TW200940606A - Colloidal silica and its CMP composition - Google Patents

Abstract

The present invention is related to a CMP(Chemical Mechanical Polishing) composition. In the first stage of GMP, it can control dishing being worsen and there are no polishing fragments left. In the second stage, it can improve fangs.

Description

200940606 VI. Description of the Invention: [Technical Field] The present invention relates to a surface-modified colloidal silica and a polishing composition for CMP (Chemical Mechanical Polishing) containing the same, in particular When forming a wiring by a damascene method or the like in the manufacture of a semiconductor device, it is preferable to use a polishing composition for CMP which is ideal for CMP. ❹ 【Prior Art】 In the CMP technology, the wafer that was flattened on the rotating plate was placed, and the pure fine wafer table was examined, and the side of the wafer was examined. Both the rotating disk and the polishing pad are rotated for polishing. By polishing the surface of the object to be polished by the mechanical action of the abrasive particles in the polishing composition and the surface of the polishing pad by CMp, the surface of the wafer is flattened by the chemical reaction of the compound of the FR material and the surface of the object to be polished. Chemical. In the manufacture of a semiconductor device, the cloth scale is formed by a metal test, and the remaining wiring layer and the gold transfer system are removed. The (10) towel is in the conventional real-time 7-grinding method, and is as follows: The polishing of the segment is carried out by grinding: the wiring layer of the surface layer is drilled in the second stage, and the layer of the remaining layer of the layer and the scale layer of the barrier layer are polished, and the surface of the surface is flattened. Shaped defect (Dishing) or Lai (_ take-grinding surface' without grinding touch, imparting damage (Cai (4) heart 200940606 grinding surface, applying sufficient grinding speed without producing production problems. In addition, in the case of grinding in the i-th stage 'Requires lion grinding, that is, effectively removes the wiring layer including copper and copper alloys. The wiring layer' strongly suppresses the barrier metal layer of the material containing the group, nitrogen, etc.; in the case of the second stage grinding, it is required Non-selective grinding, that is, a difference in polishing rate is small with respect to a raw material containing a scale material, a barrier metal layer, a second insulating layer of an organic material, and the abrasive particles used in the polishing composition for W, Surface modification with organic groups The research has been carried out on the stone eve. For example, in the patent document ι, it is disclosed that 表面 表面 将 将 将 将 以 以 以 以 以 以 以 以 以 以 以 以 以 以 以 以 以 ; ; ; ; ; ; ; ; ; ; ; ; ; As a compound which introduces a dimethyl sulphate group, it is a bis-di-dichloro-propion. In addition, in the patent document 2, it is revealed that the base-wei-coupled 継 表 表 导 之 。 。 。 。 。 In Patent Document 3, there is a GMp-filament containing a Thoracic-grinding, which is a metal oxide abrasive having a residual metal hydroxide and a Wei having a non-hydrolyzable substituent. Compounds are combined. The composition is selected by the abrasive particles, the oxidation of (4) various components for k selection and the addition of (4) tanning, (4) the foot is required to cut the cake, for various requirements and performance, there is still no improvement余 Ρέ Ρέ Ρέ Ρέ r r r r r , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , It is easy to produce the grinding of the body to be polished: 1: In the grinding, there are the following problems: Barrier metal layer and absolute 2 = 200940606 The boundary part 'excessively grinds the barrier metal layer and the insulating layer, and the barrier metal layer and the insulating layer are degraded to the inner tapping (4) beer compared with the surface of the wiring layer. [Patent Document 2] JP-A-2007-273910 (Patent Document 3) Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. 7-088499. A polishing composition for CMP which is used to continuously suppress the deterioration of dishing defects and the absence of grinding debris in the CMp polishing of the CMp polishing which is formed by a metal inlay method to form a copper wiring. The purpose of the present invention is to provide a seventh-stage de-use grinding group in the second paragraph. The inventors of the present invention have found that the implementation of the specific surface modification can effectively touch the above-mentioned results. _, thereby completing the present invention. Namely, the present invention provides a surface-modified saponin characterized by being surface-modified by at least a hydrazine group represented by the following general formulae (1), (2) and (3). A1 ^ EO ^fp〇^_(.E〇_ a2 (1) A1 f E0 V-ί ΡΟ ~~6 EO ^— R3 (2) Η 2. ^---〇— -f EO ym -^p〇v - -4 E0 + Hu-〇—¢- E〇9 J m -4p〇v -4 E0 9- Η£〇--〇— -4 EO 七一^ mp〇V EO}

(3) (wherein the lanthanide group is a group selected from the group consisting of the following formulas (all) to (al3), (a31) to (a33) 200940606 and (a51) to (a53), and the A2 group is selected from the following formula ( A21) groups of (a23), (a41) to (a43), and (a61) to (a63), r3 represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, and Y represents A2 or R3, and E0 is a system. The epoxy group is represented by an epoxy group. P0 represents an epoxy propyl group. Among m, η, and ρ, m represents 0 to 170, N represents 0 to 120, p represents 0 to 170, and m + p represents non. Number of 0.) (a1 I 0 1 cyo I NIH IX 1 - 2 R - siIR I o R - si - RIXIN - HI cyo ο (32 2 o

0 1 cnno I N——H I X I 2 ο——si——R 2) (a1 X I nih I cyo

o,12 〇lsiIR 2) 2 a 0 1 c=o IN——HIXI ^丨si— >""\ o 3) (a1 -0/ o —si—°- - X 1 NIH I cnno 3 2 a 31 (a 1 0 1 X 1.12 -- ! ow «Hi I o

0 1 a 2 R—si—R 1 X (a4 o X 12 -—, s^lp o 2) 3 (a o

-1siIQ

0 1 X 3 3 3

0 \ o \ a 2 \ 1 οI& — R o — si· 1 I X X 42) (a 43) (a 200940606 r1

I R (a51) (a52)

-〇 ~ Si - x - N _ ru I I | ch2ch-c-o-

R2 i II 0

O R

One x ch′h-c-o-R2 i I ❹

O 〇~Si-X-|\j_

/〇 A

R

R CHnCH — C — 〇 — * II o R1 (a53) ~f~CHCH2-N~X^^_ 〇 H : ^ R 〇/ : —f~CHCH2- 〇 H ' (a61) (a62)

IV RI -c - CHC o o- (a63) H2 X"i-0 -H丄_(弋中 R shirt is an alkyl group having a carbon number of 1 to 4, a phenyl group or a hydroxyl group, and X is not & Further, the present invention provides a polishing composition for CMP which comprises the above-mentioned surface-modified tannin extract, and has a hydrogen atom or a mercapto group. According to the present invention, it is possible to provide a polishing composition for CMP which is capable of controlling dishing defects in CMP in CMP, particularly in the case of forming a copper wiring by a damascene method, 7 200940606 and without grinding. Silk, this hair is provided in the second stage grinding, which can improve the CMP abrasive composition for teeth. [Embodiment] First, the surface modification of the present invention will be described. The surface modification of the present invention is to impart the above-mentioned general formula (1), (2) by forming the surface of the crushed rubber into a reaction site and forming a cerium oxide bond between the surface modifier compounds. Or (3) any of the groups, or may be modified by at least two groups selected from the above formulas (1), (2) and (3). The base impurities represented by the above formulas (all), (a21), (a3i), (a41), (a51), and (10)) are present on the surface of the township! a ferulyl group is counterproductive and a violent tool: a compound having at least one of the groups represented by the above formula (1), (2) 5 (3), and a compound of the sulphur compound bonded to Shishijiao. And formed the Shi Xi oxygen bright bond. The above-mentioned general formulas (al2), (a22), (a32), (a42), (a52), and (10)) are based on the two Weixians present in the rotating wire and reacted with the surface modifier compound. The group represented by the above formulas (al3), (a23), (a33), (a43), (a53), and (a63) is the three stanols present on the surface of the stone. The group formed by the reaction with a surface modifier compound. Further, the surface-modified silicone of the present invention may be surface-modified by a group other than the group represented by the above formula (1), (2) or (3). Further, when the surface-modified group is a group represented by the above formula (]) or (3), the terminal alkoxy group may be bonded to the same ceramide particle, or may be different from The silicone particles are bonded and the silicone particles are crosslinked. 200940606 Shixi gum is non-crosslinked or crosslinked, and can be selected according to the concentration of the compound or the reaction conditions of the modified thiocene and the introduced surface modifying group. When the surface-modified Shiqi gum of the present invention is used as the abrasive grains of the polishing composition for CMP, the particle size of the crucible is increased by crosslinking in the case of the limb joint, and the particle size distribution becomes not Evenly. Therefore, the crosslinked product is preferred because the crosslinked product deteriorates the dispersion stability of the polishing composition for CMP. (all), ❹(犯), (al3), (a21), (a22), (a23), (a31) in the group represented by the above formula (1), (2) or (3) ), (a32), (a33), (a41), (a42), (a43), (a51), (a52), (a53), (a61), (a62), and (a63) ^ have Rl, The alkyl group having a carbon number of i to 4 represented by R2 may be exemplified by a fluorenyl group or a S group of "propionate, #propylmon, stilbene, a second butyl group, an isobutyl group, a third butyl group" represented by X. The alkyl group having 1 to 18 carbon atoms may be linear or branched, and may also contain an alicyclic group. Specific examples thereof include a methymene, an ethylene, a pr〇pyiene, a methylethylene, a butylene, and a 1-f. Propyl propyl, 2-methylpropyl, 1,2-methylmethyl, 1,3-dimethylpropane, 1-methylbutyl, 2-methylbutyl , 3-methyl-tert-butyl, 2,4-dimethyl-terminated butyl, 1,3-dimethyl-butylene, pentylene, Hexylene, heptylene , octyiene, ethane-l-diyl (ethane-l, 1-diyl), propane-2, 2-diyl, decane-1,10-diyl, undecane-1 , 11-diyl, dodecane-1,12-diyl, tridecane-1,13-diyl, tetradecane-1,14-diyl, pentadecane-1,15-diyl, Hexadecane-1,16-diyl, heptadecane 200940606-1,17-diyl, octadecan-1,18-diyl, cyclopentane-1,2-diyl, cyclopentane-1 , 3_diyl, cyclohexane-1,1-diyl, cyclohexane-1,2-diyl, cyclohexane-1,3-diyl, cyclohexane-1,4-diyl, A The base ring is calcined-1, 4-diyl, cyclohexene-1,4-dimethylene, and the like. Examples of the hydrocarbon group having 1 to 30 carbon atoms represented by R3 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a second butyl group, a third butyl group, an isobutyl group, and a pentyl group. Base, isopentyl, third amyl, hexyl, tomb, tortoise, g cyclohexylethyl, heptyl, isoheptyl, third heptyl, n-octyl, isooctyl, Trioctyl, 2-ethylhexyl, decyl, isodecyl, decyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, Octadecyl and the like alkyl; vinyl, 1-methylethylen (i-Methylethenyl), 2-methylvinyl, .;· " :--· ...... ...._ 中表表_alkenyl, butenyl, isobutenyl, pentenyl, dilute, heptyl, ruthenium, decenyl, pentadecenyl, phenylene propylene Alkenyl group of _3_yl (l-Phenylpr〇pen-3-yl); phenyl, naphthyl, 2-methylphenyl, 3-methylphenyl, 4-nonylphenyl, 4-vinylbenzene Base, 3-isopropylphenyl, 4-isopropylphenyl, 4-butylphenyl, 4-isobutylphenyl, 4-tert-butylphenyl, 4-hexyl Phenyl, 4-cyclohexylphenyl, 4-octylphenyl, 4-(2-ethylhexyl)phenyl, 4-octadecyl, 2,3-dimethylsilyl, 2,4 - Dinonylphenyl, 2,5-didecylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 2, 4_ a aryl group such as a third butanyl group or a cyclohexyl group; a phenyl group, a phenethyl group, a 2-phenylpropan-2-yl group, a diphenylmethyl group, a triphenylmethyl group, a styrene group ( An aryl group such as ca), cinnamyl or the like. In the group represented by the above formula (1), (2) or (3), if _200940606 is a value of η or more, the surface-modified silicone resin in the polishing composition for CMP has good dispersion stability, and is easy to be combined according to CMP. In the case where the amount of surface-modified tannin added is controlled, it is preferable, and if m + P is small, the dish-shaped defect may be large. 'If m+p is large, polishing residue may occur. Crush, so m+p is ideally 2 to 340, more ideally 2 to 250. Further, in the group represented by the above formula (2) or (3), if the hydrophobicity of R3 is large, the dispersion stability of the surface-modified tannin in the polishing composition for CMP sometimes deteriorates. In addition, dish defects sometimes become larger. As R3, a preferred group is a group having 1 to 8 carbon atoms, and more preferably a fluorenyl group. - : in the group represented by the above formula (1), (2) or (3), in the case of the sugar, the thioxanthene thirst, and in the abrasive composition for CMP The surface modified Shishi gum has good dispersion stability, so it is desirable. As one of the methods for producing the surface-modified silicone of the present invention, for example, a decane coupling agent having an isocyanate group, and a hydroxy compound having E 〇 or having E 〇, p , are synthesized in advance to have a general formula (all ), (al2), (aig), (^1), (a22), (a23), (a3l), (a32), (a33), (a41), (a42), & (a43) The group of the above formula (1), (2) or (3), which is modified by the group, and which is reacted with the tannin; or After the coupling agent is reacted with the Shiqi gum, it may be reacted with a compound having a ruthenium or a ruthenium or ruthenium. Since the reaction control is easy and the manufacturing cost is small, it is desirable to use the former method. As the above-mentioned ceramide coupling agent having an isocyanate group, the compound 'having E0 or a hydroxy compound having E 〇 or P 以 represented by the following formula (4) 11 m 200940606 is represented by the formula (5) Examples of the compound and the modifier compound include compounds represented by the general formulae (6) and (7). R4

I Z — Si — X — N = C = 0 (4) H-°—^ E0 p〇 V-4 EO-)

P

Rc (5) R4 r6

Z-〒m—〇书〇v^p〇vE〇v x_+—z(f R Η O 0 i

Z-Si-X-N-C - O-f EO P〇 (7) (wherein Z is a reaction with a stanol group to form a base of a siloxane chain

The group 'R4 to R7' represents Z, a carbon atom number 4, a phenyl group or a phenyl group, and the lanthanide group represents a stretching group having 1 to 18 carbon atoms, and R3, Eq, PQ, m, η, ρ are The same applies to the group represented by the above formula (1), (2) or (3). Further, as a method other than the above-described method for producing a surface-modified silicone, for example, a decane coupling agent having an amine group, and a (fluorenyl) acryl compound having ruthenium or ruthenium and ruthenium, are previously synthesized and added to have The above formula (1), (magic or (3), which are selected from the groups selected from the general formulae (a51), (a52), (#3), (a61), (a62), and (a63) a group and a modifier compound, and a method of reacting the same with a tannin; or reacting a decane coupling agent having an amine group with a silicone, and further reacting with a (meth)acrylic compound having E0 or having E0 and P〇 The method of carrying out the reaction is also possible. It is easy to control the reaction by 12 200940606, and the manufacturing cost is small. Therefore, it is preferable that the method 0 of the former is used as the above-mentioned decane coupling agent having an amine group as the following general formula (8). The compound represented by the formula, which has an E 〇 or a 〇 〇 〇 ) ) ) ) 。 。 。 。 。 。 if if 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 R4

I Ο 2-Si-X-NH2 (8)

R (3)* C — 9 a 0EO

R -ep〇V-^EO^P-cc = ch a (9) R4 p ;| y R r6 Book 0)^PC%4E〇v_ l _x丄z R5 H 0 〇ib (10) 10 where The z system represents a group which reacts with a stanol group to form a siloxane coupling. R4 to R7 are Z, the number of carbon atoms is 丝, phenyl or cheng, and the lanthanide indicates the number of slave atoms is 1 to 18. The group, r is a hydrogen atom or a fluorenyl group, and the ρ〇, m, η, and ρ systems are the same as those in the group represented by the above formula (1), (2) or (3). Examples of the above formulas (4), (6), (7), (8), and (10) include methoxy, ethoxy, propoxy, isopropoxy, and butyl groups. Oxy, second butyl, isobutoxy, tert-butoxy, phenoxy-amphetoxy; chloro, aryl, block, etc. 13 200940606 , .. halo, hydrogen, hydroxyl. In order to obtain a surface-modified R11 and R2, R1 and R2 are used as raw materials, and Z, R4, R5, r6, and r7 may be used as a raw material to react with phthalocyanine. A1 is at least one of (aii), (al2), (al3), (a31), (a32), (a33), (10)), (10)), and (10)), but it is difficult to selectively control A2 also has at least one of (a21), (a22), (a23), (a41), (a42), (a43), (a61), (a62), and (station 3). Further, it is generally difficult to modify the reactive stanol groups on the entire surface of the silicone to the groups represented by the formula (1), (2) or (3), and the surface-modified stone of the present invention may be used. The surface may be modified with an unreacted oxime alcohol group and/or a surface modifying group other than the group represented by the formula: gas), ^) or (3). - In the case where the surface modification group II other than the group of the above ship type (1), (2) or (3) is modified to modify the 9-gel, it is used as a raw material, and is modified in advance as finely. It is also possible to introduce the group represented by the formula (1), (2) or (3) into the shizu gum, and after introducing the group represented by the formula (1), (2) or (3), It is also possible to introduce a group other than the group represented by the formula (1), (2) or (8). Examples of the compound to which a group other than the group represented by the formula (1), (2) or (3) is introduced include, for example, Chlorotrimethyls Uane, didecyl octadecyl vaporized decane, dimercapto-chloro Alkyl groups such as decane, fluorenyl di-vaporated decane; decanes; trimethyl methoxy oxalate, dimethyl diethoxy wei, methyl triethoxy wei, decyloxy dimethyl 14 200940606 18 Xuanji Shixia, dimethyl octadecyl sulphate, and other hospital bases, alkaloids, sulphur, sulphur, sulphur, sulphur, sulphur, sulphur, sulphur, sulphur , 3-(2-Aminoethyl)aminopropylmethyldimethoxywei, 3-(2-aminoethyl)aminopropyltrimethoxy, 3-(2-aminoethyl ) propyl triethoxy Wei, 3 贱 vinegar propyl. Triethoxy wei, 3-isocyanato (tetra)-trimethoxy-Wei-coupled; coupling acid; amino acid. ❹ ❹ Although it is difficult to directly and correctly _ the surface of the (4) surface modification _ medium surface! The degree of the mouth can be changed by the surface modifier (or Shi Xi Xuan coupling agent) and Shi Xijiao And to control. For example, when the surface-modified ceramide of the present invention is used for the CMP polishing composition, it is used in a ratio of from 1 part by mass to (10) parts by mass relative to the (10) part by mass of the yam gum. Just fine. In order to sufficiently suppress the dishing defect, the amount of the modifier compound to be used is preferably 丨, f part, and more desirably, relative to (10) parts by mass. In the surface modification of the invention, the particle size of the silk surface modification is limited to the limit of the particle size. Yu Linming] ^ When the above-mentioned Shiqi gum is used in the polishing composition for CMP, the particle size is preferably in the range of 10 to 300 nm.途:: For the surface modification of the present invention (10) for the use of the polishing composition: "_ sub-material modifier, polymer coagulant, adsorbent, coating additive, hard coating agent + 1 ^ agent, An antireflective agent for an optical film, a heat-resistant agent at a metal surface, a non-auxiliary, a domain-age agent, an antistatic agent, a catalyst carrier, 15 200940606 organosol, etc. Next, the polishing composition for CMP of the present invention will be described. The polishing composition for CMP according to the present invention contains the above-mentioned surface-modified polyester abrasive grains, and examples of the other components contained therein include an oxidizing agent component, a heterocyclic compound, a compound component, a gradual age, a hybrid polymer age, and a pH. __Component, surfactant component, solubilizer-Qn agent age, etc. The polishing composition for CMP of the present invention is excellent in film, dishing, and scratches with respect to removal of a copper-based material such as copper or a copper alloy. The characteristics of the grinding are suitable for the production of the hybrid yarn in the conductor element. The polishing composition for CMP of the present invention can be used for both the first stage grinding and the second stage grinding. In relative to the copper system The choice of materials, the 'enemy is particularly suitable for the first section of the grinding. The tree batch CMP _ heterozygous wealth of the age of _ Na content, compared with the = 0. 01 ~ (four) Wei. If the table is _ _ = = tear Late, if the surface modification content is more than the upper limit, there is Si

Set to the range of %. The J-containing composition may also contain the surface-modified stone yoghurt of the present invention. The 00-knife 3 has a /, and the amount of use is preferably compared with the mass of 5 11 11 = Table 1 It’s more desirable to be afraid of it...~ There is a research and development, but the county’s hair, the bismuth, the dioxin, the miscellaneous _ i 1 cut, the secret, the carbon cut and the -j use one type of nuclear or more. use. 200940606 Examples of the oxidizing agent used in the above oxidizing agent component include nitric acid, over-breaking acid, potassium molybdate, over-acidic acid clock, sodium sulphate, excessive acid removal, excessive acid clock, sodium permanate, Dichromic acid, dichromic acid unloading, dichromic acid clock, sodium dichromate, hydrogen peroxide, perchloric acid, perchlorate (alkali metal salt, ammonium salt, etc.), hypochlorous acid (hyp〇chl〇r 〇us ” acid), hypochlorite (alkali metal salt, ammonium salt, etc.), persulfate, persulfate (alkali metal salt, ammonium salt, etc.), peracetic acid, t-butyl hydroperoxide , benzoic acid, ozone, etc., which can be used by using or mixing 2 © or more. The oxidized ship content of the GMP composite towel of the present invention is preferably '10% by mass. If the content of the oxidizing agent component is less than the lower limit, the polishing rate may not be sufficiently obtained. If the content of the oxidizing agent component is more than the upper limit, the rot residue may not be controlled, and the defect may be caused by a dish defect or the like. . When the polishing composition for CMP of the present invention is used in the i-th stage grinding, the 〇=deuteration agent is preferably used to make the polishing rate and the micro-inhibition of the persulfate dish. Grinding, and making the flat surface of the silk surface, it is more desirable to record the persulfate. Further, in the case of the second stage grinding using the present invention, it is preferred to use hydrogen peroxide having a grinding touch suppressing effect as the oxidizing agent. The anti-ring compound component is mainly used as a rust preventive agent having a precautionary effect against copper wiring or barrier metal. J. 1 , 2, 4-diazole, 3-amino group, 2, 4~2 Azole, 4_amino group _12,4_three 3-.U,, 1H-(four), 5A, '1H-zinc 2, 4 s sit, 5 methyl-1H-tetrazole, 5-phenyltetrazole , 200940606 1H-tetrazole-1 - acetic acid, 5-amino-1H-tetrazole and the like azole monocyclic; 2-mercapto is stupid. 2-[2-(benzothiazole)thiopropionic acid), 2-[2-(benzoxanthene)]thiobutyric acid Benzotriazole, Benzotriazole, 2~Aminobenzothiazole, 2-Amino-6-mercaptobenzothiazole, 1-Hydroxybenzotriazole , 1-dihydroxybenzotriazole, 1-dihydroxypropylbenzotriazole, 2,3-dicarboxypropyl benzotriazole, 4-hydroxybenzotriazole, 5-hexylbenzotriazole, [1,2,3-benzotrisyl-1-indenyl][1' 2,4-triazolyl-1-indenyl][2-ethylhexyl]amine, 4-methyl-1H- Stupid triazole, 5-methyl-1H-benzotriazole, naphthotriazole, bis[(ι-benzotriazolyl)methyl]phosphine S夂, 1,5 pentylene tetrasal (1 , 5-pentamethylenetetrazole), 嗟 苯 苯 唾 iabhda e e) 嗤 杂环 杂环 ) 杂环 杂环 杂环 杂环 杂环 杂环 杂环 杂环 杂环 杂环 杂环 杂环 杂环 杂环 杂环 杂环 杂环 杂环 杂环 杂环 杂环 杂环 。 。 。 。 The content of the compound of the CMP material dissimilaring towel of the present invention is preferably 疋〇. _1~1胄%. If the content of the heterocyclic compound is less than the lower limit, it is difficult to use it as a dish-shaped defect of the effect of use; if the content of the heterocyclic compound is more than the limit of j, there is a difficulty in grinding speed. Shot, benzene and three rhymes are cheaper and Gu Yi controls the anti-retention effect. The organic acid component is an organic acid or a salt of an organic acid, and the effect is different depending on the structure. For example, 'aliphatic organic acids, aliphatics, and the like have the effect of improving the enthalpy of the CMP riding compound, and the metal such as I-milling copper is eluted and the polishing speed is improved! The family is ill (four) fruit. It is suitable for acid and aromatic; it has the effect of inhibiting the metal, and it is good to grind the batter. The effect of 200940606 'Amino acid and its wealth can serve as a secret agent. Examples of the organic acid include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, 2-methylbutyric acid, n-hexanoic acid, 3,3-dimethylbutyric acid, 2-ethylbutyric acid, and 4-methyl group. Valeric acid, n-heptanoic acid, glycolic acid, glyceric acid, oxalic acid, malonic acid, butyric acid, glutaric acid, adipic acid, pimelic acid, maleic acid, fumaric acid , aliphatic carboxylic acid such as lactic acid, malic acid, tartaric acid, citric acid, gluconic acid, acetic anhydride; benzoic acid, 2-hydroxybenzoic acid, 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, ® An aromatic carboxylic acid such as acid, isophthalic acid, terephthalic acid, Quinaldic acid, naphthalene-1-carboxylic acid or naphthalene carboxylic acid; methanesulfonic acid, ethyl acetate, and C Rhein, butyl sulphate, valeric acid, -i' /~: acidified, heptanoic acid, octanoic acid, norbornenesulfonic acid, adamantanesulfonic acid, ring Aliphatic acids, bismuth, dioxins, acid, five gas, acid, seven gas, and other aliphatic acid; benzoquinic acid, p-toluenesulfonic acid, octylbenzenesulfonic acid , anthracene benzene cross-acid, dodecyl benzene sulfonate, naphthalene-1-benzoic acid, naphthalene-2-protonic acid, sulfonic acid, sulfonic acid, phenanthrenesulfonic acid and other aromatic sulfonic acids; glycine, L (D)-Alanine, L(D)-2-butyric acid, L(D)-n-decanoic acid, L(D)-leucine, L(D)-leucine, L(D) -Norleucine, L(D)-isovanine, L(D)-Aloisolecine, L(D)-phenylalanine, L(D)-脯Amino acid, sarcosine, L(D)-ornithine, L(D)-glycine, bovine acid, L(D)-serine, L(D)-threonine (Threonine), L(D)-bethreyl acid, L(D)-homoserine (Homoserine), L(D)-tyrosine, /3-(3,4-dihydroxyphenyl)-L(D)- Alanine, L(D)-thyroxine, thyroxin, 4-meryl-L(D)-脯

I 200940606 . Aminic acid, L(D)-hemi-amino acid, LCD)-曱 thioglycolic acid, L(D)-ethyl thioacetate (Ethionine), L(D)-lanthione acid (Lanthionine), L(D)-cystathionine, L(D)-cyst ine, L(D)-hemi-amino acid, L(D)-aspartic acid, L( D)-glutamic acid, secondary (carboxymethyl)-l(D)-hemi-amino acid, 4-butylamine, L(D)-aspartate, L(D)- faceamine, 1(D)-arginine's 3-hydroxy-t(fc)-glycine, L(D)-histamine, L(D)-tryptophanic acid and the like; and organic acid alkali metal salts (Lithium salt, potassium salt, sodium salt), an ammonium salt, and an amine salt, and these may be used in j type or in mixture of two or more types. The content of the organic acid component in the polishing composition for CMP of the present invention is preferably from 0.0001 to 10% by mass. If the content of the organic acid component is less than 〇〇〇〇1% by mass, the rhyme may not be obtained in some cases, and if the content of the organic acid component is more than 10% by mass, the use effect becomes excessive, and Flatness, grinding efficiency, and grinding-selection are all reduced. The water-soluble polymer component is a water-soluble polymer which is improved in polishing selectivity by the barrier layer polishing, or which acts to stabilize the dispersion of the abrasive grains, and has high water dispersibility by using ◎ as an abrasive grain and a polishing agent. Molecular compound. The polishing composition for CMP of the present invention may further contain an aqueous polymer component. Examples of the water-soluble polymer to be contained include alginic acid (alginic (4), pectic acid, m-methyl cellulose, fat, curdlan, and pullulan). Polysaccharides; polyaspartic acid, polyglycolic acid, polyglycine, polymalic acid, polyacrylamide, polyacrylic acid, polyisic acid, polyisene, polybutene Dicarboxylic acid, poly(p-vinylidene), polyacrylic acid, and poly 20 200940606 polycarboxylic acid such as polyglyoxylic acid; polyammonium acrylate ammonium salt, polymethyl methacrylate sodium salt, Polycarboxylates, esters and derivatives exemplified in polypropylene decylamine, polyamino acrylamide, polyacrylic acid ammonium salt, polyacrylic acid sodium salt, polyammonium ammonium salt, polyamidate sodium salt, and the like; a vinyl copolymer such as polyvinyl alcohol, polyvinylpyrrolidone, polyacrylaldehyde, polyvinylpyrrolidone alpha olefin (ethylene, propylene, 1-butene, 1-pentene, etc.); polyglycol , polypropylene glycol, alkylene glycol or polyalkylene glycol And a polyalkylene glycol such as a random or block adduct of propylene oxide; examples of the water-dispersible polymer include a polyurethane resin and a polyamino phthalate. Polyurea resin, acrylate resin, mercapto acrylate resin, phenol resin, urea resin, melamine resin (me 1 am i r es i η ), polystyrene resin, polyacetal 001〜1〇 含量 〇 〇 〇 〇 001 001 001 001 001 001 001 001 001 001 001 001 001 001 001 001 001 001 001 001 001 001 001 001 001 001 001 001 001 001 001 001 001 001 001 001 001 001 001 001 001 001 001 001 When the content of the aqueous component to the molecular component is less than the lower limit, sufficient use effect may not be obtained, and if the content of the aqueous polymer component is more than the upper limit, sufficient polishing rate may not be obtained. The number average molecular weight (GPC measurement, standard conversion of polystyrene) varies depending on the type, and each has a suitable value. As a water-soluble polymer contained in the polishing composition for CMP of the present invention Appropriate ones, a series of poly-fine-fines, Biluoyuan, polyethylene, σ, a little entertainment, and a 1-butadiene copolymer. Compared with other water-soluble polymers, these have barrier layer grinding and suppression 200940606 The effect is large, and the choice of copper is improved by the training. In addition, the effect of improving the dispersion stability of the abrasive particles is mixed. The polyethylene-transfer fine or polyethylene-transfer fine in the GMp riding composition of the present invention. It is preferable that the content of the barrier layer polishing inhibition effect is expressed by G·She 5 to 5% by mass, and the average molecular weight is preferably 5,000 to 100,000. ..................- In addition, one of the suitable ones is a water-soluble polymer contained in the polishing composition for CMP of the present invention. Alcohol (p〇lyalkylene gi (4)) class. The poly-silylene glycol smothers with other water-hybrid polymers, and the grinding speed of the mortar is excellent, and the effect of improving the dispersion stability of the abrasive grains is also large. The content of the polyalkylene glycol in the polishing group for CMP of the present invention is preferably such that the barrier layer is __suppressed to 5% to 5% by mass. In addition, the amount of polyalkylene glycol - the average amount of split is ideally 2 〇〇 ~ 3 〇〇〇. Further, as one of the water-dispersible enamel knives contained in the polishing composition for CMP of the present invention, one of them is a polyurethane resin or a polyurethane urethane resin. As the abrasive grains and the abrasive granules, these can enhance the selective polishing property or the non-❹ selection of the polishing property, so that it is effective in selecting the polishing property. The polyaminocarbamate-lipid or polyurethane polyurea resin is preferably self-emulsified which is easy to control the CMP performance because the emulsifier which can be dispersed can exert an influence on the CMp> performance. The cationic water-dispersible polyurethane which introduces a cationic group has a strong etching effect with respect to copper and is sometimes difficult to control, and is more preferably a nonionic water-dispersible polyaminocarboxylic acid. The ester or anionic water-dispersible polyurethane has an anionic water-dispersible poly 22 200940606 amino phthalate because of the high polishing rate of copper. Further, in the case of an anionic water-dispersible polyurethane, the acid value (mgKOH/g) is preferably 1 to 2 Torr, more preferably 1 Torr to 15 Torr. The average particle diameter of the water-dispersible polyaminophthalic acid ester serves as an abrasive particle, and is preferably 5 to 2 〇〇 nm which is stably dispersed in the polishing composition for CMP. More preferably, it is 10~ 150 nm. The content of the resins in the polishing composition for CMp of the present invention is preferably 〇1 to 1% by mass. 2. The polishing composition for CMP of the present invention may function as an oxidizing agent, and may be used as an acid or in an inspective manner. For this purpose, a pH adjusting agent may also be used. The pH adjuster component used in the polishing composition for CMP of the present invention may, for example, be a water-soluble basic compound and a water-soluble acidic compound. As a water-soluble test. Examples of the materials include a hydroxide, a sodium hydroxide, a potassium hydroxide, and the like, such as a gas-oxidized tester, a calcium hydroxide, a barium hydroxide, a barium hydroxide, and the like, and a carbonic acid test metal. Potassium carbonate and other metal carbonates, tetrakisyl ammonium hydroxide, quaternary ammonium hydroxides such as choline, ethylamines such as ethylamine, diethylamine, triethylamine, and mithylamine. These can be used by using either or a mixture of two or more. Among them, ammonia and water hydroxides are preferred because of their low cost and operation. The water-hybrid acid compound can be used as a water-soluble one in the case of an ortho-acid, and an inorganic acid such as hydrochloric acid, sulfuric acid or nitric acid. The pH of the polishing composition for CMP of the invention is preferably 8 to 12, and the pH value is less than 8 and 6 or more. If the pH of the right side is less than 6, the polishing of the barrier layer may occur, and the polishing may be selected to decrease. If the pH is greater than 12, dishing defects may occur and the surface 23 200940606 deteriorates. The CMP (four) mill composition of the present invention may contain a surfactant in order to suppress the two-milling, the dissolution of each component, the dispersion stability, the defoaming property, and the like. Examples of the interface active agent to be used include a nonionic surfactant, an anionic interface active species, or a mixture of two or more. The content of the surfactant component in the polishing composition for CMp of the present invention is preferably 〇·_ 10% by mass. If the content of the surfactant component is less than the lower limit of ❹, a sufficient use effect may not be obtained, and if the content of the surfactant component is more than the upper limit, the polishing rate may be lowered. (9) & As the surfactant contained in the polishing composition for CMP of the present invention, an anionic surfactant is preferable. Examples of the anionic surfactant include a south carbon number fatty acid salt, a high carbon number sulfuric acid sulfate salt, a sulfurized thin hydrocarbon salt, a high carbon number calcination acid salt, an α-olefinsulfonate, a sulfurized fatty acid salt, and the like. Sulfonated fatty acid salt, phosphate ester salt, fatty acid ester sulfate salt, glyceride sulfate salt, fatty acid ester acid salt, sulfomethyl ester salt, polyoxyalkylene alkyl sulfate Ether sulfate), polyoxyalkylene phenyl ether sulfate, polyoxyalkylene alkyl ether carboxylate, thiolated peptide, fatty acid alkanolamine or its alkylene oxide addition Sulfate, Sulfosuccinate, alkyl benzoate, alkyl sulfonate, benzobenzimidate, polyepoxy succinic acid succinate , N-fluorenyl-N-indenyl taurate, N-mercapto glutamic acid or its salt, decyloxyethanesulfonate 24 200940606 (acyloxy ethanesulfonalt), alkoxyethane sulfonate, N -mercapto-/?- alanine or its salt, N-mercapto-N-carboxyethyl taurine or its salt, N-mercapto-N-rebellion One or a mixture of two or more kinds of methylglycine or a salt thereof, a decyl lactate, an N-mercaptocreine, and an alkyl group or an alkylaminocarbocarboxylate. The polishing composition for CMP of the present invention may further contain a metal eluting agent component for eluting the abrasive metal. For example, in the case of the CMP of copper, the organic acid ammonium salt and the alkali metal salt which are exemplified by the above organic acid component may be used as one of the above-mentioned organic solvent components. Two or more types are mixed and used. When the copper dissolution agent is used, the content is preferably 〇·01 to 10% by mass. If the content of the copper dissolution agent is less than the lower limit, a sufficient polishing rate may not be obtained. If the content of the copper dissolution agent is more than the upper limit, excessive plating may not be controlled. Further, as the above copper dissolution agent, it is preferable that the aliphatic organic sincerity salt is particularly excellent in oxalic acid, malonic acid, succinic acid, glutaric acid adipic acid, pimelic acid, It is said that the diacid, the anti-pre-acid, the sweet, the tartaric acid and the acid. Preferably, the addition of 2 in the (4) grinding composition is 05 to 2% by mass, more preferably 0.1% by mass. The polishing composition for CMP may contain a solubilizing agent component because of the organic similarity of the above description. As the solubilization contained in the 4,? Oxol 6 alcohol alcohol, acetone, methyl:,: ether (-·) and other ethers; ethylene glycol single (four), ethylene _ = = early fine; ethylene glycol, alcohol,! , 3-propanediol, propylene, 1%, glycerol, pentaerythritol, dipentaerythritol, tetramethyl 25? 200940606 r, etc. 1 alcohol, N-methyl guanlophone and other oxime The ketones may be used alone or in combination of two or more. a. In the case of using a solubilizer, the content of the ceremonial refining injection is preferably =0. 01 10%. If the content of the solubilizer is less than the lower limit, the effect of sufficient use may not be obtained. If the content of the solubilizing agent is more than the upper limit, the surface of the polished surface may be cleaved. The polishing composition for CMP of the present invention may contain other additive components as needed in addition to the above examples. Examples of the additive component include a pH buffer; ◎ an α-n-axis group of an organic compound having an effect of reducing the organic contamination of the wafer: an inclusion compound such as cyclodextrin; and a surface smoothness imparted to the polished surface. Ethyl sulphate, sulphate, sulphate, sulphate, sulphate, sulphate, sulphate, sulphate, sulphate, sulphate, sulphate, sulphate An alcoholic amine such as ethanolamine, 2-dimethylaminoethanol, 2-(2-aminoethylamino)ethanol or N-decyldiethanolamine. In the case of using other additive components, it is preferable to add 〇._~1〇% by mass to the polishing composition, and preferably 〇._❹ to 5% by mass. The polishing composition for CMP of the present invention contains the above-mentioned component of the content of the above, and the remainder is water. Therefore, in order to obtain a polishing composition for CMP containing the above-exemplified components in a predetermined amount, the total amount of water added is 1% by mass. The polishing composition for CMP of the present invention is prepared by mixing the above-described components with water and uniformly dispersing and dissolving them. When a water-soluble polymer or a water-dispersible polymer is used, it may be added in the form of Group 4 200940606 which is dissolved or dispersed in water in advance. Further, in the polishing composition of the present invention, the component may be mixed to prepare a liquid composition, or a two-component composition may be used as the two-component composition, and for example, only A 2-liquid type formed by a mixture of an oxidizing agent component as a component and all other components. The use of a peroxide in an oxidizing agent is usually made into a two-component composition. [Examples] 士一..一:....,..:...... Hereinafter, the present invention will be described in more detail using examples and comparative examples. However, the present invention is not limited to the following examples and the like. In addition, “parts, or %” in the text indicates a quality standard as long as there is no special explanation in advance. [Manufacturing Example 1] Production of Surface Modifier Compounds a to q. As a dream-burning coupling agent having an isocyanate group, 3-iso- _ lysyl trimethoxy sulphide was used as having Ε0 $ The phenol compound or the alcohol compound is added in a ratio of a hydroxyl group to an isocyanate group at a molar ratio of oh: NC〇=q. 1:1, and stirred at 10 (rc temperature for 2 hours). Among them, 四·_% of the total mass of tetraisodecyl titanium was added, and further, the surface modifier compound was obtained by separately mixing at HKTC temperature for 2 hours. The end of the reaction was carried out by using IR to eliminate the isocyanate group. The surface modifier compounds obtained are shown in Tables 1 and 2. Further, m, p, and n in the above formula (6) and formula (7) shown in the table are derived from a diol compound as a raw material, The molecular weight of the alcohol compound was calculated and calculated. Table 1: Surface modifier of the formula (6) Compound diol compound m, p (calculated value) η (calculated value) 27 200940606 a Polyethylene glycol (PEG200) m+p=4 0 b Polyethylene glycol (PEG400) 111+1)=9 0 c • Polyethylene glycol (PEG1000) m+p=22 0 d Polyethylene glycol (PEG2000) m+p=45 0 e Polyethylene glycol (PEG4000) m+p=90 0 —f Polyethylene glycol (PEG6000) m+p=136 0 g Polyethylene glycol (PEG8000) m+p=181 0 h Polyethylene glycol (PEG11000) m+p=250 0 i Polyethylene glycol adduct of polypropylene glycol (Pluronic L-44) M= 11 p=ll 20 Table 2: General formula (7) type * Softanol: a mixture of 11 carbon atoms and a carbon number of 2 grade alcohols (曰 窣 surface modifier compound alcohol compound m, p (calculated value) n ( Calculated value) j 2-methoxyethanol m+p^l 0 k Polyethylene glycol monoterpene ether (MePEG225) m+p=4 0 m Polyethylene glycol monomethyl ether (MePEG400) m+p=8 0 n Polyethylene glycol monomethyl ether (MePEGlOO) m+p=22 0 〇Softanol* epoxy Ethylene oxide adduct (SO-135) m+p=9 0 P Softanol epoxy Ethylene adduct (S0 -160) m + p=15 0 q Ethylene oxide addition product of glycerol (Uniox G-450) m+p=8 0 28 200940606 manufactured by Catalyst Inc. [Production Example 2] Surface modifier compound r and Manufacture of s as a metal-based alkane coupling agent using 3-aminopropyltrimethoxy decane as a hydroxy compound having E0 for use in poly NK glycol chain having a terminal of the vinegar-propenyl A-600. The molar ratio of propyl sulfonyl group to amine group is 丨.2: 丨: ^ ^ 杆 杆 漆 , , , , 6 6 6 6 6 6 6 6 TC TC TC TC TC TC TC TC TC TC TC TC TC TC TC TC TC TC TC TC TC TC It was confirmed by gas chromatography (Gas Chromatography) disc, which was confirmed to be a raw material, and the obtained surface-modifier compound r was the above-mentioned general formula, m + p = 13 (calculated value), (4) (calculated value). Further, as the surface modifier compound s, 31 methoxyl (hexyloxy)]propyl-methoxy oxysulphur was used. m+p=6 to 9 ( Calculated value), η^Ο (calculated value) [Examples 1 to 5] Surface-modified Shijiao No. 1 to No. 5 Manufactured by the hydrolysis method of tetraethoxy decane, average granule The diameter is 120.6 ηΠ1 particle size distribution: the cumulative 10% value is 95.3, and the cumulative 50% value is i17 4nm, : the product 90% value is 145. 5 surface township dispersion (hereinafter, referred to as surface modification before the stone Ά _ The content of the oxidized stone is 6 〇. The temperature is heated, and the titration is as follows: • 1 G of each of the above-mentioned manufacturing materials obtained by the surface modifier VIII a~e, 50 parts of water, and 丨Q The molar amount of the surface modifier compound is 3 parts. After titration, the mixture is mixed for 2 hours at a temperature of 6 〇C to obtain a surface modified stone. Xijiao No. 1~5. X-ray photoelectron spectroscopy (xps) analysis was performed on each surface-modified silicone obtained from No. 29 200940606, and the surface modification was confirmed in comparison with the surface modification of Shishijiao A. Further, the particle size distribution was measured using a laser diffraction type particle size analyzer. [Example 6r 13] Surface-modified tannin N〇. 6~N〇. 13 was produced by tetraethoxy #calcination hydrolysis method. The average particle size is 155 9 coffee, particle size distribution. The cumulative 10% value is 114. 3 nm, the cumulative 5〇% value is 153·7 coffee, the cumulative value is 208. 6 round division dispersion (hereinafter, referred to as surface Before the modification, Shishijiao B, the content of the dioxide was 1% by weight, and the mixture was heated at 6 °C, and the following mixed solution was titrated: 10 parts of each of the surface modification obtained in the above production example Compounds b, !, : j~p, 50 parts of water 'i parts of 〇.! Moer / liter of aqueous solution. Relative to 1 part of the second Oxygen cutting, the titrant of the surface modifier compound is ig. _ After titration, it is difficult to obtain the surface modification Na Nq. 6~η at the air temperature for 2 hours. The same as the above-mentioned actual situation Sexually carried out χ 光 光 光 UPS ) ) 分析 分析 分析 分析 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用(1) The carbon atom was confirmed to be derived from the peak of (3) at 282·8 eV before the surface modification. The peak was observed. (2) Oxygen atom 30 200940606 Confirmation. There is a peak at 6ev. The stone before the surface modification is a chemical shift caused by bonding.峄w to (3) Nitrogen atom Confirmed 398. There is a peak at OeV. This peak was not confirmed by (4) Shi Xi atom's before the surface modification. Confirm 101. There is a peak at OeV. Surface modification f" Less gel is the chemical shift caused by 101 7 v bonding. ·〖ev' confirms 〇 Table 3: Particle size distribution measurement results

Surface modified silicone surface modifier compound average particle size (nm) cumulative 10% value (nm) No. 6 b 153.4 135.0 No. 7 i 172.0 127.9 No. 8 j 156.7 131.4, No. 9 k 151.7 127.3, cumulative 50 % value (coffee) cumulative 90% value (nm)

31 200940606

No. 10 m 156. 1 142.3 152.4 No. 11 η 154.5 140.8 150.7 16ΐΤΓ^ No. 12 0 160.3 111.5 158.7 22677^ No. 13 Ρ 187.6 126.7 183.0 27ΐΤ^ Surface-modified silicone B 155.9 114.3 153.7 208?6^ 〔 Example 14] Preparation of surface modified Shijiao No. 14 As surface modifier compound, surface modifier compound c was used, except for the use of surface modifier compound with respect to 100 parts of cerium oxide. The amount of the surface-modified 矽# No. 14 ° [Example 15] surface-modified 矽 〇 〇 15 15 was obtained as a surface modifier in the same manner as in the above Examples 1 to 5 except for the amount of the work. The surface modifier compound c is used as the compound, except that the amount of the surface modifier compound is set to 1 part with respect to 100 parts of the cerium oxide dioxide, and the rest is the same as in the above embodiment 5 , obtained surface modified Shijiao No. 15. 〆 [Compared to #父例1] Surface modification of Shijiaojiao 1 as a surface modifier compound using methyltriethoxy Wei will contain as much as the money is ordered (4) shouting Na Na B arrogant Perform: Two 10 parts of surface modifier compound, 5. Part of water, two liters of aqueous nitric acid. The amount of the dioxide is reduced to 4 parts with respect to (10) parts of the gel. Addition example

32 200940606 The same method, get the surface modification 矽 win comparison! . [Comparative Example 2] Production of surface-modified tannin comparison 2 In addition to the di-oxygen cut of 1 GG (4) of the gel, the amount of methyltriethoxylate used was set to 10 parts, and the rest was compared with the above. The method of obtaining surface modified Shijiao was compared with 2. [Bei Shi Example 16 to 24] CMP polishing composition ν〇·1~N〇. 9 Manufacture of the polishing composition for CMP N〇. 1~Να 9, which includes the contents listed in Table 5: 1 ❿ % Surface modified Shixi gum, 1·5% of persulfate, 1% glycine, 〇•(8)1% benzotrisene, 0. 02% of t-base benzene acid, 〇. 3% Chlorine oxidation removes water (remaining components). [Comparative Example 4] The CMP polishing composition was used to obtain a polishing composition for CMP. The comparison includes: a surface-modified pre-rubber B, a 5% ammonium persulfate, a glycine, a ruthenium. 〇〇1% benzotriazole, 0.02% dodecylbenzene acid, 〇. 3% hydrazine water and water (remaining component). © [Comparative Example 5] Comparison of polishing composition for CMP to obtain a polishing composition for CMP. 帛2, which comprises: 1% of surface-modified pre-rubber B, 1.5% of persulfate, 1% Glycine, 〇. 〇〇 1% benzotriazole, 0. 02% twelve benzene acid, Q. 3% potassium hydroxide, Q. 1% number average molecular weight 400 polyethylene glycol single曱 key (MePEG4〇〇) and water (remaining ingredients). [Comparative Example 6] CMP polishing composition was compared with the production of 3 to obtain CMP 帛 polishing, composition comparison xiao 3, which included: 1% of surface modified shijiao compared with 1, 1.5% ammonium persulfate, 1% glycine, 〇. 〇〇 1% benzotriazole, 33 200940606 0.02% dodecylbenzenesulfonic acid, 0.3% 3% potassium hydroxide and water (remaining component). [Comparative Example 7] Comparison of the polishing composition for CMP with the preparation of 4 for the comparison of the polishing composition for CMP 4, which comprises: 1% of the surface-modified Shijiaojiao 2, 1.5% of ammonium persulfate, 1 % of glycine, 〇. 〇〇丨% of benzotriazine, 02% of ten; one hospital base benzoic acid, 0. 3% of gas oxidative discharge and water (remaining components). Table 5: Examples 16 to 24 and Comparative Examples 4 to 7 No. CMP polishing composition Shi Xi, MePEG Example 16 No. 1 Surface-modified silicone No. 6 - 'Example 17 No. 2 Surface-modified silicone No. 8 Example 1.8 No. 3 Surface-modified chopping rubber No. 9 - Example 19 - Νο_4 Surface-modified silicone No. 10 Example 20 No. 5 Surface-modified silicone No. 11 - Example 21 No. 6 Surface modified silicone No. 12 - Example 22 No. 7 Surface modified silicone No. 13 - Example 23 No. 8 Surface modified silicone No. 14 Example 24 No. 9 Surface modified silicone No. 15 - Comparative Example 4 Comparative use 1 Surface-modified pre-rubber B - Comparative Example 5 Comparative 2 Surface-modified pre-rubber B MePEG 400 Comparative Example 6 Comparative 3 Surface-modified Shijiao comparison 1 - Comparative Example 7 Comparative 4 Surface modification Shi Xijiao comparison 2

[Evaluation Example 1] For the CMP polishing compositions No. 1 to No. 7 and Comparative 34 200940606 described in Table 5, the first and second comparative examples were formed by electrolytic plating on a copper film. The film is cut into pieces (10) and the wafer is cut into 3αηχ3αη. The copper cover test piece (he is thin (4) Piece) is formed by the subtractive plating method on the stone substrate (10), and the wafer is cut into 3cmx3cmj£ square. In the button covering test #', and the above test # was used as the object to be polished, the evaluation of the listening speed was carried out in accordance with the following polishing conditions. The results are shown in Table 6. Further, the grinding was performed using Loresta GP (manufactured by Mitsubishi Chemical Corporation) based on the difference in film thickness before and after the polishing. §k Grinder: NF-300 (manufactured by nanofactor) Grinding pad ♦ IC1400 (with XY groove) (manufactured by R〇hm and Haas Company), grinding time: 1 minute, g 7 , number of stages of rotation: 60 rpm Number of revolutions: 60 rpm Grinding pressure: 2 psi Slurry supply speed: 35 ml/min 35 200940606 Table 6 Steel grinding speed Cnm/min) 452

503

Grinding composition for CMP

No. 1 No. 2 No. 3 No. 4 No. 4 No. 4 No. 6 No. 6 Comparative No. 1 As can be seen from the above Table 6, the abrasive composition of the present invention is used as an abrasive grain. Νο·卜此.7 任任—all show a good grinding speed with respect to copper, and it can be confirmed that it is made by research. Herein, the surface-modified stone used in the polishing composition for CMP of the fine surface-modified sand paste and the polishing composition for CMP which is additionally used and used without the surface-modified silicone rubber The comparative amount of the surface-modified group of the oxime No. 10 was comparable to that of the MePEG 400, and the polishing inhibition with respect to ruthenium was insufficient. From this, it was confirmed that the improvement of the selective grinding property with respect to copper was caused by the surface modification of the rubber as the abrasive grains. [Examples 25 to 27] CMP polishing composition No. 10 to N 〇. 12 Production of CMP polishing composition No. 1 〇 to No. 12' including the contents described in Table 7 36 200940606 1% Surface-modified silicone, L 5% ammonium persulfate, 1% glycine, 〇. 〇〇ι% stupid and di-salted, 〇 · 02% of 12-burning benzene continued acid, 〇 03% of poly-European . A 1-butene copolymer having a number average molecular weight of 17,000 (p_9〇4LC; manufactured by Isp Corporation), 0.3% potassium hydroxide and water (remaining component). [Comparative Example 8] The polishing composition for CMP was used for the production of 5, except that the surface-modified silicone A1 portion was used instead of the surface-modified silicone 1%, and the same manner as in the above Examples 25 to 27 was used to obtain the cmp. The grinding group and the compound are compared with 5. Table 7: Examples 25 to 27 and Comparative Example 8

No. CMP polishing group All Yang II: - The amount of surface-modified compound c used (parts by mass) relative to 100 parts by mass of the gelatin, Example 25 No. 10 Surface-modified silicone No. 15 10 Example 26 No. 11 Surface modified Shijiao No. 3 3 Example 27 No. 12 Surface modified Shijiao No. 14 1 Comparative Example 8 Comparative surface 5 Surface modified stone Xisheng A 0 [Evaluation example 2] The polishing composition for CMP described in the above Table 7 was evaluated by a method of electrolytically bonding a copper film on a stone substrate to a thickness of 1500 nm. Evaluation of the speed; and by making a deep ruthenium layer of 250 nm wafer into a hard ruthenium layer by a plasma CVD method using Tetrakis-ethoxy-silane, 250 nm deep and wide After a space of 50 μm of the 50(10) trench, the button/nitride film (TaN) is deposited by sputtering to 15 37 200940606 nm/15 nm ' and then deposited as a copper seed layer with a splash clock as a loo nm (seed) After that, an 8-inch wafer with a pattern of 1 〇〇〇nm copper film formed by electrolytic plating is used as the ground. Evaluation of dishing; Evaluation and copper polishing debris. The grinding conditions are as follows. The polishing rate was measured using a film thickness difference between Loresta GP (manufactured by Mitsubishi Chemical Corporation) and before and after polishing. The disc-shaped defect was measured by using an atomic force microscope (AFM) atomic microscope Nanopic^ (manufactured by Seiko Instruments Inc.) to measure the difference between the most convex portion and the most concave portion of the 5-inch copper wiring portion. Copper abrasive chips were confirmed by optical microscopy for the presence or absence of copper residue at 20% overpolish Q. The results are shown in Table 8. Grinding machine: AVANTI472 (manufactured by IPEC) Grinding sound. IC1 shed (with χγ groove) (Rohm, and; manufactured by jjaas Company) Grinding time: 1 minute Platform rotation number: 93 rpm Carrier rotation: 87 rpm ^ Grinding Pressure: 2 psi Slurry supply speed: 200 ml/min 38 200940606 Table 8 Grinding composition for CMP Copper grinding speed (nm/min) Disc-shaped defect (nm) No. 10 780 50 800 25~ No. 12 820 22 Compare No grinding was observed with 5 -- 840 21 steel grinding debris. ~~--. No J-distribution was observed---~~~-.

From the above Table 8, it was confirmed that the surface of the present invention used as the abrasive grains was modified by the CMP Liner composition N〇. 1G to Na12 had steel·== fruit. Yan Xin, the greater the reduction of the modification, the greater the steel and feather suppression effect. It can also be confirmed that, conversely, for the dish-shaped defect, t, the greater the degree of surface modification of the stone, the smaller the suppression effect. From this, it is understood that a grinding composition for cMp which does not have steel grinding debris and which suppresses dishing defects according to the amount of surface modification of the surface-modified stone can be provided. [Examples 28 to 30] CMP (tetra) paper-grinding compound l·l3~N〇. 15 Manufacture. A CMP residue Na 13 〜n was obtained. · 15, which includes the surface modified 郷 as described in Table 9, h 5% ammonium persulfate, 1% glycine, 〇.001, benzo- σ sitting, 〇 · G2% of the twelve burning Ubiquinone, U%, Ethylene, Biluo 2, number average molecular weight surface, 丨_butylene copolymer (4) 吼C; 脱 公司 迨), 〇 · 3% potassium hydroxide and water (remaining components) . 39 200940606 Table 9: Examples 28 to 30

No. ---- diol compound for CMP grinding composition surface modification compound raw material Example 28 No. 13 Surface modified silicone rubber No. 1 PEG200 Example 29 No. 14 Surface modification Dream gel No. 3 PEG1000 Example 30 No. 15 1 A surface-modified nitrile rubber No. 4 PEG2000 [Evaluation Example 3] The polishing composition for CMP described in Table 9 above was evaluated as follows: Copper film was used in the county by electrolysis. On the board, the copper of nm is not patterned. The pattern of the grinding speed of the object to be polished is determined by the method of forming the film on the stone substrate. By using a plasma CVD method using tetraethoxy decane, a hard stone layer of a 500 nm wafer of a hard stone film is formed into a space of 50 (10) of a groove of 50 μm wide, and then The plating method stacks the film into 25 nm, and after depositing a copper seed layer of 1 〇〇 nm by the bismuth ore, the 8-minute wafer on the nm side of the electrolytic ship's surface is used to test the grinding body. Defect evaluation; and evaluation of copper grinding debris. The grinding conditions are as follows. The polishing rate was determined by using Loresi: aGp (manufactured by Mitsubishi Chemical Corporation) from the difference in film thickness before polishing. The dish-shaped defect was measured using an atomic force microscope (AFM) Nanopics (manufactured by Seiko Instruments Inc.) to determine the height difference between the most convex portion and the most concave portion of the steel wiring portion. The copper was pulverized and the presence or absence of the residual film when the copper was excessively polished (〇verpc) was confirmed by optical microscopy. 200940606 The results are shown in Table 10. Grinding machine: AVANTI472 (manufactured by IPEC) Grinding 塾: ici shed (with π groove) and manufactured by Haas eQmpany) Grinding time: 1 minute Platform rotation number: 93 rpm Carrier rotation: 87 rpm © Grinding pressure: 2 psi Serving fluid supply speed: 200 ml / minute table 10

200940606 For the comparison of the polishing compositions for CMP obtained in Comparative Examples 6 and 7, 3 and 4, the same polishing evaluation as in the above-mentioned Evaluation Example 3 was carried out. The results are shown in Table u. Table 11 Grinding Composition for CMP Copper Polishing Rate (nm/min) Group Grinding Speed (nm/min) Disc Defect (nm) Copper Grinding Shoulder - Comparison 3 ------- Comparison 4 700 340 5.3 2. 6 23 ------- 20 A large amount of presence exists in a large amount ''---- From the above Table 11, it can be seen that the CMP abrasive composition using decyl triethoxy decane for surface modification Comparing with 3, comparing with 4, no copper grinding debris to suppress the effect of ❹, and JL 矽 面 面 面 面 面 。 。 。 。 。 。 。 。 。 。 。 。 。 。 In addition, it can be confirmed that the degree of surface modification becomes a contribution, and the speed of marriage is reduced. It can be seen that the surface of the invention is modified by the surface effect (4). 6 nm的粒度。 [Examples 31 to 38] The surface-modified gems of the gelatin No. 16~No. 23 Manufactured by the ethoxylates, the average particle size of 120.6 nm, the particle size. Knife cloth. The cumulative 10% value is 84·7 nm, and the cumulative 5〇% value is 112. 7 coffee, the cumulative 90% value is (10)· G nm of the second gel dispersion (hereinafter, referred to as surface modification before conversion) !^人1 Oxygen cut 4 is heated at _ temperature, and titrated as follows = mouth liquid · each part of the surface modifier compound 2 obtained in the above production example, such as water, 1 part 〇.1 mol / liter of aqueous nitric acid. Relative to 100 parts

Stone bismuth oxide, surface modifier, and high-order q

The number of violent D objects is 3 copies. After titration, the surface was obtained at 6 (TC = the same as 1 2). The surface-modified photo-spectroscopy was carried out with each surface-modified Na obtained in Example 1 to ... (4) 42 200940606 Analysis, and surface modification For the pre-sex gelatin c, the surface modification was confirmed. [Examples 39 to 46] The polishing composition No. 16 to No. 23 for CMP was used to obtain the polishing composition No. 16 to No. 23 of dlP. It is included in Table 12: 1% of surface-modified silicone, 1.5% of persulfate, 3% of ammonium sulfate, 4% of potassium hydroxide and water (remaining components;). Compared with the case of the ninth example, the CMP polishing composition was compared with the pulverized composition for CMP. The pulverizing composition for CMP was used for comparison 6, which included: 1% of the surface modification before the 矽 c c, 1. 5% of the 1 § ammonium sulphate, 〇 · 3% of sulfuric acid, 〇. 4% of potassium hydroxide and water (remaining components). Table 12: Examples 39 to 46 and Comparative Example 9

No. Composition Silicone Surface Modification Compound Raw Material Glycol Compound Example 39 No. 16 Surface Modified Silicone No. 16 PEG200 Example 40 No. 17 Surface Modified Silicone No. 17 PEG400 Example 41 No. 18 Surface Modification Gelatin No. 18 PEG1000 Example 42 No. 19 Surface modified silicone No. 19 PEG2000 Example 43 No. 20 Surface modified silicone No. 20 PEG4000 Example 44 No. 21 Surface modified silicone No. 21 PEG 6000 Example 45 No. 22 Surface-modified silicone No. 22 PEG8000 Example 46 No. 23 Surface-modified silicone No. 23 PEG11000 Comparative Example 9 Comparative surface-modified pre-gelatin C - [Evaluation Example 5] For the above Table 12 The CMP polishing composition No. 16 to No. 23, 43 200940606 and the comparative 6' are used to cut the wafer on the German board by electrolytic plating to a square copper cover test of 3 cm x 3 cm. The film will be covered by a lining method on a stone substrate of a group of 15G nm, and the test piece will be covered by a square of 3 mm. The test piece will be studied and studied under the following research and development. Grinding speed evaluation. The results are shown in Table 13. In addition, the amount of grinding amount L_ta GP (manufactured by Mitsubishi Chemical Corporation) was measured by a film thickness cover before and after polishing. Grinding machine: NF-30G (manufactured by nanofactor) 研磨 Grinding pad: κηοοο (with χγ groove) (Rohm and Haas (10)) Grinding time: 2 minutes Platform rotation: 60 rpnr : Carrier rotation: 60 rpm Grinding pressure: 3 psi Slurry supply speed: 30 ml/min. Table 13 q Grinding composition for CMP copper grinding speed (nm/min) Surface grinding speed (nm/min) Copper/钽 grinding selectivity No. 16 507 10.3 49.2 No. 17 499 8.8 56.7 No. 18 498 1 7.8 63.8 No. 19 468 7.4 63.2 No. 20 454 7.2 63.1 No. 21 434 5.9 ----- 73.6 44 200940606

No. 22 440 5.3 — 83. 0 No. 23 422 ~' 4.9 86. 1 Comparison 6- 492 -------- 12.9 ----.__ 38.1 As seen in Table 13 above, 'as used The material used in the surface modification of Shi Na is very high in the f-speed, and the larger the molecular weight of the surface hybrid, the more excellent the copper/knob grinding selectivity. ® [Examples 47, 48] Surface-modified Shijiao No. 24, No. 25 was produced as a surface-modified composition, and the surface paper was finely divided and s, in the same manner as in the above Examples 31 to 38. The method is to obtain a surface modified Shixi gum N〇24, ', ο·Έ5. [Example 49] Production of surface-modified tannin extract No. 26 As a surface modifier compound 'using a surface modifier compound r, a mixed solution containing 10 parts of a surface modifier compound r and 50 parts of water was titrated to In the 10, the temperature of the temperature of the Shishi gum c in the dispersion. The titration amount of the surface modification compound was 3 parts with respect to 1 part of Shishijiao dioxide. The surface-modified tannin No. 26 was obtained by a drop of 2 hours at a temperature of 6 (the temperature of the rc was obtained.) The CMP abrasive composition was obtained by the CMP abrasive composition n0. 24~No. Να24~Ν〇·26, which includes: i% of the above-mentioned No. 24~26 surface-modified tannin, 1.5% ammonium persulfate, 丨% glycine, 0·001% benzene K, G. G2 % decyl benzoic acid, Q _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ (Comparative Example) [Comparative Example 10] Comparison of polishing composition for CMP for the production of CMP for the comparison of 7 for the polishing composition for CMP, comprising: 1% of the surface-modified pre-tanned rubber C, 1.5% of persulfuric acid Ammonium, 1% glycine, 〇. 〇〇1% benzotriazole, 0.02% dodecylbenzene acid, 〇. 〇3% polyvinylpyrrolidone, number average molecular weight Π000 1-butyl Co-plant (p_9〇4LC; manufactured by Isp), potassium hydroxide and water (remaining component). [Evaluation Example 6] ❹ For the above Examples 5〇 to 52 and Comparative Example 1 The polishing composition for CMP was evaluated as follows: a film of 15 〇〇珈 copper film was formed on the ruthenium substrate by electrolytic plating, and no film of 8 inches was formed, and the film was formed on the substrate by sputtering. Button 15 〇 - - ^ -. button no graphic 8-inch wafer as the object to be polished, the evaluation of the polishing rate; by using plasma CVD method of tetraethoxy decane to form a hard film 5 After the hard stone layer of the wafer is opened by a trench having a depth of 5 〇〇 nm and a width of 50 μm to form a space of 5 〇 _, a 25-layer button film is deposited by sputtering, and then stacked by sputtering. After the copper ruthenium seed layer, an 8-inch wafer of 1 〇〇〇nm copper ruthenium was formed by electrolytic plating, and the wafer was used as a workpiece to be subjected to dish evaluation and copper polishing debris evaluation. The polishing conditions were as follows. The polishing rate was measured by using L〇restaGp (manufactured by Mitsubishi Chemical Corporation) from the difference in film thickness after polishing. The disk trap system uses the original and the force microscope (Na).

Nanopics (manufactured by Seiko Instruments Inc.) measures the height difference between the most convex portion and the most concave portion of the 50 _ copper cloth portion. The copper abrasive chips were confirmed by optical microscopy to confirm the presence or absence of copper residual film at 40% overpolish. The results of 46 200940606 are shown in Table 14. Grinding machine: AVANTI472 (manufactured by IPEC) Grinding 塾 IC1400 (with ▼ XY groove) (manufactured by R〇hm and Haas Company) Ο ο Grinding time: ι min Platform rotation number: 93 rpm Carrier rotation: 87 rpm Grinding Processing pressure: 2 psi Slurry supply speed: 200 ml/min. Table 14 CMP abrasive composition copper grinding arrest (nm/min) Group grinding speed (nm/min) Disc shape defect (nm) Copper grinding debris -- ----- Not observed

From the above-mentioned Table U, it was confirmed that the surface-modified Shijiao Gum of the present invention is used as the L compound No. 24 to N 〇. 26 has a copper grinding _ which is known from the above, The diol structure can effect the effect of grinding debris. In addition, the polishing composition I% to granules can be polished without causing a large loss in flatness. 壬- [Comparative Example 11] Surface-modified Shijiaojiao Comparison 3 Manufacturing 200940606, as surface modification The compound was titrated to 6 混合 using a mixture of 10 parts of a surface modifier compound, 5 parts of water, and 5 parts of 丨. 丨 mol / liter of aqueous nitric acid solution using glycidyl propyl triethoxy decane. The dispersion of Shishijiao C heated at a temperature of c. The amount of glycidyl propyl triethoxylate is 3 parts relative to 100 parts of 100 parts of Shishijiao dioxide. At a temperature of 2 hours, a surface-modified chopping rubber was obtained as compared with 3. [Comparative Example 12] Surface-modified Shijiao Gum Comparison 4 was produced as a surface modifier compound using 3_guanidinopropyltriethoxydecane. A mixture of a surface modifier compound containing 1 part of water, 50 parts of water, and a mixture of hydrazine, hydrazine/liter of aqueous nitric acid is titrated to a dispersion of cerium c which is heated at a temperature of 6{rc. For the bismuth dioxide bismuth oxide, the amount of 3_ guanidinopropyl triethoxy decane used is 3 After titration, the mixture was stirred at 6 (rc temperature for 2 hours to obtain a surface-modified tannin extract. 4. [Comparative Example 13] Surface-modified Shijiaojiao Comparative 5 was produced as a surface modifier compound (3-mercaptopropyl) Triethoxy decane, ❹ contains 10 parts of surface modifier compound, 5 parts water, 2 parts 〇. 1 mole / liter of Nisi shui water solution is titrated to warm at temperature夕胶 [in the dispersion. Compared with 100 parts of bismuth dioxide, bis (3-mercaptopropyl) triethoxy zexiyuan, the amount used is 3 parts. After titration, stir at 2 (TC temperature for 2 hours, The surface-modified tannin extract was obtained. 5. [Comparative Examples 14 to 16] The polishing composition for CMP was compared with 8 to 1 Torr. The polishing composition for CMP was used for comparison of 8 to 10, which included: 1% of the above comparison 48 200940606 Examples 11 to 13 surface modified Shijiao, 1.5% ammonium persulfate, 1% glycine, 〇. 〇〇 1% of the three and three saliva, 〇. 02% of the twelve recorded acid, Q3% Polyethylene sulphate ketone ketone dilute copolymer (p_9眺C; manufactured by ISP), 0.3% potassium hydroxide and water (Residual component) [Evaluation Example 7] The polishing composition for CMp of the above Comparative Examples 14 to 16 was evaluated as follows: a copper film of 15 〇〇nm surface was formed on the Shixi substrate by electrolytic electrowinning. Figure 8 ❹ > inch 曰曰 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉The plasma of the kiln (10) is formed into a film of 5〇〇nm hard stone film. The hard stone layer of the wafer is opened with a depth of 500 nm and a width of 50 gings. After 50 urn space, it is hoarded by the splash bond method. After the I-film is 25 nm, an 8-inch wafer of 1_nm copper film is formed by electrolytic electro-recording by depositing a copper-clad seed layer by electrolytic recording, and the wafer is used as an object to be subjected to dish-shaped defect evaluation. And copper grinding debris evaluation. © The grinding conditions are as follows. The polishing rate was measured by using L〇restaGp (manufactured by Mitsubishi Chemical Corporation) from the film thickness difference before and after the polishing. The dish-shaped defect was measured by using an atomic force microscope (AFM) Nanopics (manufactured by Seiko Instruments Inc.) to measure the height difference between the most convex portion and the most concave portion of the copper wiring portion. The copper grinding debris is based on the presence or absence of the copper residual film when the optical lens is used for the 40% over-grinding (〇verp〇i丨 oil). The results are shown in Table 15. Grinder: AVANTI472 (IPEC) Made by the company) Grinding 塾: IC1400 (with XY groove) (R〇hm _ H· c〇_y 49 200940606 Manufactured) Grinding time: 1 minute Platform rotation number: 93 rpm Carrier rotation: 87 rpm Grinding waste : 2 psi ......... .... . Slurry supply speed: 200 ml / min. Table 15 CMP abrasive composition copper grinding speed (nm / min) button grinding speed (nm / min) Shape defect (nm) ----ι Copper grinding debris comparison with 8 924 6.5 30 Small amount of dispersion comparison with 9 yang compared with p -886 2.9 - 20 Large amount exists 664 0.9 25 A small amount of dispersion can be seen from Table 15 above, used to shrink Glycerylpropyltriethoxydecane was used for surface modification. The CMP polishing composition for comparison was used for the comparison of 8, and there was no dishing defect suppressing effect, and the polishing composition after CMP was used, and the flatness after polishing 8 was also inferior. In addition, the use of cMp for the surface modification of 3-pyrouretopropyl triethoxy decane The composition comparison 9 showed no inhibition of the grinding of the button, but had no inhibitory effect on the grinding debris of copper. The CMP polishing using the surface modification of (3-mercaptopropyl)triethoxydecane was carried out. The composition was compared with 丨〇 to show no inhibition of the button = but no sufficient polishing rate for copper. [Example 53] Surface-modified 矽 N N. 27 Manufacture as a surface modifier compound using a surface modifier Compound b, surface modification was carried out in the same manner as in Examples 1 to 5, except that the amount of the surface modifier compound was 7 parts, and the amount of the surface modifier compound was changed to 5, 2009, 40,606 parts.矽胶Νο·27. [Examples 54 to 58] CMP polishing composition N〇. 28~No. 32 was produced by the CMP polishing composition No. 28 to No. 32, which included: 65% of the above No. 25~No·27 Surface modified Shijiao, 1% hydrogen peroxide, 〇. 〇2% benzotriazole, 0.02% of dodecylbenzene acid, 〇·1% Potassium hydrogencarbonate, i 2% potassium hydroxide, 0.1% polyethylene glycol (pEG4〇〇) and water (remaining components). Comparative Example 17] A polishing composition for CMP was compared with a ruthenium for the production of a polishing composition for CMP, which comprises: a surface-modified pre-rubber A, a 1% hydrogen peroxide, 〇. 02% Benzotriazole, 〇. 〇 2% of dodecylbenzenesulfonate, 0.1% potassium hydrogencarbonate, i. 2% potassium hydroxide, cesium. 1% polyethylene glycol (PEG400) and water ( Remaining ingredients). [Evaluation Example 8] With respect to the polishing compositions for CMP of the above-mentioned Examples 54 to 58 and Comparative Example 17, ® was evaluated as follows: copper of a film of 1500 nm was formed on the Shih-hs substrate by electrolytic electrowinning. A pattern-free 8-inch wafer, a 150 nm button on a Shih-hs substrate, a patterned 8-inch wafer, and a film-forming method on a ruthenium substrate by plasma CVD

800 nm PE-TEOS PE-TE0S unpatterned 8-inch wafer, film-forming CVD substrate on a 〇〇〇nm Black Dia_dl (BD1) rib 1 non-patterned 8-inch wafer as the object to be polished, The polishing rate was evaluated. A 854 pattern wafer containing a BD1 insulating film of 45 Å in thickness, which was plated with the same conditions, was removed as a workpiece to be subjected to tooth evaluation. 51 200940606: The grinding conditions are as follows. The polishing rate of the copper film and the film was measured by using Loresta GP (manufactured by Mitsubishi Chemical Corporation), and the polishing rate of the PE-TEOS film and the BD1 film was measured by using F20-2 (manufactured by FILMETRICS). The dentition was confirmed by atomic force microscopy (AFM) Nanopics (manufactured by Seiko Instruments Inc.). The results are shown in Tables 16 and 17. Grinding machine: AVANTI472 (manufactured by IPEC) Grinding pad: IC1400 (with K groove) (Rohm and Haas Company)

造) Platform rotation number: 140 rpm Carrier rotation: 125 rpm Sauce mill _ working pressure: 1.5 pSi Grinding liquid supply speed: 13 〇 mi / min No graphic wafer grinding time: 1 minute

Pattern Wafer Polishing Time: Schedule required to grind BD1 at 20 nm 16 CMP Grinding Composition Copper Grinding Speed (nm/min) Button Grinding Speed (nm/min) TE0S Grinding Speed (nra/rain) BD1 Grinding Speed ( Nm/min) No. 28 54 57 41 43 No. 29 56 55 — 44 ~~ 15 No. 30 62 54 43 34 No. 31 48 55 43 21 No. 32 56 50 54 39 Comparison 11 56 50 54 ~~ 27 52 200940606 Table 17: No. 28~ No. 29, 11 teeth for comparison (nm) Grinding composition for CMP 50/50 μπι L/S rib 0_ 18/0. 18 μιη L/S rib No. 28 8 26 No. 29 11 10 No. 30 19 40 No. 31 21 41 No. 32 5 14 Comparison 11 23 47 From Table 17 above, it can be seen that the tooth is improved by performing surface modification. In addition, = can also be confirmed from the above Table 16, by performing surface modification, compared with the unmodified Shiqi gum, without impairing the polishing rate. [Simple description of the diagram] [Explanation of main component symbols] 53

Claims (1)

200940606 VII. Patent application scope: 1. Surface modified ceramsite, characterized in that surface modification is carried out by at least one group represented by the following general formulas (丨), (2) and (3) , A1 A1 Ρ -A2 R3 (1)(2) H2?—〇—f EO Vf P〇E〇^—A2 H | ~°~^ E〇P0 EO 4—Y (3) ❹ H2C—〇—e EO p〇E〇^_Y (wherein, Al represents a group selected from the following formulae (all) to (al3), (a3i) to (10)) and (a51) to (a53), and a2 represents a group selected from the group consisting of The group of the formula (10)) to (10)), (Mi|~(a43) and (10)) to (a63), r3 represents a hydrocarbon group having a gas atom or a number of faces of 1 to 30, and γ represents a2 or r3, and the EQ system represents Epoxy Ethylene, p〇 is an epoxy propyl group, m, n, p, m system 〇~i7〇, n system 〇~120 ' ρ system 〇~170 'm+p system means non-zero Number) R1I °~Si-Xi\j-c_〇_ R1 (all) Ri CN-x_Si-〇- (a2l) OH M ❹ Ο -〇-Si-XNc-〇- (al2) FV H 〇0 CN ~x-Si-〇- (a22) Ο HR 2 O 〇-Si-Xl\l-〇_〇_ ( I | || ^ 13; H 0 0 CNX-Si-O- (a23) 〇H 54 200940606 Rj -O-Si-XO (a31) X FV o 1 - 2 R - si - R, (a41) '0 -0-Si-X-0- (a32) 0 \ I 2 o丨si - R 1 X (a42) '0 -0 -Si-X-0- (a33) 0 〇- - o丨si—“IX (a43) R1 R -0-Si —X — N _ Ch^CH — C _ 0 — 51 a H ο —Ο — Si — Χ — Ν — CH R — c 2 0 1c=o IH 2 5 a Ri Η 0 1 c = o IHR——c 2 3) 5 a RR N——H 1 2 Hc Hc Ic = o X o i-2 s·*-R 6 a R. N——H - 2 Hc Hc - cnno X \'-2 οIsi -R o 2 6 3 RN——H- 2 Hc Hc 1c=° I 0 /1-/ —1 ---- -- co 1 X 3) 6 a 55 200940606 Further, R1 and r2 are mainly represented by a group of a carbon atom having a carbon number of 1 to 4, a phenyl group or a phenyl group, a group of x 18, and a group of a hydrogen atom or a methyl group. The value of the surface modification (1), (2) or (3) described in item ii of the Shishen "month special brakes. The surface-modified gelatin according to the above-mentioned formula (1^2) or (3) wherein m+P is in the range of 2 to 340. A polishing composition for CMP comprising the surface-modified silicone of any one of items 1 to 3 of the patent application. 5' The CMp abrasive composition of claim 4, which also contains persulfate. 56