metal film or paste on a platen and place the substrate (wafer pressure) (honing pressure), by means of the machine of the present invention, relating to the process of semiconductor devices, in more detail, relates to a honing fluid for chemical mechanical honing in a semiconductor device. [Prior Art] In the semiconductor integrated circuit (hereinafter, in the development of the semiconductor device of the table, it is required to make the wiring finer and thicker for the small size. For the technology required, Chemical Mechanical Ρ ο 1 has been used. Various techniques such as ishing, hereinafter, etc. This CMP is an indispensable technique for laying a metal wiring or the like on the surface of a film to be processed such as an interlayer insulation film. To remove or remove the excess barrier layer on the excess film when the wiring is formed. The general method of CMP is to round the zf-attached pad with a honing fluid to impregnate the surface of the pad. When the surface is pressed against the pad and applied to the back surface thereof, the surface of the substrate is flattened by mechanical friction between the honing stage and the substrate. When manufacturing a semiconductor device such as LSI, it is generally fine. When the wiring is formed in a plurality of layers, when a metal wiring such as Cu is formed in each layer, the Ta or TaN is formed in advance to prevent the wiring material from diffusing into the interlayer insulating film or to improve the adhesion of the wiring of the 200907035 material. Measures for barrier metals such as Ti and TiN. When forming each wiring layer, it is generally first performed in one or more stages to remove excess wiring material plated by electroplating or the like. CMP of the metal film (hereinafter referred to as "metal film CMP"), and secondly, removing the CMP of the barrier metal material (barrier metal) exposed to the surface (hereinafter, Weigh It is "barrier metal CMP". However, due to the metal film CMP, the wiring portion is excessively honed, that is, the so-called "dishing" or even "etching" Erosion) is the cause of the problem. In order to alleviate the shallow disc formation, after the metal film CMP, the barrier metal CMP is secondarily required to adjust the honing speed of the metal wiring portion and the barrier metal portion. The honing speed is set so as to form a wiring layer in which the degree of concavity such as shallow dishing or etching is finally obtained. In other words, when the barrier metal or the interlayer insulating film has a honing speed relatively smaller than that of the metal wiring material, the wiring portion is already honed or the like, or the result is caused. The etching caused, and therefore the honing speed of the barrier metal or insulating film layer is preferably suitably large. It has the advantage of increasing the yield of the barrier metal CMP, and in fact it is mostly caused by the metal film C MP, and it is required to relatively increase the barrier metal or insulation for the reasons described above. It is also preferable from the viewpoint of the honing speed of the film layer. The honing solution for metal used in CMP generally contains etchant particles (for example, oxidized sulphur, sand dioxide) and oxidizing agent 200907035 (oxidizing agent) (for example, hydrogen peroxide, persulfuric acid). The basic mechanism is believed to be achieved by oxidizing the metal surface with an oxidizing agent and then removing the oxide film with cerium particles. However, when CMP is performed using a honing liquid containing such solid honing particles, there is a possibility that burrs (scratches) and honing surfaces are subjected to more than necessary honing (thin (thinning), honing one part of the metal surface is excessively honed to cause the surface to be dished into a dish (shallow disc), and the insulator of the metal wiring line is subjected to necessary honing, plus only a plurality of strips The central portion of the wiring metal surface is subjected to deep honing and the surface is dished into a dish (etching). In addition, since the honing liquid containing the solid honing particles is used, the washing step which is usually performed after removing the honing liquid remaining on the semiconductor surface after honing tends to be complicated, and is caused to be washed after being treated. Liquid (waste liquid), but it is required to settle and separate solid honing particles and the like in terms of cost. Regarding the honing liquid containing these solid honing grains, various investigations as described below have been made. For example, there has been proposed a CMP honing agent and a honing method for the purpose of performing high-speed honing under almost no burrs (see, for example, Japanese Patent Laid-Open No. 2003-17446), an improvement in A honing composition for scouring and a honing method (see, for example, Japanese Laid-Open Patent Publication No. 2003-142435), and a honing composition for preventing agglomeration of honing particles (see, for example, Japanese invention) Patent Laid-Open No. 2000-84832). However, even if there is a honing liquid as described above, at present, it is not possible to achieve a high honing speed at the time of honing the necessary layer, and it is possible to suppress the scraping due to agglomeration of solid honing particles. The technique of injury.

In particular, in recent years, with the further miniaturization of wiring, it has evolved to a low dielectric which has a relative dielectric constant lower than that of a conventional interlayer insulating film such as TEOS (tetraethoxysilane). A constant material is used as the insulating film. These insulating films are referred to as "low-k films", and are formed of materials such as organic polymer, SiOC or SiOF. These are generally used for lamination with an insulating film, but since the strength is lower than that of the prior insulating film, the problem of excessive honing or scratching as described above is more remarkable in the processing of CMP. SUMMARY OF THE INVENTION [Technical Problem to be Solved] An object of the present invention is to provide a honing liquid which is used for honing of solid honing particles for chemical mechanical honing in a planarization step of a semiconductor integrated circuit. A liquid which can obtain a superior honing speed for a TEOS insulating film on a substrate having an insulating film of a conventional TEOS insulating film and a low dielectric constant Low-k film, and even when using, for example, Low-k In the case of the low-strength insulating film of the film, the honing speed for the Low-k film can be effectively suppressed, and scratching due to aggregation of the solid honing particles or the like can be suppressed. [Technical method for solving the problem] The inventors of the present invention have found out that the problem as described above can be solved by using the honing liquid as described below, and the object is finally achieved. The honing fluid of the present invention is characterized in that it is used for chemical mechanical honing in the semiconductor integrated circuit flat 200907035, and contains (A) quaternary ammonium cation, (B) corrosion inhibitor, (C) non- An ionic surfactant, and (D) colloidal silica, and having a pH of 2.5 to 5.0. In the present invention, it is preferred that the (A) quaternary ammonium cation is a cation represented by the general formula (1) or the general formula (2) as follows: R3 R4_^±_R2 Formula ( 1) f R1 R2 R1 R4 II 5 N-X-N-R5 R3 R6 Ί 2+ General formula (2) [In the general formula (1), general formula (2), R1 to R6 each independently represent carbon An alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aryl group or an aralkyl group having 1 to 20 atoms, and two of R1 to R6 may be bonded to each other to form a cyclic structure. X represents a carbon. The alkyl group having an atomic number of 1 to 10, an alkylene group, an alkynylene group, a cycloalkyl group, an aryl group, or a combination of two or more of them. ]. The "(C) nonionic surfactant" of the present invention may be selected from the group consisting of an ether type nonionic surfactant, an ether ester type nonionic surfactant, and an ester type nonionic surfactant. One or more of the group; wherein, the compound represented by the formula (3) or the formula (4) as described below is suitably used: 200907035 Formula (3) R——〇—(CH2CH20)n—Η [In the general formula (3), R represents an alkyl group having a carbon number of 2 to 3 Å, a rare group, a ring-based group, an aryl group, or an aromatic group, and the η system represents a bond of a polyoxyethylene b-group. The number is an integer from 2 to 30. 〕 "〇-(CH2CH2〇)aC〇R1 -Ο-(CH2〇H2〇)bCOR^ -0-(CH2CH20)cC0R3 A General formula (4) —〇-(CH2CH2〇)dCOR4 一0—(ΟΗ2〇Η2 〇)βΗ

-0-(CH2CH20)fH a+b+c+d+e+f=20 ～70 [In the formula (4), 'R1 to R4 each independently represent an alkyl group having 2 to 30 carbon atoms, Alkenyl, cycloalkyl, aryl, or aralkyl, a, b, c, d, e, and f represent the number of bonds of the polyoxyethylene group, respectively, and a + b + c + d + e + f It is 20 to 70. ]. In the honing liquid of the present invention, the concentration of the (D) colloidal cerium oxide is 0.5 to 15% by mass based on the total weight of the honing liquid, and the primary average particle diameter of the (D) colloidal cerium oxide used is It is a preferred mode in the range of 20 to 50 nm. Further, the "(B) corrosion inhibitor" is preferably selected from the group consisting of 1,2,3-benzo-10-0.0507035 triazole, 5,6-dimethyl-1,2,3-benzotriazole, toluene Triazole, [_(丨,2_dicarboxyethyl)benzotriazole, 1-( 1,2-dicarboxyethyl)tolyltriazole, 1-[Ν,Ν·bis(hydroxyethyl) Aminomethyl]benzotriazole, unbis(hydroxyethyl)aminomethyl]tolyltriazole, 1-(2,3-dihydroxypropyl)benzotriazole, 1-(2, At least one compound of the group consisting of 3-dihydroxypropyl)tolyltriazole and hydroxymethylbenzotriazole 〇_ in the honing fluid of the present invention, preferably as described above Each component further contains (E) a compound having a residue represented by the following formula (5): Formula (5)

R7—〇-R8—COOH [In the formula (5), R7 and R8 each independently represent a hydrocarbon group. The R7 and R8 systems may also be bonded to each other to form a cyclic structure. ]. [Effect of the Invention] According to the present invention, it is possible to provide a honing liquid using solid honing particles for chemical mechanical honing in a planarization step of a semiconductor integrated circuit, which can have a laminated layer. The substrate of the insulating film of the TEOS insulating film and the low dielectric constant Low-k film obtains a superior honing speed for the TEOS insulating film, and even in the case of using a low-strength insulating film such as a Low-k film, It is also possible to effectively suppress the honing speed for the Low-k film, and at the same time, it is possible to suppress the scratch due to aggregation of the solid honing particles and the like. [Embodiment] -11- 200907035 [Best Mode for Carrying Out the Invention] Hereinafter, a specific mode of the present invention will be described. The honing fluid of the present invention is used for chemical mechanical honing in a semiconductor integrated circuit planarization step, and comprises (A) a quaternary ammonium cation, (B) a corrosion inhibitor, (C) a nonionic surfactant, And (d) colloidal cerium oxide' and having a pH of from 2.5 to 5.0. The honing fluid of the present invention may further contain any component as needed. The components contained in the honing liquid of the present invention may be used alone or in combination of two or more. The term "honing fluid" as used in the present invention means not only a honing liquid used in honing (i.e., a honing liquid which has been diluted as needed) but also a concentrated liquid of honing liquid. The so-called "concentrate or concentrated honing fluid" means a honing fluid prepared to have a higher solute concentration than the honing fluid used directly for honing, and when used for honing, It needs to be diluted with water or an aqueous solution or the like for use in honing. The dilution ratio is usually 1 to 20 times by volume. In this specification, the terms "concentrate" and "concentrate" are used according to the conventional expression to mean "denser" and "denser liquid". Semantic different terms of liquids that have undergone physical concentration operations such as evaporation have been used differently. Hereinafter, the components used to constitute the honing liquid of the present invention will be described in detail. [(A) quaternary ammonium cation] The honing liquid ' of the present invention contains a quaternary ammonium cation (hereinafter, hereinafter referred to as "specific cation" in the case of -12-200907035). The quaternary ammonium cation of the present invention is not particularly limited as long as it is a structure having one or two quaternary nitrogens in its molecular structure. In the above, from the viewpoint of achieving a sufficient honing speed, a cation represented by the following formula (1) or formula (2) is preferred. R3 R4-N^-r2 Formula (1) r R1

In the general formula (1) and the general formula (2) as described above, 'R1 to R6 each independently represent an alkyl group, an alkenyl group, an alkynyl group or a ring having 1 to 20 carbon atoms. An alkyl group, an aryl group or an aralkyl group, two of R1 to R6 may be bonded to each other to form a cyclic structure. The alkyl group having 1 to 20 carbon atoms as R1 to R6 specifically includes: methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, etc. Preferably, it is a methyl group, an ethyl group, a propyl group or a butyl group. Further, 'the alkenyl group of R1 to R6 as described above is preferably a carbon number of 2 to 1 Å, and specifically, it includes a vinyl group, a propenyl group or the like as R1 to the above. The alkynyl group of R6, specifically, includes -13 to 200907035: butynyl, pentynyl, hexynyl and the like. As the cycloalkyl group of R1 to R6 as described above, specifically, it includes a cyclohexyl group, a cyclopentyl group and the like, and among them, a cyclohexyl group is preferred. As the aryl group of R1 to R6 as described above, specifically, it includes a phenyl group, a naphthyl group and the like, and among them, a phenyl group is preferred. As the aralkyl group of R1 to R6 as described above, specifically, it includes a benzyl group or the like, and among them, a benzyl group is preferred. The substituents which may further have a substituent as described above for each of R1 to R6 include a hydroxyl group, an amine group, a carboxyl group, a heterocyclic group, a pyridyl group, an aminoalkyl group, and the like. Phosphate group, imine group, thiol group 'mineral group, nitro group and the like. X in the above formula (2) is an alkylene group, an alkenyl group, an alkynylene group, a cycloalkyl group, an extended aryl group, or a combination of two or more kinds having 1 to 1 carbon atom. The basis of these. Further, the bonding group represented by X may contain -S-, -S(=0) 2-, one-----C (=) in addition to the organic gastric group as described above. 0)-. The alkylene group having 1 to 10 carbon atoms as described above, specifically, includes: methylene, ethyl, propyl, butyl, pentyl/rX-based, Further, it is preferred to extend an ethyl group and extend an alkyl group as described above, and specifically, it comprises: a stretching & an extension propylene group, etc. Jia is a polypropylene base. The alkynyl group as described above, specifically, includes: stretching 3 $ * -14- 200907035, a propynyl group, etc., of which a propynyl group is preferred. The cycloalkyl group as described above specifically includes: a cyclohexylene group, a cyclopentyl group or the like, and among them, a cyclohexyl group is preferred. The aryl group as described above, specifically, includes a phenyl group and a naphthyl group, and among them, a phenyl group is preferred. Each of the bonding groups as described above may further have a substituent, and the substituents which may be introduced include: a hydroxyl group, an amine group, a sulfonyl group, a carboxyl group, a heterocyclic group, a pyridyl group, an aminoalkyl group, a phosphoric acid group. Base, imine group, thiol group, sulfo group, nitro group, and the like. Hereinafter, specific examples of the (A) quaternary ammonium cation (specific cation) of the present invention [exemplified compounds (A-1) to (A-46)] will be exemplified, but the present invention is not limited to the examples. By. -15· 200907035

Ch3 ch3 H3G—N+—(CH2)b~N^-CHs CH3 CH, A2

Ch3 ch3 h3c-n+—(CH2)10-N^CH3 ch3 ch, A5 C2H5 A7 C3H7 A9 C2H5 A6 dry 2H5 C2H5 C2H5 C2H5 -N+~(CH2)2-HJJ:L-C2H5 C2H5—N+~(CH2)5 —NiL-C2H5 C2H5 C2H5 C^Hb C2H5 A8 C3H7 C3H7 ^Hg C4H9 1+ (CH2)5—^-^-03^17 C4H9—N+ (CH2)5 ~ C3H7 64H9 〇4Hg A10 ch3 ch3 ch3 ch3 ~N+— (CH2)5—N ^-02^)5 C4H9-·N+ (CHJs— CH3 CH3 CH3 CH3

All

A12 H13 CeHi7 A14 ho-c2h5- ch3 ch3 t-(CH2)5-N±-CeHl7 Fly CH, A15 HO-C2H5 ch3 ch3 —N +—(CH2)5—N^-^H 5—OH CH3 CH3 -16~ 200907035 A16

_ CH3 ch3 ^ y~CH2—Ijvl"—(CH2)5—l|j—ch2-—CH3 ch3 A17

CH3 ch3 ~CH2~lj^+~(CH2)2_S_(CH2)2-~CH2 ch3 ch3 A18 A19

Ch3 CH2~ljJ+·~(CH2)2_ ch3

Ch3 (ch2)2—tjj—ch2—^ y ch3

A22

A23 CH3 CH3 GHz—l[l—(CH2)2—(CH2)2—ch2 CH3 CH3 A24

OH ch3/^ ch3 9h3 J= CH3 -lj^-ch3 h3c-n+-\ > -Ifj-CH3 ch3 ch3 ch3 ~i OH ch3 -17- 200907035 A25

Ο 9η3 H3G—_(CH2)2~^-(CH2)2--1|1~~CH3 ch3 Α27 Α26

P^(ch2)5一^^H2H〇^CH2-r^;N A28 f

(y^N^-CH 2〇CO(CH2)4〇COCH A29

A30

HsQ /—\ PH3 A31 hi-(CH2)5-Nt CH3 CH3 C4H9 Death 4H9 A32

Ch3 ch3 ch H3C-N+—(CH2)2—TfJ^HOH H3C—ijj- CH3 CH-, CH CH3 -N—GHi CH-i A33 CH3 H3C-rjj—CH,

Ch3 N—CH: CH-i -18- 200907035 A35 / C2H5 A36 C3H7 N—C2H5 C3H7—N—Cj A36 C3H7—N—C3H7C2H5 C3H7 A3 7 C4H9 A38 〇βΗΐ7 A39 C10H21 C4H9—N—C4H9 CaH-|7 — N—〇8H-i7 C10H21 —N—C10H21 C4H9 CgHi7 C10H21 A34 CH3 CH3—N—CH3 C2H5— I Chh C3H7 A40 C12H25 A41 C15H31 C12H25— -N—C12H25 C15H31—N-C10H21 C12H25 C10H2i A42 A43 〒(CH3) 3 0~CH2. —N~CH2—<—> (ch3)3〇- -N—C(CH3)3 C(CH3)3 A44 严0 A45 c2h4oh 〇-ch2. -n+-ch2-^) HOC2H4— N—C 2 H 4 OH ch 2 — — — — — — — — — — — — — — — — — Preferably, it is A8, A 1 0, A1 1, A12, A36, A37, A46. The (A) quaternary ammonium cation (specific cation) of the present invention can be synthesized by, for example, a substitution reaction using ammonia or various amines as a nucleating agent. In addition, commercially available reagents are also commercially available. The amount of the quaternary ammonium cation (specific cation) added in the (A) of the present invention is the honing liquid after dilution with respect to the honing liquid used in honing (that is, when diluted with water or an aqueous solution) In the following, "the honing liquid used in honing" is also synonymous.), preferably 0.0001% by mass or more and 1% by mass or less, more preferably 0. 0 0 1% by mass or more, 〇. 3% by mass. the following. In other words, the amount of the specific cation added is preferably from 0.02% by mass or more from the viewpoint of sufficiently increasing the honing speed, from the viewpoint of sufficient stability of the slurry. In consideration, it is preferably 0.3% by mass or less. [(B) Corrosion Inhibitor] The honing liquid of the present invention contains a corrosion inhibitor for adsorbing a film formed on the surface to be honed to control corrosion of the metal surface. The corrosion inhibitor of the present invention preferably has three or more nitrogen atoms in the molecule and contains a heteroaromatic ring compound having a condensed ring structure. The "three or more gas atoms" are preferably used to form atoms of the condensed ring, and the heteroaromatic ring compounds are preferably benzotriazole, and various substituents are introduced into the benzotriazole. a derivative. -20- 200907035 The "corrosion inhibitor" which can be used in the present invention includes: benzotriazole, 1,2,3-benzotriazole, 5,6-dimethyl-1,2,3-benzo Triazole, 1-(1,2-dicarboxyethyl)benzotriazole, 1-[N,N-bis(hydroxyethyl)aminomethyl]-indole, 1-(radiomethyl) Benzene dioxime, etc.; as described above, "(B) uranium inhibitor" includes: selected from 1,2,3-benzotriazine, 5,6-dimethyl-1,2,3 -benzotriazole, tolyltriazolium, 2_dicarboxyethyl)tolyltriazole, 1-[N,N-bis(hydroxyethyl)aminomethyl]tolyltriazole, 1-( a compound of the group consisting of 2,3-dihydroxypropyl)benzotriazole, 丨_(2,3-dihydroxypropyl)tolyltriazole, and 1-(hydroxymethyl)benzotriazole And more preferably, selected from the group consisting of 1,2,3-benzotriazole, 5,6-dimethyl-1,2,3-benzotriazole, tolyltriazole, oxime-(12-two Carboxyethyl) benzotriazole, 1-( 1,2-dicarboxyethyl)tolyltriazole, i-[n,N-bis(hydroxyethyl)aminomethyl]benzotriazole, 1-[ Ν,Ν-bis(hydroxyethyl)aminomethyl Tolyltriazole, 1-(2,3-dihydroxypropyl)benzotriazole, 1-(2,3-dihydroxypropyl)tolyltriazole, and 1-(hydroxymethyl)benzo Among the triazoles. The amount of the (B) corrosion inhibitor added is preferably 0.01% by mass or more and 0.2% by mass or less, more preferably 0.05% by mass or more and 0.2% by mass based on the mass of the honing liquid used in the honing. the following. In other words, the amount of the uranium sulphate inhibitor is preferably from 1% by mass or more from the viewpoint of not increasing the degree of the shallow-disc, and is preferably from the viewpoint of storage stability. 0.2% by mass or less. [(C) Nonionic Surfactant] The honing fluid of the present invention contains at least one nonionic surfactant-21-200907035 In the honing fluid of the present invention, by adjusting the nonionic interface used The type and amount of the active agent can increase the honing speed or control the honing speed of the insulating layer. The type of "nonionic surfactant" is not particularly limited, and may be selected from ether type nonionic surfactants, ether ester type nonionic surfactants, and ester type nonionic surfactants depending on the purpose. Among the ethnic groups that are formed. The "ether type" includes polyoxyalkylene alkyl ether, polyoxyalkylene alkyl phenyl ether, polyoxyethylene-polyoxypropylene block copolymer, and the like. The "ether ester type" includes glycerin of polyoxyethylene ether, sorbitan ester of polyoxyethylene ether, and sorbitol ester of polyoxyethylene ether. The "ester type" includes sorbitan ester, glycerin ester, propylene glycol ester, and polyethylene glycol fatty acid ester. Among these, from the viewpoint of efficacy, an ether type surfactant such as a polyoxyalkylene alkyl ether or an ester type such as sorbitan ester or polyethylene glycol fatty acid ester is preferred. Ionic surfactant. Here, the "ether type nonionic surfactant" includes a compound represented by the following formula (3). R (〇)-(CH2CH2〇)n--Η In the formula (3), R represents an alkylalkenyl group having 2 to 30 carbon atoms, a cycloalkyl group, an aryl group, or Aralkyl. -22· 200907035 The η series represents the number of bonds of the polyoxyethylene structure and represents an integer of 2 to 30, preferably in the range of 2 to 20. In the general formula (3), the balance of hydrophilicity and hydrophobicity depends on the number or structure of carbon atoms of the alkyl group or the like in R, and the number of bonds with the polyoxyethylene chain, and R and η are preferred. The combination includes the following. That is, R is preferably a compound having an alkyl group of 8, 10, 12, 16 and η is 2 to 20. Specific examples of the nonionic surfactant represented by the general formula (3) include, for example, polyoxyethylene lauryl ether, polyethylene oxide cetyl ether, polyoxyethylene lauryl ether, polyoxidation Vinyl oleyl ether, polyoxyethylene myristyl ether, polyoxyethylene octyl lauryl ether, polyethylene oxide behenyl ether, and the like. The nonionic surfactant represented by the formula (3) can be obtained from commercially available commercial grade products, for example, the EMULGEN series which can be obtained from EMULGEN 210P, 404, etc. manufactured by Kao corP. Further, other preferred examples of the "ester type nonionic surfactant" include compounds represented by the following formula (4). -23- 200907035 Formula (4)

〇-(CH2CH2〇)aC〇R1 -〇-(CH2CH2〇)bC〇R2 —〇-(CH2CH20)cC〇R3 —〇—(CH2CH2〇)dC〇R4 —〇—(CH2CH2〇)eH -0- (CH2CH20)fH a+b+c+d+e+f=20 to 70 In the formula (4), R1 to R4 each independently represent an alkyl group, an alkenyl group or a ring having 2 to 30 carbon atoms. An alkyl group, an aryl group, or an aralkyl group; a, b, c, d, e, and f represent the number of bonds of the polyoxyethylene group, respectively, and a + b + c + d + e + f is 20 to 70 . R1 to R4 in the formula (4) are the same as those in the formula (3) and the preferred mode is also the same. the following. Specific examples of the nonionic surfactant which is represented by the general formula (4) are exemplified, but the present invention is not limited thereto. -24- 200907035 / r〇-(CH2CH2〇)aC〇C6Hii -0-(CH2CH2〇)bC〇C6H11 —O - (CH2CH 2〇)cC〇〇6H 11 -O-iCHzCHzOidCOCeHn

-0-(CH2CH20)eH

-〇-(CH2CH2〇)fH 〇一(CH2CH20)aC〇C12H23 -〇-(CH2CH20)bC〇C12H23 -O-(CH2CH 2〇)cCOC-| 2H23 —〇-(CH2CH 2〇)cjC〇Ci 2H23

-〇-(CH2CH2〇)eH -〇-(CH2CH2〇)fH "0-(CH2CH2〇)aC〇C8H15 -0-(CH2CH2〇)bC〇C8H15 -〇一(CH2CH20)cC0C8H15 —〇—(CH2CH 2〇 )dCO〇9H ) 5

-0-(CH2CH2〇)eH

-0-(CH2CH2〇)fH

P〇-(CH2CH2〇)aCOC16H31 —0-(CH2CH20)bC0C16H31 -〇-(CH2CH2〇)cCOC16H31 —〇-(CH2〇H 2〇)dCOC-| βΗ 31 —0-(CH2CH2〇)eH _〇- ( CH2CH 2〇)fH

〇-(CH2CH20)aCOC17H33 -0-(CH2CH20)bC〇C17H33 —0-(CH2CH20)cC〇C17H33 —〇-(CH2CH2〇)dC〇Ci 7H33 -0-(CH2CH2〇)eH -0-(CH2CH2〇 )fH "〇-(CH2CH2〇)aC〇C18H35 -0-(CH2CH2〇)bC0C18H35 —O ~ (CH2〇H2〇)cCOCi 8H35 -〇-(CH2CH2〇)dC〇C18H35

-0-(CH2CH2〇)eH

-〇-(CH2CH2〇)fH a+b+c+d+e+f=20~70 The nonionic surfactant represented by the general formula (4) can be obtained from commercially available commercial grade products such as Kao The company manufactures RHEODOL 4 3 0V, 440V, 460V and so on. In the honing liquid of the present invention, these (C) nonionic surfactants may be used singly or in combination of two or more kinds thereof. -25- 200907035 (C) The addition amount of the nonionic surfactant is preferably 0.001 to 10 g, more preferably 0 · 0 1 in the honing liquid used for honing in honing. Up to 5 grams, especially good for 〇 01 to 1 gram. That is, the amount of the surfactant to be added is preferably 0.01 g or more in order to obtain sufficient efficacy, and is preferably not more than gram in view of preventing a decrease in the C Μ P speed. [(D) Colloidal cerium oxide] The honing fluid of the present invention contains colloidal cerium oxide in at least a portion of the honing particles. The colloidal cerium oxide is preferably a colloidal cerium oxide obtained by hydrolysis of an alkoxy decane in the absence of an alkali metal or the like inside the particles. On the other hand, although colloidal cerium oxide produced by a method of removing alkali by an aqueous citric acid solution can also be used, in this case, alkali metal remaining inside the particles is slowly eluted. Concerns about the impact and honing performance. From these viewpoints, it is more preferred to use a material obtained by hydrolysis of alkoxysilane as a starting material. The particle size of the colloidal cerium oxide can be appropriately selected depending on the purpose of use of the honing granules, and is usually about 10 to 200 nm, and is preferably one-time average granule from the viewpoint of not causing honing damage. The diameter is in the range of 20 to 50 nm. The content (concentration) of the (D) colloidal cerium oxide in the honing liquid of the present invention is preferably 5% by mass or more and 15% by mass based on the mass of the honing fluid used in honing. In the following, it is more preferably 3% by mass or more and 12% by mass or less, and particularly preferably 5% by mass or more and 12% by mass or less. That is, the content of the (D) colloidal cerium oxide is preferably from 0.5% by mass or more from the viewpoint of honing the barrier layer at a sufficient honing speed, from storage stability. From the viewpoint of the viewpoint, it is preferably 15% by mass or less. In the honing liquid of the present invention, (D) granules other than colloidal cerium oxide may be used as long as it does not impair the effect of the present invention, but in this case, all of the honing particles (D) The content of the colloidal cerium oxide is preferably 50% by mass or more, and particularly preferably 80% by mass or more. All of the honing particles contained may also be (D) colloidal cerium oxide. For the honing liquid of the present invention, the honing granules which can be used with (D) colloidal cerium oxide include: fumed silica, cerium oxide, aluminum oxide, Titanium oxide, etc. The size of the ruthenium particles used for these purposes is preferably the same as or higher than (D) colloidal cerium oxide, and more preferably 2 times or less. In the honing liquid of the present invention, components other than the essential components of (A) to (D) as described above may be appropriately added as needed. The description of these additional ingredients is as follows. [(E) Compound having a carboxyl group] The honing liquid of the present invention preferably contains (E) a compound having a carboxyl group (hereinafter referred to as "organic acid" as appropriate). The compound having a carboxyl group is not particularly limited as long as it is a compound having at least one carboxyl group in the molecule, but it is preferably selected from the viewpoint of honing speed structure to have the following formula ( 5) The compound represented. Further, the number of carboxyl groups present in the molecule is preferably from 1 to 4, and more preferably from 1 to 2 from the viewpoint of being inexpensive to use. -27- 200907035 General formula (5)

R7 - 〇-R8 - C〇〇H In the above formula (5), R7 and R8 each independently represent a hydrocarbon group, preferably a hydrocarbon group having a carbon number of from 1 to 1. R7 is a monovalent hydrocarbon group, preferably, for example, an alkyl group having 1 to 1 ring of carbon atoms (e.g., a methyl group, a cycloalkyl group, etc.), an aryl group (e.g., a phenyl group, etc.), an alkoxy group, an aryloxy group, or the like. . R8 is a divalent hydrocarbon group, preferably, for example, an alkylene group having 1 to 1 carbon atom (e.g., a methylene group, a cycloalkyl group, etc.), an aryl group (e.g., a phenyl group), an alkoxy group. Base. The hydrocarbon group represented by R7 and R8 may further have a substituent, and the substituent which may be used for introduction includes, for example, an alkyl group having 1 to 3 carbon atoms, an aryl group, an alkoxy group, a carboxyl group, etc., if the substituent is In the case of a carboxyl group, the compound will have a plurality of carboxyl groups. Further, R7 and R8 may be bonded to each other to form a ring structure. The compound represented by the above formula (5) includes, for example, '2-furancarboxylic acid, 2,5-furandicarboxylic acid, 3-furancarboxylic acid, 2-tetrahydrofurancarboxylic acid, monoglycolic acid (3 - a diglycolic acid, methoxyacetic acid, methoxyphenylacetic acid, phenoxyacetic acid or the like; wherein, from the viewpoint of honing the surface to be polished at a high speed, it is preferably 2, 5-furandicarboxylic acid, 2-tetrahydrofurancarboxylic acid, diglycolic acid, methoxyacetic acid. In the honing liquid of the present invention, '(E) a compound having a carboxyl group (preferably a compound represented by the formula (5)) is added in an amount relative to the honing liquid used in honing of -28-200907035 The weight is preferably 0.1% by mass or more and 5% by mass or less, more preferably 0.5% by mass or more and 2% by mass or less. In other words, the content of the compound having a carboxyl group (organic acid) is preferably 0.1% by mass or more from the viewpoint of achieving a sufficient honing rate, and is considered from the viewpoint of not causing excessive dishing. It is preferably 5% by mass or less. [Other Ingredients] The honing liquid of the present invention may be in addition to the component (A) to the component (D) and the preferred component (E) as described above. Other known ingredients may be employed without damaging the scope of the invention. [Interfacial Agent] The honing liquid of the present invention can be used in addition to a nonionic surfactant. Surfactants which can be used include anionic surfactants and cationic surfactants. Specific examples of the "anionic surfactant" include, for example, mercaptobenzenesulfonic acid, dodecylbenzenesulfonic acid, tetradecylbenzenesulfonic acid, hexadecanylbenzenesulfonic acid, and dodecylnaphthalene. Specific examples of the "cationic surfactant" of the compound of sulfonic acid, tetradecylnaphthalenesulfonic acid, etc. include, for example, lauryl trimethylammonium, lauryl triethylammonium, stearyl trimethylmethane a compound such as succinyltrimethylammonium, octyltrimethylammonium, dodecylpyridinium iron, decylpyridinium, octylpyridinium or the like. The anionic surfactant which can be used in the present invention includes, in addition to the sulfonate described above, a carboxylate, a sulfate salt, and a phosphate salt. -29- 200907035 More specifically, "carboxylate" includes: soap, N-methyl sulphate, polyoxyethylene or polyoxypropylene alkyl ether carboxylate, phthalic acid; "sulfate" Including: sulfated oil, alkyl sulfate, ether sulfate, polyethylene oxide or polyoxypropylene alkyl aryl ether alkyl decyl sulfate; "phosphate salt" includes: alkyl phosphate, polyoxidation Ethylene oxypropylene alkyl aryl ether phosphate. The amount of other surfactants which can be used is preferably from 0.001 to 10 g, preferably from 0.01 to 5 g, particularly preferably from 0.01 to 1 in 1 liter of the honing liquid for honing. Gram. That is, the amount of addition of the interface is preferably 0.01 g in order to obtain sufficient effect, and from the viewpoint of preventing a decrease in the CMP rate, it is preferably 1 g of hydrazine (oxidizing agent). The liquid system may contain a metal oxygen compound (oxidant) which can honing the object. "Oxidant" includes, for example, hydrogen peroxide, peroxyacid salts, iodate, periodate, hypochlorite, chlorite, chlorine, perchlorate, persulphate, heavy chromium Acid salt, permanganate, ozone silver (II) salt, iron (III) salt; among them, it is preferred to use peroxidation $ "iron (III) salt" includes, for example, iron nitrate (ΠΙ), iron ( III), other than an inorganic iron salt such as iron (III) sulfate or iron (III) oxide, it is preferred to use an organic complex salt of iron (III). Aminoalkylamine salt, or agglomerate

Nitrate, nitrate water and L. Chlorination (III -30- 200907035 The amount of oxidant added can be adjusted according to the initial amount of barrier metal CMP. If the amount of shallow crystallization of the barrier metal CMP is in the early stage, that is, in the barrier metal CMP, if When it is not desired to be too coffin, it is preferable to increase the amount of the oxidizing agent, and to increase the amount of the oxidizing agent, and to increase the amount of the oxidizing agent. Since it is preferable to change the amount of oxygen added in the initial stage of the root metal CMP, it is 0.01 mol to 1 mol in 1 liter of the honing liquid used for honing. Preferably, the pH of the honing fluid of the present invention is from 2.5 to 5.0, preferably from 3 to 0 to 4.5 by the honing liquid. When the pH is controlled, the honing speed of the interlayer insulating film can be remarkably adjusted. To adjust the pH to a preferred range as described above, an acid or a buffering agent. The honing liquid of the present invention has a pH at These ranges are more effective. "Alkali/acid or buffer" includes: ammonia, ammonium oxyhydroxide And "non-metal alkaline agent" such as an organic ammonium hydroxide such as tetramethylammonium or an alkanolamine such as diethanolamine or triethanolamine propanolamine; or a base such as potassium hydroxide or lithium hydroxide; "Metal hydroxide"; "inorganic acid" such as nitric acid or phosphoric acid: "carbonate" such as sodium carbonate, "phosphate" such as trisodium, borate, tetraborate, hydroxybenzene, etc. Excellent alkaline agent It is ammonium hydroxide, potassium hydroxide or tetramethylammonium hydroxide. When the shallow disc is used as a large-time grinding wire, it is preferably a barrier agent in the shallow state, and it is preferred to use an alkali/pH in a pH range or the like. Hydroxide, sodium triisogenate, acid, sulfur: phosphate formate: lithium and hydrogen -31- 200907035 Addition amount of base/acid or buffer 'as long as it is below the conductivity as described above' And as long as it is capable of maintaining p Η in a preferred range, then in 1 liter of the honing fluid used in honing, preferably 〇.〇0〇1 摩尔 to 1_0莫耳' More preferably, it is 0.003 mol to 〇.5 mol. (. Chelating agent) The honing liquid of the present invention is for alleviating the mixed polyvalent metal ions and the like. A good influence is preferably a chelating agent (that is, a hard water softening agent) as needed. The "chelating agent" is a hard water softening agent or the like which is a general use of a calcium or magnesium precipitation preventing agent, and includes, for example, , nitrogen triacetic acid, diethylenetriamine pentaacetic acid, ethylenediaminetetraacetic acid, nitrogen-germanium, hydrazine, hydrazine-trimethylene phosphonic acid, ethylenediamine-hydrazine, hydrazine, hydrazine, Ν' - tetramethylenesulfonic acid, trans-cyclohexanediaminetetraacetic acid, 1,2-diaminopropane tetraacetic acid, glycol ether diamine tetraacetic acid, ethylenediamine o-hydroxyphenylacetic acid, Ethylenediamine disuccinic acid (SS isomer), Ν-(2-carboxyethylate)-L-aspartic acid, β-alanine diacetic acid, 2-phosphonic acid butane-1, 2, 4-tricarboxylic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, hydrazine, Ν'-bis(2-hydroxybenzyl) ethylenediamine-oxime, Ν'-diacetic acid, I, 2 - Dihydroxybenzene-4,6-dipropionic acid, and the like. The chelating agent may be used in combination of two or more kinds as needed. The chelating agent is added in an amount as long as it is sufficient to block metal ions such as polyvalent metal ions, for example, in 1 liter of the honing liquid used for honing, 0.0003 to 0.07 m is added. . The honing fluid of the present invention is suitable for honing generally disposed between a wiring composed of a copper metal and/or a copper alloy and an interlayer insulating film, and is formed of a barrier metal material for preventing diffusion of copper-32-200907035. The barrier layer formed. [Barrier Metal Material] The material for the barrier layer constituting the honing object of the honing liquid of the present invention is usually a low-resistance metal material, and particularly preferably TiN 'TiW, Ta, TaN, W, WN, RU 'And among them, Ta and TaN are especially good. [Interlayer insulating film] The interlayer insulating film (insulating layer) to be honed by the honing liquid of the present invention includes, for example, a low dielectric layer having a relative dielectric constant of about 3.5 to 2.0 in addition to an interlayer insulating film which is generally used for TEOS or the like. An interlayer insulating film of a material having an electric constant (for example, an organic polymer system, an SiOC system, an SiOF system or the like, or simply a "Low-k film"). Specifically, a material for forming an interlayer insulating film having a low dielectric constant 'HSG-R7 (Hitachi Chemical Co., Ltd.) &gt; BLACK DIAMOND (US) Applied Materials, Inc.). These Low-k films are usually located under the TEOS insulating film, and a barrier layer and metal wiring are formed on the TEOS insulating film. The honing liquid of the present invention is characterized in that it is suitable for honing the barrier layer, and is suitable for a substrate having a laminated structure of a Low-k film and a TEOS insulating film, whereby the TEOS insulating film can be honed at a high speed, and in Low When the -k film is exposed, the honing speed is suppressed, and honing which has superior surface flatness and suppresses the occurrence of scratches can be achieved. [Wiring Metal Material] -33-200907035 In the present invention, the honed object to be honed is preferably a wiring made of a copper metal and/or a copper alloy, for example, applied to a semiconductor device such as LSI. In particular, the raw material of the wiring is preferably a copper alloy. Further, among the copper alloys, a copper alloy containing silver is preferable. Further, the silver content of the copper alloy is preferably 40% by mass or less, more preferably 10% by mass or less, still more preferably 5% by mass or less, and the most excellent effect can be obtained from 0.00001 to 0.1. Copper alloy in the range of mass %. [The thickness of the wiring] In the present invention, the honed object to be honed is preferably half-lined if it is applied to, for example, a DRAM (Dynamic Random Access Memory) device system ( The half pitch is a wiring of 0·15 or less from m, more preferably 〇.l〇/zm or less, still more preferably 0.08#m or less. On the other hand, if the object to be honed is, for example, suitable for use in an MPU (Micro Processing Unit) device system, it is preferable to have a wiring of 0 · 1 2 // m or less, more preferably 0.09 vm or less. Further better for 〇·〇7 #m below. The honing liquid of the present invention as described above can exert an excellent effect on the honed body having such wiring. [Horse method] The honing liquid system of the present invention comprises: 1. When the concentrate is used, it is diluted with water or an aqueous solution as a use liquid; 2 · The name and the component are prepared as described in the following The form of the aqueous solution is mixed with 'the case where it can be diluted with water as the use liquid as needed; and 3 · It is prepared by using the liquid - 34. 200907035. In the honing method using the honing liquid of the present invention, the honing liquid can be applied in any case. The honing method supplies the honing liquid to the honing pad on the honing platform to contact the honed surface of the honed object and to move the honed surface and the honing pad relative to each other. Regarding the apparatus used for honing, a holder having a honed object having a honed surface (for example, a wafer on which a film of a conductive material is formed, etc.) and a honing pad can be used. There are general honing devices for honing platforms, such as motors that can change the number of revolutions. The honing pad is not particularly limited, and a general non-woven fabric, a foamed urethane, a porous fluororesin, or the like can be used. In addition, the honing condition is not particularly limited, and the rotational speed of the honing platform is preferably a low-speed rotation in which the honing object does not fly below 200 rpm. The pressing force of the honed object having the honed surface (the honed film) for the honing pad is preferably 0.68 to 34.5 kPa, if the honing speed is to be uniform in the surface of the honed object and the pattern In the case of flatness, it is more preferably 3.40 to 20.7 kPa. During the honing, the honing liquid is continuously supplied to the honing pad by a pump or the like. After the honed material is sufficiently washed in the running water after the honing, the water droplets adhering to the honed object are spun and dried by a rotary dryer or the like. In the present invention, the following aqueous solution can be used if the concentrate is diluted according to the method described above. The aqueous solution contains at least one or more of the oxidizing agent -35-200907035, an organic acid, an additive, and a surfactant, and thus the total amount of the component contained in the aqueous solution and the component contained in the concentrated solution for dilution The composition should be consistent with the composition of the honing fluid (use fluid) used in the honing. As described above, when the concentrate is diluted with an aqueous solution, it is possible to prepare a more concentrated concentrate by adding a component which is not easily dissolved in the form of an aqueous solution and then mixing it. Further, when the concentrate is added to water or an aqueous solution to be diluted, the piping for supplying the concentrated honing liquid and the piping for supplying the water or the aqueous solution are combined to be mixed on the way to mix the liquids. A method of supplying a mixed and diluted aging liquid to a honing pad. When the concentrated liquid is mixed with water or an aqueous solution, the liquid can be passed through a narrow flow path to cause the liquids to collide with each other, and the glass tube or the like is filled in the pipe to repeatedly separate the flow and the flow of the liquid. The method generally used, and a method of providing a power rotary fin in a pipe, etc., are generally used. The supply speed of the honing liquid is preferably 10 to 1, 〇〇〇ml/min, and more preferably 170 to 800 ml if the honing speed is to be uniform in the honed surface and the flatness of the pattern. /minute. Further, when the concentrated liquid is diluted with water or an aqueous solution, and the honing is performed, there is a separate arrangement for supplying the honing liquid and the piping for supplying the water or the water-soluble liquid, and each is separately researched. 1 The grinding pad supplies a specific amount of liquid, and one side is honed and honed by the relative movement of the honing pad and the grinding surface. Further, it is also possible to use a method in which a specific amount of the concentrate and water or an aqueous solution are mixed in a container, and then the honing pad is supplied with a mixed slurry. In addition, in other honing methods, there is a method in which at least two components of the honing liquid should be contained, and when used, the water or the aqueous solution is diluted and supplied to the honing platform. The pad is placed in contact with the surface to be honed and the honing surface and the honing pad are moved relative to each other to perform honing. For example, the oxidizing agent may be the constituent component (A), the organic acid, the additive, the surfactant, and the water may be the constituent component (B), and when used, the constituent component (A) may be formed by water or an aqueous solution. The constituent (B) is diluted and used later. In addition, the low solubility additive can be divided into two components (A) and (B), for example, an oxidizing agent, an additive, and a surfactant are used as a constituent (A), an organic acid, an additive, a surfactant, and water. In order to constitute the component (B), when it is used, water or an aqueous solution is added to dilute the component (A) and the component (B) and use it. In the case of the above examples, three kinds of pipes for separately supplying the component (A), the component (B), and the water or the aqueous solution are required, and the dilution mixing method is to connect the three pipes to the supply to the honing pad. A method in which a pipe is mixed in its piping. In this case, a method of connecting two types of pipes and then connecting one of the other pipes may be employed. Specifically, it is a mixture of a component containing a non-dissolving additive and other constituent components and a water or an aqueous solution is connected by lengthening the mixing passage to secure the dissolution time. Other mixing methods include, as described above, directing the three pipes -37-200907035 directly to the honing pad, by mixing the honing pad with the relative movement of the honed surface, or in a container A method of mixing three constituent components and supplying the diluted honing fluid to the honing pad. The honing method as described above, if one of the components containing the oxidizing agent is kept below 40 ° C, and the other constituent components are heated from room temperature to l ° ° C, so that a constituent component and other constituent components When mixing, or adding water or an aqueous solution to dilute, the liquid temperature can be changed to 40 ° C or lower. Since the solubility is increased by using a higher temperature, the solubility of the raw material having a low solubility of the honing liquid can be improved. Therefore, the method is a satisfactory method. When the other constituent components are heated and dissolved in a range from room temperature to 100 ° C as described above, they are precipitated in the solution when the temperature is low, and therefore, other constituents are used in a low temperature state. In the case of 'there must be a liquid in advance to dissolve the precipitated material. For this purpose, a means for supplying the liquid to dissolve the other constituents of the raw material, and a means for previously stirring the liquid containing the precipitate and then supplying the liquid and heating the tube to dissolve it may be employed. If the temperature of the other constituents of the oxidizing agent is increased above 40 ° C, the oxidizing agent may decompose. Therefore, the other components of the heating and the oxidizing agent are mixed. In the case of a constituent component, it is preferably controlled to be 40 ° C or less. As described above, in the present invention, the components of the honing liquid can be supplied in two or more parts to the surface to be honed. In this case, it is preferable to supply a component containing an oxide and a component containing an organic acid. In addition, the honing liquid can be used as a concentrate to separately supply the dilution water to the surface to be honed. In the present invention, when a method of supplying the components of the honing liquid into two or more parts to the surface to be honed is applied, the supply amount thereof indicates the total amount of supply from each pipe. [Cushion] The honing pad for honing which can be applied to the honing method of the present invention may be a non-foamed structural mat or a foamed structural mat. In the former case, a hard synthetic resin block material such as a plastic plate is used as a mat. In the latter case, three types of independent foam (dry foaming), continuous foam (wet foaming), and two-layer composite (layered) may be used, and among them, particularly preferred Two-layer composite (layered system). The foaming can be in a homogeneous or heterogeneous form. Further, it may be one containing abrasive particles (for example, ceria, ceria, alumina, resin, etc.) which are generally used for honing. Further, the hardness may be obtained from each having a soft or a hard one, but may be either, and in the laminated system, it is preferred to use a layer having a different hardness. The material is preferably non-woven fabric, artificial leather, polyamide, polyurethane, polyester, polycarbonate, or the like. Further, in the surface in contact with the surface to be honed, processing such as a square groove/hole/concentric groove/spiral groove can be applied. [Wafer] The wafer to be polished of the CMP object using the honing liquid of the present invention preferably has a diameter of 200 mm or more, particularly preferably 300 mm or more. The present invention can significantly exhibit the effect on a wafer having a diameter of 300 mm or more. -39- 200907035 [Horry Grinding Device] There is no particular limitation on the device for performing honing using the honing fluid of the present invention. For example, it can be used, for example, Mirra Mesa CMP, Reflexion CMP (American Applied Materials Co., Ltd.) FREX200, FREX3 00 (manufactured by Ebara Seisakusho Co., Ltd.); NPS3301, NPS2301 (manufactured by Nikon Corp.); A-FP-310A, A-FP-210A (manufactured by Tokyo Precision Co., Ltd.); 2300 TERES ( Lam Research Co ., manufactured by Ltd.; Momentum (manufactured by Speedfam IPEC, Inc.), and the like. <<Embodiment>> Hereinafter, the present invention will be described in more detail by way of examples, but the invention is not limited thereto. [Example 1] A honing liquid having a composition as described below was prepared to carry out a honing experiment. 0.2 g / liter 0.5 g / liter 0-1 g / liter 200 g / liter 1 g / liter • (A) quaternary ammonium cation: A-1 • (B) corrosion inhibitor: benzotriazole (BTA) • (C) Nonionic surfactant: S -1 • ( D ) Colloidal cerium oxide: C-1 (secondary particle size: 65 nm, PL3 slurry, manufactured by Fuso Chemical Industry Co., Ltd.) • (E) Compound with a carboxyl group: E-1 (manufactured by Wako Pure Chemical Co., Ltd.) -40- 200907035 • Oxidizer: hydrogen peroxide 1 〇 ml • Total amount of pure water after adding 1,0 0 ml • pH (with ammonia and Nitric acid to adjust) 3.5 (Evaluation method) The honing device uses the device "LGP-6 1 2" manufactured by Lapmaster SFF Corp. to supply the honing liquid on one side to honing the wafer film as follows. . • Turntable revolutions: 90 rpm • Head rotation: 85 rpm • Honing pressure: 13.79 kPa • Honing pad: Polotexpad manufactured by Rodel-Nitta Co. • Honing fluid supply speed: 200 ml/min (honing speed evaluation) : honing object A) honing object A is used to form a film of SiOC film (BLACK DIAMOND, TEOS film, Ta film ' and copper film) in this order on a ruthenium substrate. 8-inch wafer. (Scratch evaluation: honing object B) honing object B is used by lithography by photolithography and reactive ion etching. The L 〇w - k film and the TEOS film are patterned to form a wiring trench and a connection hole having a width of 0.09 to 100/zm and a depth of 600 urn, and a Ta film having a thickness of 20 nm is formed by sputtering. After forming a copper film having a thickness of 5 〇 nm by sputtering, a 41-inch wafer obtained by a copper film having a total thickness of 1, 〇〇〇nm is formed by electroplating. &lt; Honing speed &gt; The honing speed is determined by honing the object A for honing speed evaluation in CMP The film thicknesses of the TEOS film (insulating film) and the SiOC film (Low-k film) before and after are calculated by the following formula, and the results obtained are shown in Table 1: Honing speed (A/min) = ( Film thickness before honing - film thickness after honing) / honing time. &lt;Scratch evaluation&gt; The honing object B for scratch evaluation as described above, using the wafer as described above The TEOS layer was honed and honed to a SiOC film (the SiOC film was honed at 20 nm), and then the honing surface was washed with pure water and dried. The dried honing surface was observed under an optical microscope, and according to the following The evaluation criteria were evaluated for scratches, and the first and second items were judged to be practically no problem. The results obtained are shown in Table 1. An evaluation benchmark 1: 1 is observed as a problematic scraping Injury; 2: One to two observations in the wafer surface can be a problematic scratch; 3: Many scratches that are problematic are observed in the wafer surface. [Examples 2 to 4 4, and comparison Examples 1 to 3] The composition of the first embodiment (1) was changed to the composition shown in the following Tables 1 to 4 to prepare a honing liquid, and The same honing conditions were applied to the honing conditions of Example 1. The results obtained are shown in Tables 1 to 4. -42- 200907035 V. - 1111 〇〇〇〇〇〇〇〇〇〇〇〇〇〇 TEOS honing speed (nm/min) 00 oo ON Ο cn 00 oo (N § % in SiOC honing speed (nm/min) rs o 〇\ 00 om 1-H ν〇mt·^ σν 00 inch 2 ο Rn &lt;N rn in rn ro Γ〇o — «η inch· ΓΟ o 00 ΓΟ m rn ι/Ί ri — vr&gt; r~i (he #量T 钪CQ —d &lt; 〇HHQ 03 &lt; HQ & - Trial CO 0-( Sq u Q * - 〇 · &lt;;w (Π « &lt; H CQ 2 X — Ο &lt;s 03 J i &lt; Η oa s $ m ^ d WW &lt;; CT) μ cq Sq —d &lt; CL, HQ ffl /^NH CQ N \·_Χ &lt;CH CQ 2 誃cs mg Qu (D) Colloidal cerium oxide (content) _ ύ »r&gt; in (N cn —m όό 调 CN ύ /—N 舾cn ύ __ ft® &lt;nH —m ύύ N _ in inch ύ 13⁄43⁄43⁄4 fN (N inch in όύ r&quot;s ¢1 ft yr\ &lt;N ύ /-s _ » ύ ή _ in; ft i〇fN (NV-/Nw/ &lt;N rn όό /-N _ » (N ύ /^N _ ft l〇ύ /&quot;N _ » ur~\ _ »Τί ύ ( E) organic acid (including s! 'xs! N-_«/ s§ 5§ N s! r-\ ^ hJ /-~N 2! s§ /—N /-&quot;s —Θ S—X s! /-~ N 'v·_«-, (A) Grade IV salt (with halo) &lt; fS o A-2 (〇, 2g/L) &lt; (N O' s_^ /^N &lt;N 〇• s^ A-5 (0.2 g/L) &lt; (N O' rrS &lt; (N 〇A-8 (0-2 g/L) &lt;&lt;N O' Nw/ A-10 (0.2 g/ L ) _ A-ll (0.2 g/L) A-12 (0.2 g/L) A-13 (0.2 g/L) A-14 (0.2 g/L) (C) Surfactant (content) /- N CO — o r.5 00 (N o /^N &lt;7 ^ CO (N 〇/•~N ζ/^ »-&lt; o r-\ o C/D — 〇s_x /•~N CO ( N o 〇=5 ¢/3 (N 〇/—s J ~b£ W — O \·_χ /~N 00 &lt;N o S-ll (0.1 g/L) S-12 (0.1 R/L) S-13 (〇·1 g/L) si C/3 ^ 〇Sw✓ Example 1 (N series m IK t-shirt 1 〇 IK m 蜀 闺 闺 OO 闺 κ o 闺 κ 〇 κ m 习IK (N 1~—( 握 U m 1-H 习 ***^ 习 κ - inch _ 200907035 N Wenhua 〇〇〇〇〇〇〇〇〇〇〇〇〇〇Ο S S -11 00 g ^ 0 (Ν 00 Ό 0 •T) OS g JQ ^0 00 SiOC honing speed (nm/mi (N 1- H Ο 00 On 1〇 inch〇1-H Ο 0 »n uS \Ti rr; p inch · yn ΓΛ Ό inch · fN ΓΛ ι〇rn q — «Ο rn W) CN IT) cn 00 cn in m rn _ /-~NC 1&quot;^ /*~N 1-^ '-W/ — in wd ji ^l〇c° s —0 5i C〇/-N &lt; 53⁄4 2 5 &lt; Dh 55 ^ w \_^ Yn &lt;c〇/-~N GO Η H « CH &lt;, Η H co CQ pa WQ a WQ &lt; H &lt; PL, &lt;s &lt;&gt; c^ &lt; HHS &lt; HUQ oa CQ Q Ffl HQ m Η H CQ J 卜 Q CQ W P3 u PHQ ffl &lt;Q UQ X CQ /—N /*~N /—s /&quot;S /-s /~N /—\ /^S /-' s 容 r~N /^N _ _ _ _ _ 调 咽 _ _ _ _ _ _ iM 〇HS®N 61 Km ft IT) » » l〇» κη ft •T) » Which 1\娜I , in νΊ » i〇ft l〇» amam ft H 魈^ 'v_x Sw^ ,·»✓( CN cs 'Sw/ -Vw^ &gt;w, 鹚u ?—N 1 O m ό ΰ (N ΰ ύ i—im ΰύ ύ ^-H ό rn rn ύ (N ΰ ΰ ό (E) Organic acids (with halo) /--N s! ώ ^ »-H s! s! /--N —Η r- \ ^r id s? (N r~s —J s§ Sw&gt; /^\ s! 'ws! s! s! (A) Grade IV salt (content) /—N r~-\ 213⁄4 si Art 5 si /•&quot;N r5 ^ &lt;B &lt;s \^' &Lt;2 vSw/ &lt;s \_✓^ &lt;s &lt;2 s___x &lt;2 Sw/ &lt;2 v_y &lt;2 &lt;s &lt;BS_✓ &lt;s &lt;s &lt;SN-^ /-~N -5 /~Ν ® ^ mouth 5 art s S-25 (0.2 g/L) 〇ό —· 〇 (/} ^ 0 〇〇〇εΛ ^ ο 'Ν-_·✓ 0 s^ xh ^. 0 V—✓ 1/3^ 〇〇^_✓&lt;〇〇&lt;ί O 〇's_·✓ OA 1 o yr\ v〇卜00 ON r—H (N m (N »r&gt; ( N Ό (N 00 CM 匡匡匡匡m 匡匡匡 辑 留 留 留 in in in IK κ in K Μ κ U Ιϋ w IK shirt 200907035 / 〇〇〇〇〇〇〇〇 〇〇〇〇〇〇O wins pleats! ro g 00 00 yn 00 JO 00 00 s On On 00 00 ^ο 00 r Folk 〇〇 OS OS ο O 〇 m \ m rj 00 inch II α 〇ro CO (N (N ^Τ) rn ο — vn 对 · Ό cn in — mr^io rn ^Τ) r^i Ό rn (the amount he contains) BTA (lg/L) BTA (lg/L) /^N &lt; H PQ suitable cs CQ ^ 5? ^ΙΤ5 ^ 〇fcQ 03 li ^ 〇筘ω X 1—Η m /*~N &lt; H CQ /-~N , ' KH CQ i CQ BTA (lg/L), DP (0.5 g/L) BTA (lg/L), DP (0.5 g/L) &amp; it ω X sp X /—N/^N __ /^N /—N /^N /^N /-&quot;NZ-'S 2 Secret_ _ 13⁄4 _ ft _i _ 酗__ _ m _ H _ tune » _ tune » mm j^Ul\^iu\ _ » , ✓丨丨'山s卜in ΙΛ) »r&gt; ri &lt;n ^T) in (N CN Ό l〇VwX m ^ri s_-»^ »r&gt; s—/ in «η (N CN t〇 ό (N ύ ώ · —' m όύ ύ *—&lt; cn όύ ύ ό 1—H ύ 1—H ύ &lt;N ύ ύ—m ύό (E) Organic acid (content) ώί ή /-N —Θ s! /—Ν ξ ! /*~N CN r-\ /--V &lt;N id ώ3 /-~N ώ§ s? s§ ^ J /~N s! &lt;lji ?! ^ ?ii p;5 /*~N /—S r-*dm ox /~N pi5 &lt;2 &lt;s &lt;2 &lt;2 &lt;3 &lt;S Nw^ &lt;2 &lt;s &lt;2l &lt;S &lt;2 &lt;s &lt;S Vw/ &lt;2 (C) Surfactant (content) kg s =^5 S-25 (〇.lg/L) sS S-22 (0.2 g/L) -2 O \~y CO — o ώ—· ο C/D — o ΕΛ ^ 〇A — o \_✓^ C^ »~H o ν·_^ A o '&quot;w/&lt; ΙΛ^ o S—/ -S m (N Mmm in tr\ cn 00 OS CO 〇 s 匡 辑 辑 辑 辑 留 留握习习习习{_ W IK κ i¥ Μ uu κ m IK fc κ Μ 200907035 inch 漱骊 11 〇〇&lt;] XXI TEOS honing speed (nm/min) 00 OS ON ir» SiOC honing speed ( Nm/min) 00 CN m »n cn to rn rn w-&gt; oo in (the amount he contains) BTA (lg/L) BTA (1 g/L) such as oo twist opy quite m twist sentence 03⁄4 C® mc view; 5 llm 狴(D) colloidal cerium oxide (with halo) _ 鲰rn ύ _ ft (N ύ /-~N t· _ 舾in ύ s? This Dl_ in® m r4 CN (N Rp ύύ /~s _ ft ύ (E) Organic acid (content) /--S s! (A) Grade IV salt (content) A-35 (0.2 g/L) A-36 (0.2 g/L) ( C) Surfactant (content) _ S-28 (0.1 g/L) (7) (N d Example 43 ϊ 闺 IK Comparative Example 1 CN 镒Ϊλ _9 inch - 200907035 As disclosed in Tables 1 to 4 above ( A) quaternary ammonium cations (specific cations) A -1 to A - 4 6 are meant to represent the detailed details of the compounds exemplified above as shown in Tables 1 to 4 above. As shown below: (B) Corrosion inhibitor BTA: 1,2,3-benzotriazole DBTA: 5,6-dimethyl-1,2,3-benzotriazole DCEBTA: 1-( 1,2-dicarboxyethyl)benzotriazole HEABTA: 1-[N,N-bis(hydroxyethyl)aminomethyl]benzotriazine HMBTA: 1-(hydroxymethyl)benzene Further, the names of the nonionic surfactant surfactants S-1 to S-7 which are disclosed in Tables 1 to 4 as described above are shown in Table 5 below. Further, the structure of 'S-10 to S-31 is as follows. Table 5 (C) Nonionic surfactant S-1 Polyoxyethylene undecane ether _____- S-2 Polyethylene oxide whale _ ___ S-3 Polyoxyethylene lauryl ether S-4 Polyethylene oxide Oil jacket ether S-5 Polyoxyethylene myristyl ether ___ S-6 Polyoxyethylene octyl eleven-yard ether S-7 Polyethylene oxide - + "Shocking -47- 200907035 S-8 S-9

R〇-(CH2CH2〇)aCOC6H1! -O -(CH 2CH2〇)bCOC6Hi! -0-(ΟΗ2〇Η20)〇〇〇〇6Ηι 1 —O -(OH 2〇Η2〇)(ΐ〇〇〇6Η· | ί -〇-(CH2CH2〇)eH —O -(GH 2〇H2〇)fH

pO-(CH2CH2〇)aCOC8H15 -O-iCHzCHzOJbCOCeH! 5 -0-(CH2CH20)cC〇C8H15 -〇-(CH2CH20)dC〇CgH15 —0-(CH2CH20)eH -〇-(CH2CH2〇)fH a+b+ c+d+e+f=30 a+b+c+d+e+f=30 S_10 —O ~(CH2〇H2〇)aC〇Cl 2^23 —O-(OH 2CH2O) ΐ3〇〇〇· )2Η2 3

—〇-(CH2〇H2〇)(;C〇Ci2H23——〇-(CH2CH2〇)(jCOC-)2^23 —〇-(CH2CH20)eH -0-(CH2CH20)fH S-11“0—(CH2CH20 )aC〇C16H31 —O—(CH2CH2〇)bC〇Cl6H3l —O—(CH2CH2〇)cC〇Ci 63⁄4

-0-(CH2CH2〇)dC〇C16H31 —〇-(CH2CH20)eH -〇-(CH2CH2〇)fH a+b+c+d+e+f=30 a+b+c+d+e+f= 30 S-12 "〇-(CH2CH2〇)aC〇Ci7H33 -〇_(CH 2CH2〇)tjC〇Ci 7H33 -0-(CH2CH2〇)cC〇Ci7H33 —O -(OH 2CH2〇)dCOC-| 7H33

—〇-(CH2CH20)eH S-13“〇_(CH2CH2〇)aC〇C18H35 —〇—(〇Η2〇Η2〇^〇〇〇18^35 -〇-(CH2CH20)cC〇C18H35 —O-(CH2 〇H2〇)c|C〇Ci8H35

—0-(CH2CH20)eH

L0-(CH2CH20)fH

L〇-(CH2CH20)fH a+b+c+d+e+f=30 a+b+c+d+e+f=30 [RHEODOL 430V: manufactured by Kao Corporation] -48- 200907035 S-14 S- 15

—O —(CH2〇H2〇)aC〇C6Hi 1 -〇-(CH2CH2〇)bC〇C6H1! -〇-(CH2CH2〇)cC〇C6H1! -O-CCHzCHsOJdCOCeHn -〇-(CH2CH20)eH -〇-( CH2CH2〇)fH

P〇-(CH2CH2〇)aC〇〇8Hi 5 -0-(CH2CH20)bCOC8H15 —〇-(CH2CH2〇)cC〇C8H15 -〇-(CH2CH2〇)dC〇CgH15 -〇-(CH2CH2〇)eH -0- (CH2CH20)fH a+b+c+d+e+f=40 a+b+c+d+e+f=40 f S-16“〇_(CH2CH2〇)aC〇Ci2H23 -O -(CH2CH2〇 ) b〇〇C12H23 —〇—(CH2〇H2〇)cC〇C-| 2^23 SH 7“〇_(CH2CH 2〇)aC〇Ci βΗ 31 -〇-(CH2CH2〇)bC〇C16H31 —0- (CH2CH20)cC〇C16H31 —O-(GH2〇H2〇)dCOC-|2H23 —O—(CH2CH2〇)dCOCi6H3i

-〇-(CH2CH20)eH —0-(CH2CH20)fH a+b+c+d+e+f=40

-〇-(CH2CH2〇)eH

-0-(CH2CH20)fH a+b+c+d+e+f=40 S-18"〇-(CH2CH20)aC0C17H33 S-19"〇-(CH2CH2〇)aCOC1BH35 -〇一(CH2CH20)bC0C17H33 -〇 -(CH2CH20)cCOC17H33 —〇—(CH2〇H2〇)dCO〇i 7H33

—〇-(CH2CH20)eH -0-(CH2CH20)fH —0-(CH2CH20)bC0C18H35 —〇_(CH2CH20)cC〇C18H35 —O—(CH2〇H2〇)tjCOCigH35

-0-(CH2CH20)eH

-〇-(CH2CH20)fH a+b+c+d+e+f=40 a+b+c+d+e+f=40 [RHEODOL 440V: manufactured by Kao Corporation] -49- 200907035 S-20

P〇-(CH2CH2〇)aC〇C8Hl 5 -O-iCHsCHzOibCOCeH! 5 —〇一(CH2CH20)cC〇C8H15 -O-iCHzCHzOJdCOCeHi 5 -0-(CH2CH2〇)eH -0-(CH2CH20)fH (CH2CH2〇) aCOC6H” S-21 0-(CH2CH20)bC0C6H11 -〇-(ΟΗ2〇Η2Ο)0〇〇〇6Ηιι -O-iCHzCHzOJdCOCeHn

〇-(CH2CH2〇)eH

0-(CH2CH20)fH a+b+c+d+e+f=50 a+b+c+d+e+f=50 S-22 “◦-(CH2CH2〇)aCOC16H31 -0-(CH2CH20)bC 〇Ci 6H3i —O—(CH2CH20)cC0C16H31 -0-(CH2CH20)dC0C16H31 —0-(CH2CH20)eH —〇—(CH2CH20)fH a+b+c+d+e+f=50 〇—(CH2〇H2 〇)aCOCi2H23 S-23 .〇_(CH2CH2〇)bC〇C·] 2H23

0—(CH2CH2〇)cCCKi-)2^23 〇—(ΟΗ2〇Η2〇)ς|〇〇〇,ι 2^23 O-(CH2CH20)eH

0_(CH2〇H2〇)fH a+b+c+d+e+f=50 \ S-24 〇~(CH2CH2〇)aCO〇i7H33 S-25 0—(CH2〇H2〇)bCOC-| 7H33 • 〇一(CH2CH2〇)cC〇Ci

〇-(CH2CH20)dC〇Ci 7H33 〇-(CH2CH2〇)eH O-(CH2〇H2〇)fH a+b+c+d+e+f=50 ”0-(CH2CH20)aC0C18H35 -〇-(CH2CH2 〇)bCOC18H35 -〇-(CH2CH20)cC0C18H35 -〇-(CH2CH2〇)dC〇Ci8H35

—0-(CH2CH2〇)eH

-0-(CH2CH20)fH a+b+c+d+e+f=50 50 200907035 S-26 S-27

—O —(CH2CH2〇)aCO〇6H·) ·| —O —(CH2CH2〇)bCOCgH·) i —O—(ΟΗ2〇Η2〇)〇〇〇〇6Η·| ·) —Ο—(CH2CH2〇) dCOCgH·! 1 —O _(CH2CH2〇)eH —O —(CH2〇H2〇)fH

—〇—(CH2〇H2〇)aC〇〇8Hl5 -0-(ΟΗ2〇Η2〇^008Η·, 5 —〇-(CH2CH20)cC0C8H15 -0-(CH2CH2〇)dCOC8H15 -0-(CH2CH2〇)eH - 0-(CH2CH2〇)fH a+b+c+d+e+f=60 a+b+c+d+e+f=60 / S-28 —0_(CH2〇H2〇)aC〇Cl2H23 S_29 — O -(CH2CH2〇)bCOC·) 2H23 Ο-(ΟΗ2〇Η2〇)〇^0〇ΐ2Η23 —O —(CH2〇H2〇)cjCOCi 2H23 〇-(CH2CH20)aC0C16H31 -0-(CH2CH20)bC0C16H31 —〇- (CH2CH2〇)cCOCi6H3i 0-(CH2CH20)dC0C16H31

—〇 —(CH2〇H2〇)eH

—O—(CH2〇H2〇)fH a+b+c+d+e+f=60

-0-(CH2CH20)eH

-〇-(CH2CH2〇)fH a+b+c+d+e+f=60 \ S-3〇“0-(CH2CH2〇)aC〇Ci7H33 —〇—(CH2CH2〇)bCO〇i 7H33 —〇— (ΟΗ2〇Η2〇)〇〇00·| 7H33 S-31 —〇—(CH2〇H2〇)aCOC-|0H35 —O—(CH2〇H2〇)bCOC-| eH 35 —0-(CH2CH20)cC〇 C18H35 —〇-(CH2〇H2〇)dC〇Ci 7H33 —0-(CH2〇H2〇)ciCOCi8H35

An O—(ΟΗ2〇Η2〇)βΗ—O—(CH2〇H2〇)fH

-〇-(CH2CH2〇)eH -〇-(CH2CH20)fH a+b+c+d+e+f=60 a+b+c+d+e+f=60 [RHEODOL460V: manufactured by Kao Corporation] -51 - 200907035 will be described in the shape of (D) colloidal ceria C-1 to C-5 shown in Tables 1 to 4 above, and the primary average particle diameter is shown in Table 6 below. (E) Compound having a carboxyl group The compound names of E-1 to E-5 are shown in Table 7 below. Further, the colloidal cerium oxides shown in Table 6 below were all manufactured by Fuso Chemical Industry Co., Ltd. Table 6 Name of honing grain [primary mean particle size (継), shape] C-1 PL3 [35 nm, 茧 shape] C-2 PL3L [35 nm, globular] C-3 PL3H [35 nm, agglomerate] C-4 PL2 [25 nm, 茧] C-5 PL2L [20 nm, globular] Table 7 (E) Compound E-1 with sulfhydryl group E-2 2,5-furandicarboxylic acid E- 3 2-tetrahydrofurancarboxylic acid E-4 methoxyacetic acid E-5 methyl acetate carboxylate From Tables 1 to 4, it is known that when using the honing liquids of Examples 1 to 37, compared with Comparative Examples 1 to 3, TEOS The honing speed is high, and the honing speed of the SiOC insulating film belonging to the Low-k film is suppressed, and also has superior scratching performance. On the other hand, in the honing liquids of Comparative Examples 1 to 3, the honing speed of the TEOS, the honing speed suppressing ability of the SiOC insulating film, and the scratching property were all inferior to those of the honing liquid of the examples. Therefore, it is understood that the honing liquid system of the present invention has a superior TEOS honing speed, and can effectively suppress the 硏-52-200907035 grinding speed of the SiOC insulating film belonging to the Low-k film, and also has superior scratching. performance. [Simple description of the schema] Sister. [Main component symbol description] te 〇 j\w -53-

Claims (1)

200907035 X. Patent application scope: 1. A honing fluid' is used for chemical mechanical honing in the semiconductor integrated circuit flattening step, and contains quaternary ammonium cation, corrosion inhibitor, nonionic surfactant And colloidal silica sand with a pH of 2.5 to 5.0. 2. The honing liquid according to claim 1, wherein the quaternary ammonium cation is a cation represented by the general formula (1) or the general formula (2): R3 R4 - N - R2 General formula (1) I , R2 General formula (2) R1 IN~~X R3 N-R5 R6 [In the general formula (1), general formula (2), R1 to R6 each independently represent a carbon number An alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aryl group or an aralkyl group of 1 to 20, and two of R1 to R6 may be bonded to each other to form a cyclic structure, and X represents a carbon number of 1 to 1 伸 of an alkyl group, an alkenyl group, an alkynylene group, a cycloalkyl group, an aryl group, or a combination of two or more of these groups]. 3. The honing fluid according to claim 1 or 2, wherein the non-off-54-200907035 sub-system surfactant is selected from the group consisting of an ether type nonionic surfactant and an ether ester type nonionic interface activity. One or more of the group consisting of a reagent and an ester type nonionic surfactant. 4. The honing liquid according to claim 3, wherein the nonionic surfactant is a compound represented by the general formula (3) or the general formula (4) as follows: Formula (3) R——〇——(CH2CH2〇)n——Η [In the formula (3), R represents an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group or an aralkyl group having 2 to 30 carbon atoms. Base, η represents the number of bonds of the polyoxyethylene group and is an integer of 2 to 30]; Formula (4) "〇-(CH2CH2〇)aC〇R1 -〇-(CH2CH2〇)bC〇R2 -〇 -(CH2CH2〇)cC〇R3 -〇-(CH2CH2〇)dC〇R4 -0-(CH2CH20)eH -〇-(CH2CH2〇)fH a+b+c+d+e+f=20 ～70 [at In the formula (4), R1 to R4 each independently represent an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group or an aralkyl group having 2 to 30 carbon atoms, a, b - 55 - 200907035, c , d, e, and f represent the number of bonds of the polyoxyethylene group, respectively, and a + b + c + d + e + f is 20 to 70]. 5 · As disclosed in any of claims 1 to 4 The honing liquid according to the item, wherein the concentration of the colloidal cerium oxide is from 0.5 to 15% by mass based on the total mass of the honing liquid. The honing liquid according to any one of claims 1 to 4, wherein the primary average particle diameter of the colloidal cerium oxide is in the range of 20 to 5 Onm. 7 · If the patent application is in the range of items 1 to 4 The honing liquid according to any one of the preceding claims, wherein the corrosion inhibitor is selected from the group consisting of 1,2,3-benzotriazole, 5,6-dimethyl-1,2,3-benzotriazole, toluene Triazole, 1-( 1,2-dicarboxyethyl)benzotriazole, 1-( 1,2-dicarboxyethyl)tolyltriazole, Bu [N,N-bis(hydroxyethyl) Aminomethyl]benzotriazole, 1-[N,N-bis(hydroxyethyl)aminomethyl]tolyltriazole, 1-(2,3-dihydroxypropyl)benzotriazole, At least one compound of the group consisting of 1-(2,3-dihydroxypropyl)tolyltriazole and 1-(hydroxymethyl)benzotriazole. 8. As claimed in claims 1 to 4 The honing liquid according to any one of the preceding claims, which comprises a compound having a carboxyl group represented by the formula (5): (5) r7-0-r8-OOOH [in the formula (5), R7 And R8 each independently represents a hydrocarbon group, and R7 and R8 systems may be bonded to each other to form a cyclic structure]. -56- 200907035 VII. Designated representative map: (1) The representative representative of the case is: No. (2) The symbolic symbol of the representative figure is simple: ^PR1 〇/ V NN 8. If there is a chemical formula in this case, please reveal the most A chemical formula that shows the characteristics of the invention: