TW200944582A - Aqueous dispersion for chemical mechanical polishing and chemical mechanical polishing method - Google Patents

Abstract

Disclosed is an aqueous dispersion for chemical mechanical polishing, which contains (A) silica particles and (B1) an organic acid. The silica particles (A) have such a chemical property that the silanol group density thereof as calculated based on the specific surface area determined by using a BET method and the amount of silanol groups determined by titration is 1.0-3.0 groups/nm2.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a chemical mechanical polishing aqueous dispersion and a chemical mechanical polishing method. [Prior Art] In recent years, in order to prevent an increase in signal delay due to multilayer wiring of a semiconductor device, an interlayer insulating film using a low dielectric constant (hereinafter referred to as "low dielectric constant insulating film") has been studied. . As such a low dielectric constant insulating film, for example, materials described in JP-A-2001-308089 or JP-A-2001-298023 have been studied. When the low dielectric constant insulating film as described above is used as the interlayer insulating film, copper or a copper alloy is usually used because the wiring material requires high conductivity. By metal inlaying

(Damascene, when manufacturing such a semiconductor device by 〇(1), usually has to perform the following steps: removing the barrier metal by the chemical mechanical polishing (the step of the wiring material on the barriermet film (the fourth grinding step); and thereafter The mechanical polishing is performed in addition to the gold wall of the wall, and the step of planarizing the film by chemical mechanical polishing is carried out as needed (second research, first, in the first polishing step, only for wiring The material is ground. (5) Other types such as a fast and selective wall metal film: it is difficult to suppress the light H after the wiring portion in the state of high polishing speed. 098104943 vaishing) 3 200944582 , erosion. For example, if only Increasing the polishing speed, the i_ wiring can be achieved by increasing the friction applied during the grinding to increase the friction applied to the wafer. 浅; 7 The shallow disc or the grinding (4) will be accompanied by the grinding arrest. However, there is a limit in the way from the grinding method (Qi's job h). In order to obtain a good polished surface in the second grinding step, it is necessary to suppress the copper on the fine wiring at the end of the 1 grinding step. Remaining (copper residue) ❹ As described above, in addition to the high-speed polishing performance and high flattening characteristics, it is difficult to remove the copper residue by a simple cleaning step in the first polishing step. The current grinding method is achieved to compensate for this

It also requires the development of a chemical mechanical grinding water dispersion that is acceptable for feeding.

On the other hand, in the second polishing step described above, it is particularly required to polish the surface to be polished to a flat β. Therefore, the design change of the structure of the semiconductor device has been studied in order to further improve the flatness of the surface to be polished in the second polishing step. When using a low dielectric constant insulating film having a weak mechanical strength, it is based on the following reasons: (1) due to chemical mechanical polishing, a phenomenon called [slumping or scratching (8) plus (8) is generated on the surface to be polished. (2) When the tamping and the rounding of the fine wiring structure are performed, the polishing rate of the low dielectric constant insulating film is lowered, so that the flattening and high precision polishing cannot be obtained. (3) The adhesion between the barrier metallurgy and the low dielectric constant insulating film is poor; thus, it is studied that a coating called a caplayer composed of a stone or the like is formed on the low dielectric constant insulation. The structure of the upper layer of the film, etc. In the grinding step of the construction of the second 098104943 4 200944582, the coating on the upper layer must be quickly ground and removed, and the polishing rate of the lower dielectric constant insulating film of the lower layer is suppressed as much as possible. That is, the relationship between the grinding speed (RR1) of the overlying layer and the polishing rate (RR2) of the low dielectric constant insulating film is required. RR1 > RR2 is satisfied. Further, in order to prevent breakage of the low dielectric constant insulating film or peeling off from the interface of the build-up material, there is a method of reducing the applied pressure during polishing to reduce the frictional force applied to the wafer. However, this method causes a decrease in the polishing speed by reducing the applied pressure during polishing, which results in a significant decrease in the production efficiency of the semiconductor device. In order to solve such a problem, the technique of increasing the polishing rate by including a water-soluble ruthenium molecule in a chemical mechanical polishing aqueous dispersion is described in the publication No. 2/7,677, 〇. The polishing rate in the second polishing step in the method is also not sufficient. As described above, it is required to develop a novel chemical mechanical polishing aqueous dispersion which prevents damage of the low dielectric constant insulating film and which has high polishing rate and high flattening properties for the barrier metal film and the overlying layer. However, in general, the composition of the chemical mechanical polishing aqueous dispersion is composed of abrasive grains and additive components. In recent years, the development of chemical machinery and polishing water-based dispersions has mainly focused on a combination of additive components, but the 'other aspects' are disclosed, for example, in Japanese Patent Laid-Open No. Hei. No. Hei. No. Hei. 'It was studied to improve the grinding characteristics by controlling the properties of the abrasive particles. However, when the abrasive grains described in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. 098104943 No. Hei No. 098104943 No. Hei No. 098104943 No. 2003-109921, there is a problem that a metal component such as sodium is present in the abrasive grains, and it is difficult to remain in the polishing after polishing. Since the metal component such as sodium on the object to be polished is removed, it is difficult to use it in the polishing of an actual device. Further, the abrasive grains described in Japanese Laid-Open Patent Publication No. 2003-197573 or JP-A-2003-109921 have a problem that the particle dispersion liquid lacks stability and thus has poor storage stability. SUMMARY OF THE INVENTION An object of the present invention is to provide a chemical mechanical polishing aqueous dispersion and a chemical mechanical polishing method using the same. The chemical mechanical polishing aqueous dispersion system does not cause defects on a metal film or a low dielectric constant insulating film. , reducing the polishing rate of the low dielectric constant insulating film, having a high polishing rate and high flattening property for an interlayer insulating film (overlying layer) such as a TE〇s film, and having less metal contamination of the wafer can be suppressed Surface defects such as shallow discs, abrasion, scratches, and sharp grooves ({卿). Another object of the present invention is to provide a method which does not cause defects on a metal film or a low dielectric constant insulating film even under conditions of Proton, has a high polishing rate and a high polishing selectivity to a steel film, and has a crystal. The metal contamination of κ is lower than that of the mechanical polishing water (4), and the chemical mechanical polishing using the above-mentioned "pointed groove" is a new problem to be solved by the invention of the present invention. Hereinafter, the "tip groove" will be described in detail. In this specification, the term "pointed groove" is specially generated when the metal film is recorded by 098104943 Λ 200944582 copper or copper. The area of the remaining side wiring and the fineness of steel or copper alloy are not included. On the interface of the slab (held part), the grinding defects due to chemical mechanical polishing are caused by panning or abrasion. The second is the origin of the (four) groove, the general material, the fine wiring area of the alloy, and the fineness of the steel or copper alloy.

==成? The component of S in the chemical mechanical polishing water system is locally present in the ground, and the vicinity of the interface is excessively ground. E.g,

The abrasive grain component contained in the mechanical polishing aqueous dispersion is present in the vicinity of the above interface at a higher J, and the polishing rate of the interface is locally increased, and excessive polishing is caused. If excessive polishing is performed in this way, flatness is poor. This is a grinding defect called a "pointed groove". The pointed groove has various production forms according to the cloth, and the cause of the pointed groove to be solved by the present invention is taken as an example, and the object to be processed 100 shown in FIG. . As shown in Fig. 1, the object to be processed 100 is formed by sequentially laminating an insulating film 12, a barrier metal crucible 14 and a film 16 made of copper or a copper alloy on the substrate 1 to form a structure in which the insulating film 12 is formed. There are grooves and other recesses for wiring, etc., » Hai barrier wall gold; The crucible 14 is provided so as to cover the surface of the insulating film 12 and the bottom and inner wall surfaces of the wiring recess 20, and the film 16 made of copper or a copper alloy is filled in the wiring recess 2G and formed on the barrier metal film 14. By. Further, the object to be processed 1 includes a region containing fine wiring of copper or a copper alloy, 098104943 7 200944582, a region 22, and a region μ which does not contain fine wiring of copper or a copper alloy. , == in the area 22 of the wiring, as shown in Figure 1, it is easy to form steel or copper. Figure 2 shows the grinding of copper or copper 16 by chemical mechanical polishing until the metal film 14 is in the stage. , no sharp groove has been produced. Shape I. Fig. 3 shows a state in which the barrier metal film 14 is cut and the chemical mechanical polishing of the film 12 is present on the surface. If the metallographic transition of the transfer wall is chemical mechanical polishing, fine scratches 26 are formed at the interface of the region 22 containing the fine wiring of the _ or copper alloy and the area of the fine wiring containing no copper or copper alloy. Fig. 4 shows a state in which the chemical mechanical polishing is progressed and the insulating film 12 is cut. At this stage, the "fine flaw 26" becomes the groove (28) of the groove-like flaw. This sharp groove sometimes becomes a defect of the semiconductor device, which is not preferable from the viewpoint of causing a decrease in the manufacturing yield of the semiconductor device. In the first chemical mechanical polishing aqueous dispersion according to the present invention, the (4) cerium oxide particles and the (B1) organic acid are contained, and the (A) dioxide album has the following properties. The density of the phenolic group calculated based on the specific surface area measured by the BET method and the amount of the sulphuric acid base measured by titration was i 〇 3.0 3.0 / (10) 2 . The first chemical mechanical polishing financial dispersion of the present invention may have the following state: 098104943 200944582 . . . The above (B1) organic acid may be an organic acid having two or more carboxyl groups. - the acid dissociation index of the above-mentioned organic acid having two or more sulfhydryl groups under the support of 乞κ& (wherein the organic acid having two carboxyl groups is an organic compound having a second carboxyl group as an index, and having an organic group of three or more carboxyl groups The acid may have a pKa of the third carboxyl group as an index) of 5.0 or more. The organic acid having two or more substituents may be at least one selected from the group consisting of cis-butyl diacid, acesulfonic acid, and citric acid. Further, (C1) a nonionic surfactant may be contained. The above (C1) nonionic surfactant may have at least one ethynyl group. The (C1) nonionic surfactant may be a compound represented by the following formula (1). [Chemical 1]

CH3-CH(CH3)-CH2-i C(CH3>- 0-(CH2

0-CCH2CH2(%H >-CsC-C(CH3)-CH2-CH(CH3>-CH3 CHiOfeH (1) (wherein m and n are each independently an integer of 1 or more, satisfying m + ns5Q^ and further, (D1) A water-soluble polymer having a weight average molecular weight of 50,000 or more and 5,000,000 or less. The (D1) water-soluble polymer may be a polycarboxylic acid. The polycarboxylic acid may be poly(meth)acrylic acid. 098104943 9 200944582 » * (D1) The water mass of the polymer is 0.001 mass H. mass% for the total mass of the two bodies for chemical mechanical polishing. The long diameter (Rmax) and short diameter of the oxidized stone particles The ratio of (Rmin) (Rmax/Rmin) may be 1 〇 to 15 5. The average particle diameter of the above (/) cerium oxide particles according to the specific surface area measured by the BET method may be 10 nm to 100. The pH value may be 6 to 12. The second chemical mechanical polishing aqueous dispersion of the present month contains (A) cerium oxide particles and (B2) amino acid, and is used for grinding a copper film. The above (A) cerium oxide particles have the following chemical properties. According to the specific surface area measured by the BET method and the scoline alcohol measured by titration The amount of the farinol group calculated by the amount is 丨(一)^/心 The second chemical mechanical polishing aqueous dispersion of the present invention may have the following aspect. The above (B2) amino acid may be selected from the group consisting of glycine and propylamine. At least one of an acid and a histidine. Further, the organic acid having a nitrogen-containing heterocyclic ring and a carboxyl group may be contained. Further, the (C2) anionic surfactant may be contained. The (C2) anionic surfactant may have The at least one functional group selected from the group consisting of a thiol group, a carboxylic acid group, a phosphoric acid group, and an ammonium salt and a metal salt of the functional group. The (C2) anionic surfactant may be selected from the group consisting of an alkyl sulfate and an alkyl group. Base 098104943 10 200944582 Ether sulfate ester, alkyl ether carboxylate, alkylbenzene sulfonate, α-sulfonate fatty acid ester salt, alkyl polyoxyethylene sulfate, alkyl phosphate, monoalkyl dish One of the acid ester salt, the naphthalene sulfonate, the α-olefin sulfonate, the alkane sulfonate, and the alkenyl succinate. The above (C2) anionic surfactant may be represented by the following formula (2) ) the compound represented. [Chemical 2]

(2) (In the above formula (2), R1 and R2 each independently represent a hydrogen atom, a metal atom or a substituted or unsubstituted alkyl group, and R3 represents a substituted or unsubstituted alkenyl group or a sulfonic acid group (- SOd), wherein X represents a hydrogen ion, an ammonium ion or a metal ion. Further, "D2" may contain a water-soluble polymer having a weight average molecular weight of not less than 10,000 and not more than 150,000, which has a property as a Lewis test. The above (10) water-soluble polymer may have at least one molecular structure selected from the group consisting of a heterocyclic ring and a cationic functional group. The (D2) water-soluble polymer may be a homopolymer having a nitrogen-containing monomer as a repeating unit or a copolymer containing a nitrogen-containing monomer as a repeating unit. The above nitrogen-containing monomer may be selected from the group consisting of N-vinyl pyrrolidinium, (,) propylene 098104943,, 200944582 decylamine, N-pyridyl porphyrin, N, N-碲醯^, N-2_ Hydroxyethyl acrylamide, propylene sulfonium salt, N,N-dimethylheptylaminopropyl acrylamide and its diethyl sulphate, sulfhydryl field amide, N' isopropyl propylene hydride At least one of the amine, the N-vinylethyl salt, and the N-ethylglycine N'N-didecylaminoethyl vinegar and the diethylsulfonic acid thereof (1) dicentric meglumine. (Rzu/Rmin) ratio of long diameter (RmaX) to practice (10) in) 々I 〇~1. 5. The above (A) two gasification, and the particle diameter of the tantalum particles can be from 10 nm to 100 nm based on the specific surface area measured by the BET method. The pH can be 6 to a. In the first chemical mechanical polishing aqueous dispersion and the second chemical mechanical polishing aqueous dispersion of the present month, the (A) dioxins may have the following chemical properties. According to the elemental analysis using ICP (Inductively Coupled) illuminating knife method or Icp mass spectrometry, and the quantitative analysis of Γ ammonium ion, the _, potassium and Nazi 糸 are sufficient for the relationship : 5~5G0ppm, which is selected from the group consisting of a clock and a syrup to a cerium: 10 〇 to 20000 ppm. The mechanical polishing method is characterized in that the water-based dispersion of the first chemical mechanical polishing is used to polish the surface of the polished surface selected from the group consisting of a metal film, a barrier metal film, and a smashing device. 098104943 200944582 When the first chemical mechanical polishing aqueous dispersion is used, the polishing rate of the low dielectric constant insulating film can be reduced, and the interlayer insulating film (overcoat layer) such as the te〇s film can be simultaneously satisfied. High grinding speed and high flattening characteristics. Further, when the first chemical mechanical polishing aqueous dispersion is used, defects are not caused on the metal film or the low dielectric constant insulating film, and shallow dishing, abrasion, scratching or sharp grooves can be suppressed. High quality chemical mechanical polishing of surface defects and reducing metal contamination of the wafer. 〇 If the second chemical mechanical polishing aqueous dispersion is used, the high polishing rate and high polishing selectivity to the copper film can be satisfied at the same time. Further, when the above-described chemical mechanical polishing aqueous dispersion is used, defects are not caused on the metal film or the low dielectric constant insulating film under ordinary pressure conditions, and high-quality chemical mechanical polishing can be achieved and can be reduced. Metal contamination of small wafers. [Embodiment] Hereinafter, preferred embodiments of the present invention will be described in detail.第 丨. First chemical mechanical polishing aqueous dispersion The first chemical mechanical polishing aqueous dispersion of the present embodiment contains (A) cerium oxide particles and (B1) organic acid, and the above (A) is oxidized. 0〜3. 0个/nm2。 The 矽 矽 nm 」 」 」 」 」 」 」 」 」 」 」 」 」 」 」 」 」 」 」 」 」 」 」 」 」 」 」 」 」 」 」 」 」 」 」 」 」 」 」 」 」 」 」 」 」 Chemical properties. First, each component constituting the aqueous dispersion for chemical mechanical polishing of the present embodiment will be described. 1.1 (A) cerium oxide particles 098104943 13 200944582 The "stone smelting alcohol base" of the cerium dioxide particles of the present embodiment refers to the secret of the direct bonding of the surface of the smear particle of the shovel, and the read configuration = body Do not limit. Further, the conditions for the formation of the fine base are not limited. The "Wei density" in the fourth embodiment of the present invention refers to the number of the group of the thiol groups per unit area of the surface of the diced particles, and is a purity indicating the electrical or chemical properties of the diced particles. In the chemical mechanical research (4) water system dispersion, the "H+ dissociation of the Shixi burning alcohol base (_) and the existence of SiG. Thereby, the electrical characteristics or drying characteristics of the diced particles are expressed. The unit of the density of the stanol group is expressed in units of / nm 2 . The (A) dioxy-cut particles used in the present embodiment are based on the surface area of the dioxo particles measured by the BET method and the amount of the prol base determined by the determination of c-oxygen. The sulphate of the cut particles can be compared with the commonly known potential difference (4), or the syllabus of the lectures of the syllabus of the Spring Society of the Institute of Precision Engineering, p84?~ 848. The chemical mechanical water of the oxidized stone particles is divided into regions, and the well-known alkali of the sulphate is used for titration. The density of the thiol group of (Α) dioxo (4) used in the form of shirt application ~ "W. If the weight of the alcohol base is 1.2 Λ W (4) on the density of two phases, the electrical or chemical properties of the surface of the dioxin = sub-surface To attract or repel the organic mechanical water-containing polymer contained in the chemical mechanical grinding of the ship, add 098104943 14 200944582 Additive ingredients. The result is generally considered as 'the chemical mechanical grinding water dispersion in the additive component in the H green The micro-nano concentration is produced in the chamber to achieve good polishing characteristics, so that an optimal chemical mechanical polishing aqueous dispersion can be formed. Moreover, it is generally considered that the region containing fine wiring of copper or copper alloy does not contain The area of the fine wiring of the copper or copper alloy (salt part) is the boundary of the chemical system. The age of the water is dispersed in the vicinity of the interface to cause excessive grinding, thereby producing a sharp groove 'but if the residual alcohol density In the above range, a slight concentration gradient is generated around the (Α)-gas servant stone, and the formation of a sharp groove can also be suppressed. For the above Within the range, the chemical mechanical polishing water hydrazine dispersion is moderately stabilized by the interaction of the dioxo prior particles with other additions, and the oxidized recordings are separated from the chemical mechanical mortar by the water dispersion. When the polishing is performed, the cause of the defect is not formed. If the degree of confidentiality exceeds 3·G cores 2, the service method obtains such a balanced state of dispersion, and thus the polishing rate ratio is insufficient or the flattening characteristics are insufficient. On the other hand, in the case of y 2 , when the density of the stanol group is less than 1 / / (10), the dispersion of the sulphur dioxide particles in the chemical mechanical water dispersion is mixed, and the oxidization record It is not good for the sub-generation to deteriorate in the county. The U used in the present embodiment is preferably 5 to 500 ppm, more preferably the cerium oxide particles may contain sodium, and the sodium content is 10 to 400 ppm. Particularly preferred is 15 to 098104943 200944582 300 ppm. Further, it may contain 100 to 2 〇〇〇〇 ppm of one selected from the group consisting of potassium and ammonium ions. In the case where the above (A) sulphur dioxide particles contain potassium, When the potassium content is preferably from 100 to 20000 ppm More preferably, it is 5 〇〇 15 15 m, and particularly preferably 1 _ 1 〇〇 () () ppm < 5 when the (A) dioxide contains a recording ion, the ammonium ion content is better. It is 100 to 20000 P eggs, more preferably 200 to 10000 ppm, and particularly preferably 5 to 8 〇〇〇 ppm. Even if the content of potassium or ammonium ions contained in the above (A) cerium oxide particles is not the above In the case of the range, the total content of the unloading ammonium ions is preferably in the range of 100 to 20000 ppm, more preferably 500 to 15000 ppm, particularly preferably in the range of 1 〇〇〇 to 1 〇〇〇〇 ppm. . If the sodium content exceeds 500 ppm', wafer contamination occurs after polishing, which is not preferable. On the other hand, in order to make the nano content less than 5 ppm, it is necessary to perform a plurality of ion exchange treatments, but it is technically difficult. The content of at least one of the potassium and ammonium ions selected from the right is higher than that of the fine 〇〇, and the pH value of the sulphur dioxide sub-ship will become too high, and the sulphur dioxide will dissolve in another aspect. When the content of at least one of the ions is less than 100 ppm, the dispersion stability of the silica dioxide particles is lowered to cause aggregation of the particles of the cerium oxide, which causes defects in the wafer to be defective. Further, the sodium content and the potassium content contained in the above cerium oxide particles are quantified by icp luminescence analysis (ICP-AES) or Icp mass spectrometry (icp_Ms), and the H ICp luminescence analyzer can be used, for example. "ICPE-Deleted (made by Shimadzu Corporation)". For example, "ICPM-8500 (manufactured by Shimadzu Corporation)", "ELAN DRC PLUS (manufactured by PerkinElmer Co., Ltd.)", etc., can be used as the i (: p mass fraction 098104943 200944582), and the above-mentioned cerium oxide particles are included. The ammonium ion content is a value obtained by ion chromatography. For ion chromatography, for example, a non-suppressor ion chromatography "HIS-NS" can be used.

It is manufactured by the company, and it is manufactured by the company. Further, sodium and potassium contained in the cerium oxide particles may be sodium ions or potassium ions, respectively. The sodium, potassium, and ammonium ions contained in the cerium oxide particles can be quantified by measuring the contents of sodium ions, potassium ions, and ammonium ions. Further, the contents of sodium, potassium, and chlorin described in the present specification are relative to the amount of sodium, potassium, and ion recorded by the amount of the diced particles. By the inclusion of at least one of the above-mentioned (4), selected from the unloading and the money ion, the dioxic cut is purely mechanically milled, and the coagulation is read. (4) The grinding of the forest will produce the dioxane When the particle size is in the above range, the metal data of the wafer after polishing can be prevented from being measured by the specific surface area measured by the BET method, and the chemical fiber is studied as: The above range is not full of slippery polished surfaces. If the average particle size of the oxidized oxidized layer is 168104943 17 200944582, the grinding speed of the interlayer insulating chess (upper layer) is not too practical. When the other average particle diameter exceeds the above range, the cerium oxide particles: - oxygen: cerium particles are poor, which is not preferable. The storage stability of the sub-particles is smaller than the average particle diameter of the oxygen-cut particles, for example, the root is calculated by the flow-type specific surface area automatic measuring device "Mic-TurstriesFlQwSQrbn Manufacturing Co., Ltd." and the ratio is calculated by the method of the method. (4) The method of cutting the average particle size of the table is calculated. < 〇 It is assumed that the shape of the cerium dioxide particles is spherical and d(f), and the specific gravity is p (g/cm3). The surface area A of the particles is the mass of the material. The mass N is NK/6. The specific surface area constitutes the surface area of the particles. In this case, the particle 'specific surface area sw6/heart' substitutes the specific gravity t 2·2 of the dioxide particle to the money unit, and can be changed by the following formula (3). The average particle size (nm) = 2727/S (m2/g) (3) In addition, the dioxin (3) formula in the present specification is calculated. The thousand-average particles (4) of the preparation are all based on the long pole (Rmax) and the short diameter (four) of the dioxo prior particles :: It is preferably 1:0 to ", more preferably 1" to "excellently, if the right Rmax/Rmin is within the above range, the metal film or the insulating film does not cause defects", which can exhibit high polishing speed and high planarization. Characteristics: If RmaX/Rmin is greater than L5, it will cause defects after grinding. 098104943 18 200944582 Here, the long diameter (Rmax) of the so-called dioxo prior particles is taken by a transmission electron microscope. An image of an independent dioxygen-cut particle, in which the end of the image is the longest distance from the end of the image. The short diameter (Rmin) is the shortest distance between the end of the image and the end of the image in the image of a separate ion monoxide particle captured by a transmission electron microscope. As shown in Figure 5, when the image of a gate dioxin particle 3Ga captured by a transmission electron microscope is in the shape of an ellipse, the ellipse is broken to the long diameter of the dioxoparticle, and the ellipse = wear : child - the image of the particle 鸠 is the longest distance between the end and the end of the dioxine (4). The U image (Rmax) will be connected, and the long diameter of the cerium oxide particle will be broken. The shortest distance d between the end and the end of the Shixi particle is judged as ^KRmin of the second emulsified stone particle. As shown in the micro-mirror, the image of the oxidized stone particles 3〇C is separated by the transmission electrons. The image of the three-dimensional long distance e is determined as the dioxide dioxide. The shortest end of the end and end of the end and the end of the end are separated from the gods (Rmax) and will be connected to the image (Rmin). f is judged to be the short diameter of the oxidized hair particles. The long diameter (Rmax) and the short diameter (Rmin) are calculated by the long diameter (R dirty) and the short 50 SiO2 particles as described above. 098104943 19 200944582 After the average value, the ratio of the long diameter to the short diameter can be calculated (8). The content of the (A) cerium oxide particles is preferably 丨% by mass, more preferably 15% by mass, based on the total mass of the chemical mechanical polishing aqueous dispersion at the time of use. . If the content of the above-mentioned cerium oxide particles is less than the above range, a sufficient polishing rate cannot be obtained, so it is not true. If the content of the cerium oxide particles exceeds the above range, the cost increases and the enthalpy is not obtained. Chemical research (4) water dispersion. The method for producing the (A) cerium oxide cerium particles used in the present embodiment is not particularly limited as long as the cerium is obtained in the range of the above-mentioned range. A well-known method of the well-known. For example, it can be produced by the method of producing a dioxate dispersion of the Japanese Patent Laid-Open Publication No. 20-301-9921 or the No. 2006-80 side. Further, as a well-known method of the prior art, there is a method of preparing a dioxide from the aqueous solution of the sulphuric acid. Examples of the aqueous solution to be tested include sodium citrate aqueous solution, aqueous ammonium citrate solution, lithium citrate aqueous solution, and potassium citrate aqueous solution which are generally known as water glass. The ammonium sulphate is exemplified by the oxidized ruthenium and the fluorinated ruthenium hydroxide. The gasified ruthenium particles are 20 to 38% by mass or less, and are produced for the (A) two-body used in the present embodiment. One of the methods is explained. The cerium oxide content is 20 098104943 200944582 and the Si (h/Na2 莫 molar ratio is 2 〇~ diluted, and the second inclination is 2~5 H 财 _ water is carried out. Then the dilution _ aqueous solution is passed Acid:: dissolves the layer, and removes most of the axons and replaces the resin. The Qi value of the solution is adjusted to: often:; liquid. In the heat of cooking, it is grown until it reaches the target particle. ^ ❹ - 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化The particle size of the oxidized flat:: sub-dispersion _ concentration, so that two = = go two and make it again through the gas-type cation exchange tree 曰 layer 'removal of all _ sub, and _ ❹ ❹ ❹ content is 5~~ And from the unloading and Nazi to = the content of 1 〇〇 ~ 2 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Calculated by the following method: a chemical mechanical polishing water system from 3-oxidized 11 particles by a known method such as centrifugation or super-ruthenium The porous body recovers the composition of the cerium oxide, and then the nano, smear, and ionic ions contained in the recovered dioxo component are added. Therefore, the water system is chemically mechanically ground by the above method by a known method. The analysis of the dioxin component recovered by the dispersion confirmed that the constituent elements of the present invention were sufficient. 12 (B1) Organic Acid 098104943 200944582 The chemical mechanical polishing aqueous dispersion of the present embodiment contains (B1) an organic acid. The (B1) organic acid is preferably an organic acid having two or more carboxyl groups. The effect of the organic acid having two or more carboxyl groups is as follows: (1) elution to chemical machinery by polishing By collating the metal ions such as copper, ruthenium, or the like in the aqueous dispersion, the precipitation of the metal can be prevented. As a result, polishing defects such as scratches can be suppressed.

(2) It has an effect of improving the polishing rate of a polishing object such as a copper film, a barrier metal film, or a TEOS film. When a water-soluble polymer described later is added, the surface of the object is tilted by the water-soluble polymer, which causes a decrease in the polishing rate. Even in such a case, the polishing rate of the above-mentioned polishing object can be increased by using (4) an organic acid having two field groups.

(3) As described above, due to the ability to coordinate with metal ions (_dlnatlng ability), it is broken with the Nazi or miscellaneous particles from the cerium oxide particles during the grinding process. (4) Saki _ : Unloading ions The surface of the object of bribery. The result _ sub or Nazi free ^ solution in the '(4) can be easily removed to cut the Nazi or _ sub. (4) It is generally considered that it is adsorbed on the surface of the cerium oxide particles, and it can be mentioned that the dispersion of the shixi particles is ambiguous. As a result, it is possible to enhance the enthalpy of the dioxins, and it is possible to greatly suppress the speculation that the particles are agglomerated by the condensed particles. Acid, (10), and propylene have. The organic acid of the base cannot be expected to have a higher coordination ability for the metal ion, and 098104943 22 200944582 improves the polishing rate of the above-mentioned abrasive object. An acid dissociation index (pKa) under an organic acid having two or more carboxyl groups, preferably a dissociation phase of 5Q or more in terms of a hunger index (pKa), and having a pKa value of the acidolytic group of the present invention浐俨, and the organic acid of =* has a second carboxy value and has a 3-field-like index of the index ^== for the copper which is eluted into the chemical mechanical polishing dispersion by grinding, The metal ions of the group, titanium and the like have a higher coordination ability, thereby preventing metal precipitation. Thereby, the surface of the object to be polished can be prevented from being smooth. Further, it is possible to suppress the change in the enthalpy value in the polishing composition in the polishing step, and it is possible to suppress the aggregation of the above-mentioned (cerium) cerium oxide particles used in the present invention due to a change in pH during the polishing step. On the other hand, if the acid dissociation index (pKa) is less than 5.0 Å, the above effects cannot be expected. The acid dissociation index (pKa) can be obtained, for example, by (a) The Journal of ❹

The method described in Physical Chemistry vol. 68, number6, pagel560 (1964), (b) the method using a potentiometric automatic titrator (COM-980Win, etc.) manufactured by Hiranuma Sangyo Co., Ltd., etc. c) Chemical Handbook compiled by Sakamoto Chemical Society (Revised 3rd Edition, issued on June 25, 1984), the acid dissociation index described in Maruzen Co., Ltd., (d) pKaBASE manufactured by Compudrug Co., Ltd., etc. The data base or the like is 0. The organic acid having the acid dissociation index (pKa) of 5.0 or more and having two or more rebel bases is 098104943 23 200944582 organic acid, and examples thereof include the organic acids described in Table 1. The pKa value shown in Table 1 indicates the pKa value of the second carboxyl group in the organic acid having two carboxyl groups, and the pKa value of the third rebel group in the organic acid having three or more carboxyl groups. . 098104943 24 200944582 [Table 1] Organic acid pKa maleic acid having more than 2 carboxyl groups 5. 83 Malonic acid 5. 28 phthalic acid 5. 41 succinic acid 5. 64 phenyl succinic acid 5 55 citric acid 6.40 2-mercaptomalonic acid 5. 76 2-ethylmalonic acid 5.81 2-isopropylmalonic acid 5. 88 2, 2-dimethylmalonic acid 5. 73 2 - Ethyl-2-methylmalonic acid 6. 55 2, 2-diethylmalonic acid 7.42 2, 2-diisopropylmalonic acid 8.85-hydroxybenzoic acid 9.96 p-hydroxyl Benzoic acid 9.46 1,2-cyclohexanedicarboxylic acid (trans isomer) 6.06 1, 2-cyclohexanedicarboxylic acid (cis isomer) 6. 74 1,2-cyclopentanedioic acid ( Trans-body) 5. 99 1,2-cyclopentanedioic acid (cis isomer) 6. 57 1,2-cyclooctane dicarboxylic acid (trans-form) 6. 24 1,2-cyclooctane Dicarboxylic acid (cis isomer) 7. 34 1,2-cycloheptanedioic acid (trans isomer) 6. 18 1,2-cycloheptanedicarboxylic acid (cis isomer) 7. 60 2, 3-two Methyl succinic acid 6. 00 2, 3-diethyl succinic acid 6.46 2-ethyl-3-methyl succinic acid 6. 10 Tetramethyl succinic acid 7.41 2, 3-di-third butyl Butyric acid 10.26 3, 3-dimercaptoglutaric acid 6.45 3, 3-diethylglutaric acid 7.42 3-isopropyl-3-methylglutaric acid 6. 92 3-tert-butyl-3-mercaptoglutaric acid 7.49 3, 3-diisopropyl Glutaric acid 7. 68 3-mercapto-3-ethylglutaric acid 6. 70 3, 3-dipropylglutaric acid 7.48 2-ethyl-2-(1-ethylpropyl)sebacic acid 7. 31 cyclohexyl-1,1-diacetic acid 7. 08 2-methylcyclohexyl-1, 1-diacetic acid 6. 89 cyclopentyl-1, 1-diacetic acid 6. 77 3-mercapto-3 -Phenylglutaric acid 6. 17 3-ethyl-3-phenylpentanedioic acid 6. 95 25 098104943 200944582 Among the organic acids having two or more carboxyl groups described in Table 1, more preferably butylene Diacid, malonic acid, and citric acid are particularly preferred as maleic acid. Such an organic acid not only has a preferable PKa i but also has a small steric steric hindrance in molecular structure, and thus is eluted into a chemical mechanical polishing aqueous dispersion by copper, titanium, or the like. The ions have a high coordination ability' to prevent precipitation of metals. The content of the above (B1) organic acid (iv) relative to the total mass of the chemical mechanical polishing water dispersion is preferably 〇. Xie~3Q% by mass, more preferably (4) to 2.0% by mass. If the content of the above (10) organic acid is less than the above range, surface defects such as many scratches are generated on the copper film. On the other hand, if the content of the above (8)) organic acid exceeds the above _, the condensation of the dioxo prior particles is caused, and the storage stability is impaired. 1. 3 (C1) Nonionic Surfactant In the present embodiment, the German (4) (4) partial scattering contains (9) a nonionic surfactant. By adding (1) a nonionic surfactant, the polishing rate of the interlayer insulating film can be controlled. That is, the polishing rate to the low dielectric constant insulating film can be suppressed, and the polishing rate of the upper cladding layer such as the TEGS film can be improved. Examples of the (C1) nonionic surfactant include an acetylene glycol ethylene oxide adduct, a nonionic surfactant having at least one ethynyl group such as acetylene alcohol, and a polyoxon surfactant. An alkyl ether-based surfactant, polyvinyl alcohol, cyclodextrin, polyvinyl decyl ether, hydroxyethyl cellulose, etc. The above-mentioned nonionic interface can be used alone or in combination of two or more kinds 098104943 26 In the case of the above, a nonionic surfactant having at least one ethynyl group is preferred, and a nonionic surfactant represented by the following formula (1) is more preferred.

O-iCHzCHaOJirH CH3-CH(CH3)-CHz-C(CH3)-CsC-C(CH3)-CH2-CH(CH3)-CH3 (1)

0-(CH2CH2〇)terH (wherein 'm and η are each independently an integer of 1 or more, satisfying m + n each j ❹ In the above formula (1), 'addition of ethylene oxide by control' The number of m and η, and the hydrophilic and lipophilic balance can be adjusted (HLB, Hydr〇ph丨丨e_L丨p〇ph丄je

Balance). In the above formula (i), m and n are preferably 20Sm + ng5〇, more preferably 20$in + nS40. Examples of the commercially available product of the nonionic surfactant represented by the above formula (1) include surfynol 440 (HLB value = 8), Surf^w 465 CHLB value = i3, and Surfynol 485 CHLB value = 17). (The above are all manufactured by Air © Products Japan). The HIB value of the above (ci) nonionic surfactant is preferably 5 to 2 Å, more preferably 8 to 17. If the HLB value is less than 5, the solubility in water is too small, and it is not suitable for use. Generally, if the amount of (4) or obliquely oxidized dioxin particles in the chemical mechanical polishing aqueous dispersion is large, the sodium or unloading from the cerium oxide particles may remain even after the polishing operation. On the surface of the object to be polished, the electrical characteristics of the device are deteriorated. _ also depends on the _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ The lower dielectric dip is the same as the hydrophobic granules, and the dioxo granules can inhibit the sodium or potassium ions that are broken in the process (4) from being adsorbed on the low dielectric constant insulating film. The cleaning is easy to remove the nano surface from the surface of the object to be polished. Further, the nonionic r-surfactant has a smaller molecular polarity, so that it can be easily removed by the cleaning operation. It does not remain on the surface of the object to be polished, and the electrical characteristics of the device deteriorate. The above (ci) non-ionic interface-grinding water component (4) is preferably 0.001 to 1.0% by mass, more preferably 0.005 to 0.5% by mass, based on chemical mechanical means. If the content of the nonionic surfactant is in the above-mentioned range, it is expected that the surface of the non-ionic surfactant is well-corrected. 1.4 (D1) Water-soluble polymer The chemical mechanical polishing aqueous dispersion of the present embodiment may contain (10) a water-soluble polymer having a weight average molecular weight of 50,000 or more and 5 GG or less. Although the technique of adding a water-soluble molecule to a chemical mechanical polishing aqueous dispersion is known, the present invention has the following features: from the viewpoint of reducing the polishing pressure generated on the low dielectric constant insulating film: The water-soluble polymer in the molecule is larger than the water-soluble polymer used in the hanging. The weight average molecular weight of the above (D1) water-soluble polymer can be, for example, a weight average molecular weight (e.g.) in terms of polyethylene glycol converted by a gel permeation chromatography (GPC, Gel Permeation Chromatography) 098104943 28 200944582. The weight average molecular weight (黯) of the above (10) water-soluble polymer may be 50,000 or more and 10,000 or less, preferably 200,000 or more and 500,000 or less, more preferably 2,000,000 or more and 1.5 million or less m average molecular weight. In the above-described manner, the polishing speed of the interlayer insulating film (overcoat layer) can be increased while greatly reducing the polishing friction. Further, it is possible to suppress the metal-disc or the gold-based corrosion (10)r〇si〇n), thereby stably grinding the metal film. If the weight average molecular weight is less than the above ❹ lower limit 贞 1 minus, the grinding friction or the suppression of the metal film shallow dish and the metal film rot are less effective. Further, when the weight average molecular weight is more than the above upper limit, there is a problem in that the stability of the chemical mechanical polishing aqueous dispersion is deteriorated, and the viscosity of the aqueous dispersion is excessively increased to cause a burden on the polishing liquid supply device. In particular, when the weight average molecular weight of the (D1) water-soluble polymer exceeds 5,000,000, precipitation occurs due to aggregation of the abrasive component when the aqueous dispersion is stored for a long period of time, and precipitation occurs with slight change in storage temperature. Water-soluble bismuth polymer makes it difficult to obtain stable polishing characteristics. As described above, it is considered that if the abrasive grains having a large content of sodium or potassium are used in the chemical mechanical polishing aqueous dispersion, even after grinding Cleaning. Operation, the sodium or potassium derived from the abrasive grains may remain on the surface of the object to be polished, and the electrical characteristics of the device may deteriorate, so it is avoided. However, by adding the above-mentioned (D1) water-soluble polymer, the cerium oxide particles can be coated with the water-soluble polymer, so that the sodium or potassium elution of the cerium dioxide particles can be suppressed. Further, the (D1) water-soluble polymer may adsorb sodium or potassium remaining on the surface of the surface to be polished. Result 098104943 29 200944582 It is also possible to perform a simple cleaning operation after grinding to remove the nano or clock from the surface to be polished, so that the polishing operation can be ended without deteriorating the electrical characteristics of the device. Examples of the (10) water-soluble polymer include polyacrylic acid and pot salts, polymethyl methic acid and salts thereof, polyethylene glycol, polyethylene occlusion, and poly-acrylamide. Among these water-soluble polymers, preferred are repeating units and have a retinal polymethyl acrylate acid and a salt thereof, polyacrylic acid and salts thereof, or derivatives. In view of the fact that the stability of the abrasive grains is not affected, it is more preferable that the polyacrylic acid and the polymethylpropionic acid can impart appropriate viscosity to the chemical mechanical polishing aqueous dispersion of the present embodiment. The content of the (D1) water-soluble polymer is preferably 〇1 to 1% by mass or less, more preferably 0.01 to 0.5% by mass based on the total mass of the aqueous dispersion for chemical mechanical polishing. If the content of the (10) water-soluble polymer is less than the above range, the improvement of the polishing rate of the low dielectric constant interlayer insulating film is not observed. On the other hand, when the content of the water-soluble polymer exceeds the above range, aggregation of the cerium oxide particles is caused. Further, the ratio of the content of the above (B) organic acid to the content of the above (10) water-soluble polymer is preferably 1:1 to 1:40, more preferably! : 4 is called · 30. By the ratio of the content of the above (8) organic acid to the content of the above (10) water-soluble polymer, it is within the above range, and it is possible to more reliably satisfy the appropriate degree of polishing and the flatness of the surface to be polished. - 1. 5 Oxidant The chemical mechanical polishing aqueous dispersion of the present embodiment may contain 098104943 30 200944582 oxidizing agent as needed. Examples of the oxidizing agent include barium persulfate, hydrogen peroxide, iron nitrate, nitric acid nitrate, iron sulfate, barium, potassium salt, potassium peroxide, and peracetic acid. These oxidized lactic acid lactic acid and its combination are used in combination of two or more kinds of such hydrating agents, such as chemical power, compatibility with a protective film, and selection of the county, Geng Chu ^ ^ η "Ease of use, etc. , particularly preferably ammonium persulfate, potassium persulfate, and hydrogen peroxide. The amount is based on chemical mechanical, abrasive water dispersion, and sputum, preferably 〇. 05~5 mass%, more If it is less than the above range, the amount of the oxidizing agent may not be sufficient. On the other hand, if it exceeds the above range, there is a corrosion of a metal film such as a copper film. #或浅碟化大虞。 1. 6 pH The chemical mechanical polishing of the present embodiment is dispersed in water for 6 to 12', more preferably 7 to 11.5, and particularly preferably 8 to n.

The pH of the body is preferably such that if the pH is less than 6, the hydrogen bond between the 0 (tetra) groups on the surface of the dioxygen particles cannot be collected to cause agglomeration of the particles. On the other hand, if the pH is more than 12, the wafer is defective due to excessive alkalinity. As a method for adjusting the pH, for example, a pH adjuster represented by an alkaline salt such as potassium hydroxide, ammonia, ethylenediamine or tetramethylammonium hydroxide (TMAH 'Tetramethyl amm〇niumhydroxide) may be added. To adjust the value of Qiu. 1.7 Method for Producing Chemical Mechanical Grinding Water Dispersion The chemical mechanical polishing aqueous dispersion of the present embodiment can be prepared by the following formula: 098104943 31 200944582; direct addition of (A) SiO2 particles in pure water, (B1) Organic acid, and = other additives 'and mix, (four). The chemical mechanical time dispersion obtained in the above manner can be used as it is, or the chemical rhyme sputum water-containing sub-ship containing the components (flare) at a high concentration can be prepared and diluted to the required degree of agricultural use at the time of use. . A plurality of liquids (e.g., 'two or three liquids') containing any of the above components may be damaged and used in combination at the time of use. In the case of the IT shape, a plurality of liquids may be mixed to prepare a chemical mechanical polishing ruler blade, and then supplied to the chemical mechanical polishing device, or a plurality of liquids may be secretly supplied to the chemical mechanical polishing device. A chemical mechanical polishing aqueous dispersion is formed on the platform. As a specific example, 'the composition of water (and (4) (1), the liquid containing water and (B1) organic acid (9) is mixed and the liquid is mixed and used for the preparation of the above chemical mechanical polishing. a kit of water-based dispersions. The concentration of each component in the chemical mechanical polishing aqueous dispersion prepared by mixing the liquids with respect to the concentrations of the components in the liquids (1) and (II) is The range is not particularly limited. For example, the liquid (I) and (II) containing the respective components are prepared at a concentration higher than the concentration of the dispersion at the time of chemical mechanical polishing, and (4) the liquid (1) is diluted as needed. ((1) Mixing these to prepare a chemical mechanical polishing aqueous dispersion having a concentration of each component in the above range. Specifically, when the liquid (1) and ((1) are mixed in a weight ratio of i: i 098104943 32 200944582) 'Prepare the liquid (I) and (π) at a concentration twice that of the chemical mechanical polishing aqueous dispersion. Alternatively, the concentration can be prepared. The chemical mechanical polishing aqueous dispersion is twice the concentration. The above liquids (I) and - (11) are mixed in a weight ratio of 1:1, and then diluted with water until the respective components are in the above range. As described above, liquid G) and liquid (II) are separately prepared. Moreover, the storage stability of the chemical mechanical polishing aqueous dispersion can be improved. ❹ When the above-mentioned kit is used, 'If the above-mentioned chemical mechanical polishing aqueous dispersion is formed during grinding, the liquid (1) and the liquid (11) The mixing method and the timing are not particularly limited. For example, the liquid chemical (1) and the liquid (11) may be mixed to prepare the chemical mechanical polishing aqueous dispersion, and then supplied to the chemical mechanical polishing device, or the liquid may be used. (I) independently supplied to the chemical mechanical polishing device with the liquid (π), and mixed on the platform. Alternatively, the liquid (1) and the liquid (II) can be independently supplied to the chemical mechanical polishing device, and the pipeline can be mixed in the device. It is also possible to provide a mixing tank in the chemical mechanical polishing apparatus to mix in the mixing tank, and to obtain a more uniform chemical mechanical polishing water dispersion in the pipeline mixing. A line type mixer (line. mixer# ° - 2) second chemical mechanical polishing water-based dispersion The second chemical mechanical polishing aqueous dispersion of the present invention contains (A) oxidized granules and (B2) The amino acid is used to polish the copper film, and the (A) cerium oxide particle has a "the density of the thiol group of 1.0 based on the phenolic group* determined by the specific surface area of 098104943 33 200944582 measured by the BET method. The chemical properties of ~3. 0 / nm." 夕 槐 槐 槐 益 益 益 先 先 先 先 先 先 先 先 先 先 先 先 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. Shi Xi particles this implementation of the "German _ research _ material 矽 particles. (4) The cerium oxide particles of the (4) oxidized water-based dispersing agent (A)_t The above-mentioned first chemical machine is abbreviated. (1) The oxidized stone particles are the same, so the ❹ 2. 2 (B2) amino acid ❹ The chemical mechanical polishing aqueous dispersion of the present embodiment contains (10) the amine group I. The above (10) amine grade is preferably at least one amino acid selected from the group consisting of a bribe, an alanine and a histidine. These amino acids have a property of easily forming a coordinate bond with copper ions, thereby forming a coordinate bond with the surface of the copper film on the surface to be polished. By this, the surface roughness of the copper film can be suppressed and the flatness can be maintained high, and the affinity with copper and impurities can be improved, and the polishing speed of the film can be promoted. Further, the amino acids can be easily coordinated to the copper ions which are eluted by the polishing of the copper film to prevent the precipitation of copper. As a result, it is possible to suppress the occurrence of scratches such as scratches on the copper film. Further, the amino acid can effectively capture unnecessary metals from the surface of the object to be polished after grinding, thereby effectively removing unnecessary metals from the surface of the object to be polished. In addition, in the case of using (D2) a water-soluble polymer described later, 'depending on the type or amount of addition, the water-soluble polymer is adsorbed on the surface of the copper mat, and the polishing speed is hindered. decline. In the case of such 098104943 34 200944582, it is also effective to increase the polishing rate of the copper film by using the above (B2) amino acid in combination with or without the addition of the water-soluble polymer. Further, by containing the above (B2) amino acid, the sodium ion or potassium ion which is prevented from being broken by the grinding process and eluted from the cerium oxide particles can be adsorbed on the surface of the copper film, thereby promoting the in-liquid phase. The free 'results can also be effectively removed from the surface of the object to be polished. ❹ ❹ The content of the above (B2) amino acid is preferably from G·咖 to 3.0% by mass relative to the total mass of the chemical mechanical polishing aqueous dispersion. Good for 〇.〇1~ 2. 〇Quality/. If the content of the above (B2) amino acid is less than the above range, a shallow disc is formed on the copper film. On the other hand, if the (B2) amino acid content exceeds the above range, there is a tendency for the dioxins to agglomerate. 2· 3 (C2) Anionic surfactant The chemical mechanical polishing aqueous dispersion of the present embodiment may contain (C2) an anionic interfacial impurity. It is generally considered that if the abrasive grains having a large content of sodium or potassium are used in the chemical mechanical polishing, the sodium or potassium derived from the abrasive grains may remain in the pressed particles even after the β washing operation after the polishing. The surface of the abrasive causes the electrical characteristics of the device to deteriorate, so that its use is avoided. However, the affinity of the above (C2) anionic surfactant to copper and copper ions is generally better than that of cations of ionic or ionic ions, so that it can be adsorbed on steel, thereby inhibiting The secret or the (four) sub-sludge that is broken and eluted from the dioxo particles is equal to the surface of the object to be polished. Therefore, even if it is used in the dioxin-cut particles, 098104943 35 200944582 has a metal such as sodium as a miscellaneous

_ The chemical mechanical polishing of the aqueous solution of water and alkali (water glass) is dispersed in water, + H can also be cleaned after grinding, and the surface is removed by the polished surface (10), (4) Excessive contamination of copper wiring. Further, it is also described that (C2) an anionic surfactant can be adsorbed on the surface of the particles of the Dioxin particles to improve the dispersion stability of the particles. As a result, the preservation stability of the phase can be enhanced, and the number of scratches caused by the agglomerated particles can be greatly suppressed.

The (C2) anionic interface activity content is preferably a total mass of the chemical mechanical polishing aqueous dispersion, preferably G. 9% by mass, more preferably 娜 〜 to 质化, if the above (10) anionic surfactant If s篁 is not above (4), then the protective effect of the surface of the matte is weakened and the rot or excessive sage is carried out. On the other hand, when the content of the (2) anionic surfactant exceeds the above range, the surface of the surface may become a turn, and the lion's full polishing rate may cause copper residue (copper residue). There is a practical disadvantage in that the cerium dioxide particles are agglomerated and cause intense foaming. (2) The anionic surfactant preferably has a selected from the group consisting of a county, a base, and a phosphoric acid. The base, and the ammonium salt of the functional group and the metal solute to 41 g energy groups. As such ((2) anionic surfactant, fatty acid salt, alkyl sulfate, alkyl ether sulfate , sulphuric acid vinegar salt, benzoic acid benzoate, linear alkyl benzoate, heart acid 098104943 36 200944582 base fatty acid vinegar, burnt polyoxyethylene sulphate, burnt base acid, single Pyridinium salt, naphthalene 4 acid salt, α-olefin acid salt, pyrocarbonic acid salt and dilute base, succinate salt, etc. Among these, 'better-like phenyl lysine salt, linear burnt Benzene • Zengwenwen salt, Cai Shi page acid salt, dilute succinate salt. These anionic interfaces Agent may be used alone, or in combination of two or more of them. Examples of the group Τ dilute acid salt, particularly preferably a compound represented by the following formula by ⑵. ❹ The [Chemical Formula 4]

(2) In the above formula (2), R1 and R2 each independently represent a hydrogen atom, a metal atom, or a substituted filament-substituted domain group. When R1A R2 is a wire, it is preferably a substituted or unpeaked alkyl group having a carbon number of 1 to 8. Further, in the case of Ri and R2, it is preferred that the metal atom is more preferably "nano or potassium" to represent a substituted or unsubstituted alkenyl group or a sulfonic acid group. It is a substituted or unsubstituted county of alkenyl to mei 2 as Wei 2~8. When R3 is continued 2眭3X), 'X is a hydrogen ion, a money ion or a metal ion. X is a metal X is preferably a nano ion or an unloading ion. The trade name of the compound represented by the above formula (2) is 098104943 37 200944582. The trade name "Newc〇129 Bu M" having a sulfonic acid group (-soa) in R (available from 曰 Emulsifiers Limited) §3 purchase), the trade name "NeweQl 292_pG" (available from Japan Emulsifier Co., Ltd.), the trade name "peiex ta (available from Kaowang Co., Ltd.), and the product name of the county succinic acid "Lateoud ASK" (available from Kao Corporation) and so on. The compound of the above formula (2) is rhythmic to the surface of the copper, and the effect of protecting it from excessive or rotted surface is particularly high, and a smooth polished surface can be obtained. According to the research of the inventors of the present invention, it can be understood that the most effective combination of the above (C2) anionic surfactant is the county of the succinic acid salt of the 12th hospital of the sage. A combination of T diacids. 2. (D2) Water-soluble polymer The chemical mechanical polishing aqueous dispersion of the present embodiment preferably has a (D2) weight average molecular weight of 10,000 or more and (10) or less and has a water solubility as a Lewis test. molecule. The above-mentioned (D2) water-hybrid polymer has the following effect 4 as having the property f as a path (four), so that the material is adsorbed and (coordinatingly bonded) on the surface of the copper film, and the shallow disc formation and the spoilage of the crucible can be suppressed. . The above (10) water-soluble polymer is recorded as at least one molecular structure of a surface-derived heterocyclic ring and a sub-functional group. Further, the cationic functional group ' is preferably secret. The above-mentioned money conversion and cationic material have the property of being tested as a Lewis, and therefore have the following effects: '''junction) on the surface of the copper film' and inhibiting the shallow-disc absorption of the copper film (coordination bond kumba eclipse generation). Further, 098104943 38 200944582 can be easily removed in the cleaning step, so that it does not contaminate the object to be polished. The above (10) water-soluble polymer is preferably a carbon (tetra) riding homopolymer or a nitrogen-containing monomer as a repeating unit. In common, the gas monomer can be exemplified by vinyl scales, (meth), , , / N-methyl methacrylate, N 2 , ethyl acrylamide, acrylonitrile. :: N'N--Methylaminopropyl acrylamide and its diethyl sulphate dimethyl propyl amide, N-isopropyl propyl amine, Ethyl amide, A Acrylic acid ruthenium, ruthenium-dimethylaminoethyl vinegar and its diethyl sulphate: Ν-vinyl carbamide, among other monomers, especially in the molecular structure of B-vinyl (IV) The nitrogen atom easily forms a coordination bond with the copper ion, thereby improving the affinity between the copper and the copper ion, and (4) performing moderate protection on the copper surface. When the (D2) water-soluble polymer is a copolymer containing a nitrogen-containing monomer as a repeating unit, it is not necessary that all of the monomers are nitrogen-containing monomers, and at least one of the above-mentioned human nitrogen monomers is used as a core material. Examples of the polymerization of the monomer with a nitrogen-containing monomer include acrylic acid, methacrylic acid, methyl acrylate, methyl acrylate, ethyl acetophenone, diethyl benzene, ethyl acetate, and benzene. The above-mentioned (D2) water-soluble polymer is preferably a homopolymer or a copolymer having a cationic functional group. For example, it may be represented by the following formula (4) or the following formula (5). A homopolymer or a copolymer (hereinafter also referred to as "specific polymer") of at least one of the single oximes is repeated. 098104943 39 200944582 [Chemical 5]

[Chemical 6]

(5) 〇 (In the above formula (4) and the above formula (5), R1 represents a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, and R2 represents a substituted or unsubstituted group. A methylene group or a substituted or unsubstituted alkylene group having a carbon number of 2 to 8 or a substituted alkyl group or a non-substituted alkyl group, and A represents a single bond or a ~π i sub ❹ ^ , — or indicate an overcast

A is represented by the above formula (4) and the above formula (5), and it is more preferable that Ha is Ha, and in the repeating unit of the second, "the cerium oxide particles may precipitate. Or the relationship between the content of other components, such that the second gas sometimes has a stable shape due to a decrease in characteristics and a long-term storage. In this case, it must be super-living before use. Processing, and the burden on the work is added to the 'knife 098104943 40 200944582 Counter anion (M-) is preferably a tooth ion, an organic anion, an inorganic anion. More preferably hydroxide ion, chloride Ion, * / stinky ion, NH3, a total of NIL · -, alkyl sulfate, perchloric acid, sulphate, acetate, alkyl benzene sulfonate, especially chloride ion, alkane Sulfate ion, hydrogen sulfate ion, acetate ion, alkylbenzenesulfonate ion. By using an organic anion, metal contamination of the object to be polished can be avoided, and from the viewpoint of easy removal after polishing, an alkyl group is preferred. Barium sulfate ion Further, the specific polymer is more preferably a copolymer containing a repeating unit represented by the following formula (6), and a copolymer containing a repeating unit represented by the following formula (8), which may be a formula (4) and the repeating unit 70 represented by the above formula (5) and the repeating unit represented by the following formula (6) may be formed by the above formula (4) and the above formula (5). Table: The repeating unit of the repeating unit and the block copolymerized by the heavy formula of the following formula (8) [Chemical 7]

Substitution of 1 to 6 (In the above formula (6), R6 represents a hydrogen atom or a carbon number or an unsubstituted alkyl group). When the specific polymer is a copolymer containing a repeating unit of the formula (4) and a repeating unit represented by the above formula (5): 098104943 41 200944582, if the number of the repeating units represented by the formula (4) is η,财 The fiscal unit of the repeating unit of the formula (5) is set to (4), and even if the ratio of the molars = 10/0 to G/1G', sufficient performance can be obtained, preferably -9, more preferably 1 〇/〇~2/8, especially good 9/1~3/7 Good results. ? In the case of ratio, the repeating unit represented by the above formula (4) and the above formula

= = The content of the repeating unit can be calculated from the addition amount of the monomer having an amine group to I and 1, and can also be determined by titrating a specific polymer using an acid or an assay.

If the specific polymer is a comon containing a repeating unit of the above formula (4) or the above formula (5) and a repeating unit represented by the above formula (8), the repeating unit represented by the above formula (6) The number of moirs is set to q, and the μ repeating unit of the superfluous type (4) or the loading type (5) is set to p, and the molar ratio q/p is in the range of 9/1 to 1/9. At the time, ? obtained particularly good results. The content of the amine group of the specific polymer is 〇~0. 100 mol/g, preferably 〇· _~〇. 〇1〇m〇i/g, based on the amount of addition of the military body. More preferably 〇. 002~0. 006 mol/g. The content of the cationic functional group of the specific polymer may be 0 to GG.1 GGmQl/g, preferably q._5 to 〇〇1 〇mol/g', more preferably 计算, based on the amount of the monomer added. 〇〇2~〇. Q06 mol/g. 098104943 42 200944582 The weight average molecular weight of the above (D2) water-soluble polymer, for example, a polyethylene glycol equivalent weight average molecular weight (Mw) measured by gel permeation chromatography (GPC, Gel Permeation Chromatography) . (D2) The weight average molecular weight (Mw) of the water-soluble polymer is 10,000 or more and 1.5 million or less, preferably 40,000 or more and 1.2,000,000 or less. If the weight average molecular weight is within the above range, the polishing friction can be reduced, and the dishing or corrosion of the copper film can be suppressed. Further, the copper film can be stably polished. If the weight average molecular weight is less than 10,000, the effect of reducing the polishing friction is small, so that the dishing or corrosion of the copper film cannot be suppressed. On the other hand, when the weight average molecular weight exceeds ^, the oxidation due to agglomeration causes the following problems: In general, the dispersion stability of the cerium oxide particles is impaired, and the scratches on the copper film are increased by the stone particles. In addition, the name of the chemical mechanical sputum dispersion is excessively reduced (4) _ supply device causes load. Further, when the fine wiring pattern is polished, copper remains in the pattern, which is not practical.

Ding double does not 琰 赝 赝 赝 decline.

Even if the sodium or potassium from the abrasive grains is left on the surface of the object to be polished by the cleaning operation after the grinding, the electrical characteristics of the device are deteriorated, so that the use thereof is avoided. However, the above (D2) water-soluble polymer has a property as a Lewis test, and therefore can be efficiently placed on the surface of the copper film on the surface to be polished. Thereby, the surface of the copper film can be effectively protected, and sodium or potassium can be inhibited from adsorbing on the surface of the copper film, and sodium or potassium can be easily removed from the surface of the copper film by washing. Further, since the water-soluble polymer can be easily removed by a cleaning operation, it does not remain on the surface of the copper film, and the electrical characteristics of the device are deteriorated. 2.5 Organic acid having a nitrogen-containing heterocyclic ring and a thiol group The chemical mechanical polishing aqueous dispersion of the present embodiment may contain an organic acid having a nitrogen-containing hetero ring and a carboxyl group. The above organic acid having a nitrogen-containing heterocyclic ring and a carboxyl group can be used in combination with the above (B2) amino acid to enhance the effect of the (3) phantom amino acid. Examples of the organic acid having a nitrogen-containing heterocyclic ring and a thiol group include an organic acid containing a heterocyclic ring having at least one nitrogen atom, and an organic acid containing a hetero compound composed of a heterocyclic ring. More specifically, citric acid, quinolinic acid, quinoline-8-carboxylic acid, pyridinecarboxylic acid, xanthurenic acid, kynurenic acid, nicotinic acid, and ophthalmic acid may be mentioned. Aminobenzoic acid and the like. The content of the organic acid having a nitrogen-containing heterocyclic ring and a mercapto group is preferably 0.001 to 3 〇% by mass, more preferably 0 to 01 to 20.0% by mass, based on the total mass of the chemical mechanical polishing aqueous dispersion. If the content of the organic acid having a nitrogen-containing hetero ring and a carboxyl group is less than the above range, it may cause a dishing on the copper film. Another 098104943 44 200944582 On the one hand, if the content of the nitrogen-containing heterocyclic ring and the organic acid exceeds the above range, there is a cohesion of the particles of the cerium dioxide. 2.6 Oxidizer Φ ❹ The quaternary system of the present embodiment (4) (4) may contain an oxidizing agent as needed. Examples of the oxidizing agent include (IV) sulfuric acid money, hydrogen peroxide removal, hydrogen peroxide, _ iron, Gu Erlang, iron sulfate, ozone, hypochlorous acid and salts thereof, potassium molybdate and peracetic acid. These oxidizing agents may be used singly or in combination of two or more kinds. In addition, in the case of the oxidizing power, considering the oxidizing power, the compatibility with the lysine, and the age, the sulphuric acid, potassium persulfate, and hydrogen peroxide are used as the dispersion of the hydrazine system relative to the chemical mechanical polishing water dispersion. The total mass is preferably US mass%, mr. When the content of the oxidizing agent is less than the above range, the sufficient polishing rate for the copper film may not be obtained in the above range, and it may be on the copper film. (4) Shallow dishing 2. 7 pH The chemical mechanical polishing water system of the present embodiment The dispersion is 6 to 12, more preferably 7 to 11.5, and the special oxygen value is 1 ', '~11. If the pH is less than 6, the stone present on the surface of the dioxide can not be cut off. The gas bond between the alcohol groups causes the agglomeration of the particles of the cerium dioxide. On the other hand, if the pH is greater than 12, the method of causing the pH value due to excessive alkalinity, such as defects, is used. The adjustment of J fine is added by potassium hydroxide B, the surface (the pH value represented by tetramethylhydrogen oxide is adjusted to adjust the pH value of 09810404^45 200944582. 8 use of the chemical mechanical polishing water dispersion of this embodiment, can be compared It is preferably used for chemical mechanical polishing of a processed object (for example, a semiconductor device) having a steel film on its surface. That is, if the chemical mechanical polishing aqueous dispersion of the present embodiment contains (10) an amino acid, Can suppress the surface roughness of the copper film and maintain the southerly Flatness, and improve the affinity of the oil and the y, so that the grinding speed of the film can be m. Therefore, even under ordinary grinding pressure conditions, the defect is not called at the _ and the low dielectric constant, and the surface can be The copper film is subjected to high-speed and selective polishing. Further, when the chemical mechanical polishing aqueous dispersion of the present embodiment is used, the metal of the P-_2 to 4 Japanese yen is dyed. More specifically, the chemistry of this embodiment The mechanically studied aqueous dispersion is produced by, for example, a damascene method using: ?% constant insulating film as an insulating film and using steel or a copper alloy as a cloth, which can be recognized by Kawada, and a step of "a bovine conductor device"; _Chemical machinery step of the copper film on the barrier metallurgy (the first polishing treatment step). , , and in the present invention, the so-called "_" is made of steel or steel as the copper content of the copper alloy. The film of the film is more than 95% by mass. 2.9 The process of chemical mechanical polishing water dispersion The present embodiment is a chemical machine handle grinding preparation: directly added in pure water (A) == can be as follows And other additives, and add them together (10) Amino acid 098104943 ❿ 槐 Mixing. The chemical mechanical polishing aqueous dispersion obtained in the above manner 46 200944582 can be directly used, and the chemical mechanical polishing aqueous dispersion containing the components (concentrated) at a high concentration can also be prepared. And used at the time of dilution to release into a desired concentration. Further, a plurality of liquids (for example, 'two or three liquids') containing any of the above components may be prepared and mixed at the time of use. In this case, a plurality of liquids may be mixed to prepare a chemical mechanical polishing aqueous dispersion, and then supplied to a chemical mechanical polishing apparatus, or a plurality of liquids may be separately supplied to the chemical mechanical polishing apparatus. A chemical mechanical polishing aqueous dispersion is formed on the platform. Specific examples include a liquid (I) containing an aqueous dispersion of water and (cerium) cerium oxide particles, and a liquid (π) containing water and (Β2) amino acid, and The above-described chemical mechanical polishing aqueous dispersion is prepared by mixing the liquids. The concentration of each component in the liquids (I) and (II) is not particularly high if the concentration of each component in the chemical mechanical polishing aqueous dispersion finally prepared by mixing the liquids is within the above range. limited. For example, preparing liquid-body (I) and (II) containing each component at a concentration higher than that of the chemical mechanical polishing aqueous dispersion, and if necessary, diluting the liquid and (11) as needed, and mixing the same. Further, a chemical mechanical polishing aqueous dispersion having a concentration of each component in the above range was prepared. Specifically, when the liquids (1) and (11) are mixed in a weight ratio of 1:1, the liquids (I) and (11) having a concentration twice the concentration of the chemical mechanical polishing aqueous dispersion are prepared. Just fine. Further, it is also possible to prepare a liquid having a concentration of 098104943 47 200944582 which is twice or more the concentration of the chemical mechanical polishing aqueous dispersion (1) and (I), and then mixing them in a weight ratio of 1.1, and then diluting with water until each component becomes the above. Within the scope. As described above, by separately preparing the liquid (1) = the body (II), it is possible to improve the storage of the chemical mechanical polishing aqueous dispersion in the case where the above-mentioned kit is used, and if the above-mentioned chemical mechanical polishing water dispersion is formed during the polishing, For the body, the method of mixing (I) and liquid (II) and the order of 4 are not specified. For example, the above chemical axis (4) aqueous dispersion can be prepared by mixing the lanthanide (I) with (4) (II), and then supplying it to the chemical mechanical polishing device, and the slag (1) hull ((1) is independently supplied to the chemical: mechanical Grinding t, and then mixing on the platform. Alternatively, the liquid and liquid (II) can be independently supplied to the chemical mechanical polishing device, the pipeline can be mixed in the device, or the mixing tank can be set in the chemical mechanical polishing device. In order to obtain a more uniform chemical mechanical polishing aqueous dispersion, a pipeline type mixer or the like may be used in the mixing of the pipelines. 3. The chemical mechanical polishing method uses a pattern for the present invention. Specific examples of the chemical mechanical polishing method according to the embodiment will be described in detail. 3. 1 Object to be processed Fig. 8 shows the object to be processed 200 used in the chemical mechanical polishing method of the present embodiment. (Firstly, 'by coating method or Plasma chemical vapor deposition (CVD, Chemical 098104943 48 200944582

The Vapor Deposition method forms a low dielectric constant insulating film. Examples of the low dielectric constant insulating crucible 40 include an inorganic insulating film and an organic insulating film. As

The inorganic insulating film ′ is, for example, a SiOF film (k = 3.5 to 3 7), a Si-H-containing film, a (10) 2 film (k = 2.8 to 3.0), and the like. Examples of the organic insulating film include a carbon-containing Si〇2 film (k=2.7 to 2.9), a methyl-containing coffee film (k=2.7 to 2.9), and a polyimide-based system. Membrane (k = 3.〇~3.5), parylene (reduced to (6) mesangial (Bu), Teflon (10) miscellaneous film (4)" (2) on low dielectric constant insulating film 40, by (10) The insulating film 5G is formed by a method or a thermal oxidation method. For example, a ruthenium film or the like is exemplified as the insulating film 5 。. (3) The low dielectric constant insulating film 4 〇 and the insulating film 5 are connected to each other to form a film. (4) The barrier metal film μ is formed by the CVD method so as to cover the surface of the insulating film 5 and the bottom # and the inner wall surface of the wiring recess 60. The adhesion to the copper film and the From the viewpoint of excellent barrier properties, the barrier metal film 70 is preferably Ta or TaN, but is not limited thereto, and may be Ti, plus,

Co, Μη, Ru, etc. () The object to be processed 200 is obtained by depositing copper on the surface of the early-wall metal film 7〇 to form a copper film. 3·2 chemical mechanical polishing method 3·2·1 First step First, in order to remove the 098104943 49 200944582 copper film 80 deposited on the barrier metal film 7 of the object to be processed 200, the second chemical mechanical polishing water system is used. The dispersion is subjected to chemical mechanical polishing. The copper film 8 is continuously polished by chemical mechanical polishing until the barrier metal film 70 is exposed. Usually, it is necessary to confirm that the barrier metal film 70 is exposed before stopping the grinding. However, the polishing rate with respect to the copper film is extremely high. On the contrary, the second chemical mechanical polishing aqueous dispersion hardly polishes the barrier metal film. Therefore, as shown in FIG. 9, the barrier metal film 70

Chemical mechanical polishing is not possible at the time of exposure, so chemical mechanical polishing can be automatically stopped (selfstop). In the first step, a commercially available chemical mechanical polishing device can be used. As a commercially available chemical mechanical polishing apparatus, for example, "EPO-112" and "EP〇-222" manufactured by Ebara Seisakusho Co., Ltd.; 5=•LGP 510" LGP-552 manufactured by Lapmaster SFT Co., Ltd., Appl The type "Mirra" manufactured by ied Material Company.

The preferred polishing conditions in the first step should be appropriately set in accordance with the chemical mechanical polishing device. For example, when "brain_112" is used as the chemical mechanical polishing device, the following conditions can be employed. The number of rotations of the flat mouth is preferably 3〇~12〇_, more preferably 仙~(10) 犷 硕 硕 ,, preferably 3〇~12() _, more preferably (10)^. Platform rotation number / The number of rotations of the grinding head is preferably 0. 5~2, more preferably 〇~1. 5 " 100~150 • Grinding pressure; preferably gf/cm2 60~200 gf/cm2, more preferably 098104943 50 200944582. Chemical mechanical polishing water dispersion supply speed; preferably 50 to 400 mL/min, more preferably 1 to 300 mL/min, as described above, in the first step, excellent flatness can be obtained. The abrasive surface is 'and the chemical mechanical polishing can be automatically stopped without excessively grinding the copper film'. Therefore, the load on the lower insulating film 50 or the low dielectric constant insulating film 40 can be reduced. 3· 2. 2 Step 2

Then, the first chemical mechanical polishing aqueous dispersion is used, and the barrier metal film 70 and the copper film 8 are chemically polished. As shown in Fig. 1A, even after the insulating film 5G is exposed, chemical mechanical polishing can be continued to remove the film 5G. As shown in Fig. 11, the low dielectric constant insulating film 4 is exposed to stop the chemical mechanical polishing, whereby the semiconductor device 9 can be obtained. In the second step, a commercially available chemical mechanical polishing apparatus shown in the step i can be used. The best research and development of the hemp should be possible. (4) The chemical mechanical polishing to be applied to the 适 适 适 Μ ' For example, when using "EP (M12) as a chemical mechanical polishing device", the following conditions can be used. Preferably, it is 3G~12G ΓΡΠ1 'better 40~100 rpm. Flat 4轳: 'preferably 3〇~HPTM, more preferably 40~100rpm grinding ratio; preferably Q.5~2, More preferably 〇.7 • Grinding Lili; preferably 098104943 60~200 gf/cm2, more preferably 100~150 51 200944582 gf/cm2. Chemical mechanical polishing water dispersion supply speed; preferably 5〇~ 3 〇〇 mL / min ' more preferably 1 〇〇 ~ 200 mL / min 4. EXAMPLES Hereinafter, the present invention will be described by way of examples, but the present invention is not limited by the examples. The active citric acid aqueous solution was adjusted to a pH of 7.2 in an aqueous solution of the sputum of the sulphuric acid. , the particle control grows to 26 nm. 'Add 10 times the amount of pH and then average the cerium oxide particles.

098104943 The oxidized stone eve/farm ratio is 3.0% by mass of the diluted cerium acid aqueous solution. The diluted sodium citrate aqueous solution was passed through a hydrogen-type cation exchange resin layer, and the active material water-soluble f having a pH value of 3.1 was removed, and immediately 10% by mass of hydrogen was added under the transfer. The potassium hydroxide aqueous solution was adjusted to pH 7.2, and the heating was continued to make it fermented and heat-cured for 3 hours. Obtained 52 200944582 cerium oxide particle dispersion A. The obtained cerium oxide particles were dispersed using a 0.1 N aqueous sodium hydroxide solution. The bulk A was titrated in the range of pH 4 to 9, and the sterol group density was calculated from the titration value and the BET ratio table area value. 2. 0 / nm2. The cerium oxide particles recovered from the cerium oxide particle dispersion A by centrifugation are dissolved in dilute hydrofluoric acid, and the cerium oxide particles recovered by using ICP_MS (Perkin Elmer, model "ELAN DRC PLUS") are used. ) Measure sodium and potassium. Further, ammonium ions were measured using an ion chromatograph (manufactured by DIOXEX, model "ics-iooo"). Results Sodium content: 88 ppm, potassium content: 5500 ppm, ammonium ion content: 5 ppm. The cerium oxide particle dispersion A is diluted to 〇.〇1% by ion-exchanged water, and one drop of the diluted solution is applied dropwise to the mesh size (mesh sjze) as "claw" with a g-grain (grit) C〇n〇di〇n) The film was dried at room temperature. Thus, a sample of the observation crucible was prepared on the Cii pellet in such a manner that the shape of the crucible was not destroyed, and a transmission electron microscope (Hitachi Hi-Tech ( _ High-Technologies) manufactures 'h_765〇') to capture images of particles at a magnification of 20,000 times, measure 5 long and short diameters of rubber, and calculate the average value of the long diameter (10). And the average value of the short diameter (Rmin), calculate the ratio (Rnmx/Rrain), and the result is 1". The average grain calculated based on the specific surface area measured by the BET method was 26 mn. Further, the surface area of the colloidal gasified fossil particles was measured by the BET method. 098104943 53 200944582 The value obtained by measuring the cerium oxide particles recovered from the dispersion of the cerium dioxide particles was used. We have obtained the method of obtaining a method and a method of controlling the type and amount of time-sensitive compounds for thermal curing. The bismuth-cut particle dispersion E 上 制作 = = ================================================================================== 1 kg of kg and ion-exchanged water are put into 4〇l high-pressure green plus ill _ under '3 hours, 〇·5ΜΡ& under pressure to carry out water", and then, at the boiling point of 7 generations, will contain the above-mentioned dioxin After dicing the particles, the aqueous dispersion solution was concentrated under reduced pressure to obtain a concentration of cerium dioxide of 20% by mass in terms of solid content concentration, an average secondary particle diameter of 62 nm, and a pH value of Η; The 二1 N hydrogen storage solution was used to titrate the obtained oxidized recording agent dispersion E in the range of pH 4 to 9, and the value of the sputum value and the brittle specific surface area was calculated. 1 · 5 / η π] 2. 々 々 々 夕 粒子 粒子 粒子 粒子 粒子 粒子 粒子 粒子 粒子 粒子 粒子 粒子 粒子 粒子 粒子 粒子 粒子 粒子 粒子 粒子 粒子 粒子 粒子 粒子 粒子 粒子 粒子 粒子 粒子 粒子 粒子 粒子 粒子 粒子 而 而 而 而 而 而 而 而 而 而The cerium oxide particle dispersion H is produced by the same method as the above-described cerium oxide particle dispersion A. After the dispersion is obtained by the method, it is produced by hydrothermal treatment at 098104943 54 200944582 (when the above-mentioned cerium oxide particle dispersion is prepared, and subjected to a high pressure enthalpy treatment for a longer period of time and subjected to a dream alcohol condensation). The cerium particle dispersion I was produced in the following manner. First, a high-purity colloidal cerium oxide manufactured by Fuso Chemical Industry Co., Ltd. (part No.: PL-2; solid content concentration: 20% by mass, pH 7.4, average twice The sputum of the sulphuric acid concentration of the sulphuric acid concentration of the sulphuric acid is 20% by mass, the average secondary particle size is 62 nm, and the 〇 pH value is 7.5. The cerium oxide particle dispersion I. The obtained cerium oxide particle dispersion I was titrated in the range of pH 4 to 9 using a 0.1 N aqueous sodium hydroxide solution, and the stanol was calculated based on the titration value and the BET specific surface area value. The base density was found to be 3.8/nm 2. The physical property values of the prepared cerium oxide particle dispersions A to J are summarized in Table 2.

098104943 55 200944582

Rraax/Rmin T—Η (N1 CD t—HH TH 卜rH F "'4 FH ammonium ion concentration (ppm) 5 C^J oo 2190 1 C<l o- oo LO 1 LO Potassium concentration (ppm) 5500 3280 7000 OO 1 7600 T·^ V LO 1 in Sodium concentration (ppm) §§ 1-H t—CO oo oo tH 1 〇CO (ΝΪ V 11250 1 stanol density (units/nm2) 05 1—H 卜i —Η CM oi LO tH oi οα OO CD oo CO C3 oa Average particle size (nm) LO OO LO OO CO § LO CO Csl <NI CO CO <NI pH <=> oo ai OO ai &lt ;=> LO Bu· 10.2 οα Bu·C=3 CD 1' H LO CO cerium oxide concentration (% by weight) o <NI CO C5 oo (NI CD oi CO c=> s CD LO CO cz> In 1 ( o oo Cv3 CZ5 «〇<N1 c=> oo CM cerium oxide particle dispersion CQ 〇O SC HH l~~J

9S ο 96S-60 200944582 4.2 Synthesis of water-soluble polymer 4. 2·1 Preparation of aqueous solution of polyvinylpyrrolidone, adding N-vinyl-2-pyrrolidine _ 6〇g, water 24〇g, 1〇•Quality «Sodium sulfite aqueous solution 0.3 § and 10 #% by weight of hydrogen peroxide in the third butyl aqueous solution 3. 3 g, in 6 (rc gas environment for 5 hours, whereby raw silk vinyl (4) (10)) . Using gel permeation chromatography (Tongshao (T〇s〇h) 1 system 4, device model "HLC-8120", column type "tsk-gEL· ® α M"' eluent is NaC1 aqueous solution / acetonitrile The measurement of the obtained polyethylene "birolidinone (K30), the weight average molecular weight (Mw) in terms of polyethylene glycol was 40,000. Further, the amount of the amine group calculated based on the amount of the monomer added was 〇 ra〇l / g '. The amount of the cationic functional group was 〇 mol / g. Further, polyvinylpyrrolidone (K60) and polyvinylpyrrolidone (K9®) are produced by appropriately adjusting the amount of the above components, the reaction temperature, and the reaction time. Further, the weight average molecular weight (Mw) of the obtained polyvinylpyrrolidone oxime (Κ60) and polyvinylpyrrolidine _(Κ90) was measured by the same method as above, and the results were 700,000 and 1.2 million, respectively. . The amount of the amine group calculated based on the amount of the monomer added was 0 mol/g, and the amount of the cationic functional group was 〇 m〇1/g. " 4. 2. 2 vinyl pyrrolidine _ / diethylaminomethyl methacrylate copolymer. In a flask equipped with a reflux cooler, a dropping funnel, a thermometer, a glass tube for nitrogen replacement, and a stirring device 70 parts by mass of diethylaminomethyl methacrylate, 5 parts by mass of cetyl acrylate, 10 parts by mass of octadecyl methacrylate, and 1 part by mass of N-vinylpyrrolidone , butyl methacrylate 098104943 57 200944582 ester 5 parts by mass and isopropyl alcohol loo parts by mass, adding azobisisobutyronitrile (Aibn, aZ〇biSiS〇butyr〇nitrile) 0.3 parts by mass, under nitrogen flow, 6〇〇c The polymerization was carried out for 15 hours. Then, compared with the diethylaminoethyl acrylate of 丨mol, 〇. 35 times the molar number of diethyl sulfate, and heated under reflux at 50 C for 1 hr under a nitrogen stream to synthesize a vinyl group. ^Bilopyryl acrylic acid monoethylamine based copolymer. Using a gel permeation chromatography (manufactured by Tosoh Corporation, device model "HLC-8120", column type "TSK-GEL α-Μ", the eluent is NaCl aqueous solution / acetonitrile), the obtained copolymer was subjected to As a result, the weight average molecular weight (Mw) in terms of polyethylene glycol was 100,000. Further, the amount of the amine group calculated based on the amount of the monomer added was 0.001 mol/g, and the amount of the cationic functional group was 0.0006 mol/g. By appropriately adjusting the amount of the above components, the reaction temperature and the reaction time, a vinylpyrrolidone/diethylamino methacrylate copolymer having a weight average molecular weight of 400,000 and 1.8 million, respectively, was synthesized. 4.2.3 Vinyl pyrrolidone/didecylaminopropyl acrylamide copolymer is added to a flask equipped with a reflux cooler, a dropping funnel, a thermometer, a glass tube for nitrogen replacement, and a stirring device, and water is added. 2'-Azobis(2-methylpropionamidine) dihydrochloride (manufactured by Wako Pure Chemical Industries, Ltd., trade name "V-50") 0.6 parts by mass, and heated to 70 °C. Then, 70 parts by mass of N-ethylene η pirone, hydrazine (hydrazine, hydrazine-dimethylaminopropyl propylene decylamine), 3 parts by mass, and polymerization under a nitrogen stream at 75 C were placed. hour. Then, 2,2' - 098104943 58 200944582 azobis(2-mercaptopropene) dihydrochloride (trade name "V-50" manufactured by Wako Pure Chemical Industries, Ltd.) was added in an amount of 2 parts by mass under a nitrogen stream. 7 (r) was heated under reflux for 6 hours to obtain an aqueous dispersion containing 11% by mass of a vinylpyrrolidone/didecylaminopropyl acrylamide copolymer. The polymerization yield was 99%. 〇 30 30 , , , , , 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 Diethyl sulfate was heated under reflux at 5 ° C for 1 hour to cationize a part of the amine group. Using a gel permeation chromatography instrument (manufactured by Tosoh Corporation, device model "HLC-8120", The column type "TSK_GEL α_Μ", the eluent is NaCl aqueous solution / acetonitrile)' The obtained copolymer was measured, and the weight average molecular weight (Mw) in terms of polyethylene glycol was 600,000. The amount of the amine group calculated by adding the amount is 0.0010 mol/g, and the amount of the cationic functional group is 0.0006 mol/g. ® 4·2·4 vinylpyrrolidone/vinyl acetate copolymer vinyl pyrrolidone/vinyl acetate copolymer using the trade name “PVP/VA Copolymer W-735C with a molecular weight of 32,000, vinylpyrrole _ ketone: vinyl acetate = 70 : 30)" (manufactured by ISP Japan). 4. 2.5 Hydroxyethyl Cellulose The hydroxyethyl cellulose was sold under the trade name "Daicel HEC SP900" (molecular weight: 1.4 million) manufactured by Daicel Chemical Co., Ltd. 4.2.6 Polyacrylic acid 098104943 59 200944582 In a container having an internal volume of 1 liter of ion-exchanged water and 5% by mass of an aqueous ammonium persulfate solution ig, 70 is added. While stirring under reflux, 500 g of an aqueous solution of 2% by mass of acrylic acid was added dropwise uniformly over 8 hours. After completion of the dropwise addition, the mixture was kept under reflux for 2 hours, whereby an aqueous solution containing polyacrylic acid was obtained. Using a gel permeation chromatograph (manufactured by Tosoh Corporation, model number "HLC-8120", column type rTSK_GEIj α_Μ", the eluent was Nan aqueous solution / acetonitrile), and the obtained polyacrylic acid was measured. The weight average molecular weight (MW) in terms of diol is 10,000. Moreover, the amount of addition of the above components, the reaction temperature, and the reaction time were appropriately adjusted, whereby polyacrylic acid having a weight average molecular weight (Mw) of 200,000 was obtained. 4. 3 Preparation of Chemical Mechanical Polishing Water-Based Dispersion 50 parts by mass of ion-exchanged water was converted into cerium oxide and 5 parts by mass of cerium oxide particle dispersion A was placed in a polyethylene bottle and added thereto. 1 part by mass of malonic acid, 0.2 parts by mass of quinaldine, and a nonionic surfactant of acetylene glycol type (trade name "Surfynol 465", manufactured by Air Pr〇duct) 1. 1 part by mass, and converted into polymerization The amount of the polyacrylic acid aqueous solution (weight average molecular weight is 20,000) in an amount of 0.05 parts by mass, and further adding 10% by mass of 51 oxidized bell aqueous solution' to adjust the pH of the chemical mechanical polishing aqueous dispersion to 10.0. Then, 30% by mass of hydrogen peroxide water, which was converted to nitrogen peroxide and equivalent to 0.05 parts by mass, was added and was searched for ^ minutes. Finally, after adding ion-exchanged water to make the total amount of the total components as a part by mass, it is carried out by a filter having a pore size of 5 Am: 097104943 60 200944582 This obtains a chemical mechanical polishing water having a pH of 1.00. Is the dispersion si. The oxidative deuteration is recovered by centrifugation from the chemical mechanical polishing aqueous dispersion 81, and the (4) hydrofluoric acid is dissolved in the dioxins, and the ICP-MS (manufactured by Philippine Elmer) is used. , Model "EUN Hearing") Determination of sodium and sputum. Further, the ion to be recorded was measured using an ion chromatography (manufactured by Tosoh Corporation, "ICS-1000"). The result was nano content: 88 qing, bell content: 5500 卯m, ammonium ion content: 5 PPm. According to the results, it is understood that the sodium, potassium and ammonium ions contained in the cerium oxide particles can be quantified even if the oxidized particles are recovered from the chemical mechanical polishing aqueous dispersion, and the cerium oxide particles can be dispersed. The same result. The chemical mechanical polishing water is produced in the same manner as the chemical mechanical polishing aqueous dispersion S1 except that the type and content of the cerium oxide particle dispersion, the organic acid, and other additives are changed as described in Tables 3 to 8 In the case of the dispersions S2 to S4, in addition, in Tables 3 to 8, "Surfynol" and "Surfynol" are both Ai = 2 4 7, 9_tetramethyl + decyne 4' 7 manufactured by the company. Alcohol-polyoxyethylene ether (acetylene glycol type nonionic surfactant) 'The name of the name of the trade name' polyoxyethylene addition moles varies. "Emulgen 104P" • The trade name of the polyoxyethylene laurel scale (formyl ether type nonionic surfactant) manufactured by King A. The obtained chemical mechanical polishing aqueous dispersion was placed in a glass & amp of cc and stored at 25 ° C for 6 months, and visually confirmed that there was no precipitation of 098104943 61 200944582. The results are shown in Tables 3 to 8. In Tables 3 to 8, it was confirmed that the case of no particle precipitation and the difference in density was evaluated as "〇", and the case where only the difference in density was confirmed as "△" was evaluated, and the precipitation of the particles and the difference in the darkness were confirmed. It is "X". 4. 4 Experimental Example 1 4. Evaluation of the polishing of the non-patterned substrate. The porous polyamine phthalate polishing pad was attached to the chemical mechanical polishing device (manufactured by Ebara Seisakusho Co., Ltd., type "EP0112").

The Haas company manufactures the "material number "Cai (10)"), and supplies the chemical mechanical polishing & water-based dispersions S1 to S12, and grinds the following various polishing rate measurement substrates for one minute according to the following polishing conditions. The treatment was carried out, and the polishing speed and wafer contamination were evaluated by the following methods. The results are shown together in Tables - Table 4. 3 4·4· Measurement of la polishing rate (1) Substrate for polishing rate measurement An 8-inch substrate with a coating film having a film thickness of 15,000 angstroms (Angstrom) was laminated. ·, , , 虱 The laminate has a ruthenium substrate with a film thickness of 2 and a thermal oxide film attached to the button film of 〇〇〇. The film thickness of the film is l〇, and the low dielectric constant of GGG is based on the 8-inch 矽 substrate manufactured by the company, which is manufactured by the company, under the trade name “Black Diamond”. τ 098104943 200944582 • A plasma-enhanced Tetraethylorthosilicate film (PETE0S) with a film thickness of 10,000 angstroms. (2) Grinding conditions • Grinding head rotation number: 70 rpm • Grinding head load: 200 gf/cm2 • Table rotation: 70 rpm © • Chemical mechanical grinding water dispersion speed: 200 mL/min The supply rate of the chemical mechanical polishing aqueous dispersion at this time is the total of the supply amount of the total supply liquid divided by the value obtained per unit time. (3) Calculation method of the polishing rate The thickness of the copper film and the button film after the polishing treatment was measured using a conductive film thickness measuring device (manufactured by KLA-Tencor Co., Ltd., type "OmniMap RS75"), and by chemical mechanical polishing. Reduce the film thickness and grinding time to calculate the grinding speed. The film thickness after the polishing treatment was measured for the PETE0S film and the low dielectric constant insulating film using a light interference type film thickness measuring device (manufactured by Nanometrics Co., Ltd., type "Nanospec 6100"), and was reduced by chemical mechanical polishing. - The film thickness and the grinding time are used to calculate the polishing rate. 4. 4 lb wafer contamination The PETE0S film and the low dielectric constant insulating film were polished in the same manner as in the above "4.4. la polishing rate measurement". About pETE〇s 098104943 63 200944582 Membrane, which is subjected to gas phase decomposition treatment on a substrate, and is diluted with hydrofluoric acid on the surface to dissolve the surface oxide film, and then used by ICP-MS (Perkin Elmer, model "ELAN" DRC PLUS") quantifies the dissolved liquid. For the low dielectric constant insulating film, ultrapure water is dropped on the surface of the substrate, and the residual metal on the surface of the low dielectric constant insulating film is extracted, and then Ϊ CP _ M s (manufactured by Yokogawa Analytical Systems Co., Ltd.) , model "Agilent 7500s") to quantify the extract. The wafer contamination is preferably 3. 〇 挪 / coffee 2 or less, more preferably 2. 5 atom / cm 2 or less. 4. 4· 2 Grinding evaluation of patterned wafers. Installation of porous polyamine-based f acid on a chemical mechanical polishing device ("EP0112" manufactured by Ebara Seisakusho Co., Ltd.) § Grinding _ = Haas company's part number "(4) (9)"), the surface-feeding chemical machine a, any of the water-based dispersions S1 to S12, is subjected to a polishing treatment according to the following polishing conditions = the following patterned wafer, and is evaluated by the following method. , the presence of frankness and defects. The results are shown together in Tables 3 to 4. Ping Ping Ping (1) The patterned wafer is used as a test substrate: a film of 1000 angstroms deposited on a tantalum substrate, on which a low dielectric constant insulating film (Diamond film) is laminated, and then laminated 5 〇〇 之 p p p p 「 SEM SEM SEM SEM SEM SEM SEM SEM SEM SEM SEM SEM SEM SEM SEM SEM SEM SEM SEM SEM SEM SEM SEM SEM SEM SEM SEM SEM SEM SEM SEM SEM SEM SEM SEM SEM SEM SEM SEM SEM SEM SEM SEM SEM SEM SEM SEM SEM . Coffee (2) Polishing conditions of the first polishing treatment step 098104943 64 200944582 • The chemical machine maple polishing water dispersion used as the first polishing treatment step uses "CMS7401" and "CMS7452" (both jsr) The system is made of a mixture of ion-exchanged water and a 4 mass% ammonium persulfate aqueous solution in a mass ratio of i: 丨.2:4. Number of rotations of the grinding head: 70 rpm. Weight of the grinding head: 200 gf/cm2 • Number of rotations of the table: 70 rpm ❹ Supply speed of chemical mechanical polishing water dispersion: 2 〇〇mL/min Chemical mechanical polishing at this time The supply rate of the water-based dispersion refers to the total amount of the supply of the total supply liquid divided by the value obtained per unit time. Grinding time: 2.75 minutes (3) Polishing conditions of the second polishing treatment step. As the aqueous dispersion for the second polishing treatment step, the chemical mechanical polishing aqueous dispersion ~S12 was used. ❹. Number of grinding head rotation: 70 rpm • Grinding head load: 200 gf/cm2. Table rotation: 70 rpm. Supply speed of chemical mechanical grinding water dispersion: 200 mL/min • Chemical mechanical polishing water at this time The supply rate of the dispersion is the total of the supply amount of the total supply liquid divided by the value obtained per unit time. Grinding time: The time from the time when the PETEOS film was removed from the surface to be polished, and the time of polishing for 30 seconds was used as the polishing end point, and the polishing time of the substrate having the pattern of 098104943 65 200944582 was described in Tables 3 to 4. 4.4. 2a flatness evaluation type using the local resolution roundness instrument (manufactured by KLA_Tencor, HRP24〇ETCH)) 'attached to the second grinding treatment step, the rounded surface to be polished' is just fixed steel wiring width c line, L ) / Insulation medium width: day S) is the (10) "ra copper wiring part:, ' (nm). In addition, when the upper surface of the wiring is convexly higher than the surface of the reference recording amount, the shallow-disc I k insulating 祺 Ο ,, preferably - 2 〜 2 〇 · for ^ 〜 3 〇 a pair of second grinding After the processing step, the polished surface of the patterned wafer is measured, and the copper wiring ML)/sand carrier (gap, S) is 9 β11^1, respectively, and the length of the fine wiring is continuous. Milling part of the amount of 1000 (nm). In addition, the amount of wear is indicated by a negative sign when the upper surface of the surface wiring is convex higher than the reference surface (the upper surface of the insulating film). The grinding amount is preferably -5 to 30 nm', more preferably -2 to 2 Å nm. The pattern-attached wafer after the first surface grinding process is ground. "Using a stylus profiler (KLA-Tencor, Inc., cracked HRP240 j 1 Λ 1〇〇 wiring pattern portion of the sharp groove) In addition, the insulating film of Dong + 曰, Yang Yuan, or the notch formed in the barrier metal film and the wiring portion =, , , , 邑 臈, or the barrier metal film, the evaluation of the tip concave § 1 groove Small, indicating that the planarization performance of the wiring portion is excellent. The pointed groove is preferably 〇~nm, more preferably 〇25 nm. 098104943 66 200944582 4. 4. 2b Scratch evaluation using defect inspection device (KLA-Tencor The company manufactures the type "2351"), and measures the number of polishing scratches (scratches) on the polished surface of the patterned wafer after the second polishing process. In Tables 3 to 4, for each wafer The number of scratches is marked with the unit of "piece/wafer". The number of scratches is preferably less than 100/wafer.

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Gw te 萑 peak 3⁄4 瓣··gt; ε inch 6 inch 0S60 200944582 Comparative Example 6 (MI-H c=> LO Η ΙΟ c> Turning acid S <=> I g <r> gc= > Ο O' 呀1, ss C3 Hydrogen peroxide 〇 to CTS 〇S § CD 05 CO <=> CO 〇CO <=> 05 OO 05 0〇c^a S m Comparative Example 5 CO ◦ ltJ Ί 宁 1 CD Love go S <=> 1 < g OS <=> o C5 X sm S 〇〇g 〇§ 1〇CO cJ 05 CO Ο CO 〇<=> 2ί · LO tn ο 卜 in s 1 Comparative Example 4 S CO 〇LO 卜 · 槪 槪 f f—^ 1 | Another G? f CD go 1 is o' $ 〇LT5 <=> X c> Another 1 § S CO 〇ΙΛ 〇· CO 00 ο CO eg 〇CO Ci 03 rH rH CO along Comparative Example 3 1 cis-succinic acid m ο 咬 酸 S S- 1,000,000 CD os I 1 s <=> $ 窜CD r· ^ Ο m 05 〇s CVI ΙΛ § LT3 10.00 〇oo ο Ο oi g LO in c=> CO Comparative Example 2 88 ο Ο CO 1 1 1 1 $ m- 错 CD Ο in od 〇1 i 〇§ S ΙΛ g oi CO ο m C3 〇4 Ming oo CM to Comparative Example 1 &5 〇ΙΛ Bu· 1 1 ooso CM 〇1 Eraul 卿104P oo iBf 〇· ΙΛ C> 〇1 i S tn ο ο <>i <=> CO Bu G5 oo ο 2 s § 1 Chemical mechanical polishing water dispersion 1 Green body 1 φί m «Wul content (% by mass) mw / •—N φί 4〇.ΙΙΚ.Ι φ>1 tt^lf ηβη Ns-/ dH 4〇HOC iiS? •Krj $1 4〇V8B( aw ΡρΊ «Η *4〇si f Cu grinding touch (A/min 1 1 1 BD Grinding Sister (Ai/Lai) PEIE0S Grinding Touch (Angstrom/fine Cu/Ta grinding speed is better than Cu/PETBOS grinding speed than BD/PETB0S grinding speed than Blade Diamond film PETEOS film with patterned substrate grinding time) (seconds) m =t 31 MS Jj ^ (4) Grinding allowance (nm) L/S=9/l um r·^ 1% 3f Scratch (piece/wafer) Dioxygenated organic acid lacquer polymer Surfactant oxidant wafer contamination (atans/cm2) Flatness of the continent f peaks W 辜 单 69 69-6SIS60 200944582 4. 4. 3 Evaluation results of the experimental example 1 The results of the polishing test of the substrate for the measurement of the polishing rate It can be seen that in the chemical mechanical polishing aqueous dispersions of Examples 1 to 6, the polishing rate of the steel ruthenium, the ruthenium film, and the PETEGS film can be more sufficiently suppressed against the low dielectric constant = the edge film. Speed, and will not produce wafer contamination. As a result of the polishing test of the patterned wafer, it is understood that the chemical mechanical polishing aqueous dispersion of Examples 丨 to 6 has excellent flatness of the surface to be polished, and the number of scratches can be kept low. Further, it was found that the cerium oxide particles of the chemical mechanical polishing aqueous dispersion of Examples 1-6 were excellent in storage stability. In contrast, the comparison example! The S7 system used in the above was equivalent to the composition of the component corresponding to the organic acid removed from S3 used in Example 3. When the results of Example 3 and Comparative Example were compared, the storage stability of any of the cerium oxide particles was good. On the other hand, in the polishing test of the substrate for polishing rate measurement, the polishing rate of the copper film and the barrier metal film was remarkably increased as compared with Comparative Example 1. Further, in the polishing test of the patterned wafer, the trace on the copper film of Example 3 was significantly reduced as compared with Comparative Example 1. The above results show the superiority of using organic acids. Since S8 used in Comparative Example 2 does not contain an organic acid, a water-soluble polymer, and a surfactant, the polishing rate of the low dielectric constant insulating film is remarkably increased in the polishing test of the substrate for polishing rate measurement. Since S9 used in Comparative Example 3 does not contain cerium oxide particles, a practical polishing rate cannot be obtained in any substrate for measuring the polishing rate. 098104943 70 200944582 The sub-group used in Comparative Example 4 contains the dioxo-particle dispersion G having a density of 4·2, and thus the storage of the dioxins is not qualitatively good. In the investigation of the polishing speed of the wire receiving plate, it was confirmed that the polishing of the barrier metal film was increased. On the other hand, it can be confirmed: a tendency to exceed the copper film and: Grinding test on patterned wafers β 广 子 子 生 生 ( ( ( ( ( ( ( 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 The S11 used in =5 contains a dispersion of the oxidized cerium particle having a 〇8 basis, and thus the alcohol stability is poor. Preservation of the polishing rate measurement substrate ^Shixi particles The occurrence of wafer contamination 1 with a patterned wafer = during inspection, it was confirmed that a plurality of scratches were formed on the agglomerated silica. In the π test, the S12 system used in Comparative Example 6 is a dioxoparticle dispersion containing a sulfhydryl density, but can be made by a balance of 8 or (10) 2 of the alcohol or concentration. The oxidized stone cerium particles are steadily built into the grinding test of the wafer of the additive type pattern, which is widely used. However, it is known that the groove of the surface to be polished and the type of the crucible (four) is not obtained, and as described above, when the water of the embodiment 1 to the dispersion of Hi is used, Meet the steel film, film and PETE0S film, "grinding degree" and the same characteristics. Moreover, it can be seen that high-quality chemical mechanical polishing can be achieved without using a metal film or a low dielectric constant insulating film by performing a door grinding degree and a chemical mechanical polishing water system 200944582 dispersion of 098104943 3 6 . Causes defects and reduces metal contamination of the wafer. 4. 5 Experimental Example 2 4. 5.1 Polishing Evaluation of Non-patterned Substrate A porous polyamine phthalate polishing pad (manufactured by Nitta Haas Co., Ltd.) was attached to a chemical mechanical polishing device (manufactured by Ebara Seisakusho Co., Ltd., model "EP0112"). In the case of the chemical mechanical polishing aqueous dispersions S13 to S41, one of the following polishing rate measurement substrates is subjected to one-minute polishing treatment according to the following polishing conditions, and the following method is used. Evaluation of polishing speed and wafer contamination. The results are shown together in Tables 5 to 8. 4. 5. Measurement of la polishing speed (1) Substrate for polishing rate measurement • An 8-inch tantalum substrate with a thermal oxide film on a copper film with a film thickness of 15,000 angstroms was laminated. • An 8-inch tantalum substrate with a thermal oxide film on the tantalum film with a film thickness of 2,000 angstroms. (2) Grinding conditions • Grinding head rotation number: 70 rpm • Grinding head load: 200 gf/cm2 • Table rotation number: 70 rpm 098104943 72 200944582 Chemical mechanical grinding water dispersion supply speed: 2〇〇mL/min The supply speed of the chemical mechanical polishing aqueous dispersion is the total of the supply of the liquid supply divided by the value obtained per unit time. - (3) Calculation method of polishing speed Using a conductive film thickness measuring device (manufactured by KLA_Tenc〇r Co., Ltd., plastic type)

OmniMap RS75")' The steel film and the button film were measured for the film thickness after the polishing treatment, and the film thickness and the polishing time were reduced by chemical mechanical polishing to calculate the polishing rate. 4. 5. lb wafer contamination The copper film was polished in the same manner as described in "4. 5. la polishing rate" above. Then, ultrapure water was added to the surface of the sample to extract residual metal on the surface of the copper film, and then the extract was quantified by ICP_MS (manufactured by Yokogawa Analytical Systems, model "Agilent 7500s"). The wafer contamination is preferably 3.0 atom/cm2 or less, more preferably 2.5 at (10)/cm2. 4. 5.2 The polishing of the patterned wafer is mounted on a chemical mechanical polishing apparatus (manufactured by Ebara Seisakusho Co., Ltd., type "EP0112"). The porous polyamine phthalate polishing pad manufactured by Haas Co., Ltd., material number "ici", is supplied to any of the chemical mechanical polishing aqueous dispersions S13 to S41, and is patterned as follows. The wafer was polished in the same manner as the polishing conditions of "4.5.1a polishing rate measurement" except that the button film was detected on the surface to be polished, and the flatness was evaluated by the following method. And the defects are 098104943 73 200944582 None. The results are shown together in Tables 5 to 8. (1) The wafer with the pattern is as follows: a low dielectric constant insulating film (Biack Diamond film) having a thickness of 4,500 angstroms deposited thereon on a stone lining film of 1000 angstroms on a stone substrate. Then, a PETEOS film of 500 angstroms was laminated, and a "SEMATECH 854" mask pattern was processed, and a 250 angstrom film, a 1000 angstrom copper film, and a 1QQQQ Ai copper film were sequentially laminated thereon.

G 4. 5. 2a flatness evaluation Using a resolution rim (KLA-Tencor, model "HRP240ETCH") 'Measure the copper wiring width for the patterned wafer = polishing surface after the polishing process step (Line, L) / Insulation film width (gap, s) The blade is the amount of shallow disc ((10)) of the copper wiring portion of 1GG 〃m/iGQ. In addition, when the upper surface of the steel wiring is convex higher than the reference surface (the upper surface of the insulating film), the shallow dish is indicated by a minus sign. The amount of shallow disc formation is preferably _5 to 3G (10) to 2 to 20 nm. Ma Wei cloth Sr: the polished surface of the patterned wafer after the processing step, measuring copper! = (line 'L) / insulating film width (gap, _ is 9 - the length of the line length of the grinding surface - the amount When the surface is on the upper surface of the table (4), the protrusion is higher than the reference surface (the insulation film is preferably -2~2〇(10). The negative wire is not. The grinding name is preferably -5~30 coffee' more 4. 5. 2b Corrosion evaluation 098104943 74 200944582 Using a defect inspection device (manufactured by KLA-Tencor Co., Ltd., type r2351), evaluation of the copper area of 1 CD1X1 • cm of the polished surface of the patterned wafer after the polishing process The number of defects in the size of 10 nm2 to 100 rnn2. In Tables 5 to 8, '〇 indicates the number of corrosions is 0 to 10 and the best state. △ indicates 11 to 100 and the state of hysteresis. X indicates the presence of 1〇. It is judged that the polishing performance is poor in one or more states of the rot. 4. Evaluation of copper residue on the 5.2c fine wiring pattern ❹ Ultra-high-resolution field emission scanning electron microscope "S-48〇〇 (Hitachi High-Tech Co., Ltd.) Manufactured), the width of the surface to be polished of the patterned wafer after the polishing process is 〇·18 The wiring portion and the pattern in which the width of the 〇18 is alternately connected by the insulating portion of the claw (the length is 16 mm) is h25 mm continuous in the direction perpendicular to the longitudinal direction, and the isolated wiring portion having the width 〇\8 _ is evaluated. The presence or absence of the CU residue (copper residue). The evaluation results of the steel residue are shown in Tables 5 to 8. The residual value of the evaluation item in the table indicates the Cu residue on the above-mentioned figure, and "〇" indicates that Cu is completely eliminated. The optimum state is "△", which indicates that some of the patterns have a slight residue and are inferior. "X" indicates that CU is mixed in all the patterns and the polishing performance is poor. 098104943 75 2 8 5 44 09 200 si A fragrant w383^ 38 13⁄4 3 0〇〇·0 ΑΊ ΓΟ ooocvico coo.o dsl SMlnug oro is .1

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ssdA (payment/姊(53/1«|-|->|0) goes up 4 sleepy dark one yj00l/001=s/1 ειΙ)«Ν^#^ =yJl/6=s/HJI (mu )»H^«5l £ inch 6SS60 200944582 4. 5.3 Evaluation results of the experimental example 2 According to the results of the polishing test substrate, the results of the polishing test, the chemical thieves and water dispersions of Examples 7 to 23 were used. The polishing rate is 8 or less, and the polishing rate of the barrier metal film is 1 to 3 Å/min. Therefore, the polishing selectivity to the copper film is excellent. Also, it is confirmed that there is almost no crystal contamination. The results of the polishing test of the wafer according to the time pattern were as follows. * In the chemical mechanical polishing aqueous dispersion of Examples 7 to 23, the flatness of the surface to be polished was excellent, and it was confirmed that no impurities or sequestration occurred. Further, it is understood that the sulfur dioxide particles of the chemical mechanical polishing aqueous dispersion of Examples 7 to 23 are excellent in storage stability. In contrast, in the polishing test of the substrate for polishing rate measurement, the polishing rate of the copper film used in the polishing rate measurement substrate was reduced to 1,000 Å in the polishing test of S3 使用 used in Comparative Example 7. Minutes, but not practical. In the polishing test of the substrate for polishing rate measurement, the polishing rate of the opposite surface was reduced to 200 Å/min, which was not practical, since the composition used in Comparative Example 8 did not contain a component corresponding to an amino acid. In the polishing test of the substrate for polishing rate measurement, the polishing rate of the copper film was reduced to 2,000 angstroms/minute, in which S32 used in Example 9 contained maleic acid instead of amino acid. And can't be practical. Since S33 used in Comparative Example 10 does not contain the cerium oxide particles, the polishing rate of the copper film in the polishing test for the polishing rate measurement substrate was reduced to 420 Å/min, which was not practical. 098104943 80 200944582 S34 used in Comparative Example 11 does not contain silica dioxide particles, so the polishing rate of the polishing rate/the substrate is reduced to '50 angstroms per minute. . The coffee used in Comparative Example 12 does not contain a component corresponding to an amino acid. Therefore, the polishing test at the polishing rate of the sheet is reduced to a fineness of 300 Å/min, which is not practical. Also, with a pattern

In the polishing test of the wafer, the shallow dish cannot be suppressed. Further, since the water-soluble polymer is not contained, the effect of suppressing the copper cloth is small, and the green color can be corroded. The shape (10) obtained in Comparative Example 13 contained the dioxoparticle dispersion G having a density of 4.2/(10) 2 of the thiol group, but the dioxin-cut particles were stabilized by achieving the balance of the kind or concentration of the additive. However, in the polishing test of the substrate for measuring the polishing rate, the polishing rate of the copper film was 7 gal/min, and the material was sufficient. On the other hand, the polishing rate of the impurity film was increased to 30 Å/min. It was confirmed that the polishing selectivity was lowered. In the grinding test with the figure circle, it can be confirmed that the production of ±short disc, pure, residual, and steel residual yang cannot obtain a good surface to be polished. The S37 used in the comparative example contains a heterogene dispersion G having 42 ruthenium, but the dioxin-cut particles can be deuterated by achieving an equilibrium of the additive core or the degree of turbulence. However, in the grinding test, the polishing rate of the copper film was 6: Angola was insufficient. In the grinding test of patterned wafers

• J 098104943 200944582 It was confirmed that copper residue was generated and a good polished surface could not be obtained. The phantom 8 used in Comparative Example 15 contained the cerium oxide particle dispersion H having a decyl alcohol group density of 0.8 / nm 2 , and thus the storage stability of the cerium oxide particles was poor. In the polishing test of the substrate for polishing rate measurement, the polishing rate of the copper film was 8 Å/min, which was relatively sufficient, but the polishing rate of the film was increased to 1 Å/min, and the polishing selection was confirmed. Sexual decline. © S39 used in Comparative Example 16 contains a cerium oxide particle dispersion 〇 having a density of 矽. 8 / nm 2 of decyl alcohol, but cerium oxide particles can be obtained by achieving the balance of the kind or concentration of the additive. Stabilized. However, in the polishing test roll of the substrate at the polishing rate, the polishing rate for the fineness was 6, Å / min, which was insufficient, and wafer contamination was confirmed. In the polishing test of the patterned wafer, it was confirmed that the shallow disc, the rot #, and the copper remained, and a good polished surface could not be obtained. S S40 used in Comparative Example 17 contains the dioxoparticle dispersion 1 having a density of 8 angstroms, but can be obtained by achieving the balance of the additive or concentration of the additive. The oxidation wire is stabilized. However, in the study of the substrate for measuring the polishing rate, the polishing rate of the copper film was reduced to 280 angstroms per minute, and the polishing rate of the steel was significantly increased to 820 angstroms/minute. The grinding selectivity deteriorates. The S41 used in Comparative Example 18 contains oxalic acid " lysine, for example, instead of the amino acid, so the polishing rate of the film in the polishing test for the polishing rate of the substrate is increased to 2 Å/min. It can be confirmed that in the grinding test of the wafer of the grinding selection 098104943 82 200944582, it is confirmed that the shallow dish rot (4) (4) has a good grinding surface. As described above, if the use of Example 7 to high polishing rate is used to cause defects in metal germanium or low dielectric chemical mechanical polishing without round metal contamination, and the crystal can be reduced. Description Figure 1 is a cross-sectional view showing the process of forming a pointed groove. Figure 2 is a cross-sectional view showing the process of forming a pointed groove. Figure 3 is a cross-sectional view showing the process of forming a pointed groove. Figure 4 is a cross-sectional view for explaining the process of forming a pointed groove. Fig. 5 is a conceptual diagram schematically showing the long drumming of the diced particles. Figure 6 is a conceptual diagram showing the long practice of dioxin particles. Fig. 7 is a conceptual diagram showing the green drum indicating the long-cutting of the dioxotomy. Fig. 8 is a cross-sectional view showing the object to be treated used in the chemical polishing method of the embodiment of the table. Fig. 9 is a cross-sectional view for explaining a polishing step of the chemical mechanical polishing method of the embodiment. Fig. 10 is a cross-sectional view for explaining a polishing step of the chemical mechanical polishing method of the embodiment. 098104943 83 200944582 Fig. 11 is a cross-sectional view for explaining a polishing step of the chemical mechanical polishing method of the embodiment. [Main component symbol description] 10 12 14 16 20 22 24 26 28 30a ' 30b 40 50 60 70 80 90 100 200 a ' c ' eb, d, f base insulating film barrier metal film made of copper or copper alloy The recessed portion for the wiring includes a region where the fine wiring is not included in the region of the fine wiring, and the flaw is sharp. The recessed groove 30c, the cerium oxide particle, the low dielectric constant insulating film, the insulating film (overlying layer), the recessed portion of the wiring, the metal film, the copper film semiconductor device Short diameter of long-path cerium oxide particles of treated body cerium oxide particles 098104943 84

Claims (1)

200944582 VII. Patent application scope: 1. A chemical mechanical polishing aqueous dispersion containing (A) dioxide, cerium particles, and (B1) organic acid, • The above (A) cerium oxide particles have the following The chemical density: The density of the base of the base is 1.0 to 3. 0 / nm2, based on the specific surface area measured by the BET method and the amount of the base. 2. The chemical mechanical polishing water according to the first aspect of the patent application is a dispersion, wherein the (B1) organic acid is an organic acid having two or more carboxyl groups. 3. The chemical mechanical polishing aqueous dispersion according to claim 2, wherein the organic acid having two or more carboxyl groups has an acid dissociation index pKa at 25 ° C (wherein an organic acid having two carboxyl groups) 0以上。 The pKa of the second carboxyl group as an index, in the organic acid having three or more carboxyl groups, the pKa of the third carboxyl group is used as an index) is 5.0 or more. 4. The chemical mechanical polishing water dispersion product according to the second aspect of the patent application, wherein the organic acid having two or more carboxyl groups is at least selected from the group consisting of maleic acid, malonic acid and citric acid. 1 species. 5. The chemical mechanical polishing water according to the first aspect of the patent application is a dispersion of a hydrazine, which further contains (C1) a nonionic surfactant. 6. The chemical mechanical polishing aqueous dispersion according to claim 5, wherein the (C1) nonionic surfactant has at least one acetylene group. 7. The chemical mechanical polishing water dispersion according to claim 5, wherein the (ci) nonionic surfactant is a compound represented by the following formula (1), [Chem. 8] CH3-CH(CH3)-CH2 -c(ch3)- 0-(CH2i 0-(CH2CH2〇)sH !)-CsC-C(CH3)~CH2-CH(CH3)-CH3 :CH2〇kH (1) (In the formula, m and n are each independently an integer of 1 or more, and satisfy m + n$50). 8. The chemical mechanical polishing aqueous dispersion according to the first aspect of the invention, further comprising (D1) a water-soluble polymer having a weight average molecular weight of 50,000 or more and 5,000,000 or less. 9. The chemical mechanical polishing aqueous dispersion according to the eighth aspect of the invention, wherein the (D1) water-soluble polymer is a polycarboxylic acid. 10. The chemical mechanical polishing aqueous dispersion according to the ninth aspect of the invention, wherein the polycarboxylic acid poly(indenyl)acrylic acid. 11. The chemical mechanical polishing aqueous dispersion according to the eighth item, wherein the content of the (D1) water-soluble polymer is 〇.嶋% by mass relative to the total mass of the chemical mechanical polishing aqueous dispersion. 1·0 mass%. 12. For the chemical mechanical polishing aqueous dispersion according to the scope of the patent application, wherein the ratio of the long diameter (Rmax) to the short diameter (Rmin) of the above (Α) dioxide is 〇?1^ And /跔111) is 丨^ min; 1 · 5 〇13. The chemical mechanical polishing water dispersion of the patent scope No. 1 is disperse 098104943 86 200944582 body, wherein the above (A) ruthenium dioxide work-A dream The average particle diameter of the particles calculated based on the specific surface area measured by the BET method is 1 G (10) to (10) (10). 14. A chemical mechanical polishing aqueous dispersion according to the first application of the patent scope 1st, wherein the pH is 6 to 12. 15. The chemical mechanical polishing aqueous dispersion according to the first application of the patent scope, wherein the (A) cerium oxide particles have the following chemical properties, according to elemental analysis by ICP luminescence analysis or ICP mass spectrometry The content of sodium, potassium and ammonium ions determined by quantitative analysis of ammonium ions by ion chromatography satisfies the following relationship: sodium content: 5 to 5 ppm, selected from at least 1 of potassium and ammonium ions Species content: 1〇〇~20000 ppm. 16. A chemical mechanical polishing aqueous dispersion comprising (A) cerium oxide particles and (B2) amino acid and used for polishing a copper film, wherein the (A) cerium oxide particles have the following 0〜3. 0个/nm2。 The sulphate base density is 1. 0~3. 0 / nm2. The chemical mechanical polishing aqueous dispersion according to claim 16, wherein the (B2) amino acid is at least one selected from the group consisting of glycine, alanine and histidine. 18. The chemical mechanical polishing aqueous dispersion according to claim 16, which further comprises an organic acid having a nitrogen-containing heterocyclic ring and a carboxyl group. 19. The chemical mechanical polishing aqueous dispersion according to claim 16, wherein the (C2) anionic surfactant is further contained. 098104943 87 200944582 20. The chemical mechanical polishing aqueous dispersion according to claim 19, wherein the above (C2) anionic surfactant has a selected from the group consisting of a slow group, a repeating acid group, a phosphoric acid group, and the functional groups. At least one of the ammonium salt and the metal salt. 21. The chemical mechanical polishing aqueous dispersion according to claim 19, wherein the (C2) anionic surfactant is selected from the group consisting of alkyl sulfates, alkyl ether sulfates, and alkyl ether carboxylates. Alkylbenzenesulfonate, α-sulfonate fatty acid ester salt, alkyl polyoxyethylene sulfate, alkyl phosphate, monodecyl phosphate salt, naphthalenesulfonate, olefin sulfonate, alkane One of a sulfonate and an alkenyl succinate. 22. The chemical mechanical polishing aqueous dispersion according to claim 19, which is used for grinding a copper film, wherein the (C2) anionic surfactant is represented by the following general formula (2). Compound, [Chemical 9] (In the above formula (2), R1 and R2 each independently represent a hydrogen atom, a gold atom or a substituted or unsubstituted alkyl group, and R3 represents a substituted or unsubstituted alkenyl group or a sulfonic acid group (-SOd). Wherein, X represents hydrogen ion, money ion or 098104943 88 200944582 metal ion) 23. The chemical mechanical polishing body of claim 16 which further contains (D2) a weight average molecular weight of i million or more and a knife A water-soluble high score of 10,000 or less having a property as a Lewis test + 50 24. Chemical mechanical polishing as in claim 23 of the patent application. Further, the above (10) water-soluble polymer has at least one molecular structure selected from the group consisting of nitrogen-containing heterocyclic IS ionic sulfonium groups. 25. The chemical mechanical polishing body according to claim 23, wherein the (10) water-soluble polymer contains a (10)-dispersed homopolymer or a nitrogen-containing monomer as a repeating unit; the polymer unit 26 For example, the scope of patent application is 24. Body, wherein the above-mentioned nitrogen-containing monolithic n-machine mechanical phase water dispersion ', is selected from the group consisting of ethylene, piroxime, (methacrylamide, N-methylol propylene amine) olefin Porphyrin, N-Baijiamei _ &-ethyl ethinamide, propane W, N-methylaminopropyl propyl-amine, one of N,N-dimethyl decylamine, ethyl sulphide Acetamide, methyl acrylate N, N-dimethyl isopropyl propyl amide, N-ethylene dibasic acid salt, and N-ethylene thiophene ketone Diethyl sulphate 27. As in the scope of the patent application, the ratio of the dispersion of the chemical mechanical polishing water in the upper paste dioxide (RmaX/RminM [〇~! 5的长#(Rmax) and short diameter (Μη) 28 According to the 16th aspect of the patent application, wherein the above-mentioned (A) chemical mechanical polishing water dispersion 098104943 _ ^ is calculated according to the specific surface area measured by the BET method 89 200944582 is 1 〇 nm ~1〇〇nm. 29·For example, the chemical mechanical polishing water dispersion of the scope of the patent scope is in the range of 6 to 12. 30. The mechanical polishing aqueous dispersion 'where' further the above (A) cerium oxide particles have the following chemical properties, according to elemental analysis by ICP luminescence analysis or lcp mass spectrometry, and quantification of ammonium ions by ion chromatography The content of the sodium, potassium and ammonium ions determined by the analysis satisfies the following relationship: sodium content: 5 to 500 ppm, at least one selected from the group consisting of unloading and recording ions: 100 to 20000 ppm. 31. A method of polishing a surface of a semiconductor device having at least one selected from the group consisting of a metal film, a barrier metal film, and an insulating germanium by using a chemical mechanical polishing aqueous dispersion according to the first aspect of the invention. 098104943 90