TW200837822A - Water-based dispersion for chemical mechanical grinding, chemical mechanical grinding method and kit used for preparing water-based dispersion for chemical mechanical grinding - Google Patents

Abstract

To provide a water-based dispersion for chemical mechanical grinding, a chemical mechanical grinding method and a kit used for preparing water-based dispersion for chemical mechanical grinding, wherein the physical property of insulated layer would not change, and surface imperfection of material coming unstuck or being scratched would not occur, therefore, a grinded surface with high precision could be obtained. A water-based dispersion for chemical mechanical grinding comprises (A)abrasive grain, (B)quinoline carboxy acid and/or pyridine carboxy acid, (C)organic acid other than said (B), (D)oxidation agent, (E)non-ionic surfactant having a triple bond and (F)dispersing medium, and said (A)abrasive grain is a colloidal silica having a average primary particle diameter of 5 to 55 nm and a associated degree of 1.5 to 4.0.

Description

200837822 IX. INSTRUCTIONS OF THE INVENTION: TECHNICAL FIELD The present invention relates to a chemical mechanical honing water dispersion and a chemical mechanical honing method, and a kit for modulating a chemical mechanical honing water dispersion. More specifically, there is a chemical mechanical honing water dispersion and a chemical mechanical honing method using the same, and a set for modulating a chemical mechanical honing water dispersion, the chemical mechanical honing water system The dispersion can be used in the formation step of the copper wiring (the interlayer insulating layer of the two-layer structure of the low dielectric constant insulating layer/high dielectric constant insulating layer formed in the semiconductor device), and can be effectively chemically mechanically honed on the semiconductor substrate. A variety of honed materials are available, and a highly precise finished surface that is sufficiently flattened can be obtained. [Prior Art] In recent years, as the density of semiconductor devices has increased, the wiring formed in the semiconductor device has progressed toward miniaturization. A technique called a damascene method is known, and is a technique capable of making the wiring more fine. In this method, by burying the wiring material in a groove or the like formed in the insulating layer, the necessary wiring is formed by chemical mechanical honing to remove excess wiring material deposited outside the groove. Here, when copper or a copper alloy is used as the wiring material, in order to prevent the copper atoms from moving into the insulator, the interface between the copper or the copper alloy and the insulator is usually formed of giant, arsenic, and nitrided. High-strength high dielectric constant insulating layer (conductive barrier layer). @ _ or copper alloy is used as a wiring material to manufacture a semiconductor device and -6-200837822 When the metal damascene method is used, the chemical mechanical honing method has various methods', but it is preferable to perform a two-stage chemical mechanical honing. The two-stage chemical mechanical honing method includes a first honing step and a second honing step, the first honing step is mainly for removing copper or a copper alloy; and the second honing step is mainly for removing the conductive barrier. Floor. The second honing step may not only remove the conductive barrier layer, but also honing the interlayer insulating layer existing under the conductive barrier layer, thereby achieving high-precision processing with sufficient planarization. surface. In addition, as the fine wiring progresses, the copper wiring width becomes very narrow. When only low-resistance copper wiring is used, sufficient electrical characteristics are not gradually obtained, and a low dielectric constant material having a low dielectric constant is gradually applied ( Low-k material) as a wiring structure of an interlayer insulating layer. In addition, by using a low dielectric constant material having a relative dielectric constant (k) of less than 2.5, the capacitance of the interlayer insulating layer between the copper wirings can be reduced, whereby the electrical characteristics of the copper wiring can be utilized. To the maximum. Further, when a layer is formed using a low dielectric constant material, since a plurality of holes can be formed in the material, the relative dielectric constant of the layer can be adjusted by adjusting the ratio or size of the holes. When the ratio of holes is large, the relative dielectric constant of the layer becomes very low. On the other hand, since the mechanical strength of the material becomes very poor, the resulting layer may not be able to withstand the chemistry. The possibility of the strength of the stress applied during mechanical honing. Further, since the hole ratio of the low dielectric constant insulating layer having holes described above is large, the film is easily damaged by chemical mechanical honing. When the Low-k film is damaged as described above, in the manufacturing step 200837822, such as etching, ashing, or wet cleaning, the number of layers of the dielectric phase is extremely large, and the current is increased. The electric leakage of the junction shape, the leakage of the difference, the difference between the characteristics of the special gas, the semi-layer of the gas conductance, the number of damages, the regularity of the electrical conductivity, the low frequency will make the special, after the gas, the electricity Waiting is not good. According to the above technique, in the second honing step, when a ceria film having a relatively high dielectric constant and a relatively hard cyanide film is used as the interlayer insulating layer, the surface to be honed does not cause surface defects, and a relatively high precision can be obtained. flattened. However, when using a low dielectric constant insulating layer with poor mechanical strength, (i) due to chemical mechanical honing, surface defects may occur on the surface to be flaking, or called scratches; (ii) because of honing In the case of a wafer having a fine wiring structure, the honing speed of the low dielectric constant insulating layer of the honed material is remarkably high, so that a highly processed surface having high flatness cannot be obtained; and (iii) the barrier layer and the low layer The dielectric constant insulating layer has poor adhesion, and the like, and an insulating layer called a cap layer is formed on the upper layer of the low dielectric constant insulating layer (relative dielectric constant ratio low dielectric) The electric constant insulating layer is high and composed of ruthenium dioxide or the like to form a low dielectric constant insulating layer/(upper layer) high dielectric constant insulating layer (relative dielectric constant is lower than low dielectric constant insulating) A method of a two-layered interlayer insulating layer of a high-level insulating layer. The upper dielectric high dielectric constant insulating layer must be quickly removed during chemical mechanical honing, and the honing speed of the lower low dielectric constant insulating layer must be suppressed as much as possible. That is, the honing speed (RR2) of the high dielectric constant insulating layer and the honing speed (RR1) of the low dielectric constant insulating layer are required to have a relationship of RR2 > RR1. When honing the low dielectric constant insulating layer, not only the honing speed is suppressed, but also the physical properties (relative dielectric constant and leakage) of the surface to be honed can be changed without 200837822. With the progress of fine wiring, it must be further reduced. The relative dielectric constant of the low insulating layer is accompanied by the necessity of making the material large. When the hole diameter of the low dielectric constant insulating layer is larger, the insulating layer becomes brittle due to the non-electrical constant, and the chemical mechanical honing has a substance. There is a possibility of change, so there must be a technique that does not change the physical properties of the constant insulating layer and can suppress the honing speed. Thus, since the second honing step is equivalent to the so-called processing in the second honing step' A chemical mechanical honing water system can suppress the peeling or surface of the material generated on the brittle honed surface without changing the physical properties of the honed surface, and can suppress the second honing step. Dielectric constant | The viewpoint of shortening the honing process time must have a degree to the honed surface, but if the honing speed is increased, the brittle honed fabric is peeled off or surface defects. As described above, when a hard coating layer is formed on the upper layer of the low dielectric constant, the cerium oxide film must have a grinding speed. Therefore, in order to obtain a highly precise honed surface, the honing pressure is performed to perform a high dielectric constant insulating layer. The honing, and the honing speed of the high dielectric constant insulating layer and the cerium oxide film to a high honing pressure. In the specific example, Patent Document 1 discloses a honing granule containing an oxidizing agent, In the case of using the honing solution, the honing speed of the insulating layer can be sufficiently obtained, but the low S flow cannot be sufficiently suppressed. The dielectric properties are low dielectrics: steps, dispersions, surface defects, and grinding speed. The g-edge layer, which has a high enthalpy from the sorghum grinding rate, must have a low enthalpy, and even if it can be obtained, it can be obtained by yttrium oxide. The dielectric constant of the group is -9 - 200837822 At the same time, when the above-mentioned coating layer is formed, a sufficient honing speed cannot be obtained for the cerium oxide film, and the honing process time becomes long, and the throughput is lowered. Further, Patent Document 2 discloses a honing composition containing a specific polyether-modified anthrone and various additives, and discloses that by using the honing liquid, the effect of the polyether-modified anthrone can be sufficiently suppressed. The honing speed of the low dielectric constant insulating layer. However, the honing liquid is honed to have a relative dielectric constant of 2.8, a high dielectric constant, a strong mechanical strength, and a material which is not easily changed by physical properties. Therefore, when such a honing liquid is used to honing a low dielectric constant insulating layer having a hole structure in the film (for example, a layer having a relative dielectric constant of 2.4 or less), since not only a low dielectric constant insulating layer but also a low dielectric constant insulating layer is used. It causes mechanical damage and changes the physical properties of the low dielectric constant insulating layer, so it is not suitable as the honing liquid used in the second honing step. [Patent Document 1] JP-A-2000-24 8 2 6 5 [Patent Document 2] JP-A-2000- 1 2 9 6 3 7 SUMMARY OF THE INVENTION In view of the above circumstances, an object of the present invention is to provide A chemical mechanical honing water-based dispersion, a chemical mechanical honing method using the same, and a kit for preparing the above-mentioned chemical mechanical honing water-based dispersion, wherein the chemical mechanical honing water-based dispersion is used for the insulating layer In chemical mechanical honing, the physical properties of the insulating layer are not changed, surface defects such as peeling or scratching of the material are not generated on the surface to be honed, and a highly honed surface to be honed can be obtained. [Means for Solving the Problem] The chemical mechanical honing aqueous dispersion according to the first aspect of the present invention contains -10 200837822 (A) honing abrasive particles, (B) quinolinecarboxylic acid and/or pyridinecarboxylic acid, C) an organic acid other than the above (B), (D) an oxidizing agent, (E) a nonionic surfactant having a triple bond, and (F) a dispersion medium, wherein the average primary particle diameter of the aforementioned (A) honing particles It is a colloidal cerium oxide having a degree of association of 5 to 55 nm and an association degree of 1.5 to 4.0. In the above chemical mechanical honing aqueous dispersion, the aforementioned (D) oxidizing agent is hydrogen peroxide. In the above chemical mechanical honing aqueous dispersion, the (E) nonionic surfactant can be represented by the following general formula (1).

(wherein η and m are each independently an integer of 1 or more and satisfy n + m^50) in the above-described chemical mechanical honing water-based dispersion, wherein the (E) nonionic surfactant is blended with respect to the above The ratio (B/E) of the compound (B) quinolinecarboxylic acid and/or pyridinecarboxylic acid may be 0.01 to 5. In the above-described chemical mechanical honing water-based dispersion in which the conductive barrier layer and the first insulating layer are chemically honed under the same conditions, the honing speed (RB) of the conductive barrier layer and the first insulating layer The honing speed ratio (RB/(Rin-i) of the honing speed (Rln_l} is 1.2 to 4.0. In the above chemical mechanical honing water-based dispersion, in which the same condition is -11-200837822 mechanical honing copper layer When the conductive barrier layer, the first insulating layer, and each layer of the second insulating layer having a higher dielectric constant than the first insulating layer, the honing speed (Rb) of the conductive barrier layer and the 铜 of the copper layer The honing speed ratio (RB/RM) of the grinding speed (RM) is 1.5 or more, and the honing speed ratio of the honing speed (Rln_2) of the second insulating layer to the honing speed of the copper layer (Rm) ( RIn_2/RM) is 0.9 to 2_5, and the honing speed ratio of the honing speed (RIn_2) of the second insulating layer to the honing speed of the first insulating layer (Rln-1) (Rln-2/ is 0.5 to 5) ° In the above chemical mechanical honing water dispersion, in which a water-insoluble matrix material (containing a cross-linked polymer) is used and dispersed in the non-aqueous solution a honing pad of water-soluble particles made of a matrix material, chemically honing a copper layer, a conductive barrier layer, a first insulating layer, and a second insulating layer having a higher dielectric constant than the first insulating layer under the same conditions In each layer, the honing speed (RI η _ 1 ) of the first insulating layer, the honing speed (RB ) of the conductive barrier layer, the honing speed (Rm) of the copper layer, and the second insulating layer The honing speed (RIn_2) of the layer can satisfy Rlnd'RB'RM'Rln-1. The chemical mechanical honing method according to the second aspect of the present invention comprises the following steps: a first honing step, which is a chemical mechanical honing process a stop layer provided on the insulating layer having the recessed portion and embedded in the metal layer of the recessed portion until the stop layer is exposed; and a second honing step using the chemical mechanical honing water-based dispersion to chemical mechanically In the chemical mechanical honing method, the insulating layer contains the insulating layer of i--12-200837822 and has a dielectric constant higher than that of the first insulating layer. a layered body of the second insulating layer' The second honing step is a step of chemically honing the metal layer, that is, the stop layer and the second insulating layer. In the chemical mechanical honing method, the relative dielectric constant of the first insulating layer may be In the above chemical mechanical honing method, the stop layer may be a conductive barrier layer. (The third aspect of the present invention is used to modulate a chemical mechanical honing water dispersion. a mixture (I) and a liquid (11) for modulating the above-mentioned chemical mechanical honing water dispersion, wherein the liquid (I) contains (A) an average primary particle size of 5 to 5 5 nm And the degree of association is 1.5 to 4.0% of the colloidal cerium oxide cerium particles, (B) the quinoline carboxylic acid and/or the pyridinic carboxylic acid, (C) the organic acid other than the above (B), (E) A non-ionic surfactant having a triple bond and (F) an aqueous dispersion of a dispersion medium containing (D) an oxidizing agent. (The fourth aspect of the present invention is a kit for preparing a chemical mechanical honing water-based dispersion, which is a mixture (I) and a liquid (11) for modulating the above-mentioned chemical mechanical honing water-based dispersion. a group, wherein the liquid (I) contains (A) colloidal cerium oxide particles having an average primary particle diameter of 5 to 55 nm and an association degree of 1.5 to 4.0, and (F) aqueous dispersion of a dispersion medium The liquid (11) contains (B) quinolinecarboxylic acid and/or pyridinic acid, (c) an organic acid other than the above (b), (D) an oxidizing agent, and (E) a nonionic having a triple bond. Surfactant. -13 - 200837822 The fifth aspect of the present invention is a kit for preparing a chemical mechanical honing water-based β-steroid, which is a mixed solution (I), a liquid (π), and a liquid (111). a kit for preparing the above-mentioned chemical mechanical honing water-based dispersion, wherein the liquid (I) contains colloidal dioxide having an average primary particle diameter of 5 to 55 nm and an association degree of 1.5 to 4.0. An aqueous dispersion of 硏 硏 abrasive grains and (F) dispersion medium, the liquid (Π) containing (B) quinolinecarboxylic acid and/or pyridine carboxylic acid, and (E) having a triple bond a non-ionic surfactant, and the liquid (III) contains (D) an oxidizing agent. The kit according to the fourth or fifth aspect, wherein the liquid (I) may further comprise (B) quinoline carboxylate. One or more types of components of an acid and/or a pyridine carboxylic acid, (C) an organic acid other than the above (B), (D) an oxidizing agent, and (E) a nonionic surfactant having a triple bond. By chemical mechanical honing of the insulating layer by using the above-mentioned chemical mechanical honing water-based dispersion, the chemical properties of the insulating layer are not changed when the chemical mechanical honing of the insulating layer, and no material is generated on the honed surface. Surface defects such as peeling or scratching, and high-accuracy honed surfaces can be obtained. For example, the chemical mechanical honing water-based dispersion is used to chemically honing an insulating layer having poor mechanical strength (for example, relative dielectric constant) When the insulating layer of 3.5 or less is used as the semiconductor substrate of the interlayer insulating layer, the physical properties of the insulating layer are not changed, surface defects such as peeling or scratching of the material are not generated on the surface to be honed, and high precision can be obtained. Being polished, Further, it is possible to sufficiently suppress the honing speed of the insulating layer. In particular, when the above-described metal damascene-14-200837822 method is subjected to the two-stage honing treatment, the above-described chemical mechanical honing water-based dispersion is used as the second honing step. Further, for example, when the conductive barrier layer provided on the insulating layer is honed, the first dielectric layer having a higher relative dielectric constant than the first insulating layer is provided. In the case of the insulating layer, the physical properties of the insulating layers are not changed, and the surface defects such as peeling or scratching of the material are not caused by the honing surface, and the honed surface with high precision can be obtained. Embodiments of the present invention will be described with reference to the drawings. The present invention is not limited to the embodiments described below, and various modifications may be made without departing from the scope of the invention. 1. Chemical mechanical honing water-based dispersion The chemical mechanical honing water-based dispersion system according to one embodiment of the present invention contains (A) honing abrasive particles, (B) quinolinecarboxylic acid and/or pyridinecarboxylic acid, (C) An organic acid other than the above (B), (D) an oxidizing agent, (E) a nonionic surfactant having a triple bond, and (F) a dispersion medium (hereinafter also referred to as "(A) to (F) components, respectively). ). Hereinafter, each component contained in the chemical mechanical honing water dispersion according to one embodiment of the present invention will be described in detail. 1·1. (A) honing granules (A) colloidal cerium oxide having an average primary particle diameter of 5 to 55 nm and an association degree of 1.5 to 4.0. (A) When the degree of association of the honing particles is less than 1.5, since the component (E) tends to adhere to the (A) honing particles, the honing is suppressed, so that the honing speed of the insulating layer tends to be slow. On the other hand, when (A) the degree of association of the honing particles is more than 4.0, the honing speed becomes too high, and it is impossible to obtain a good honed surface by -15-200837822. (A) The average primary particle diameter of the honing particles can be calculated from the average 値 of the particle diameters of 50 (A) honing particles obtained by observation by transmission electron microscopy. Further, the average secondary particle diameter of the (A) honing particles can be measured by a dynamic light scattering method or a laser scattering diffraction method. Among them, the measurement by the laser scattering diffraction method is relatively simple, and is preferable. Further, (A) the degree of association of the honing particles can be calculated by using the following calculation formula using the average primary particle diameter and the average secondary particle diameter of the (A) honing particles calculated by the above method. The degree of association = (average secondary particle diameter) / (average primary particle diameter) The colloidal cerium oxide can be obtained, for example, by an inorganic colloid method obtained by using a raw material purified in advance. The content of the impure metal of the (A) honing particles is preferably 1 ppm or less, more preferably 5 ppm or less, more preferably 3 ppm or less, and particularly preferably 1 p p or less, relative to the honing particles. Examples of the impurity metal include iron, nickel, and zinc. Further, (A) the degree of association of the honing particles is preferably from 1.9 to 3.8, more preferably from 2.2 to 3.5. Further, (A) the average primary particle diameter of the honing particles is preferably 10 to 45 nm, preferably 15 to 40 nm, more preferably 20 to 35 nm. Further, (A) the average secondary particle diameter of the honing particles is preferably from 60 to 170 nm, preferably from 6 5 to 140 nm, and from 7 to 1 200 nm. good. By using the (A) honing particles having the degree of association, the average primary particle diameter, and the average secondary particle diameter in this range, it is possible to achieve a good balance between the honed surface and the honing speed. Colloidal silica sand with (A) honing particles having an average primary particle size of 5 to 55 nm and an association degree of 1.5 to 4.0 '-16 - 200837822 in honing of honed objects (especially conductive barriers) When the layer and/or the insulating layer are used, a good honed surface and a honing speed can be obtained at the same time. The amount of the (A) honing particles is 0.05 to 10% by mass, preferably 2 to 7% by mass, based on the total amount of the chemical mechanical honing water dispersion. The chemical mechanical honing water-based dispersion of the embodiment is adjusted, for example, by a pH of 7 to 12 (preferably 7.5 to 11), an average primary particle diameter of 5 to 55 nm, and an association degree of 1.5 to 4.0. The (A) honing particles of the colloidal cerium oxide can improve the honing speed of the conductive barrier layer. 1.2. (B) Quinolinecarboxylic acid and/or pyridinecarboxylic acid as quinoline carboxylic acid used as (B) quinoline residual acid and/or pyridyl residual acid (hereinafter also referred to as component (B)) For example, an unsubstituted quinolinecarboxylic acid or a substituted quinolinecarboxylic acid obtained by substituting one or a plurality of hydrogen atoms with a hydroxyl group, a halogen atom or the like at a site other than the carboxylic acid group of D-quinolinecarboxylic acid. The pyridine carboxylic acid may, for example, be an unsubstituted pyridine carboxylic acid or a substituted pyridine carboxylic acid obtained by substituting a hydroxyl group, a halogen atom or the like at a site other than the carboxylic acid group of the pyridine residual acid. Among these, unsubstituted quinolinecarboxylic acid and unsubstituted pyridinic acid are preferred, and 2-quinolinecarboxylic acid (quinolinecarboxylic acid) and 2,3-pyridinedicarboxylic acid (quinoline acid) are used. It is better. Further, the quinolinecarboxylic acid and the pyridinecarboxylic acid may be a residual acid salt obtained by mixing a salt such as a sulfonium salt or an ammonium salt. The compounding amount of the component (B) is preferably 0.001 to 2% by mass, more preferably 0.005 % by mass, based on the total amount of the chemical mechanical honing water-based dispersion of the present embodiment, to 〇·〇1 to 0. · 5 mass% is particularly good. When the amount of the component (B) is less than 0.001% by mass, there is a possibility that a sufficient copper film honing rate cannot be obtained -17-200837822. On the other hand, when the compounding amount of the component (B) is more than 2% by mass, it is not possible to contain other components in accordance with the required blending amount. In the chemical mechanical honing aqueous dispersion of the present embodiment, for example, by adjusting the pH to 7 to 12 (preferably 7.5 to 11) and containing the component (B), the metal layer (especially the copper layer) can be used. The honing speed is controlled to an appropriate range. (C) The organic acid other than the above (B) (C) The organic acid other than the above (B) is preferably an aliphatic organic acid having 4 or more carbon atoms. An aliphatic organic acid having a carbon number of 4 or more is, for example, a carbon number of 4

The aliphatic polycarboxylic acid having 1 or more and the hydroxy acid having 4 or more carbon atoms are preferred. Specific examples of the aliphatic polyvalent carboxylic acid having 4 or more carbon atoms include maleic acid, succinic acid, fumaric acid, glutaric acid, and adipic acid. Specific examples of the hydroxy acid having 4 or more carbon atoms include citric acid, malic acid, and tartaric acid. Among them, an aliphatic organic acid having 4 to 8 carbon atoms is preferred, and an aliphatic organic acid having 4 to 6 carbon atoms is more preferred, and maleic acid, citric acid, and malic acid are preferred. good. & The amount of the organic acid other than the above (B) is preferably 0.005 to 3% by mass, more preferably 0.05 to 2% by mass, based on the total amount of the chemical mechanical honing aqueous dispersion. 0. 1 to 1% by mass is more preferable. 1.4 (D) Oxidizing agent (D) Examples of the oxidizing agent include persulfate, hydrogen peroxide, inorganic acid, organic peroxide, and polyvalent metal salt. Examples of the persulfate include ammonium persulfate and potassium persulfate. Examples of the inorganic acid include nitric acid, sulfuric acid, and the like. The organic peroxide may, for example, be peracetic acid, perbenzoic acid, or t-butyl hydroperoxide. Examples of the polyvalent metal salt include a permanganic acid compound and a dichromated -18-200837822 compound. Specific examples of the permanganic acid compound include potassium permanganate, and the dichromic acid compound may be potassium dichromate. Wait. Among these, 'hydrogen peroxide, persulfate, and inorganic acid are preferred, and hydrogen peroxide is particularly preferred. The amount of the (D) oxidizing agent is preferably 1-5 % by mass based on the total amount of the chemical mechanical honing water-based dispersion, and is preferably 0. 5 to 3 % by mass, preferably 0.0 5 to 1% by mass. 5 mass% is more preferred. 1. (E) A nonionic surfactant (E) having a triple bond, and a nonionic surfactant (hereinafter also referred to as (E) Γ: component) having a triple bond, and examples thereof include the following A compound represented by the formula (1).

H3C—CH—CH2-—C——CEC—c—CH2—CH—CH3 〇-(~CH2CH2〇4—H 〇4cH2CH2〇4-H mx / ni, ····(!) (where, n and m are each an integer of 1 or more, and satisfy n + 5 0). In the above formula (1)', n + m$40 is preferable, and n + mS30 is more preferable. (E) component is commercially available. For example, SARFINOL 440 (HLB値=8), SARFINOL 465 (2,4,7,9-tetramethyl-5-decyne-4,7-diol-dipolyoxyethylene ether, HLB 値= 13), SARFINOL 485 (2,4,7,9-tetramethyl- 5-decyne-4,7-diol-diallyl ether, HLB値=17) (hereinafter, AIR PRODUCTS) The amount of the component (E) represented by the above formula -19-200837822 (1) is preferably 0.001 to 4% by mass, and 0.01 to 2 by mass, based on the total amount of the chemical mechanical honing water-based dispersion. % is more preferably. In the chemical mechanical honing water-based dispersion of one embodiment of the present invention, the ratio of the component (B) is preferably from 0 to 1 to 5, based on the amount of the component (E). Thereby, a high-precision honed surface which does not cause defects in the physical properties of the insulating layer and which can be well flattened can be obtained. (6) Dispersion medium (F) The dispersion medium may, for example, be a mixed medium of water, water and alcohol, and a mixed medium containing an organic solvent containing water and water-compatible with water. It is preferred to use water or a mixed medium of water and alcohol, and it is particularly preferable to use water. 1. Other components The chemical mechanical honing water-based dispersion system according to one embodiment of the present invention contains the above (A) to (() The component F) may contain (G) an anticorrosive agent and (H) a pH adjuster as necessary. (G) The anticorrosive agent may be benzotriazole or a derivative thereof. Here, benzotrien III The azole derivative is one in which one or two or more hydrogen atoms of the benzotriazole are substituted with, for example, a carboxyl group, a methyl group, an amine group, a hydroxyl group or the like. 4-carboxybenzotriazole and its salts, 7-carboxybenzotriazole and its salts, benzotriazole butyl ester, 1-hydroxymethylbenzotriazole or 1-hydroxybenzotriazole, etc. In the total amount of the chemical mechanical honing water-based dispersion, the amount of the (G) anti-corrosion agent is preferably 〇·〇〇5~〇·1% by mass' 0 · 0 1 〇 〇 〇 5 % by mass is more preferable. (H) The pH adjusting agent may, for example, be an organic base or an inorganic or inorganic acid. -20- 200837822 The base may be, for example, tetramethylammonium hydroxide. And triethylamine, etc. The inorganic base may, for example, be ammonia, potassium hydroxide, sodium hydroxide, calcium hydroxide, or magnesium hydroxide. Examples of the inorganic acid include nitric acid, sulfuric acid, hydrochloric acid, and acetic acid. The pH of the chemical mechanical honing aqueous dispersion according to one embodiment of the present invention is preferably 7 to 12, more preferably 7.5 to 11, and even more preferably 7.5 to 10. By the pH in this range, a good balance between the honed surface and the honing speed can be achieved. The amount of the (H) pH adjustment C' and the amount of the agent is preferably 0.005 to 5% by mass, more preferably 0.01 to 3.5% by mass, based on the total amount of the chemical mechanical honing aqueous dispersion. 1 . 8 . A set for dissolving a chemical mechanical honing water-based dispersion The above-described chemical mechanical honing water-based dispersion can be directly supplied in a state capable of being used as a honing composition after preparation. Alternatively, a honing composition (that is, a concentrated honing composition) containing the components of the above-described chemical mechanical honing aqueous dispersion at a high concentration is prepared in advance, and the concentrated honing is used at the time of use. The composition was diluted to obtain the desired chemical mechanical honing aqueous dispersion. I j For example, the above-described chemical mechanical honing water-based dispersion may be separately prepared into a plurality of liquids (for example, two or three kinds of liquids) and prepared in advance, and these plural liquids may be used in combination at the time of use. For example, the above-described third to third sets of groups can be used to prepare the aqueous dispersion for chemical mechanical honing by mixing a plurality of liquids. 1 · 8 · 1 Group 1 The first set of the mixture (I) and liquid (II) is used to prepare the above-mentioned chemical mechanical honing water dispersion. In the i-th set, the liquid (1) contains (A) honing-21 - 200837822 granules (colloidal cerium oxide having an average primary particle diameter of 5 to 55 nm and an association degree of 1.5 to 4.0), (Β) Quinolinecarboxylic acid and/or pyridinecarboxylic acid, (C) an organic acid other than the above (()), (D) an oxidizing agent, a nonionic surfactant having a triple bond, and (F) a dispersion medium The aqueous dispersion, liquid (II) contains (D) an oxidizing agent. When the liquid (I) and the liquid (II) constituting the first set are prepared, the concentration of each component contained in the liquid (I) and the liquid (II) must be determined so that the mixed liquid (I) and the liquid (II) In the obtained aqueous dispersion, each of the above f components is contained in the above concentration range. Further, the liquid (I) and the liquid (11) can also be contained in a high concentration (i.e., can be concentrated), and at this time, the liquid (I) and the liquid can be obtained by dilution. (11). In the first set, the storage stability of the oxidizing agent (D) can be improved by, in particular, separating the liquid (I) and the liquid (II) in advance. When the above-mentioned chemical mechanical honing water-based dispersion is prepared by using the first set, it is sufficient to prepare the liquid (I) and the liquid (11) separately, and to integrate them at the time of honing, the mixing method and the timing. There is no particular limitation. For example, the liquid (I) and the liquid (II) may be separately supplied to the honing device, and the I may be mixed by the turntable, or may be mixed before being supplied to the honing device, or may be mixed in the honing device. Alternatively, a mixing tank may be provided and mixed in the mixing tank. Further, in order to obtain a more uniform aqueous dispersion during mixing of the pipeline, a mixer for the pipeline can also be used. 1·8·2·Second Set The second set of the mixture (I) and the liquid (II) is used to prepare the above-mentioned chemical mechanical honing water dispersion. In the second set, the liquid contains (Α) 硏 abrasive grains (colloidal silica sand with an average primary particle size of 5 to 55 nm and an association degree of ι·5 to 4 )), and (F) dispersion medium. The aqueous dispersion, the liquid (ί) contains (β) -22- 200837822 quinolinecarboxylic acid and/or pyridine carboxylic acid, (C) organic acid other than the above (B), (D) oxidizing agent, and (E) a nonionic surfactant having a triple bond. When preparing the liquid (I) and the liquid (II) constituting the second set, it is necessary to determine the concentration of each component contained in the liquid (1) and the liquid (Π). In the aqueous dispersion obtained in the mixed liquid (I) and the liquid (II), the above-mentioned respective components are contained in the above-mentioned concentration range. Further, the liquid (I) and the liquid (II) can be contained in a high concentration. The component (that is, it can be a concentrated product), in this case, it can be diluted to obtain the liquid (I) and the liquid (II). When the second set is separated, the liquid (I) and the liquid (Π) are separated in advance. 'In particular, it is possible to improve the storage stability of the aqueous dispersion. When the second set of the chemical mechanical honing water dispersion according to one embodiment of the present invention is prepared, In the case of preparing the liquid (I) and the liquid (II) separately, and integrating them during honing, the mixing method and timing are not particularly limited. For example, liquid (I) and liquid (II) may be used. They are separately supplied to the honing device and mixed by the turntable. 'The mixture may be mixed before being supplied to the honing device, or may be mixed in the honing device, or a mixing tank may be provided and mixed in the mixing tank. Further, in order to obtain a more uniform aqueous dispersion during the mixing of the pipeline, a mixer for the pipeline can also be used. 1. 8.3. The third set of the third set is a mixed liquid (I), a liquid (11), and a liquid ( III) A kit for preparing a chemical mechanical honing aqueous dispersion according to an embodiment of the present invention. In the third set 'liquid (I), (a) honing abrasive particles (average primary particle diameter 5 An aqueous dispersion of ~55 nm with an association degree of 1.5 to 4. 胶 colloidal cerium oxide) and (F) dispersion medium, and liquid (II) containing (B) quinolinecarboxylic acid and/or pyridine carboxy- 23- 200837822 Acid, and (E) a nonionic surfactant with a two bond, and liquid (z) contains (D) Oxidizer. When preparing the liquid (1), liquid (π), and liquid (111) of the third set, it is necessary to determine the components contained in the liquid (I), the liquid (II), and the liquid (111). In the aqueous dispersion obtained in the mixed liquid (I), the liquid (H), and the liquid (111), the above-mentioned respective components are contained in the above-mentioned concentration range. Further, the liquid (][), ( 〖), and the liquid (111) can also contain each component at a high concentration (that is, it can be concentrated), and at this time, it can be diluted to obtain a liquid (〗), a liquid (II), And liquid (III). In the third set, the preservation stability of the aqueous dispersion can be improved by separating the liquid (I), the liquid (11), and the liquid (Π) in advance. When the chemical mechanical honing aqueous dispersion according to one embodiment of the present invention is prepared by using the third set, the liquid (1), the liquid (11), and the liquid (I Π ) are separately prepared and supplied. The grinding method may be integrated, and the mixing method and timing are not particularly limited. For example, the liquid (I), the liquid (II), and the liquid (III) may be separately supplied to the honing r device 'and mixed using the turntable', or may be mixed before being supplied to the honing device, or may be honed. The line is mixed in the apparatus, or a mixing tank may be provided and mixed in the mixing tank. Further, in order to obtain a more uniform aqueous dispersion during mixing of the pipeline, a mixer for the pipeline can also be used. Further, the liquid (I) in the second set and the third set may further contain an organic acid selected from the group consisting of (B) quinolinecarboxylic acid and/or pyridinecarboxylic acid, (C) (B), and (D). An oxidizing agent and (E) one or more types of components having a three-bond nonionic surfactant. 1.9. Uses -24- 200837822 ## B月@ - The chemical mechanical honing water dispersion of the embodiment is used as a honing material for chemical mechanical honing of the insulating layer contained in the semiconductor device. For example, in the chemical machine according to one embodiment of the present invention, the 1 jg $ water-based dispersion can be used as a honing material when forming a copper (or copper alloy) damascene wiring by chemical mechanical honing. At this time, the step of forming a copper (or copper alloy) damascene wiring using chemical mechanical honing is constituted by a first honing step and a second honing step, the first honing step is mainly to remove copper (or The second honing step mainly removes the conductive barrier layer formed on the lower portion of the copper (or copper alloy). The second honing step may be performed not only by removing the conductive barrier layer but also by honing the interlayer insulating layer existing under the conductive barrier layer, whereby high precision of sufficient planarization can be obtained. Degree of processing finish. Here, the chemical mechanical honing aqueous dispersion according to one embodiment of the present invention is suitably used as a honing material in the second honing step. By using the chemical mechanical honing water-based dispersion as the honing material in the second honing step, it is possible to exhibit more excellent honing characteristics and an insulating layer (especially an insulating layer having a relative dielectric constant of 3.4 or less). ) low damage. The insulating layer may be a silsesquioxane (relative dielectric constant: about 2.6 to 3.0), a fluorinated SiO 2 (relative dielectric constant: about 3. 3 to 3.5), and a polyfluorene-based resin (relative) Dielectric constant: about 2.4 to 3.6), benzocyclobutene (relative dielectric constant: about 2.7), hydrogen-containing SOG (relative dielectric constant: about 2.5 to 3.5), and organic SOG (relative dielectric constant: about 2.9) Wait. Among these, the interlayer insulating layer containing a bismuth salt as a main component may have a film thickness of 0, 2 to 20 μm, a density of 〇.3 to 1.85 g/cm 3 , and a -25-200837822 A porous insulating layer having fine pores having a pore diameter of 1 ο 0 nm or less. The above-mentioned insulating layer having a relative dielectric constant of 3.5 or less has an elastic modulus of 20 GPa or less, preferably 10 GPa or less, more preferably 5 GPa or less. The elastic modulus of the edge layer can be measured by a rigid measurement method by attaching a BERKOVICH type indenter to a Nanoindentator XP manufactured by MTS Corporation. The chemical mechanical mill aqueous dispersion according to one embodiment of the present invention can be suitably used for the honing of such a brittle insulating layer. Further, the insulating layer can be used as the first insulating layer 2 1 to be described later (see FIGS. 2(a) to 2(C). The chemical mechanical honing water-dispersing body according to an embodiment of the present invention, and the like a non-water-soluble matrix material (containing a cross-linked polymer) and a lining pad of water-soluble particles dispersed in a water-insoluble matrix material to chemically honing the elastic modulus measured by a continuous rigidity measurement method When it is an insulating layer of 20 GP a, it is particularly preferable because it can suppress 5 or less scratches on the surface to be honed. ^ Although it is possible to visually observe the presence or absence of scratches, its size, number, and quantitative The measurement can be performed by observing an image obtained by an optical microscope, a scanning electron microscope, or the like, and analyzing the photographed photograph or the like. It is also possible to measure the surface state by using a specific device for inspecting the surface state. The total number of scratches. In the chemical mechanical honing water-based dispersion of the present embodiment, when the chemical mechanical honing of the conductive barrier layer and the insulating layer is performed in the same strip, the honing speed (RB) of the conductive resist layer and the 绝缘 of the insulating layer The speed (Rm) honing speed ratio (RB/RIn-i) may be 1.2 to 4.0. Thus, for example, the second figure described later is a continuation of 硏眧 y \ \n, the machine is considered to be an equal mirror 5 In the honing shown in (b) -26-200837822 and Fig. 2(c), since the unevenness of the surface to be honed can be minimized, excellent flatness can be obtained and good results can be obtained. For example, when the multilayer wiring including the upper wiring portion and the lower wiring portion is formed by using the chemical mechanical honing aqueous dispersion of the present invention, the upper wiring portion contains an insulating layer and a conductive barrier. When the layer (to cover the surface of the recess provided in the insulating layer) and the conductive layer (the surface of the recess provided in the insulating layer) are embedded, deformation of the upper wiring portion can be suppressed. Further, the chemical mechanical structure of the present embodiment When the water-based dispersion is chemically honed under the same conditions, the copper layer, the conductive barrier layer, the first insulating layer, and the second insulating layer having a higher dielectric constant than the first insulating layer are electrically resistive. Damping speed (R b ) and copper layer The honing speed ratio (Rb/Rm) of the honing speed (RM) is 1.5 or more, and the honing speed ratio (RIn2) of the second insulating layer to the honing speed (RM) of the copper layer (RIn_2) /RM) is 〇·9 to 2.5, and the honing speed ratio (Rin_2/Rin-1) of the honing speed (RIn_2) of the second insulating layer to the honing speed of the first insulating layer (Rln-1) is 〇·5 to 5. By this, for example, in the honing shown in Figs. 2(a) to 2(C) which will be described later, a good honed surface and a honing speed can be obtained. The chemical mechanical honing water-based dispersion of the form is chemically mechanically honed under the same conditions using a lining pad containing a water-insoluble matrix material (containing a cross-linked polymer) and water-soluble particles dispersed in the water-insoluble matrix material. When the copper layer, the conductive barrier layer, the first insulating layer, and each layer of the second insulating layer having a higher dielectric constant than the first insulating layer, the honing speed (Ri^i) of the first insulating layer and the The honing speed (RB) of the conductive barrier layer, the honing speed (Rm) of the copper layer, and the honing speed of the second insulating layer (Rln_2) -27-2008378 22 can satisfy R I η - 2 > R B > R Μ > R I η · 1. Thereby, for example, in the honing shown in FIGS. 2(b) and 2(C) to be described later, the honing of the first insulating layer can be suppressed as much as possible, and the copper layer and the conductive resistance can be selectively removed. The barrier layer and the second insulating layer can obtain a good honed surface and a honing speed. 2. Chemical honing method The chemical mechanical honing method according to an embodiment of the present invention includes the following steps: a first honing step of chemical mechanical honing through a stop layer and an insulating layer having a recess and being embedded in the a metal layer of the recessed portion until the stop layer is exposed; and a second honing step of chemically mechanically honing the metal layer and the stop layer by using the chemical mechanical honing water-based dispersion of one embodiment of the present invention Until the insulating layer is exposed. Hereinafter, a chemical mechanical honing method according to an embodiment of the present invention will be described with reference to Figs. 1 to 3, but is not limited thereto. 2.1. First specific example Fig. 1 (a) to Fig. 1 (c) are schematic cross-sectional views showing a specific example (first specific example) of a chemical mechanical honing method according to an embodiment of the present invention. As shown in Fig. 1(a), the object to be honed la includes a substrate 11, an insulating layer 12 provided on the substrate 11 and including the recess 20, and a metal layer formed by the transmission stop layer 13 being provided on the insulating layer 12. 1 4. Further, the metal layer 14 is buried in the recess 20. Here, the substrate 11 is, for example, a germanium substrate, and the insulating layer 12 may be either an inorganic material or an organic material, and the stop layer 13 and the metal layer 14 are layers having different etching speeds for the honing material, and the metal layer 1 4 can be composed of a metal material that is generally used as a wiring. The insulating layer 12 can be composed of, for example, a -28-200837822 PE TEOS film or an insulating layer having a relative dielectric constant of 3.5 or less, and an insulating layer having a relative dielectric constant of 5.3 or less is preferably 3 or less. The insulating layer is better. Further, the intermediate layer 13 is preferably made of, for example, a conductive barrier layer. Further, the metal layer 14 can be composed of a metal (for example, a metal such as aluminum, copper or gold or an alloy of the above-mentioned metal) which is usually used as a wiring, and copper or a copper alloy is preferable. When the intermediate layer 13 is composed of a conductive barrier layer, it can be composed of, for example, a metal, a metal alloy, and a metal nitride (for example, Ti, TiN, Ta, TaN, and TaNb). Here, the material of the stop layer i 3 is particularly preferably Ta and/or TaN. The stop layer 13 may also have a two-layer structure. First, in the first honing step, the metal layer 14 is chemically honed to the exposed stop layer 13 except for the portion embedded in the concave portion 20 (see Fig. 1(b)). Here, as the honing material, the above-described chemical mechanical honing water-based dispersion may be used, and the first honing water-based dispersion described later may be used. Next, in the second honing step, the chemical mechanical honing aqueous dispersion according to one embodiment of the present invention described above is used, and the residual metal layer 14 and the stop layer 13 are chemically honed to the exposed insulating layer 1 2 . In the above, the portion of the intermediate layer 13 other than the bottom portion and the inner wall surface of the concave portion 20 can be removed. Thereby, the wiring shown in Fig. 1(c) can be obtained. According to this specific example, in the second honing step, the insulating layer 12 is chemically mechanically honed by using the above-described chemical mechanical honing aqueous dispersion, without changing the physical properties of the insulating layer 12. Surface defects such as peeling or scratching of the material are not generated on the surface to be honed, and high-precision honed -29-200837822 surface can be obtained. In particular, the insulating layer 12 is composed of a relative dielectric constant of 3.5. When the following insulating layer is formed, it is extremely useful to prevent the physical properties of the insulating layer 12 from being changed and to prevent the occurrence of the surface defects on the surface to be honed. 2.2. Second Specific Example FIG. 2 ( a) ~ Figure 2 (c) shows the invention modematically A cross-sectional view of another specific example (second specific example) of the chemical mechanical honing method of one embodiment. ^. Fig. 2(a) shows a honing object 2a of the chemical mechanical honing method of the second specific example. In Fig. 2(a), the insulating layer 1 12 includes the first insulating layer 21 and the second insulating layer 22 having a higher dielectric constant than the first insulating layer 21, and the first layer. The structure shown in Fig. (a) has the same structure, and the same components as those of the components shown in Fig. 1(a) are denoted by the same reference numerals. Here, the second insulating layer 2 2 has a function as a cover layer. g. The second insulating layer 2 2 may be, for example, a yttrium oxide film or a yttrium oxide (a boron phosphide glass film (BPSG film) made of a small amount of boron and phosphorus, and a cerium oxide doped with / fluorinated fluorine). A yttria-based insulating layer called FSG (Fluorine-doped silicate glass). The yttrium oxide-based insulating layer may, for example, be a thermal oxide film, Ρ Τ Ε Ο S (plasma enhanced - Τ Ε Ο S film; P 1 asma Enhaced-TEOS film), HDP film (high density plasma reinforced - TE0S film; High Density Plasma Enhace The d-TEOS film), the ruthenium oxide film obtained by the thermal CVD method, etc., that is, the second insulating layer 22 is preferably a hydrophilic surface composed of ruthenium oxide or the like.

The first insulating layer 2 1 is, for example, HSQ -30-200837822 旲 (hydrogen silicate type; Hydrogen Silsesquioxane film) using triethoxy decane as a raw material, tetraethoxy decane and a small amount of methyltrimethoxy A MSQ film (methyl sulphate; Methyl Silsesquioxane film) containing quinone as a raw material, and other sand compound as a raw material film. Further, the first insulating layer 2 1 may be formed by mixing an appropriate organic polymer particle or the like with a raw material, and burning the polymer in a heating step to form a cavity to obtain a film having a lower dielectric constant. Alternatively, the first insulating layer 21 may be an organic polymer such as a polycondensation aryl polymer, a poly(arylene ether) polymer, a polyamidene polymer, or a benzocyclobutene polymer. The first insulating layer 2 1 is preferably an insulating layer having a relative dielectric constant of 3.5 or less, and more preferably an insulating layer of 3.0 or less. In other words, in order to lower the relative dielectric constant of the first insulating layer 21, a layer containing a hydrophobic group functional group such as an alkyl group (methyl group or the like) as a main chain may be used. First, in the first honing step, the metal layer 14 is chemically mechanically honed to the exposed stop layer 13 except for the portion embedded in the concave portion 20 (see Fig. 2(b). Here, the honing material is used. The above-described chemical mechanical honing water-based dispersion or the first honing water-based dispersion described later may be used. Next, in the second honing step, the chemical mechanical raft according to one embodiment of the present invention described above is used. Grinding water dispersion (second honing water dispersion), chemically honing the remaining metal layer 14 , the stop layer 13 , and the second insulating layer 2 2 until the first insulating layer 21 is exposed (refer to Fig. 2(c)) By this, it is possible to remove a portion other than the bottom portion and the inner wall surface of the concave portion 20 in the intermediate layer 13. Thus, the wiring structure shown in Fig. 2(c) can be obtained. 2. According to this specific example, the effect is the same as that of the first specific example described above - 31 - 200837822. In addition, according to this specific example, the second insulating layer 22 is selectively removed by chemical mechanical honing. Therefore, it is possible to reduce the chemical mechanical honing to the first insulating layer 2 1 For example, when the first insulating layer 2 1 contains a layer having a hydrophobic functional group as a main chain, and the second insulating layer 22 has a surface composed of relatively rich hydrophilic sand oxide, The second honing aqueous dispersion honing the first insulating layer 2 1 because the (E) surfactant contained in the second honing aqueous dispersion is a surfactant represented by the above formula (1). Therefore, the hydrophobic portion of the (E) surfactant has a high affinity with the hydrophobic surface of the first insulating layer 21. Therefore, (E) the surfactant is adsorbed on the surface of the first insulating layer 21 to protect the surface. Thereby, it is possible to suppress (A) direct honing of the honing abrasive particles and suppress an increase in the honing speed. 2.3. Third Specific Example FIGS. 3(a) to 3(c) schematically show the present invention A cross-sectional view of another specific example (third specific example) of the chemical mechanical honing method according to one embodiment. Fig. 3(a) shows a honing object of the chemical mechanical honing water-based dispersion of the third specific example. 3a. In Fig. 3(a), a third insulating layer 3 1 is provided in addition to the lower portion of the insulating layer 12. Other than the fourth insulating layer 3 2, the same configuration as the configuration shown in Fig. 1(a), and the same constituent elements as those shown in Fig. 1(a) are denoted by the same reference numerals. The insulating layer 31 is made of, for example, tantalum oxide or the like, and the fourth insulating layer 32 is made of, for example, tantalum nitride. The chemical mechanical honing method of the specific example is the chemical-32- of the first specific example. 200837822 The mechanical honing method is the same. The honing device and the honing condition are the chemical mechanical honing method according to the first embodiment of the present invention. 1 The honing step and the second honing step can be performed using a commercially available chemical mechanical honing device (for example, LGP510, LGP 5 5 2 (above, LAPMASTER-SFT), EPO-112, EPO -222 (above, manufactured by Ebara Seisakusho Co., Ltd.), Mirra (manufactured by APPLIED MATERIALS Co., Ltd.), AVANTI-472 (manufactured by I-PEC Co., Ltd.), etc., and carried out under known honing conditions. Preferably, the honing condition should be appropriately set according to the chemical mechanical honing device used. For example, when the chemical mechanical honing device is used with EP 0-1 12, both the first honing step and the second honing step can be set. For example, the following conditions. Turntable speed: 30~130rpm is better, 40~130rpm is better, rotor speed: 30~130rpm is better, 40~130rpm is better turntable speed/rotor speed ratio: 0.5~2 is better Preferably, the honing pressure is 0.7 to 1.5, preferably 0.5 to 2.5 psi, and 1.0 to 2.0 psi is the preferred chemical mechanical honing water dispersion supply speed: preferably 50 to 300 cc / min. It is preferably 100 to 200 ml/min. 2.5. First honing water-based dispersion, in the first honing water-based dispersion which can be used in the first honing step, in the first to third specific examples, chemically honing the metal layer 14 and under the same conditions In the case of stopping each layer of the layer 13, the honing speed ratio (Rm/Rs) of the honing speed (R s ) of the -33-200837822 having the metal layer 14 and the honing speed (R s ) of the intermediate layer 13 can be used. A chemical mechanical honing water dispersion having a honing characteristic of 50 or more. Here, when the honing speed ratio (RM/RS) is less than 50, after the ith honing step is finished, excess metal remains in the portion where the metal layer 14 should be removed, so that it takes a second honing step. More time, and there is a need for a large amount of processing fluid. The honing speed ratio (Rm/rs) of the first honing water-based dispersion is preferably 60 f or more, more preferably 70 or more. When the honing speed of the first honing water-based dispersion is in the above range, the composition thereof is not particularly limited. For example, the organic medium contains (A) honing particles and (C) organic substances other than the above (B). The acid, the (D) oxidizing agent, the (F) dispersion medium, and the ammonia component selected from at least one of the group consisting of ammonia and ammonium ions are preferred. The (F) dispersion medium used in the first honing water-based dispersion is, for example, the chemical mechanical honing water-based dispersion (second honing water-based dispersion) of the present embodiment described above, and is exemplified as (F) In the case of dispersing a medium, it is preferred to use only water as a dispersion medium. The (A) honing particles used in the first honing aqueous dispersion may be inorganic particles. Examples of the inorganic particles include particles of cerium oxide, aluminum oxide, titanium oxide, chromium oxide, and xenon. The cerium oxide and the cerium oxide particles are preferably used, and cerium oxide is more preferable. Examples of the cerium oxide include cerium oxide synthesized by a vapor phase method of cerium oxide or a sol-gel method, and colloidal cerium oxide. The gas phase ruthenium dioxide can be obtained by reacting ruthenium chloride or the like with oxygen-34-200837822 and water in the gas phase. The silica sand synthesized by the sol-gel method can be obtained by using alkoxy ruthenium compound as a raw material and hydrolyzing and/or condensing. The colloidal cerium oxide can be obtained, for example, by an inorganic colloid method using a pre-refined raw material or the like. (C) The organic acid other than the above-mentioned (B) used in the first honing water-based dispersion, for example, an organic acid which constitutes the component (C) in the second honing water-based dispersion, among these, It is possible to obtain a larger honing speed ratio (RM/Rs) or better than using citric acid and malic acid. (1) The first honing water-based dispersion can further contain (G) an anticorrosive agent, glycine, and alanine. The (G) anticorrosive agent used in the first honing aqueous dispersion can be used in the second Examples of the (G) anticorrosive agent exemplified in the honing water-based dispersion include carboxybenzotriazole. When the first honing aqueous dispersion contains (G) an anticorrosive agent, the first honing is performed. The total amount of the aqueous dispersion is preferably 5% by mass or less, preferably 0. 0.001 to 5% by mass, more preferably 〇〇5 to 1% by mass, and I is 0.0. The (D) oxidizing agent used in the first honing water-based dispersion may, for example, be used as the (D) oxidizing agent in the second honing water-based dispersion, and can be used. At least one type of oxidizing agent, etc., among which hydrogen peroxide or persulfate is preferred, and ammonium persulfate is particularly preferred. The ammonia component contained in the first honing aqueous dispersion can be The presence of ammonia can also be present in the form of ammonium ions, and it is also possible to dope the two. Ammonium ions can The free state exists, and it can also exist as an ammonium salt of an acid, and it can also be doped, and exists in the equilibrium state of -35 - 200837822. Such ammonia and ammonium ion can add ammonia water independently. The first honing water-based dispersion is formed, and it can also be produced from an ammonium salt of an inorganic acid such as ammonium persulfate added as a money salt or an oxidizing agent of the organic acid, or can be used as an anionic interface to be described later. The first honing aqueous dispersion is (A) honing abrasive, (C) an organic acid other than the above (B), (D) an oxidizing agent, and selected from the group consisting of ammonia and ammonium ions.群组 群组 ζ 至少 至少 至少 至少 至少 至少 至少 至少 至少 至少 至少 至少 至少 至少 至少 至少 至少 至少 至少 至少 至少 至少 至少 至少 至少 至少 至少 至少 至少 至少 至少 氨 氨 氨 氨 氨 氨 氨 氨 氨 氨 氨 氨 氨 氨 氨 氨 氨3% by mass, preferably 〇1 to 3 mass%, preferably 0·0 1 to 2 · 5 mass%, and 〇· 〇1 to 2 mass. /. is better. Relative to the first Honing the total amount of water dispersion, (C) blending of organic acids other than (B) above It is usually from 0.01 to 10% by mass, preferably from 1 to 5% by mass. Relative to the total amount of the first honing water-based dispersion, (D) the oxidizing agent is adjusted (the amount is usually 〇·〇1) ～10% by mass, preferably 0.02 to 5% by mass. The amount of the ammonia component is usually 0.005 to 20 m, and 0.01 to 15 mol, based on the total amount of the 1 liter first honing aqueous dispersion. Preferably, it is better to use 〇·〇3~15 mol, and it is especially good for 0.05~10 mol. Brother 1 honing water dispersion can also contain additives such as surfactant and defoamer as necessary. Examples of the surfactant include a cationic surfactant, an anionic surfactant, an amphoteric surfactant, a nonionic surfactant, and a water-soluble polymer. In particular, it is preferred to use an anionic surfactant, and a nonionic-36-200837822 surfactant or a water-soluble polymer. The anionic surfactant may, for example, be a carboxylate, a sulfonate, a sulfate or a phosphate. Examples of the carboxylate include a fatty acid soap and an alkyl ether carboxylate. Examples of the sulfonate include an alkylbenzenesulfonate, an alkylnaphthalenesulfonate, and an α-olefinsulfonate. Examples of the salt include, for example, a higher alcohol sulfate ester salt, an alkyl ether sulfate, and a polyoxyethylene alkylphenyl ether sulfate. Examples of the phosphonium salt include an alkyl phosphate salt. Among these, a sulfonate is preferred, an alkylbenzenesulfonate is more preferred, and a dodecylbenzenesulfonate is particularly preferred. The nonionic surfactant may, for example, be a polyethylene glycol type surfactant, an acetylene glycol, an ethylene oxide adduct of an acetylene glycol, or a nonionic surfactant such as an alkyne alcohol. The water-soluble polymer may, for example, be an anionic polymer, a cationic polymer, an amphoteric polymer or a nonionic polymer. Examples of the anionic polymer include polyacrylic acid and salts thereof, polymethacrylic acid and salts thereof, and polyvinyl alcohol. Examples of the cationic polymer include polyethylenimine and polyvinylpyrrolidone. Examples of the polymer include polypropylene decylamine, and examples of the nonionic polymer include polyethylene oxide and polypropylene oxide. The amount of the surfactant to be added is preferably 20% by mass or less based on the total amount of the first honing aqueous dispersion, and is preferably from 0.oo to 20% by mass, and more preferably from 0.01 to 1% by mass. Good, with 0. 0 5~5 mass% is especially good. The ρ Η of the first honing water-based dispersion can be set to an acidic region, a neutral vicinity region (weakly acidic region to a weakly alkaline region), and any enthalpy of the alkaline region. The pH of the acidic region is preferably 2 to 4, and the ρ 中 in the vicinity of the neutral region is preferably 6 to 8 and the Ρ 碱性 in the alkaline region is preferably 8 to 12 2 . Among these, the pH of the alkaline region is preferably from -37 to 200837822, that is, 6 to 12 is preferred. In the present invention, the same apparatus can be used in the first honing step and the second honing step, and the honing water-based dispersion can be continuously switched in the state in which the object to be honed is attached, and the honing water-based dispersion can be continuously performed. 'The same honing device may be used, and after the first honing step is completed, the object to be honed is temporarily taken out, and the honing water-based dispersion is supplied, and then the removed retanning step is performed to perform the second honing step. . r; Further, the first honing step and the second honing step may be performed using respective honing devices. Further, when a honing device having a plurality of honing pads is used, different types of honing pads can be used in the first honing step and the second honing step, and the first honing step and the second honing step can be used. The procedure uses the same type of honing pad. In the chemical mechanical honing water-based dispersion of the present embodiment, for example, a lining pad containing a water-insoluble matrix material (containing a cross-linked polymer) and water-soluble particles dispersed in the water-insoluble matrix material is used to honing the bedding. When grinding, it is possible to obtain a better honing surface and honing speed, especially when honing the conductive barrier layer or the insulating layer, a very good honing speed can be obtained. In this case, it is possible to prevent fatigue and excessive abrasion, and to use a crosslinked rubber such as 1,2-polybutadiene which has been crosslinked as a water-insoluble matrix material and to use it in order to stably maintain the honing performance. A honing pad made of hydrazine-cyclodextrin as a water-soluble particle is preferred. Such a honing pad may be, for example, a J S R (stock) system or a product number "F P 8 0 0 0". 3. EXAMPLES Hereinafter, the present invention will be described by way of Examples, but the present invention is not limited to the Examples. In the present embodiment, the average primary particle diameter and the average secondary particle diameter of the -38- / 200837822 particles are measured by a laser diffraction method (measurement device, dynamic light scattering type particle distribution measuring device manufactured by Horiba, Ltd.) Product number "HORIBA LB 5 5 0"). 3.1. Preparation of aqueous dispersion containing inorganic particles 3 · 1 · 1 · Preparation of aqueous dispersion containing gas phase cerium oxide In 6 kg of ion-exchanged water, a planetary mixer (trade name TK HABISTISUPERMIX, HDM-3D-20 type, special machine industry (manufactured by the company), while rotating the main rotating shaft at 1 〇 rpm and rotating the auxiliary rotating shaft at 30 rpm (turning blades for mixing, 30 minutes) 6 kg of gas phase ruthenium dioxide (manufactured by Japan AEROSIL Co., Ltd., trade name "AEROSIL #90") was continuously added. Further, the sub-rotation shaft of the torsion blade was rotated at 3 O rpm to make a diameter of 80 mm. The secondary rotating shaft of the COREX type high-speed rotating blade is rotated at 200 rpm, and the main rotating shaft is rotated at 1 rpm for 1 hour. Subsequently, 〇·45 kg of 20% by mass of potassium hydroxide is added. The aqueous dispersion obtained by the aqueous solution was diluted with ion-exchanged water to obtain an aqueous dispersion of silica sand containing a Ci amount of 30% by mass. The aqueous dispersion was filtered using a depth cartridge filter having a pore size of 5 μm. Obtained gas phase cerium oxide Water dispersion of sub-H1 R3. Preparation of aqueous dispersion containing colloidal cerium oxide particles 3.1.2a·Preparation of aqueous dispersion containing colloidal cerium oxide particles C1 Colloidal cerium oxide particles C1 (made by Fuso Chemical Industry Co., Ltd., under the name "colloidal cerium oxide PL-3H") to prepare an aqueous dispersion S 1 containing 25% by mass of colloidal cerium oxide particles C 1 . The colloidal ceria particle C 1 containing the flat-39-200837822 has a primary primary particle diameter of 32 nm, an average secondary particle diameter of 83 nm, and an average degree of association of 2.6. 3.1.2b. Each contains a colloidal The aqueous dispersions S2 to S9, R1 and R2 of the cerium oxide particles C2 to C11 are prepared by the following methods to prepare the aqueous dispersions S2 to S9 containing the colloidal cerium oxide particles C2 to C11 shown in Table 1, R1 and R2 were each used in Examples 2 to 9 and Comparative Examples 1 and 2. A three-capacity tetraethoxysilane and a 1-volume ethanol were mixed to obtain a raw material solution, and pre-mixed ethanol was added to the reaction vessel. A reaction solvent of water and ammonia to fix the water concentration in the reaction solvent to 15% by weight, ammonia concentration Each of them is as shown in Table 1. Further, the concentration of ethanol is the residual enthalpy after removal of water and ammonia, and the temperature of the reaction solvent is kept at 20 ° C while cooling, and the reaction solvent per vol. The solution was added dropwise to the reaction tank at the dropping rate shown in the following table to obtain an alcohol dispersion of colloidal ceria C2 to C1 1. Next, 'the rotary alcohol was used, and the obtained alcohol dispersion was repeated several times. The temperature was maintained at 80 ° C, and the operation of removing the alcohol while adding ion-exchanged water was carried out. By this operation, aqueous dispersions S2 to S9, R1, and R2 containing 25% by mass of the colloidal cerium oxide particles C2 to C11 were prepared. -40^ 200837822 [Table l] Colloidal cerium oxide~Ammonia concentration (% by weight) Drop rate (g/min) C2 0.8 3 0 C3 0.8 50 C4 0.8 45 C5 0.8 55 C6 1.0 5 5 C7 1.0 20 C8 0.6 3 5 C9 0.6 3 5 C10 0.8 80 C 1 1 1 .3 50 3 . 2 . Modification of the first honing aqueous dispersion and its honing performance § 3.2.1. Modification of the first honing water dispersion In 6.7 kg of ion-exchanged water, 2 kg of gas phase cerium oxide particles (manufactured by E. AEROSIL Co., Ltd., trade name "AEROSIL #90", average primary particle diameter of 20 nm) were dispersed using an ultrasonic disperser. This was filtered through a filter having a pore size of 5 μm to obtain an aqueous dispersion containing 23 mass% of gas phase cerium oxide particles. The average secondary particle diameter of the gas phase silica sand particles contained in the aqueous dispersion was 2,200 nm. An aqueous dispersion containing gas phase cerium oxide particles in an amount equivalent to 1% by mass (in terms of cerium oxide) was placed in a polyethylene bottle. This was added in an order of 0.5% by mass of 2-quinolinecarboxylic acid. 0.05% by mass of 2,4,7,9-tetramethyl-5-decyne-4,7-diol-diallyl oxide (manufactured by AIR PRO DUCTS (trade name "SARFINOL 465") And converting hydrogen peroxide to 30% by mass of hydrogen peroxide water of 〇·1 mass%, and stirring for 15 minutes. Subsequently, the first honing aqueous dispersion was obtained by filtering to pH 9.5 with 1 equivalent of an aqueous potassium hydroxide solution, followed by filtration using a filter having a pore size of 5 μm -41 - 200837822. 3 · 2.2. Evaluation of the honing performance of the first honing water-based dispersion The ramming pad made of foamed polyurethane was installed in a chemical mechanical honing device (manufactured by APPLIED MATERIALS, "Mirra") NITta, HASS (manufacturing system, product number "ic 1"), while supplying the chemical mechanical honing water-based dispersion, the following honing speed measuring substrates are subjected to the following honing conditions. The chemical mechanical honing treatment was carried out for 1 minute, and the honing speed was calculated by the following method. I. 硏 速度 速度 • • 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 Copper-clad film wafer"): 8-inch thermal-coated oxide substrate made of a nitride film (corresponding to the stop layer (conductive barrier layer) of the present invention) having a thickness of 300 Å ("3 000A Nitrided Giant Film Wafer" manufactured by WAFERNET Co., Ltd.) - 8 inch substrate made of BD film (corresponding to the first insulating layer of the present invention) having a thickness of 1 000 A (atdf company) "1000 〇 覆 覆 b 」 」 」 」 」 」 」 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 0000A coated TEOS film wafer") II. Honing conditions • Turning revolutions: 13Q]: Pm • Platen revolutions: 13Gfpm -42- 200837822 • Rotor load: 1.5psi • Chemical mechanical honing water dispersion Feeding speed: 200 ml/min III. Calculation of honing speed For the copper film and the nitriding giant film, an electrically conductive film thickness measuring device (KLA-T) was used. The ENCOR (stock) system, the form "OMNIMAPRS75") measures the film thickness after honing, and calculates the honing speed from the film thickness and honing time reduced by chemical mechanical honing. For the PETEOS film, the film thickness after honing treatment was measured using a light interference film thickness measuring device (NANOMETRICS JAPAN, model "Nanospec 6100"), and the film thickness and honing reduced from chemical mechanical honing. Time to calculate the honing speed. IV. Honing speed • Metal layer (copper) honing speed (Rm): 5 5 00 A/min • Honing speed (RB) of conductive barrier layer (titanium nitride layer): 30 A/min • Insulation Honing speed (RIn) of (PETEOS film): 40 A/min 3.3. Example 1. 3.3.1 Preparation of the second honing water-based dispersion (the chemical mechanical honing water-based dispersion of the present invention) An aqueous dispersion containing colloidal cerium oxide particles C 1 prepared by converting the above-mentioned "3.1.2 a. Preparation of an aqueous dispersion containing colloidal cerium oxide particles" of cerium oxide equivalent to 4% by mass, and adding polyethylene In the bottle, (E) a nonionic surfactant (2,4,7,9-tetramethyl-5-decyne-4,7-diol-diallyl vinyl ether (11 +) was added in order. 111=1〇) (eight 111?11〇〇1; (: Ding 8 JAPAN (share) system, trade name "S ARFINOL 4 6 5")), (B) quetiapyridine carboxy-43 - 200837822 acid (2, 3 -pyridinedicarboxylic acid), (C) an organic acid (maleic acid) other than the above (b), and (D) an oxidizing agent (30% by mass of hydrogen peroxide equivalent to 3 mass% of hydrogen peroxide) Water) and stir for 15 minutes Then, 0.98 mass% (H) of a pH adjuster (potassium hydroxide) was added, and the aqueous dispersion was adjusted to pH 9.0. Then, ion exchange water was added in such a manner that the total amount of the total constituents was 100% by mass. Thereafter, the second honing aqueous dispersion S 1 was obtained by filtration through a filter having a pore size of 5 μm. The blending amount of each component in the second honing aqueous dispersion S 1 is shown in Table 2. rk 3 ·3·2·Evaluation of the honing performance of the second honing water-based dispersion. The chemical mechanical honing device (manufactured by APPLIED MATERIALS, type "Mirra") was installed to disperse water-soluble particles ($-cyclodextrin). A honing pad (JSR (stock system, product number "FP 8000") made of a water-insoluble matrix (1,2-polybutadiene) which has been crosslinked, and supplied to the above-mentioned chemical mechanical honing water system The dispersion was subjected to chemical mechanical honing for the following various honing conditions for one minute, and the honing speed was calculated by the following method. ^ I·Thining speed measuring substrate • a copper film having a thickness of 15,000 A (corresponding to the metal layer of the present invention) 8 inch thermal-coated oxide substrate • substrate; laminated film with a thickness of 200,000 molybdenum nitride film (corresponding to the stop layer (conductive barrier layer) of the present invention)矽Substrate • 8 Å substrate made of PETEOS film (corresponding to the second insulating layer of the present invention) having a thickness of 1 0000 A. • 44-200837822 Black Diamond process developed by APPLIED MATERIALS JAPAN AG (black) Diamond process), a first insulating layer (BD film) with a laminated film thickness of 4000 A (relative dielectric constant k = 2.8); 8 mm substrate; laminated film thickness of MSQ type developed by JSR AG 5000A The first insulating layer (LKD film) (relative dielectric constant k = 2.3) is made up of 8 inches of substrate II. Honing conditions • Number of revolutions: 1 3 0 rpm • Platen revolutions: 1 30 rpm • Turn Head load: 1.5 psi • Supply rate of chemical mechanical honing water dispersion: 200 ml/min III. Calculation of honing speed For copper film and molybdenum nitride film, an electrically conductive film thickness measuring device (KLA- TENCOR (share) system, the form "Ο Μ N IM APRS 7 5") after the honing treatment The film thickness, polishing rate was calculated from the chemical WH WH mechanical grinding to reduce the film thickness and the grinding time WH. For the PETEOS film, the BD film, and the LKD film, the film thickness after the honing treatment was measured using a light interference film thickness measuring device (NANOMETRICS JAPAN, model "Nanospec 6 1 00"), and chemical mechanical honing was performed. The honing speed was calculated from the reduced film thickness and honing time. IV. Honing speed • Metal layer (copper) honing speed (Rm): 2 5 0A/min • Honing speed (RB) of conductive barrier layer (nitride layer): 8 00A/min • 2nd Honing speed (RIn_2) of insulating layer (PETEOS film): 3 8 0A/min -45- 200837822 • Honing speed (Rmn) of the first insulating layer (BD film): 170 A/min • 1st insulating layer ( Honing speed of LKD film (Rm-O: 190 A/min V. Method for evaluating the number of scratches of the first insulating layer) The outer peripheral portion of the first insulating layer after honing was observed by a visual observation and an optical microscope. Using the unpatterned wafer defect inspection device (KLA-TENCOR Co., Ltd., format "KLA23 5 1"), the number of defects averaged by the honing surface was measured to calculate the number of scratches. The result was referred to as "the number of scratches of the first insulating layer". Further, as shown in Table 2. Further, the wafer defect inspection device calculates the object as a defect, and examples of the scratched object include, for example, adhered dust, spots generated by wafer fabrication, and the like. "Method for evaluating the number of scratches in the first insulating layer", the inspection parameters of the defect inspection device are as follows • Check field of view: Bright field of view • Check wavelength: visible light • Pixel size: 〇. 3 9 • Critical 値 (defect detection sensitivity): 5 0 VI· concave distortion honing (dishing) and evaluation of scratches. (i) In the manufacture of the substrate for honing in which the copper wiring is formed, a 5000A insulating layer (PETEOS film (thickness 5 〇〇 A)) having a pattern of a plurality of grooves having a depth of 1 μm is laminated on the surface of the substrate formed of ruthenium. a composite film of BD film (45 00A). Next, a conductive barrier layer (TaN film) having a thickness of 25 A was formed on the surface of the insulating layer, and then, in the groove covered by the TaN film, sputtering and sputtering were used. Plating method to deposit a metal layer (C u layer) having a thickness of 1.1 μm. -46- 200837822 (ii) Evaluation after the first honing step For the wafer manufactured by the above (i), use "3.2. 1) The first honing water-based dispersion prepared by the preparation of the first honing water-based dispersion was honed at a honing speed of 5,500 Å for 2.25 minutes. After the first honing step, a stylus type differential meter was used ( KLA-TENCOR (share) system, the form "HRP240") to evaluate the width of the honed surface is 1〇〇 In the case of the concave twist honing of the micro-wiring, it is 400. Here, the "concave twist honing" means the upper surface of the wafer (the plane formed by the insulating layer or the conductive barrier layer) and the wiring portion. The distance between the lowest part (the height difference). (iii) Evaluation after the second honing step The aqueous dispersions of Examples 1 to 9 and Comparative Examples 1 to 3 were used for the wafer produced in the above (ii), in accordance with The time calculated by the following formula is honed. Honing time (minutes) = {(thickness of barrier layer (A) + (Immediate barrier layer I calculated in "3.3.2. Evaluation of honing performance of second honing water dispersion" The honing speed of the chemical giant) + (the thickness of the first insulating layer (50 〇 A)) + (calculated in the above "3 · 3 · 2 · evaluation of the honing performance of the second honing water-based dispersion" The honing speed of the first insulating layer (PETEOS)) + (the thickness of the second insulating layer (200 persons)) + (In the above-mentioned "3.3.2. Evaluation of the honing performance of the second honing water-based dispersion" The honing speed of the second insulating layer (BD) is calculated.} The honed surface is evaluated by a stylus type differential meter (KLA - TENC 0 R (form) "HRP240"). A concave twist honing of the width of the 10 () micron wire in the face. The results are shown in Table 2. Here, "concave twist honing" means the distance (height difference) between the upper surface of the wafer (the plane formed by the insulating layer -47-200837822 or the conductive barrier layer) and the lowest portion of the wiring portion. In addition, in the field of the unpatterned field (field area larger than 120 micrometers by 120 micrometers), a light interference type film thickness measuring device (NANOMETRICS JAPAN, type "Nanospec 6100") is used. When the film thickness after the honing treatment was measured and the film thickness decreased from the initial film thickness of 50,000, the water dispersions of Examples 1 to 5 and Comparative Examples 1 and 2 were all 7 5 0 to 900A. Further, an optical microscope was used to observe 200 portions of the copper wiring portion in a dark field with a region of 120 μm x 20 μm, and the number of unit regions where scratches occurred was measured as "the number of scratches of the copper wiring". The results are shown in Table 2. VII. Elastic modulus of the first insulating layer The BERKOVICH type indenter was mounted on a Nanoindentator XP manufactured by MTS Co., Ltd., and the elastic modulus of the first insulating layer was measured by a continuous rigidity measurement method. The results are as follows. • Elastic modulus of the first insulating layer (BD film): 4.5 GP a • Elastic modulus of the first insulating layer (LKD film): 3.0 GPa 3.4. Examples 2 to 9 and Comparative Examples 1 to 3 In Example 1 The same procedure as in Example 1 was carried out except that the type and amount of each component of the chemical mechanical honing water-based dispersion, the p Η of the aqueous dispersion, and the honing pad used were as described in Table 2. mill. Further, the honing pad used in Examples 5 to 7 is a hard foaming polyurethane honing pad (ΝΙΤΤΑ·HASS (shares), trade name number "IC1000", Shi-48-200837822 Example The honing mats used in 8 and 9 (manufactured by NITTA, HASS, and the trade name number, except for chemical mechanical honing; the respective aqueous dispersions S2 to S9 and the system were evaluated in the same manner as in Example 1. The urethane pad "Politex" is used. The under-dispersion system uses the above-mentioned R1 to R3 instead of S1, and the results are shown in Table 2. -49- 200837822 i [CN« 镒CO gas phase Germanium dioxide (HI) 1 o (N • ΓΟ 2,3 pyridine dicarboxylic acid ο maleic acid hydrazine hydroperoxide 〇 SARFINOL 485 oi; secret Ο < I FP8000 1 in m m rs o ON o m oo o o IT) g tr> (N m 镒 ΛΛ (N colloidal cerium oxide (C11) U^) <N Os csi m 2,3 pyridine dicarboxylic acid sd maleic acid 〇 \ 〇 hydrogen peroxide water m ο SARFINOL 485 (N os ampoule FP8000 | 00 (N inch 卜gp (N 〇\ om 'O ΓΟ g rn iT) S mi 镒Jj S Colloidal cerium oxide (C10) yn m On VO uo (N 2,3 pyridine dicarboxylic acid ο ο succinic acid On 〇 hydrogen peroxide water m ο SARFINOL 485 (N o cut m os | FP8000 | <N inch 00 Bo Bo Co OO S r- o oo o 00 i〇 o g o (N 卜 wo <N os series m a colloidal cerium oxide (C9) ^r> 00 <N On (N 2,3 pyridine dicarboxylic acid s ο maleic acid ο hydrogen peroxide water m ο SARFINOL 485 (N mft an m _ On Politex (N δ m oo ms two oo tr> o On Cn G\ rn ^sO o § ΓΠ rn o — 〇 (N Example 8 i 00 CO colloidal cerium oxide (C8) ΓΛ P; oo (N-inch 2-quinolinecarboxylic acid s ο succinic acid ο hydrogen peroxide water m ο SARFINOL 485 CN d Secret _ oo 00 Politex 1 On S vo mmmg oo o CN Os fN g rn § oo rn two rn — — 〇 <N (N ub U 00 colloidal cerium oxide (C7) in 〇 〇 0 〇 s 2-quinoline carboxylic acid s ο maleic acid ΟΝ ο hydrogen peroxide 永 m ο SARFINOL 485 so secret 00 1 iciooo | fN m 〇 <N U^) U-) (N 3 (N inch inch s <N o <n (N oo <N m series s colloidal cerium oxide (C6) (X oo 卜 cn 2-quinoline carboxylic acid s ο glutaric acid yn ο hydrogen peroxide water <N SARFINOL 465 (N 跋 Jii _ ON I iciooo 1 Bu <N m ON <N inch o 宕 (N S A OS 〇 oo m <N rs CN (N 卜m grip K in oo colloidal cerium oxide (C5) (N mo rn (N 2,3 pyridine dicarboxylic acid oo fumaric acid ο hydrogen peroxide water O SARFINOL 485 |駄嘁ιέ Q\ | ICIOOO sm oo inch V"» s <NA \〇\ vq oo IT) On ? rn uo m inch m series W colloidal cerium oxide (C4) i/Ί cn IT) ON t> rs 2,3 pyridine dicarboxylic acid s ο succinic acid οο ο Hydrogen peroxide water mo SARFINOL 485 o 跋m inch On I FP8000 | oa O JO 〇s cs £ cs yr> K (N MD oo m vq rN — § mm series U Ώ colloidal cerium oxide (C3) (N - oo m 2,3 pyridine dicarboxylic acid ο citric acid U-) ο hydrogen peroxide water o SARFINOL 465 som CN Os I FP8000 | (N 'sO oo m ON m $ CN in SSS et o CO o (N (N IK colloid) Cerium oxide (C2) ON (N m <N m 2,3 pyridine dicarboxylic acid s ο malate 苹果 Ο hydrogen peroxide water o SARFINOL 485 om oo oo FP8000 〇m Os CN inch S (N inch · OO oo r4 (N o CN m (N - — Oo (N ί Wei Wei colloidal cerium oxide (C1) <N m ΓΟ oo 'O (N inch 2,3 pyridine dicarboxylic acid s ο maleic acid Ον Ο peroxidation 1 hydrogen water m o SARFINOL 485 CN o δ Jiff FP8000 s; <N call inch (N (N inch On inch On r- r4 - <N slave s Φ * name i piece gs 1 to g 11 4〇fil _ » g « type 1» m type S Μ m type winter h ft mm type ft mm type Sao.0 mm K frost mmmmsm teng m ω &amp m variable Q DQ § 1 • 0 2 : i : § .S ά s PQ ί s ; S r — H > csi ώ '2 'S mg 幽 , S x — ^ i _ Avoid : S ; < c 瘛 [Ο : 〇 (A) 硏 趦愁荽 趦愁荽 mu mu a (C 洧 acid (9) oxidant 4 ± ti barrier - I s fe HlB nn] (2n g (Η) ΡΗ adjust agent to do a $ ί 丨g • si $ < £ a | s ά 2 1 ί 2 ά ea S CN 1 征, 超mm; ^13⁄4 丨 07 .200837822 According to Table 2, it is known that the chemical mechanical honing water dispersion is used by using Examples 1 to 9. When the body is subjected to chemical mechanical honing of the insulating layer formed on the semiconductor substrate, the abrasion and concave distortion of the honed surface can be greatly suppressed, and the relative dielectric constant of the insulating layer is not greatly changed. Moreover, the above-mentioned insulating layer is not excessively honed, and the honed surface having the accuracy of the cylinder can be sufficiently flattened. In contrast, when the chemical mechanical honing aqueous dispersions of Comparative Examples 1 to 3 were used, large concave distortion honing occurred after honing. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 (a) to Fig. 1 (c) are schematic views showing a specific example of the chemical mechanical honing method of the present invention. Fig. 2 (a) to Fig. 2 (a schematic view showing another specific example of the chemical mechanical honing method of the present invention. Fig. 3 (a) to Fig. 3 (the chemical mechanical honing of the present invention) A schematic diagram of another specific example of the method. [Description of component symbols] 1, 2, 3 wiring structure la, 2a, 3 a honing object 11 substrate (for example, 矽) 12 insulating layer (for example, PETEOS film, or relative media Insulation layer having an electric constant of 3.5 or less) 13 Stop layer (for example, barrier layer) 14 Metal layer 20 Concave portion - 51 - 200837822 21 First insulating layer (for example, insulating layer having a relative dielectric constant of 3.5 or less) 2 2 Second insulating layer Layer 3 1 third insulating layer (for example, tantalum oxide) 32 fourth insulating layer (for example, tantalum nitride) 112 insulating layer

-52 -

Claims (1)

200837822 X. Patent application scope: 1. A chemical mechanical honing water dispersion containing (A) honing abrasive particles, (B) quinoline carboxylic acid and/or pyridine carboxylic acid, (C) other than the above (B) An organic acid, (D) an oxidizing agent, (E) a nonionic surfactant having a triple bond, and (F) a dispersion medium, wherein the (A) honing particles have an average primary particle diameter of 5 to 55 nm and are associated with each other. A colloidal cerium oxide having a degree of combination of 1.5 to 4.0. 2. The chemical mechanical honing water dispersion according to claim 1 of the patent scope, wherein the (D) oxidant is hydrogen peroxide. 3. The chemical mechanical honing water-based dispersion according to claim 1, wherein the (E) nonionic surfactant is represented by the following general formula (1): 0 ch3 ch3 ch3 ch3 h3c-ch-ch2 —ς—c three c—c—ch2—ch—ch3 〇-fcH2CH2〇)^-H 0 plus 2〇120七11 (l) (where n and m are each an integer of 1 or more, and satisfy n + m $ 50). 4. The chemical mechanical honing water-based dispersion according to claim 1, wherein the (B) quinolinecarboxylic acid and/or pyridinecarboxylic acid is relative to the (E) nonionic surfactant. The ratio of the blending amount (B/E) is 0.01 to 5. -53 - 200837822 5 - The chemical mechanical honing water-based dispersion according to any one of claims 1 to 4, wherein the conductive property is honed by the chemical mechanical honing of the conductive barrier layer and the insulating layer under the same conditions The ratio of the honing speed (Rb) of the barrier layer to the honing speed of the insulating layer (RB/(Rin i) is 1 · 2 〜 4 · 0 〇 6 · as in the scope of claims 1 to 4 Any one of the chemical mechanical honing water-based dispersions wherein the chemical layer honing the copper layer, the conductive barrier layer, the first insulating layer, and the second insulating layer having a higher dielectric constant than the first insulating layer In each layer of the layer, the honing speed (rb) of the conductive barrier layer and the honing speed ratio (rb/Rm) of the honing speed (Rm) of the copper layer are 1.5 or more, and the second insulating layer is honed The honing speed ratio (11111_2/111^) of the speed (R ! n _ 2 ) to the honing speed (1^) of the copper layer is 0.9 to 2.5, and the honing speed (RIn_2) of the second insulating layer is The honing speed ratio (Rin_2/RIn-1) of the first insulating layer is 0.5 to 5. 7 - The chemical machine according to any one of claims 1 to 4 A water-based dispersion in which a copper layer including a water-insoluble matrix material containing a cross-linked polymer and water-soluble particles dispersed in the water-insoluble matrix material is used to chemically honing a copper layer and conduct electricity under the same conditions. When the barrier layer, the first insulating layer, and each layer of the second insulating layer having a higher dielectric constant than the first insulating layer, the honing speed (Rln_l} of the first insulating layer, and the conductive barrier layer The honing speed (RB), the honing speed (Rm) of the copper layer, and the honing speed (Rm·2) of the second insulating layer are over $ RlnjSRBSRMSRln-l. 8 · A chemical mechanical honing method The method includes the following steps: -54-, 200837822 a first honing step, wherein the chemical mechanical honing is performed on the insulating layer having the concave portion and embedded in the recessed portion of the concave portion; and the second honing step is performed The chemical mechanical honing water dispersion according to any one of the patent applications, the metal layer and the suspension layer are exposed to the insulating layer. 9. The chemical mechanical honing of the eighth aspect of the patent application includes the first layer. Insulating layer, and second insulating layer with high dielectric layer The layered body, and the second honing step is chemical mechanical honing of the layer and the second insulating layer. 10. The relative dielectric constant of the chemical mechanical honing 1 insulating layer according to claim 9 5.3 or less. 1 1. The method of any one of claims 8 to 10 wherein the suspension layer is a conductive barrier layer. 1 2 · A method for modulating chemical mechanical honing water dispersion ( Liquid (I) and liquid (II) for modulating the chemical mechanical honing water according to any one of the patent applications. Dispersing Yanhai's liquid (I) contains (A) an average primary particle size of 5 degrees 1.5 to 4.0 colloidal cerium oxide cerium abrasive grains or ceramide carboxylic acid, (C) organic acid nonionic surfactant other than (B), and (F) dispersion medium 5 stomach 'liquid (II ) contains (D) an oxidizing agent. 1 3 · A metal layer used to modulate the chemical mechanical honing water to disperse the discontinuous layer, up to the first to seventh ranges of this range, to chemical mechanical 硏. The method, wherein the constant is greater than the first semi-metal layer, the suspension method, wherein the first chemical mechanical honing body set is a set of the first to seventh body, wherein ～5 5 nm and a mixture of (B) quinoline carboxylic acid and (E) a two-component dispersion having a triple bond, a mixture of -55 - .200837822 combined liquid (I) and liquid (II), used to prepare The chemical mechanical honing water dispersion according to any one of claims 1 to 7, wherein the liquid (I) contains (A) an average primary particle diameter of 5 to 55 nm and an association degree An aqueous dispersion of colloidal cerium oxide of 1.5 to 4.0 and (F) an aqueous dispersion of a dispersion medium containing (B) quinolinecarboxylic acid and/or pyridinecarboxylic acid, (C) An organic acid other than (B), (D) an oxidizing agent, and (E) a nonionic surfactant having a triple bond. C: 1 4 . A kit for preparing a chemical mechanical honing water dispersion, which is a mixture (I), a liquid (II) and a liquid (ΙΠ) for modulating the first to seventh ranges as claimed in the patent application. The chemical mechanical honing water-based dispersion of any one of the items, wherein the liquid (I) contains (A) colloidal dioxide having an average primary particle diameter of 5 to 55 nm and an association degree of 1.5 to 4_0. An aqueous dispersion of cerium lanthanum and (F) dispersion medium, ^ This liquid (II) contains (B) quinolinecarboxylic acid and/or pyridinecarboxylic acid, and (E); a surfactant, and the liquid (ΠΙ) contains (D) an oxidizing agent. 1 5 . The kit for modulating the aqueous dispersion of chemical mechanical honing according to claim 13 or 4, wherein the liquid (I) further comprises (B) quinolinecarboxylic acid and/or a pyridinium carboxylic acid, (C) an organic acid other than the (B), (D) an oxidizing agent, and (E) a component having one or more types of a triple bond nonionic surfactant. -56 -