JP2006352096A - Chemical mechanical polishing aqueous dispersion, chemical mechanical polishing method, and kit for preparing chemical mechanical polishing aqueous dispersion - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a chemical mechanical polishing aqueous dispersion in which occurrence of scratch and peeling, etc. in a semiconductor substrate to-be-polished is reduced even when the semiconductor substrate which has a low dielectric constant material having low mechanical strength as an insulating film is chemically and mechanically polished. <P>SOLUTION: The chemical mechanical polishing aqueous dispersion includes: (A) inorganic particles; (B) at least one type of particles selected from the group consisting of organic particles and organic-inorganic composite particles; (C) at least one selected from the group consisting of quinolinecarboxylic acid, quinolinic acid, a divalent organic acid (excluding quinolinic acid), and a hydroxyl acid; (D) at least one selected from the group consisting of benzotriazole and benzotriazole derivatives; (E) an oxidizing agent; and (F) water. The chemical mechanical polishing aqueous dispersion contains the component (A) in an amount of 0.05 to 2.0 mass% and the component (B) in an amount of 0.005 to 1.5 mass%, has a ratio (W<SB>A</SB>/W<SB>B</SB>) of the amount (W<SB>A</SB>) of the component (A) to the amount (W<SB>B</SB>) of the component (B) of 0.1 to 200, and has a pH of 1.0 to 5.0. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a chemical mechanical polishing aqueous dispersion, a chemical mechanical polishing method, and a kit for preparing a chemical mechanical polishing aqueous dispersion.

  More specifically, it is an aqueous dispersion for chemical mechanical polishing used in the manufacturing process of a semiconductor device, and each of various materials to be polished provided on a semiconductor substrate can be chemically mechanically polished with high efficiency. And a chemical mechanical polishing aqueous dispersion capable of obtaining a sufficiently flat and highly accurate finished surface, a chemical mechanical polishing method using the same, and a kit for preparing the chemical mechanical polishing aqueous dispersion .

  In recent years, with the increase in the density of semiconductor devices, miniaturization of formed wirings has progressed. As a technique that can achieve further miniaturization of the wiring, a technique called a damascene method is known. This method is a method of forming a desired wiring by embedding a wiring material in a groove or the like formed in an insulating material and then removing excess wiring material deposited other than the groove by chemical mechanical polishing. Here, when copper or a copper alloy is used as a wiring material, tantalum or tantalum nitride is usually used to avoid migration of copper atoms into the insulator at the interface between copper or the copper alloy and the insulator. A barrier metal film made of titanium nitride or the like is formed.

  When the damascene method is employed in the manufacture of a semiconductor device using copper or a copper alloy as a wiring material, there are various chemical mechanical polishing methods. The first polishing process step mainly removes copper or the copper alloy, and mainly the barrier. Two-stage chemical mechanical polishing comprising a second polishing treatment step for removing the metal film is preferably performed.

  Here, in the second polishing treatment step, in order to obtain a highly flat surface to be polished by correcting concave surface defects such as dishing and erosion that occur in the wiring portion in the first polishing treatment step. In addition to removing the barrier metal film other than the wiring portion, the insulating film exposed after removing the barrier metal film is slightly polished. At this time, in addition to the insulating film, in the wiring portion, copper or copper alloy as a wiring material and a barrier metal film formed between the wiring material and the insulating film are simultaneously subjected to chemical mechanical polishing.

  Therefore, in order to obtain a sufficiently flat finished surface with high accuracy, the chemical mechanical polishing aqueous dispersion used in the second polishing process is made of copper or a copper alloy, a barrier metal film, and an insulating film. It is desirable that the removal rates are equal.

Under such a purpose, JP 2001-196336 A discloses an aqueous dispersion for chemical mechanical polishing containing an abrasive, an oxidizing agent, and a specific polishing rate adjusting agent. , the ratio _R Cu _{/ R BM} of the polishing rate _{R BM} of the polishing rate _{R Cu} and the barrier metal film of copper film is 0.66 to 1.11, the polishing speed _{R an in} the polishing rate _{R Cu} and the insulating film of the copper film The two-stage polishing is performed using the chemical mechanical polishing aqueous dispersion having a ratio R _Cu / R _In of 0.72 to 1.42 in the second polishing treatment step.

  Conventionally, as an insulating film in a semiconductor device, a silicon oxide film formed by a vacuum process such as a chemical vapor deposition method (CVD (Chemical Vapor Deposition) method) has been widely used. The silicon oxide film has a relatively high dielectric constant.

  In recent years, for the purpose of improving the performance of a semiconductor device, the dielectric constant of the insulating film has been reduced, and a semiconductor device using a low dielectric constant insulating film material has been developed. Examples of the low dielectric constant insulating film material include an insulating film obtained by plasma polymerization of a silicon-containing compound, polysiloxane, polysilazane, polyarylene ether, polybenzoxazole, polyimide, silsesquioxane, and the like.

However, these low dielectric constant insulating films have a lower mechanical strength than a silicon oxide film formed by a vacuum process, and are soft and brittle. Therefore, a semiconductor substrate using these materials as an insulating film is manufactured by a damascene method. In this case, if chemical mechanical polishing is performed using a known chemical mechanical polishing aqueous dispersion, scratches or peeling may occur on the semiconductor substrate, which is an object to be polished, resulting in a problem in product yield. Yes.
JP 2001-196336 A

  The present invention has been made in view of the above circumstances, and its purpose is to be able to polish various objects to be polished with high efficiency, and to obtain a sufficiently flat finished surface with high precision, An aqueous dispersion for chemical mechanical polishing that can reduce the occurrence of scratches and peeling in a semiconductor substrate to be polished even when the semiconductor substrate having a low dielectric constant material with low mechanical strength as an insulating film is chemically mechanically polished. And a chemical mechanical polishing method using the same, and a kit for preparing an aqueous dispersion for chemical mechanical polishing.

The chemical mechanical polishing aqueous dispersion according to the first aspect of the present invention comprises:
(A) component: inorganic particles,
(B) component: at least one selected from the group consisting of organic particles and organic-inorganic composite particles,
(C) component: at least one selected from the group consisting of quinolinecarboxylic acid, quinolinic acid, divalent organic acid (excluding quinolinic acid) and hydroxyl acid,
(D) component: at least one selected from the group consisting of benzotriazole and its derivatives,
(E) component: oxidizing agent, and (F) component: containing water,
The amount of the component (A) is 0.05 to 2.0% by mass, the amount of the component (B) is 0.005 to 1.5% by mass, and the amount of the component (A) is The ratio (W _A / W _B ) between (W _A ) and the blending amount (W _B ) of the component ( _B ) is 0.1 to 200, and the pH is 1 to 5.

  In the chemical mechanical polishing aqueous dispersion, the amount of the component (C) may be 0.005 to 3.0% by mass.

  In the chemical mechanical polishing aqueous dispersion, the component (A) may be silica particles.

  In the chemical mechanical polishing aqueous dispersion, the component (D) may be benzotriazole, and the blending amount may be 0.01 to 5.0% by mass.

  In the chemical mechanical polishing aqueous dispersion, the component (E) may be hydrogen peroxide, and the amount thereof may be 0.01 to 5.0% by mass.

The kit for preparing the chemical mechanical polishing aqueous dispersion according to the second aspect of the present invention comprises mixing the liquid (I) and the liquid (II) to prepare the chemical mechanical polishing aqueous dispersion. A kit,
The liquid (I) is at least one selected from the group consisting of (A) inorganic particles, (B) organic particles and organic-inorganic composite particles, (C) quinolinecarboxylic acid, quinolinic acid, divalent organic acid ( However, quinolinic acid is excluded.) And at least one selected from the group consisting of hydroxyl acids, (D) at least one selected from the group consisting of benzotriazole and derivatives thereof, and (F) an aqueous dispersion containing water And
The liquid (II) contains (E) an oxidizing agent and (F) water.

The kit for preparing the chemical mechanical polishing aqueous dispersion according to the third aspect of the present invention is for mixing the liquid (I) and the liquid (II) to prepare the chemical mechanical polishing aqueous dispersion. A kit,
The liquid (I) is an aqueous dispersion containing (A) inorganic particles, (B) at least one selected from the group consisting of organic particles and organic-inorganic composite particles, and (F) water.
The liquid (II) comprises (C) at least one selected from the group consisting of quinolinecarboxylic acid, quinolinic acid, divalent organic acid (excluding quinolinic acid) and hydroxyl acid, and (F) water. Including.

The kit for preparing the chemical mechanical polishing aqueous dispersion according to the fourth aspect of the present invention comprises mixing the liquid (I), the liquid (II), and the liquid (III) to obtain the chemical mechanical polishing aqueous dispersion. A kit for preparing the body,
The liquid (I) is an aqueous dispersion containing (A) inorganic particles, (B) at least one selected from the group consisting of organic particles and organic-inorganic composite particles, and (F) water.
The liquid (II) comprises (C) at least one selected from the group consisting of quinolinecarboxylic acid, quinolinic acid, divalent organic acid (excluding quinolinic acid) and hydroxyl acid, and (F) water. Including
The liquid (III) contains (E) an oxidizing agent and (F) water.

  In the kit, the liquid (I) is (C) at least one selected from the group consisting of quinolinecarboxylic acid, quinolinic acid, divalent organic acid (excluding quinolinic acid) and hydroxyl acid, (D ) At least one selected from the group consisting of benzotriazole and derivatives thereof, and (E) one or more components selected from oxidizing agents.

  In the kit, the liquid (II) is at least one selected from the group consisting of (A) inorganic particles, (B) organic particles, and organic-inorganic composite particles, and (D) a group consisting of benzotriazole and derivatives thereof. It can further contain at least one selected from one or more components selected from (E) an oxidizing agent.

In the chemical mechanical polishing method of the fifth aspect of the present invention, when the copper film, the barrier metal film, and the insulating film are respectively chemically mechanically polished under the same conditions, the polishing rate R _Cu of the copper film and the polishing of the barrier metal film are performed. the ratio _R Cu _{/ R BM} rate _{R BM} is 50 or more, and the chemical mechanical polishing aqueous ratio _R Cu _{/ R in} the polishing rate _{R an in} the polishing rate _{R Cu} and the insulating film of the copper film is 50 or more After chemical mechanical polishing of the object to be polished using the dispersion, the object to be polished is subjected to chemical mechanical polishing using the chemical mechanical polishing aqueous dispersion of the first aspect.

  According to the chemical mechanical polishing aqueous dispersion and the chemical mechanical polishing method using the same, and the kit for preparing the chemical mechanical polishing aqueous dispersion, it is possible to polish various objects to be polished with high efficiency, Even if a semiconductor substrate having a low dielectric constant material with low mechanical strength as an insulating film can be obtained by a chemical mechanical polishing, a sufficiently flat finished surface with high accuracy can be obtained. The occurrence of scratches and peeling can be reduced.

1. Chemical mechanical polishing aqueous dispersion The chemical mechanical polishing aqueous dispersion according to the first embodiment of the present invention is composed of (A) component: inorganic particles, (B) component: organic particles and organic-inorganic composite particles. At least one selected from component (C): at least one selected from the group consisting of quinolinecarboxylic acid, quinolinic acid, divalent organic acid (excluding quinolinic acid) and hydroxyl acid, component (D) : At least one selected from the group consisting of benzotriazole and derivatives thereof, (E) component: oxidizing agent, and (F) component: water. In the chemical mechanical polishing aqueous dispersion, the blending amount of the component (A) is 0.05 to 2.0 mass%, the blending amount of the component (B) is 0.005 to 1.5 mass%, (a) the amount of component _{(W a)} and (B) the amount of component _{(W B)} and the ratio of _(W a / W _B) is 0.1 to 200, and a pH of 1-5 is there. The chemical mechanical polishing aqueous dispersion according to the first embodiment of the present invention is obtained by dissolving and / or dispersing the above-described components in an aqueous medium.

  Hereinafter, each component blended in the chemical mechanical polishing aqueous dispersion according to the first embodiment of the present invention will be described in detail.

1.1. (A) component (A) component (henceforth "(A) inorganic particle") mix | blended with the chemical mechanical polishing aqueous dispersion which concerns on the 1st Embodiment of this invention is inorganic particle. Examples of (A) inorganic particles include silica, alumina, titania, zirconia, and ceria. Examples of the silica include fumed silica, silica synthesized by a sol-gel method, and fumed silica. Fumed silica can be obtained by reacting silicon chloride or the like with oxygen and water in the gas phase. Silica synthesized by the sol-gel method can be obtained by hydrolysis and / or condensation reaction using an alkoxysilicon compound as a raw material. Colloidal silica can be obtained, for example, by an inorganic colloid method using a raw material purified in advance.

  (A) Among the above, silica is more preferable as the inorganic particles.

  (A) As an inorganic particle, it is preferable that impurity metal content shall be 10 ppm or less with respect to an abrasive grain, More preferably, it is 5 ppm or less, More preferably, it is 3 ppm or less, Especially 1 ppm or less. Examples of the impurity metal include iron, nickel, and zinc.

  (A) The average dispersed particle diameter of the inorganic particles is preferably 5 to 1,000 nm, more preferably 7 to 700 nm, and still more preferably 10 to 500 nm. By using abrasive grains having an average dispersed particle diameter in this range, both the polishing rate and the quality such as the smoothness of the surface to be polished can be achieved.

  The compounding amount of the inorganic particles (A) blended in the chemical mechanical polishing aqueous dispersion according to the first embodiment of the present invention is 0.05-2. Although it is 0 mass%, Preferably it is 0.1-2.0 mass%, More preferably, it is 0.1-1.5 mass%. (A) By making the compounding amount of the inorganic particles 0.05 to 2.0% by mass with respect to the total amount of the chemical mechanical polishing aqueous dispersion, damage to the insulating film having a low dielectric constant is minimized. An aqueous dispersion for chemical mechanical polishing having a high polishing rate can be obtained.

1.2. (B) Component (B) component mix | blended with the chemical mechanical polishing aqueous dispersion according to the first embodiment of the present invention is at least one selected from the group consisting of organic particles and organic-inorganic composite particles. .

  Examples of organic particles usable as the component (B) include polyvinyl chloride, styrene (co) polymer, polyacetal, polyester, polyamide, polycarbonate, olefin (co) polymer, phenoxy resin, acrylic (co) polymer, and the like. Can be mentioned. Examples of the olefin (co) polymer include polyethylene, polypropylene, poly-1-butene, poly-4-methyl-1-pentene, and the like. Examples of the acrylic (co) polymer include polymethyl methacrylate.

  Moreover, as the organic-inorganic composite particles usable as the component (B), it is sufficient that the organic particles and the inorganic particles are integrally formed to such an extent that they are not easily separated during the chemical mechanical polishing step. The type, configuration, etc. are not particularly limited. As an inorganic particle which can be used for an organic inorganic composite particle, what was illustrated as said (A) inorganic particle can be used, for example.

  The organic-inorganic composite particles can take the following configuration, for example.

  (I) Organic-inorganic composite particles obtained by polycondensation of metal or silicon alkoxide compounds in the presence of organic particles. Here, examples of the metal or silicon alkoxide compound include alkoxysilane, aluminum alkoxide, and titanium alkoxide. In this case, the polycondensate to be purified may be directly bonded to the functional group of the organic particles, or may be bonded via an appropriate coupling agent (for example, a silane coupling agent).

  (Ii) Organic-inorganic composite particles in which organic particles and inorganic particles having zeta potentials with different signs are combined by electrostatic force. In this case, it may be a composite particle formed by mixing both in a pH range where the sign of the zeta potential of the organic particle and the sign of the zeta potential of the inorganic particle are different, or the sign of the zeta potential of the organic particle. Formed by changing the liquidity to a pH range where the zeta potential of organic particles and the zeta potential of inorganic particles are different from each other after mixing both in the same pH range. It may be a particle.

  (Iii) Organic-inorganic composite particles obtained by polycondensation of a metal or silicon alkoxide compound in the presence of the composite particles of (ii) above. Here, as the metal or silicon alkoxide compound, the same compounds as in the above (1) can be used.

  The average dispersed particle size of the component (B) particles is preferably 20 to 5,000 nm, more preferably 30 to 2,000 nm, and still more preferably 50 to 1,000 nm. By setting the average dispersed particle size within this range, a good balance between the polished surface and the polishing rate can be achieved.

  (B) The compounding quantity of a component is 0.005-1.5 mass% with respect to the total amount of the chemical mechanical polishing aqueous dispersion which concerns on the 1st Embodiment of this invention, Preferably it is 0.01-1. It is 0.0 mass%, More preferably, it is 0.05-0.5 mass%. (B) By making the compounding quantity of component 0.005-1.5 mass% with respect to the total amount of the said chemical mechanical polishing aqueous dispersion, both dishing of wiring parts and defects on the substrate are minimized. It can be set as the chemical mechanical polishing aqueous dispersion.

(A) the amount of component _{(W A)} and (B) the amount of component _{(W B)} ratio of _(W A / W _B) is 0.1 to 200, preferably 0.5 to 150 Yes, more preferably 1-100. By setting the ratio of both particles (W _A / W _B ) to 0.1 to 200, particularly when a semiconductor device having a low dielectric constant material as an insulating film is chemically mechanically polished, damage to the insulating film and the wiring portion A chemical mechanical polishing aqueous dispersion that minimizes dishing can be obtained.

1.3. (C) Component (C) component mix | blended with the chemical mechanical polishing aqueous dispersion according to the first embodiment of the present invention excludes quinolinecarboxylic acid, quinolinic acid, and divalent organic acids (however, quinolinic acid is excluded). And at least one selected from the group consisting of hydroxyl acids.

  The component (C) is more preferably a compound having 4 or more carbon atoms. Examples of the divalent carboxylic acid having 4 or more carbon atoms include maleic acid, succinic acid, fumaric acid, glutaric acid, and adipic acid. Examples of the hydroxyl acid having 4 or more carbon atoms include citric acid, malic acid, tartaric acid and the like.

  The component (C) is more preferably at least one selected from quinaldic acid (2-quinolinecarboxylic acid), quinolinic acid (2,3-pyridinedicarboxylic acid), maleic acid, citric acid, and malic acid. .

  The amount of component (C) is preferably 0.005 to 3.0% by mass, more preferably 0.01 to 2.0% by mass, based on the total amount of the chemical mechanical polishing aqueous dispersion. . By setting the blending amount of the component (C) to 0.005 to 3.0% by mass, a balance between the polishing rate and a good surface to be polished can be achieved.

1.4. (D) component (D) component mix | blended with the chemical mechanical polishing aqueous dispersion which concerns on the 1st Embodiment of this invention is at least 1 sort (s) selected from the group which consists of a benzotriazole and its derivative (s). Here, the “benzotriazole derivative” refers to one obtained by substituting one or two or more hydrogen atoms of benzotriazole with a functional group such as a carboxyl group, a methyl group, an amino group, or a hydroxyl group.

  As the component (D), benzotriazole, methylbenzotriazole, 4-carboxybenzotriazole and its salt, 7-carboxybenzotriazole and its salt, benzotriazole butyl ester, 1-hydroxymethylbenzotriazole, 1-hydroxybenzotriazole, 1- (2,3-dihydroxypropyl) -benzotriazole, 1- (2-hydroxyethyl) -benzotriazole, 2- (benzotriadiyl) -ethanesulfonic acid and its salts, 1- (2-ethylhexylaminomethyl) -Benzotriazole and the like are preferable, benzotriazole, methylbenzotriazole, 4-carboxybenzotriazole and its salt, 7-carboxybenzotriazole and its salt, benzotriazole butyl ester, 1- Mud carboxymethyl benzotriazole, more preferably 1-hydroxybenzotriazole, benzotriazole is most preferred.

  The amount of component (D) is preferably 0.01 to 5.0% by mass, more preferably 0.05 to 2.0% by mass, based on the total amount of the chemical mechanical polishing aqueous dispersion. . The blending amount of the component (D) is 0.01 to 5.0% by mass with respect to the total amount of the chemical mechanical polishing aqueous dispersion, thereby achieving a balance between the polishing rate and a good surface to be polished. Can do.

1.5. (E) component (E) component mix | blended with the chemical mechanical polishing aqueous dispersion which concerns on the 1st Embodiment of this invention is an oxidizing agent (henceforth "(E) oxidizing agent"). (E) As an oxidizing agent, a persulfate, hydrogen peroxide, an inorganic acid, an organic peroxide, a polyvalent metal salt etc. can be mentioned, for example. Examples of the persulfate include ammonium persulfate and potassium persulfate. Examples of the inorganic acid include nitric acid and sulfuric acid. Examples of the organic peroxide include peracetic acid, perbenzoic acid, tert-butyl hydroperoxide, and the like. Examples of the polyvalent metal salt include permanganic acid compounds and dichromic acid compounds. More specifically, examples of the permanganic acid compounds include potassium permanganate and the like. Examples thereof include potassium dichromate. Among these, as (E) oxidizing agent, hydrogen peroxide, persulfate and inorganic acid are more preferable, and hydrogen peroxide is particularly preferable.

  (E) The compounding amount of the oxidizing agent is preferably 0.01 to 5.0% by mass, more preferably 0.05 to 2.0% by mass, based on the total amount of the chemical mechanical polishing aqueous dispersion. It is. (E) By making the compounding quantity of an oxidizing agent 0.01-5.0 mass% with respect to the total amount of the said aqueous dispersion for chemical mechanical polishing, the balance between a polishing rate and a favorable to-be-polished surface is aimed at. be able to.

  In the chemical mechanical polishing aqueous dispersion, when (E) hydrogen peroxide is used as the oxidizing agent, an appropriate polyvalent metal ion may be further contained. By containing polyvalent metal ions in the presence of hydrogen peroxide, the function of hydrogen peroxide as an oxidizing agent can be promoted, and the polishing rate can be further improved.

1.6. Component (F) The component (F) blended in the chemical mechanical polishing aqueous dispersion according to the first embodiment of the present invention is water (hereinafter also referred to as “(F) water”). (F) Water functions as an aqueous medium of the chemical mechanical polishing aqueous dispersion. Examples of the aqueous medium include (F) a mixed medium of water and an organic solvent miscible with water (for example, alcohols, alkylene glycol derivatives, etc.). More preferably, it is water or a mixed medium of water and a water-soluble alcohol, and examples of the water-soluble alcohol include methanol and ethanol. More preferable is a mixed medium of water and methanol.

1.7. (G) Other components The chemical mechanical polishing aqueous dispersion according to the first embodiment of the present invention may contain (G) other components as necessary in addition to the above-described components. Examples of other components (G) include surfactants and pH adjusters.

  Examples of the surfactant include a cationic surfactant, an anionic surfactant, an amphoteric surfactant, a nonionic surfactant, a water-soluble polymer, and the like, and in particular, an anionic surfactant and a nonionic surfactant. An activator or a water-soluble polymer is preferably used.

  Examples of the anionic surfactant include carboxylate, sulfonate, sulfate ester salt, phosphate ester salt and the like. Examples of the carboxylate include fatty acid soaps and alkyl ether carboxylates, and examples of the sulfonate include alkylbenzene sulfonate, alkyl naphthalene sulfonate, and α-olefin sulfonate. Examples of sulfate salts include higher alcohol sulfate salts, alkyl ether sulfate salts, polyoxyethylene alkylphenyl ether sulfate salts, and phosphate ester salts such as alkyl phosphate ester salts. Can be mentioned. Of these, sulfonates are preferred, alkylbenzene sulfonates are more preferred, and potassium dodecylbenzene sulfonate is particularly preferred.

  Examples of the nonionic surfactant include a polyethylene glycol type surfactant, acetylene glycol, an ethylene oxide adduct of acetylene glycol, and a nonionic surfactant such as acetylene alcohol.

  As said pH adjuster, an organic base, an inorganic base, or an inorganic acid can be mentioned.

  Examples of the organic base include tetramethylammonium hydroxide and triethylamine.

  Examples of the inorganic base include ammonia and potassium hydroxide.

  Examples of the inorganic acid include nitric acid and sulfuric acid.

  The pH of the chemical mechanical polishing aqueous dispersion according to the first embodiment of the present invention is 1 to 5, preferably 1.5 to 4.5, more preferably 2.0 to 4.0. . When the pH of the chemical mechanical polishing aqueous dispersion is 1 to 5, a balance between the polishing rate and a good surface to be polished can be achieved. It should be understood that the pH value is a value measured at 25 ° C.

1.8. Kit for Preparing Chemical Mechanical Polishing Aqueous Dispersion The chemical mechanical polishing aqueous dispersion according to the first embodiment of the present invention can be supplied in a state where it can be used as a polishing composition as it is after preparation. Alternatively, a polishing composition containing a high concentration of each component of the chemical mechanical polishing aqueous dispersion described above (ie, a concentrated polishing composition) is prepared, and this concentrated polishing composition is used at the time of use. May be diluted to obtain the desired chemical mechanical polishing aqueous dispersion.

  For example, the chemical mechanical polishing aqueous dispersion according to the first embodiment of the present invention is prepared by dividing it into a plurality of liquids (for example, two or three liquids), and these liquids are mixed at the time of use. Can be used. For example, the chemical mechanical polishing aqueous dispersion according to the first embodiment of the present invention described above can be prepared by mixing a plurality of liquids using the first to third kits shown below. .

1.8.1. First Kit The first kit is a kit for preparing the chemical mechanical polishing aqueous dispersion according to the first embodiment of the present invention by mixing the liquid (I) and the liquid (II). In the first kit, the liquid (I) is at least one selected from the group consisting of (A) inorganic particles, (B) organic particles and organic-inorganic composite particles, (C) quinolinecarboxylic acid, quinolinic acid, 2 At least one selected from the group consisting of divalent organic acids (excluding quinolinic acid) and hydroxyl acids, (D) at least one selected from the group consisting of benzotriazole and derivatives thereof, and (F) water The liquid (II) contains (E) an oxidizing agent and (F) water.

  When preparing the liquid (I) and the liquid (II) constituting the first kit, the respective components described above are described in the aqueous dispersion obtained by mixing the liquid (I) and the liquid (II). It is necessary to determine the concentration of each component contained in the liquid (I) and the liquid (II) so as to be included in the concentration range. In addition, the liquid (I) and the liquid (II) may contain each component at a high concentration (that is, may be concentrated). In this case, the liquid (I) is diluted by use at the time of use. And liquid (II) can be obtained. According to the first kit, the storage stability of the (F) oxidizing agent can be improved by separating the liquid (I) and the liquid (II).

  When the chemical mechanical polishing aqueous dispersion according to the first embodiment of the present invention is prepared using the first kit, the liquid (I) and the liquid (II) are separately prepared or supplied, and are integrated during polishing. The mixing method and timing are not particularly limited.

  For example, the liquid (I) and the liquid (II) may be separately supplied to the polishing apparatus and mixed on the surface plate, or may be mixed before being supplied to the polishing apparatus, or in the polishing apparatus. Or may be mixed in the mixing tank by providing a mixing tank. Further, a line mixer or the like may be used in order to obtain a more uniform aqueous dispersion during line mixing.

1.8.2. Second Kit The second kit is a kit for preparing the chemical mechanical polishing aqueous dispersion according to the first embodiment of the present invention by mixing the liquid (I) and the liquid (II). In the second kit, the liquid (I) is an aqueous dispersion containing (A) inorganic particles, (B) at least one selected from the group consisting of organic particles and organic-inorganic composite particles, and (F) water. The liquid (II) is (C) at least one selected from the group consisting of quinolinecarboxylic acid, quinolinic acid, divalent organic acid (excluding quinolinic acid) and hydroxyl acid, and (F) water including.

  When preparing the liquid (I) and the liquid (II) constituting the second kit, the respective components described above are contained in the aqueous dispersion obtained by mixing the liquid (I) and the liquid (II). It is necessary to determine the concentration of each component contained in the liquid (I) and the liquid (II) so as to be included in the concentration range. In addition, the liquid (I) and the liquid (II) may contain each component at a high concentration (that is, may be concentrated). In this case, the liquid (I) is diluted by use at the time of use. And liquid (II) can be obtained. According to the second kit, the storage stability of the aqueous dispersion can be improved by separating the liquid (I) and the liquid (II).

  When the chemical mechanical polishing aqueous dispersion according to the first embodiment of the present invention is prepared using the second kit, the liquid (I) and the liquid (II) are separately prepared or supplied, and are integrated during polishing. The mixing method and timing are not particularly limited.

  For example, the liquid (I) and the liquid (II) may be separately supplied to the polishing apparatus and mixed on the surface plate, or may be mixed before being supplied to the polishing apparatus, or in the polishing apparatus. Or may be mixed in the mixing tank by providing a mixing tank. Further, a line mixer or the like may be used in order to obtain a more uniform aqueous dispersion during line mixing.

1.8.3. Third Kit The third kit mixes the liquid (I), the liquid (II), and the liquid (III) to prepare the chemical mechanical polishing aqueous dispersion according to the first embodiment of the present invention. It is a kit for. In the third kit, the liquid (I) is an aqueous dispersion containing (A) inorganic particles, (B) at least one selected from the group consisting of organic particles and organic-inorganic composite particles, and (F) water. The liquid (II) is (C) at least one selected from the group consisting of quinolinecarboxylic acid, quinolinic acid, divalent organic acid (excluding quinolinic acid) and hydroxyl acid, and (F) water The liquid (III) contains (E) an oxidizing agent and (F) water.

  When preparing liquid (I), liquid (II), and liquid (III) constituting the third kit, an aqueous system obtained by mixing liquid (I), liquid (II), and liquid (III) It is necessary to determine the concentration of each component contained in the liquid (I), the liquid (II), and the liquid (III) so that the above-described components are included in the dispersion in the concentration range described above. In addition, liquid (I), liquid (II), and liquid (III) may contain each component at a high concentration (that is, may be concentrated), and in this case, dilute at the time of use. Thus, it is possible to obtain liquid (I), liquid (II), and liquid (III). According to the third kit, the storage stability of the aqueous dispersion can be enhanced by separating the liquid (I), the liquid (II), and the liquid (III).

  When the chemical mechanical polishing aqueous dispersion according to the first embodiment of the present invention is prepared using the third kit, the liquid (I), the liquid (II), and the liquid (III) are separately prepared or supplied. The mixing method and timing are not particularly limited as long as they are integrated during polishing.

  For example, the liquid (I), the liquid (II), and the liquid (III) may be separately supplied to the polishing apparatus and mixed on the surface plate, or may be mixed before being supplied to the polishing apparatus. Then, line mixing may be performed in the polishing apparatus, or mixing may be performed by providing a mixing tank. Further, a line mixer or the like may be used in order to obtain a more uniform aqueous dispersion during line mixing.

  In the second and third kits, the liquid (I) is selected from the group consisting of (C) quinolinecarboxylic acid, quinolinic acid, divalent organic acid (excluding quinolinic acid) and hydroxyl acid. The liquid (II) may further contain at least one component selected from the group consisting of at least one (D) benzotriazole and derivatives thereof, and (E) an oxidizing agent. (A) inorganic particles, (B) at least one selected from the group consisting of organic particles and organic-inorganic composite particles, (D) at least one selected from the group consisting of benzotriazole and derivatives thereof, and (E) One or more components selected from oxidizing agents may be further included.

2. Chemical Mechanical Polishing Method A chemical mechanical polishing method according to the second embodiment of the present invention includes a step of chemical mechanical polishing using the chemical mechanical polishing aqueous dispersion. More specifically, in the chemical mechanical polishing method according to the second embodiment of the present invention, the chemical mechanical polishing aqueous dispersion is a second in a two-step polishing process described later for forming a copper damascene wiring, for example. It can be suitably used as an aqueous dispersion for chemical mechanical polishing in the polishing process. In particular, when the chemical mechanical polishing aqueous dispersion is used as the chemical mechanical polishing aqueous dispersion for the first polishing treatment, the second chemical polishing polishing step described later is used. By using it as an aqueous dispersion for chemical mechanical polishing, it is possible to exhibit more excellent polishing characteristics. Here, the object to be polished by chemical mechanical polishing preferably has at least a copper film, a barrier metal film, and an insulating film.

In the chemical mechanical polishing method according to the second embodiment of the present invention, when each of the copper film and the barrier metal film is chemically mechanically polished under the same conditions, the copper film polishing rate (R _Cu ) and the barrier metal film polishing are performed. A chemical mechanical polishing aqueous dispersion (hereinafter, also referred to as “first polishing aqueous dispersion”) having polishing characteristics with a polishing rate ratio (R _Cu / R _BM ) of 50 or more with respect to the speed (R _BM ). A first polishing process for performing chemical mechanical polishing on the surface to be polished, and the chemical mechanical polishing aqueous dispersion (hereinafter referred to as the chemical mechanical polishing aqueous dispersion) And a second polishing treatment step in which chemical mechanical polishing is performed using “second polishing aqueous dispersion”).

  In the present embodiment, the first polishing process step and the second polishing process step are continuously performed by sequentially switching the polishing aqueous dispersion to be supplied with the object to be polished mounted while using the same polishing apparatus. Alternatively, using the same polishing apparatus, after the first polishing process step is finished, the object to be polished is once taken out, and after switching the polishing aqueous dispersion to be supplied, the object to be polished taken out is mounted again. Two polishing processes may be performed.

  Moreover, you may implement a 1st grinding | polishing processing process and a 2nd grinding | polishing processing process using a separate grinding | polishing apparatus.

  Furthermore, when using a polishing apparatus having a plurality of polishing pads, the first polishing process step and the second polishing process step may be polished using different types of polishing pads, or the first polishing process step The same type of polishing pad may be used in the second polishing treatment step.

  The copper film as the object to be polished is not limited to one made of pure copper, and may be made of, for example, a copper alloy having a copper content of 95% by mass or more such as copper-silicon or copper-aluminum.

  The barrier metal film that is the object to be polished is formed of a metal having high hardness such as tantalum or titanium, a nitride or oxide thereof. The metal forming the barrier metal film is not limited to a pure metal, and may be an alloy such as tantalum-niobium. In addition, when the barrier metal film is formed of nitride, tantalum nitride, titanium nitride, or the like is not necessarily pure. The material of the barrier metal film is particularly preferably tantalum and / or tantalum nitride.

  The barrier metal film is often formed of only one of tantalum and titanium, but different materials, for example, both tantalum film and tantalum nitride film may be formed on the same substrate as the barrier metal film. Good.

Insulating film to be polished body, for example, SiO ₂ film, a boron phosphorus silicate film (BPSG film) obtained by adding a small amount of boron and phosphorus to SiO _2, FSG fluorine-doped _{SiO 2 (Fluorine-doped silicate glass} ) And an insulating film called a low dielectric constant silicon oxide insulating film, an organic insulating film, and the like.

Examples of the SiO ₂ film include a thermal oxide film, a PETEOS film (Plasma Enhanced-TEOS film), an HDP film (High Density Plasma Enhanced-TEOS film), and a silicon oxide film obtained by a thermal CVD method.

  The thermal oxide film can be formed by exposing silicon heated to a high temperature to an oxidizing atmosphere and chemically reacting silicon and oxygen or silicon and moisture. The PETEOS film can be formed by chemical vapor deposition using tetraethylorthosilicate (TEOS) as a raw material and using plasma as a promoting condition. The HDP film can be formed by chemical vapor deposition using tetraethylorthosilicate (TEOS) as a raw material and using high-density plasma as an acceleration condition.

  The silicon oxide film can be formed by a thermal CVD method. Examples of the thermal CVD method include an atmospheric pressure CVD method (AP-CVD method) or a low pressure CVD method (LP-CVD method). The boron phosphorus silicate film (BPSG film) can be obtained by an atmospheric pressure CVD method (AP-CVD method) or a low pressure CVD method (LP-CVD method). An insulating film called FSG (Fluorine doped silicate glass) can be formed by chemical vapor deposition using high-density plasma as an accelerating condition.

  Further, the low dielectric constant silicon oxide insulating film can be obtained by applying a raw material on a substrate by, for example, a spin coating method and then heating in an oxidizing atmosphere. As the low dielectric constant silicon oxide insulating film thus obtained, an HSQ film (Hydrogen Silsesquioxane film) using triethoxysilane as a raw material, an MSQ film using tetraethoxysilane and a small amount of methyltrimethoxysilane as a raw material ( Methyl Silsesquioxane film) and other low dielectric constant silicon oxide insulating films made from silane compounds. A silicon oxide insulating film having a low dielectric constant can be obtained by, for example, mixing suitable organic polymer particles and the like with raw materials, so that the polymer is burned out in the heating process and voids are formed. An insulating film having a dielectric constant may be used.

  Examples of the organic insulating film include low dielectric constant organic insulating films made from organic polymers such as polyarylene polymers, polyarylene ether polymers, polyimide polymers, and benzocyclobutene polymers.

  As an object to be polished used in the chemical mechanical polishing method according to the second embodiment of the present invention, for example, a composite substrate material 1 having a structure as shown in FIG. The composite substrate material 1 is, for example, a PETEOS film (formed by CVD using tetraethoxysilane) which is laminated on the surface of the substrate 11 and formed with a wiring recess such as a groove. A barrier metal film 13 made of a refractory metal such as tantalum or tantalum nitride, and the like. And a metal film made of a metal wiring material such as copper formed on the barrier metal film 13.

  Further, the object to be polished provided for the chemical mechanical polishing method of the second embodiment of the present invention is made of silicon oxide or the like between the substrate 11 and the insulating film 12 as shown in FIG. And an insulating film 22 made of silicon nitride or the like formed on the insulating film 21.

  In the chemical mechanical polishing method of the second embodiment of the present invention, such an object to be polished (composite substrate material 1) may be polished, for example, according to the following procedure. First, in the first polishing treatment step, using the first polishing aqueous dispersion, the metal material to be removed other than the metal wiring portion embedded in the wiring recess in the metal film 14 is, for example, the barrier metal film 13. Chemical mechanical polishing is performed until the surface is exposed (see FIGS. 1B and 2B). Thereafter, in the second polishing treatment step, using the chemical mechanical polishing aqueous dispersion according to the first embodiment of the present invention, portions of the barrier metal film 13 other than the bottom of the wiring recess and the inner wall surface. Chemical mechanical polishing is performed so that the formed barrier metal film 13 is completely removed. At that time, the surface of the insulating film 12 is also polished at the same time, so that highly planarized damascene wiring is obtained (see FIGS. 1C and 2C).

In the first polishing aqueous dispersion, the polishing rate of the copper film, as described above _{(R Cu)} and the polishing rate _{(R BM)} and the polishing rate ratio of the barrier metal film _(R Cu _{/ R BM)} of 50 or more And a polishing characteristic in which the ratio (R _Cu / R _In ) of the polishing rate (R _Cu ) of the copper film to the polishing rate (R _In ) of the insulating film is 50 or more. The polishing rate ratio (R _Cu / R _BM ) is preferably 60 or more, and more preferably 70 or more. When the polishing rate ratio (R _Cu / R _BM ) is less than 50, after the first polishing process step, excessive copper remains in the portion where the copper film is to be removed, and much time is spent in the second polishing process step. In addition, a large amount of chemical mechanical polishing aqueous body may be required.

The composition of the first aqueous dispersion for polishing is not particularly limited as long as the polishing rate ratio (R _Cu / R _BM ) is in the above range. For example, in the aqueous medium, abrasive grains The organic acid and the oxidizing agent are preferably contained. It is more preferable that the first polishing aqueous dispersion further contains ammonia or ammonium ions in addition to these components.

  Examples of the aqueous medium used in the first polishing aqueous dispersion include those exemplified as the aqueous medium in the chemical mechanical polishing aqueous dispersion of the first embodiment of the present invention. It is preferable to use only.

  Examples of the abrasive grains used in the first polishing aqueous dispersion include the components (A) and (B) used in the chemical mechanical polishing aqueous dispersion according to the first embodiment of the present invention. And at least one kind of abrasive selected from these can be used. Of these, silicon dioxide, organic particles, or organic-inorganic composite particles are preferably used.

Examples of the organic acid used in the first polishing aqueous dispersion include those exemplified as the component (C) and amino acids used in the chemical mechanical polishing aqueous dispersion of the first embodiment of the present invention. And at least one selected from these can be used. Of these, glycine, alanine, citric acid, malic acid, 2-quinolinecarboxylic acid, and 2,3-pyridinedicarboxylic acid are preferably used from the viewpoint that a larger polishing rate ratio (R _Cu / R _BM ) can be obtained. .

  Examples of the oxidizing agent used in the first polishing aqueous dispersion include those exemplified as the component (E) used in the chemical mechanical polishing aqueous dispersion of the first embodiment of the present invention, At least one selected from these can be used. Of these, hydrogen peroxide or persulfate is preferable, and ammonium persulfate is particularly preferably used.

  The first polishing aqueous dispersion may further contain ammonia or ammonium ions. In the case where the first polishing aqueous dispersion contains ammonium ions, ammonium ions can be generated from the above-mentioned ammonium salts of organic acids, ammonium salts of inorganic acids as oxidizing agents, or optionally You may add as a counter cation of the anionic surfactant which can be added.

  The content of abrasive grains is preferably 0.001 to 3.0% by mass, more preferably 0.01 to 3.0% by mass, and still more preferably based on the entire first polishing aqueous dispersion. Is 0.01 to 2.5% by mass, particularly preferably 0.01 to 2.0% by mass.

  The content of the organic acid is preferably 0.01 to 10% by mass, more preferably 0.1 to 5.0% by mass with respect to the entire first polishing aqueous dispersion.

  The content of the oxidizing agent is preferably 0.01 to 10% by mass and more preferably 0.02 to 5.0% by mass with respect to the entire first polishing aqueous dispersion.

  When the first polishing aqueous dispersion contains ammonia or ammonium ions, the content thereof is preferably 5.0 mol / L or less in the first polishing aqueous dispersion, more preferably 0.8. It is 01-5.0 mol / L, More preferably, it is 0.01-1.0 mol / L, Most preferably, it is 0.03-0.5 mol / L.

  The first polishing aqueous dispersion may further contain a surfactant, benzotriazole or a derivative thereof, an antifoaming agent, and the like, if necessary.

  Examples of the surfactant include a cationic surfactant, an anionic surfactant, an amphoteric surfactant, a nonionic surfactant, and a water-soluble polymer.

  Examples of the benzotriazole or derivatives thereof include those exemplified as (D) benzotriazole or derivatives thereof used in the chemical mechanical polishing aqueous dispersion of the first embodiment of the present invention. The content is preferably 5.0% by mass or less, more preferably 0.001 to 5.0% by mass, and more preferably 0.005 to 1%, based on the entire first polishing aqueous dispersion. The content is more preferably 0.0% by mass, and particularly preferably 0.01 to 0.5% by mass.

  The pH of the first polishing aqueous dispersion may be set to any value in the acidic region, the neutral region, and the alkaline region. When the pH of the first polishing aqueous dispersion is set in the acidic region, the pH is preferably 2-4. When the pH of the first polishing aqueous dispersion is set in a neutral region and an alkaline region, the pH is preferably 6-12. The pH of the first polishing aqueous dispersion is more preferably 6-12.

  The chemical mechanical polishing by the chemical mechanical polishing method according to the second embodiment of the present invention is performed by using a commercially available chemical mechanical polishing apparatus (for example, LGP510, LGP552 (manufactured by Lapmaster SFT Co., Ltd.), EPO112, EPO222 (and above, (Made by Ebara Corporation), Mirra (Applied Materials Co., Ltd.), AVANTI-472 (Ipec Co., Ltd.), etc.) can be performed under known polishing conditions.

  Preferred polishing conditions should be appropriately set depending on the chemical mechanical polishing apparatus to be used. For example, when EPO112 is used as the chemical mechanical polishing apparatus, both the first polishing processing step and the second polishing processing step are, for example, the following: It can be a condition.

Surface plate rotation speed: preferably 30 to 120 rpm, more preferably 40 to 100 rpm
Head rotation speed: preferably 30 to 120 rpm, more preferably 40 to 100 rpm
Surface plate rotation speed / head rotation speed ratio: preferably 0.5 to 2, more preferably 0.7 to 1.5
Polishing pressure: preferably 100 to 500 g / cm ² , more preferably 200 to 350 g / cm ²
Feed rate of chemical mechanical polishing aqueous dispersion: preferably 50 to 300 ml / min, more preferably 100 to 200 ml / min

3. Examples Hereinafter, the present invention will be described by way of examples. However, the present invention is not limited to the examples.

3.1. Preparation of aqueous dispersion containing inorganic particles 3.1.1. Preparation of aqueous dispersion containing fumed silica particles 2 kg of fumed silica particles (manufactured by Nippon Aerosil Co., Ltd., trade name “Aerosil # 90”, average primary particle size 20 nm) are ion-exchanged water using an ultrasonic disperser. Dispersed in 6.7 kg. This was filtered with a filter having a pore size of 5 μm to obtain an aqueous dispersion containing 23% by mass of fumed silica particles. The average secondary particle diameter of fumed silica contained in this aqueous dispersion was 220 nm.

3.1.2. Preparation of aqueous dispersion containing colloidal silica particles 3.1.2-1. Preparation of aqueous dispersion containing colloidal silica particles C1 A flask was charged with 75 parts by mass of ammonia water having a concentration of 25% by mass, 40 parts by mass of ion-exchanged water, 165 parts by mass of ethanol and 15 parts by mass of tetraethoxysilane, and stirred at a rotational speed of 180 rpm. The temperature was raised to 60 ° C. Stirring was continued for 2 hours while maintaining the temperature at 60 ° C., and then cooled to room temperature. Thereby, an alcohol dispersion of colloidal silica particles was obtained.

  Subsequently, using a rotary evaporator, the operation of removing the alcohol content while adding ion-exchanged water was repeated several times while maintaining the temperature of the obtained dispersion at 80 ° C. By this operation, an aqueous dispersion containing 20% by mass of colloidal silica particles C1 was prepared.

  The average primary particle diameter of the colloidal silica particles C1 contained in this aqueous dispersion was 15 nm, the average secondary particle diameter was 40 nm, and the average degree of association was 2.7.

3.1-2. Preparation of Water Dispersion Containing Colloidal Silica Particles C2 to C4 In the above “3.1.2-1. Preparation of Water Dispersion Containing Colloidal Silica Particles C1”, 75 parts by mass of ammonia water having a concentration of 25% by mass, ethanol A water dispersion containing colloidal silica particles C2 to C4 was prepared by the same procedure as described above except that 165 parts by mass and the amount of tetraethoxysilane used were as described in Table 1.

3.1.3. Preparation of aqueous dispersion containing organic-inorganic composite particles 3.1.3-1. Preparation of aqueous dispersion containing surface-treated organic particles 90 parts by mass of methyl methacrylate, 5 parts by mass of methoxypolyethylene glycol methacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name “NK Ester M-90G”, # 400) Part, 4-vinylpyridine 5 parts by mass, azo polymerization initiator (manufactured by Wako Pure Chemical Industries, Ltd., trade name “V50”) 2 parts by mass and ion-exchanged water 400 parts by mass were placed in a flask, under a nitrogen gas atmosphere The temperature was raised to 70 ° C. with stirring. The mixture was held for 6 hours while stirring at this temperature. By diluting this reaction mixture with ion-exchanged water, an aqueous dispersion containing 10% by mass of polymethyl methacrylate particles having an average particle diameter of 150 nm and having a functional group having an amino group cation and a polyethylene glycol chain was obtained. . The polymerization yield was 95%.

  100 parts by mass of this aqueous dispersion was charged into a flask, 1 part by mass of methyltrimethoxysilane was added thereto, and the mixture was stirred at 40 ° C. for 2 hours. Thereafter, a 1N aqueous nitric acid solution was added to adjust the pH to 2.0, whereby an aqueous dispersion containing surface-treated organic particles was obtained. The zeta potential of the surface-treated organic particles contained in this aqueous dispersion was +17 mV.

3.1.3-2. Preparation of Water Dispersion Containing Inorganic Particles (Colloidal Silica Particles) Colloidal silica particles (manufactured by Nissan Chemical Co., Ltd., trade name “Snowtex O”, average primary particle size 12 nm) are dispersed in water, and 1 N water is added thereto. By adjusting the pH by adding an aqueous potassium oxide solution, an aqueous dispersion having a pH of 8.0 containing 10% by mass of colloidal silica particles was obtained.

  The zeta potential of the colloidal silica particles contained in this aqueous dispersion was −40 mV.

3.1.3-3. Preparation of aqueous dispersion containing organic-inorganic composite particles To 100 parts by weight of the aqueous dispersion prepared in “3.1.3-1. Preparation of aqueous dispersion containing surface-treated organic particles” above, “3.1. By gradually adding 50 parts by mass of the aqueous dispersion prepared in “3-2.Preparation of aqueous dispersion containing inorganic particles (colloidal silica particles)” over 2 hours while stirring, and further stirring for 2 hours thereafter. Then, an aqueous dispersion containing particles in which silica particles are adhered to polymethyl methacrylate particles was obtained.

  Next, 2 parts by mass of vinyltriethoxysilane was added to the obtained aqueous dispersion and stirred for 1 hour, and then 1 part by mass of tetraethoxysilane was further added. This was heated to 60 ° C., and stirring was continued for 3 hours, followed by cooling to room temperature to prepare an aqueous dispersion containing 10% by mass of inorganic / organic composite particles having an average particle diameter of 180 nm.

  When the inorganic-organic composite particles contained in the aqueous dispersion were observed with a scanning electron microscope, silica particles were adhered to 80% of the surface of the polymethyl methacrylate particles.

3.1.4. Preparation of aqueous dispersion containing organic particles 90 parts by weight of methyl methacrylate, 10 parts by weight of styrene, 5 parts by weight of acrylic acid, 2 parts by weight of ammonium persulfate, 0.1 part by weight of surfactant and 400 parts of ion-exchanged water are placed in a flask. The temperature was raised to 70 ° C. with stirring in a nitrogen gas atmosphere, and polymerization was carried out for 8 hours until the polymerization conversion was about 100%. Thus, an aqueous dispersion containing organic particles composed of a polymethacrylate-styrene polymer having a carboxyl group and an average particle diameter of 150 nm is obtained, and by adding water to this and diluting it, the content ratio of the organic particles An aqueous dispersion adjusted to 10% by mass was obtained.

3.1.5. Production of insulating film with low dielectric constant 3.1.5-1. Preparation of polysiloxane sol A mixed solution consisting of 101.5 g of methyltrimethoxysilane, 276.8 g of methyl methoxypropionate and 9.7 g of tetraisopropoxy titanium / ethyl acetoacetate complex was heated to 60 ° C. A mixture of 92.2 g of γ-butyrolactone and 20.1 g of water was added dropwise over 1 hour. After completion of dropping, the reaction was carried out at 60 ° C. for 1 hour to obtain a polysiloxane sol.

3.1.5-2. Manufacture of polystyrene particles 100 parts of styrene, 2 parts of azo polymerization initiator (trade name “V60”, manufactured by Wako Pure Chemical Industries, Ltd.), 0.5 part of potassium dodecylbenzenesulfonate and 400 parts of ion-exchanged water are charged into a flask. The mixture was heated to 70 ° C. with stirring under a nitrogen gas atmosphere and polymerized for 6 hours. Thereby, polystyrene particles having an average particle diameter of 150 nm were obtained.

3.1.5-3. Production of insulating film having low dielectric constant 3.1.5-1. 15 g of the polysiloxane sol obtained in the above and 3.1.5-2. 1 g of the polystyrene particles obtained in 1 above was mixed, and the resulting mixture was applied by spin coating on a silicon substrate with a thermal oxide film having a diameter of 8 inches to form a coating film. For 5 minutes, followed by heating at 200 ° C for 5 minutes, then under vacuum at 340 ° C for 30 minutes, 360 ° C for 30 minutes, 380 ° C for 30 minutes, and further at 450 ° C for 1 hour By heating, a colorless and transparent film having a thickness of 2000 mm was formed.

  When the cross section of this film was observed with a scanning electron microscope, it was confirmed that many fine pores were formed. The relative dielectric constant was 1.98, the elastic modulus was 3 GPa, and the porosity was 15%.

3.1.6. Preparation of aqueous dispersion for first polishing and evaluation of polishing performance 3.1.6-1. Preparation of aqueous dispersion for first polishing 2 kg of fumed silica particles (manufactured by Nippon Aerosil Co., Ltd., trade name “Aerosil # 90”, primary particle diameter 20 nm, secondary particle diameter 220 nm) using an ultrasonic disperser After being dispersed in 6.7 kg of ion-exchanged water, it was filtered through a filter having a pore size of 5 μm to obtain an aqueous dispersion containing 23.0% by mass of fumed silica particles.

  Next, the above-mentioned aqueous dispersion was charged into a polyethylene bottle in an amount corresponding to 1.2% by mass in terms of silica, and quinaldic acid was added to 0.5% by mass, Surfynol 465. (Trade name, nonionic surfactant having a triple bond, manufactured by Air Products Japan Co., Ltd.) 0.05 mass% equivalent amount and ammonium persulfate equivalent 1.0 mass% equivalent amount, and further ion exchange water After addition and dilution, the mixture was thoroughly stirred. Subsequently, after adjusting pH to 9.5 with 1 N potassium hydroxide aqueous solution, it filtered with the filter of the hole diameter of 5 micrometers, and obtained the 1st polishing aqueous dispersion.

3.1.6-2. Evaluation of polishing performance of first aqueous dispersion for polishing 3.1.6-2A. Chemical mechanical polishing experiment on wafer without pattern Chemical mechanical polishing equipment (Ebara Manufacturing Co., Ltd., model “EPO112”) was equipped with a porous polyurethane polishing pad (Nitta Haas Co., product number “IC1000”). While supplying the first polishing aqueous dispersion, the following various polishing rate measurement substrates were subjected to a chemical mechanical polishing treatment under the following polishing conditions for 1 minute, and the polishing rate was calculated by the following method.

(I) A polishing rate measuring substrate / a silicon substrate with an 8-inch thermal oxide film provided with a 15,000 mm thick copper film.
-A tantalum film with a thickness of 2,000 mm is provided on a silicon substrate with an 8-inch thermal oxide film.
-A tantalum nitride film with a thickness of 2,000 mm is provided on a silicon substrate with an 8-inch thermal oxide film.
-A PETEOS film with a thickness of 10,000 mm is provided on an 8-inch silicon substrate.

(Ii) Polishing conditions and head rotation speed: 70 rpm
Head load: 250 g / cm ²
・ Table rotation speed: 70rpm
-Supply rate of the first polishing aqueous dispersion: 200 ml / min

(Iii) Calculation method of polishing rate About copper film, a tantalum film, and a tantalum nitride film, after polishing processing using an electric conduction type film thickness measuring device (manufactured by KLA Tencor Co., Ltd., type “Omnimap RS75”) The film thickness was measured, and the polishing rate was calculated from the film thickness reduced by chemical mechanical polishing and the polishing time.

  For the PETEOS film, the film thickness after the polishing treatment was measured using an optical interference film thickness measuring instrument (manufactured by SENTEC, model “FPT500”), and the polishing rate was determined from the film thickness decreased by chemical mechanical polishing and the polishing time. Was calculated.

(Iv) Polishing rate / Copper film polishing rate (R _Cu ): 5200 Å / min · Tantalum film polishing rate (R _BM (Ta)): 30 Å / min · Tantalum nitride film polishing rate (R _BM (TaN)) : 40 Å / min · PETOS film polishing rate (R _In ): 20 Å / min · Copper film polishing rate / Tantalum film polishing rate (R _Cu / R _BM ): 173
Copper film polishing rate / tantalum nitride film polishing rate (R _Cu / R _BM ): 130
Polishing rate of copper film / Polishing rate of PETEOS film (R _Cu / R _In ): 260

3.1.6-2B. Chemical Mechanical Polishing Experiment on Patterned Substrate A porous polyurethane polishing pad (made by Nitta Haas Co., product number “IC1000”) was attached to a chemical mechanical polishing device (manufactured by Ebara Corporation, model “EPO112”). While supplying the first polishing aqueous dispersion, chemical mechanical polishing treatment was performed on the following two kinds of patterned substrates under the following polishing conditions.

(I) Substrate with a pattern, manufactured by SEMATECH, product number “854CMP100”, a concave portion formed of various patterns is formed on a silicon substrate, and a tantalum film (thickness 250 mm), a copper seed film (thickness 1,000 mm) ) And a copper plating film (thickness 10,000 mm) in sequence.
-SEMATECH Co., product number "854CMP101", concave portions made of various patterns are formed on a silicon substrate, and a tantalum nitride film (thickness 250 mm), a copper seed film (thickness 1,000 mm), and a copper plating film (Thickness 10,000 mm) stacked in sequence.

(Ii) Polishing conditions and head rotation speed: 70 rpm
Head load: 250 g / cm ²
・ Table rotation speed: 70rpm
-Feed rate of the first polishing aqueous dispersion: 200 ml / min-Polishing time: 2.75 min After the completion of the first polishing treatment, all of the excess copper film above the barrier metal film is removed, and the barrier metal film It is presumed that the upper surface is exposed.

  After completion of the first polishing process, the size of dishing in the copper wiring portion having a width of 100 μm on the surface to be polished was measured using a surface roughness meter (model “P-10” manufactured by KLA-Tencor). As a result, it was 500cm.

  Here, “dishing” refers to the difference in height between the upper surface of the barrier metal film sandwiching the copper wiring at the measurement position and the lowest part of the copper wiring at the measurement position on the polished surface after polishing.

  In addition, using an optical microscope, in a dark field, the copper wiring portion was observed at 200 random locations with a region of 120 μm × 120 μm as a unit region, and the number of scratched unit regions was measured as the number of scratches. The number of scratches was 0.

3.2. Example 1
3.2.1. Preparation of Second Polishing Aqueous Dispersion (Chemical Mechanical Polishing Aqueous Dispersion of First Aspect of the Present Invention) Prepared in “3.1.2-1. Preparation of Aqueous Dispersion Containing Colloidal Silica Particles C1” above. In an amount equivalent to 1% by mass in terms of silica of the aqueous dispersion containing the colloidal silica particles C1 and the organic-inorganic composite prepared in the above "3.1.3. Preparation of aqueous dispersion containing organic-inorganic composite particles" An amount corresponding to 0.1% by mass in terms of organic-inorganic composite particles of an aqueous dispersion containing particles is put in a polyethylene bottle, and 0.2% by mass of benzotriazole, 0.1% by mass of maleic acid, And the amount corresponding to 0.3% by mass in terms of hydrogen peroxide of 35% by mass hydrogen peroxide was sequentially added and stirred for 15 minutes. Next, ion-exchanged water is added so that the total amount of all the constituent components becomes 100% by mass, and then filtered through a filter having a pore diameter of 5 μm to obtain a second polishing aqueous dispersion S1 having a pH of 2.3. It was.

3.2.2. Evaluation of polishing performance of second polishing aqueous dispersion 3.2.2-1. Polishing test of unpatterned substrate A chemical polishing machine (made by Ebara Manufacturing Co., Ltd., model “EPO112”) was equipped with a porous polyurethane polishing pad (made by Nitta Haas Co., product number “IC1000”). While supplying the two polishing aqueous dispersions, the following various polishing rate measurement substrates were subjected to a chemical mechanical polishing treatment under the following polishing conditions for 1 minute, and the polishing rate was calculated by the following method.

(I) A polishing rate measuring substrate / a silicon substrate with an 8-inch thermal oxide film provided with a 15,000 mm thick copper film.
-A tantalum film with a thickness of 2,000 mm is provided on a silicon substrate with an 8-inch thermal oxide film.
-A tantalum nitride film with a thickness of 2,000 mm is provided on a silicon substrate with an 8-inch thermal oxide film.
-A PETEOS film with a thickness of 10,000 mm is provided on an 8-inch silicon substrate.
-A silicon substrate with an 8-inch thermal oxide film provided with a low dielectric constant insulating film having a thickness of 2,000 mm manufactured in "(5) Production of low dielectric constant insulating film" above.

(Ii) Polishing conditions and head rotation speed: 70 rpm
Head load: 250 g / cm ²
・ Table rotation speed: 70rpm
-Supply rate of the second polishing aqueous dispersion: 200 ml / min

(Iii) Calculation method of polishing rate About copper film, tantalum film, and tantalum nitride film, after polishing treatment using an electric conduction type film thickness measuring device (model OMNIMAP RS75, manufactured by KLA-Tencor Corporation) The film thickness was measured, and the polishing rate was calculated from the film thickness decreased by chemical mechanical polishing and the polishing time.

  For the PETEOS film and the low dielectric constant insulating film, the film thickness after the polishing treatment was measured using an optical interference film thickness measuring instrument (manufactured by SENTEC, model “FPT500”). The polishing rate was calculated from the polishing time.

(Iv) Polishing rate / Copper film polishing rate (R _Cu ): 70 Å / min · Tantalum film polishing rate (R _BM (Ta)): 550 Å / min · Tantalum nitride film polishing rate (R _BM (TaN)) : 620 Å / min · Polishing rate of PETEOS film (R _In ): 40 Å / min · Polishing rate of low dielectric constant insulating film (R _In ): 15 Å / min · Polishing rate of tantalum film / Polishing rate of copper film (R _BM (Ta) / R _Cu ): 7.86
-Polishing speed of tantalum nitride film / polishing speed of copper film (R _BM (TaN) / R _Cu ): 8.86
Polishing rate of tantalum film / Polishing rate of PETEOS film (R _BM (Ta) / R _In (TEOS film)): 13.75
Polishing rate of tantalum nitride film / Polishing rate of PETEOS film (R _BM (TaN) / R _In (TEOS film)): 15.50
Polishing rate of tantalum film / polishing rate of low dielectric constant insulating film (R _BM (Ta) / R _In (low dielectric constant insulating film)): 36.67
Polishing speed of tantalum nitride film / polishing speed of low dielectric constant insulating film (R _BM (TaN) / R _In (low dielectric constant insulating film)): 41.33

(V) Evaluation method after polishing of low dielectric constant insulating film The presence or absence of peeling at the outer periphery was observed visually and with an optical microscope.

  Further, the entire surface to be polished was observed by visual inspection, an optical microscope, and a pattern-less wafer surface foreign matter inspection apparatus (manufactured by KLA-Tencor Co., Ltd., type “Surfscan SP1”), and the number of scratches was evaluated.

3.2.2-2. Polishing test of patterned substrate A chemical polishing machine (made by Ebara Manufacturing Co., Ltd., model “EPO112”) was equipped with a porous polyurethane polishing pad (made by Nitta Haas Co., product number “IC1000”). Two-stage chemical mechanical polishing was performed on the two types of patterned substrates under the following polishing conditions.

(I) Substrate with a pattern, manufactured by SEMATECH, product number “854CMP100”, a concave portion formed of various patterns is formed on a silicon substrate, and a tantalum film (thickness 250 mm), a copper seed film (thickness 1,000 mm) ) And a copper plating film (thickness 10,000 mm) in sequence.
-SEMATECH Co., product number "854CMP101", concave portions made of various patterns are formed on a silicon substrate, and a tantalum nitride film (thickness 250 mm), a copper seed film (thickness 1,000 mm), and a copper plating film (Thickness 10,000 mm) stacked in sequence.

(Ii) Polishing conditions of first polishing treatment step / type of chemical mechanical polishing aqueous dispersion: first polishing aqueous dispersion prepared in “3.1.6-1. Preparation of first polishing aqueous dispersion” above Body / first polishing aqueous dispersion supply speed: 200 ml / min. / Head rotation speed: 70 rpm
Head load: 250 g / cm ²
・ Table rotation speed: 70rpm
・ Polishing time: 2.75 minutes

(Iii) Polishing conditions of the second polishing treatment step / type of chemical mechanical polishing aqueous dispersion: “3.2.1. Second polishing aqueous dispersion (chemical mechanical polishing aqueous system according to the first aspect of the present invention) Supply speed of second polishing aqueous dispersion / second polishing aqueous dispersion prepared in “Preparation of dispersion)”: 200 ml / min. Head rotation speed: 70 rpm
Head load: 250 g / cm ²
・ Table rotation speed: 70rpm
Polishing time: 0.68 minutes per patterned substrate using 854 CMP100, 0.60 minutes per patterned substrate using 854 CMP101

The polishing time is a time calculated by the following formula.
Polishing time (min) = {thickness of barrier metal film (÷) / polishing rate of barrier metal film (tantalum or tantalum nitride) calculated in the above “3.2.2-1. Polishing test of unpatterned substrate” ( Å / min)} x 1.5 (min)

  After the second polishing process is completed, it is estimated that all of the excess barrier metal film above the uppermost surface of the PETEOS film is removed and the upper surface of the PETEOS film is exposed.

  After completion of the second polishing treatment step, the size of dishing generated on the copper wiring portion having a width of 100 μm on the surface to be polished was measured using a surface roughness meter (model “P-10” manufactured by KLA-Tencor). As a result, it was 330 mm per patterned substrate using 854 CMP100 and 320 mm per patterned substrate using 854 CMP101.

  Here, “dishing” refers to the difference in height between the upper surface of the PETEOS film sandwiching the copper wiring at the measurement position and the lowest part of the copper wiring at the measurement position on the polished surface after polishing.

  In addition, the amount of polishing of the insulating film in the field region having no pattern (field region wider than 120 μm × 120 μm) is measured by using an optical interference film thickness measuring device (manufactured by SENTEC, model “FPT500”). When the film thickness was calculated from the initial film thickness of 5000 mm, it was found to be 20 mm or less for both the patterned substrate using 854CMP100 and the patterned substrate using 854CMP101.

  Furthermore, using an optical microscope, in a dark field, the copper wiring portion was observed at 200 random locations with a region of 120 μm × 120 μm as a unit region, and the number of scratched unit regions was measured as the number of scratches. The number of scratches was 0 in both the patterned substrate using 854CMP100 and the patterned substrate using 854CMP101.

3.3. Examples 2 to 5 and Comparative Examples 1 to 2
In Example 1, the second polishing water was prepared in the same manner as in Example 1, except that the types and amounts of each component of the second polishing aqueous dispersion and the pH of the aqueous dispersion were as shown in Table 2. System dispersions S2 to S5 and R1 to R2 were prepared. In Table 2, “-” indicates that the component corresponding to the corresponding column was not added. In addition, Example 4 used two types of particles as the component (B), and Example 5 used two types of particles as the component (A).

  Evaluation was conducted in the same manner as in Example 1 except that each of the aqueous dispersions synthesized above was used instead of S1 as the second polishing aqueous dispersion. The results are shown in Table 3.

  According to Table 2 and Table 3, by using the chemical mechanical polishing aqueous dispersion of the first aspect of the present invention as the second polishing aqueous dispersion, the low dielectric constant having low mechanical strength for the second polishing treatment step. Even when used for polishing a polished body made of a semiconductor substrate having an interlayer insulating film with a high rate, the generation of scratches on the surface to be polished is greatly suppressed, and the insulating film is excessively polished. It was found that a highly polished surface with sufficient flatness was obtained.

3.4. Example 6
3.4.1. Preparation of second polishing aqueous dispersion (kit for preparing chemical mechanical polishing aqueous dispersion of first aspect of the present invention) 3.4.1-1. Preparation of liquid (I) 1.06 mass in terms of silica of the aqueous dispersion containing colloidal silica particles C1 prepared in the above-mentioned "3.1.2-1. Preparation of aqueous dispersion containing colloidal silica particles C1". % And 0.11 in terms of organic-inorganic composite particles of an aqueous dispersion containing organic-inorganic composite particles prepared in “3.1.3. Preparation of aqueous dispersion containing organic-inorganic composite particles”. An amount corresponding to mass% was placed in a polyethylene bottle, and 0.21 mass% of benzotriazole and an amount corresponding to 0.11 mass% of maleic acid were sequentially added thereto and stirred for 15 minutes. Subsequently, after adding ion-exchange water so that the total amount of all the structural components may be 100 mass%, it filtered with a filter with a hole diameter of 5 micrometers, and obtained liquid (I) A1 which is an aqueous dispersion.

3.4.1-2. Preparation of Liquid (II) The concentration was adjusted with ion-exchanged water so that the hydrogen peroxide concentration was 5% by mass to obtain Liquid (II) B1.

3.4.2. Evaluation of polishing performance of second polishing aqueous dispersion 100 parts by mass of liquid (I) A1 prepared above and 6.38 parts by mass of liquid (II) B1 were mixed to obtain an aqueous dispersion for chemical mechanical polishing. S6 was prepared. The pH of this chemical mechanical polishing aqueous dispersion S6 was 2.3. Since this chemical mechanical polishing aqueous dispersion S6 has the same composition and pH as the chemical mechanical polishing aqueous dispersion S1 prepared in Example 1, the chemical mechanical polishing aqueous dispersion S6 is used in the above Examples. It can be considered that the chemical mechanical polishing aqueous dispersion S1 prepared in 1 is the same chemical mechanical polishing aqueous dispersion S1.

  In this example, as the second polishing aqueous dispersion, the chemical mechanical polishing aqueous dispersion S6 synthesized above was used instead of the chemical mechanical polishing aqueous dispersion S1 in the same manner as in Example 1. The same results as in Example 1 were obtained.

3.5. Example 7
3.5.1. Preparation of second polishing aqueous dispersion (kit for preparing chemical mechanical polishing aqueous dispersion of first aspect of the present invention) 3.5.1-1. Preparation of liquid (I) 2.0 mass in terms of silica of the aqueous dispersion containing colloidal silica particles C1 prepared in the above “3.1.2-1. Preparation of aqueous dispersion containing colloidal silica particles C1”. % In terms of the amount corresponding to% and 0.2 in terms of the organic-inorganic composite particles of the aqueous dispersion containing the organic-inorganic composite particles prepared in “3.1.3. Preparation of aqueous dispersion containing organic-inorganic composite particles”. The amount corresponding to mass% and the amount corresponding to 0.6 mass% in terms of hydrogen peroxide of 35 mass% hydrogen peroxide water were sequentially put into a polyethylene bottle and stirred for 15 minutes. Next, ion-exchanged water was added so that the total amount of all components was 100% by mass, followed by filtration with a filter having a pore diameter of 5 μm to obtain liquid (I) A2 as an aqueous dispersion.

3.5.1-2. Preparation of Liquid (II) In a polyethylene bottle, an amount corresponding to 0.4% by mass of benzotriazole and 0.2% by mass of maleic acid was sequentially added and stirred for 15 minutes. Next, ion-exchanged water was added so that the total amount of all the constituent components was 100% by mass, followed by filtration with a filter having a pore size of 5 μm to obtain liquid (II) A3 as an aqueous dispersion.

3.5.2. Evaluation of Polishing Performance of Second Polishing Aqueous Dispersion 50 parts by mass of the liquid (I) A2 prepared above and 50 parts by mass of the liquid (II) A3 were mixed, and the chemical mechanical polishing aqueous dispersion S7 was prepared. Prepared. The pH of this chemical mechanical polishing aqueous dispersion S7 was 2.3. Since this chemical mechanical polishing aqueous dispersion S7 has the same composition and pH as the chemical mechanical polishing aqueous dispersion S1 prepared in Example 1, the chemical mechanical polishing aqueous dispersion S7 is the same as that of the above example. It can be considered that the chemical mechanical polishing aqueous dispersion S1 prepared in 1 is the same chemical mechanical polishing aqueous dispersion S1.

  In this example, as the second polishing aqueous dispersion, the chemical mechanical polishing aqueous dispersion S7 synthesized above was used instead of the chemical mechanical polishing aqueous dispersion S1 in the same manner as in Example 1. The same results as in Example 1 were obtained.

3.6. Example 8
3.6.1. Preparation of Second Polishing Aqueous Dispersion (Kit for Preparing Chemical Mechanical Polishing Aqueous Dispersion of First Aspect of the Present Invention) 3.6.1-1. Preparation of liquid (I) 2.13 mass in terms of silica of the aqueous dispersion containing colloidal silica particles C1 prepared in the above-mentioned "3.1.2-1. Preparation of aqueous dispersion containing colloidal silica particles C1". % And 0.21 in terms of organic-inorganic composite particles of an aqueous dispersion containing organic-inorganic composite particles prepared in “3.1.3. Preparation of aqueous dispersion containing organic-inorganic composite particles”. The amount corresponding to mass% was sequentially put into a polyethylene bottle and stirred for 15 minutes. Subsequently, after adding ion-exchange water so that the total amount of all the structural components may be 100 mass%, it filtered with the filter of the hole diameter of 5 micrometers, and obtained liquid (I) A4 which is an aqueous dispersion.

3.6.1-2. Preparation of Liquid (II) In a polyethylene bottle, an amount corresponding to 0.43% by mass of benzotriazole and 0.21% by mass of maleic acid was sequentially added and stirred for 15 minutes. Next, ion-exchanged water was added so that the total amount of all components was 100% by mass, followed by filtration with a filter having a pore size of 5 μm to obtain liquid (II) A5 which was an aqueous dispersion.

3.6.2. Evaluation of polishing performance of second polishing aqueous dispersion 50 parts by mass of liquid (I) A4 prepared above, 50 parts by mass of liquid (II) A5, 6.38 parts by mass of liquid (III) B1 Were mixed to prepare a chemical mechanical polishing aqueous dispersion S8. The pH of this chemical mechanical polishing aqueous dispersion S8 was 2.3. Since this chemical mechanical polishing aqueous dispersion S8 has the same composition and pH as the chemical mechanical polishing aqueous dispersion S1 prepared in Example 1, the chemical mechanical polishing aqueous dispersion S8 is used in the above Examples. It can be considered that the chemical mechanical polishing aqueous dispersion S1 prepared in 1 is the same chemical mechanical polishing aqueous dispersion S1.

  In this example, the chemical mechanical polishing aqueous dispersion S8 synthesized above was used in place of the chemical mechanical polishing aqueous dispersion S1 as the second polishing aqueous dispersion, in the same manner as in Example 1. The same results as in Example 1 were obtained.

It is the schematic which shows an example of the to-be-polished surface of the chemical mechanical polishing method which concerns on the 2nd Embodiment of this invention. It is the schematic which shows an example of the to-be-polished surface of the chemical mechanical polishing method which concerns on the 2nd Embodiment of this invention.

Explanation of symbols

1 Composite substrate material 11 Substrate (for example, silicon)
12 Insulating film (for example, made by PETEOS)
13 Barrier metal film 14 Metal film 21 Insulating film (for example, made of silicon oxide)
22 Insulating film (eg, silicon nitride)

Claims (11)

(A) component: inorganic particles,
(B) component: at least one selected from the group consisting of organic particles and organic-inorganic composite particles,
(C) component: at least one selected from the group consisting of quinolinecarboxylic acid, quinolinic acid, divalent organic acid (excluding quinolinic acid) and hydroxyl acid,
(D) component: at least one selected from the group consisting of benzotriazole and its derivatives,
(E) component: oxidizing agent, and (F) component: containing water,
The amount of the component (A) is 0.05 to 2.0% by mass, the amount of the component (B) is 0.005 to 1.5% by mass, and the amount of the component (A) is Chemical mechanical polishing water having a ratio (W _A / W _B ) of (W _A ) to the blending amount (W _B ) of the component ( _B ) of 0.1 to 200 and a pH of 1 to 5. System dispersion. In claim 1,
An aqueous dispersion for chemical mechanical polishing, wherein the amount of the component (C) is 0.005 to 3.0% by mass. In claim 1 or 2,
An aqueous dispersion for chemical mechanical polishing, wherein the component (A) is silica particles. In any one of Claims 1 thru | or 3,
The chemical mechanical polishing aqueous dispersion, wherein the component (D) is benzotriazole and the blending amount is 0.01 to 5.0% by mass. In any of claims 1 to 4,
The chemical mechanical polishing aqueous dispersion, wherein the component (E) is hydrogen peroxide and the blending amount is 0.01 to 5.0 mass%. A kit for preparing an aqueous dispersion for chemical mechanical polishing according to any one of claims 1 to 5, comprising mixing liquid (I) and liquid (II),
The liquid (I) is at least one selected from the group consisting of (A) inorganic particles, (B) organic particles and organic-inorganic composite particles, (C) quinolinecarboxylic acid, quinolinic acid, divalent organic acid ( However, quinolinic acid is excluded.) And at least one selected from the group consisting of hydroxyl acids, (D) at least one selected from the group consisting of benzotriazole and derivatives thereof, and (F) an aqueous dispersion containing water And
The liquid (II) is a kit for preparing an aqueous dispersion for chemical mechanical polishing containing (E) an oxidizing agent and (F) water. A kit for preparing an aqueous dispersion for chemical mechanical polishing according to any one of claims 1 to 5, comprising mixing liquid (I) and liquid (II),
The liquid (I) is an aqueous dispersion containing (A) inorganic particles, (B) at least one selected from the group consisting of organic particles and organic-inorganic composite particles, and (F) water.
The liquid (II) comprises (C) at least one selected from the group consisting of quinolinecarboxylic acid, quinolinic acid, divalent organic acid (excluding quinolinic acid) and hydroxyl acid, and (F) water. A kit for preparing a chemical mechanical polishing aqueous dispersion. A kit for preparing an aqueous dispersion for chemical mechanical polishing according to any one of claims 1 to 5, comprising mixing liquid (I), liquid (II), and liquid (III),
The liquid (I) is an aqueous dispersion containing (A) inorganic particles, (B) at least one selected from the group consisting of organic particles and organic-inorganic composite particles, and (F) water.
The liquid (II) comprises (C) at least one selected from the group consisting of quinolinecarboxylic acid, quinolinic acid, divalent organic acid (excluding quinolinic acid) and hydroxyl acid, and (F) water. Including
The liquid (III) is a kit for preparing a chemical mechanical polishing aqueous dispersion containing (E) an oxidizing agent and (F) water. In claim 7 or 8,
The liquid (I) is (C) at least one selected from the group consisting of quinolinecarboxylic acid, quinolinic acid, divalent organic acid (excluding quinolinic acid) and hydroxyl acid, (D) benzotriazole and A kit for preparing an aqueous dispersion for chemical mechanical polishing, further comprising at least one selected from the group consisting of derivatives thereof and one or more components selected from (E) an oxidizing agent. In any of claims 7 to 9,
The liquid (II) is at least one selected from the group consisting of (A) inorganic particles, (B) organic particles and organic-inorganic composite particles, and (D) at least selected from the group consisting of benzotriazole and derivatives thereof. A kit for preparing an aqueous dispersion for chemical mechanical polishing, further comprising one type and one or more components selected from (E) an oxidizing agent. Copper, a barrier metal film and the insulating film, when each chemical mechanical polishing in the same conditions, the ratio R _{Cu /} R _BM of the polishing rate R _BM of the polishing rate R _Cu and the barrier metal film of copper film 50 or more There, and was chemically mechanically polishing objects using the ratio R _{Cu /} R _in the polishing rate R _{an in} the polishing rate R _Cu and the insulating film of the copper film is 50 or more chemical mechanical polishing aqueous dispersion 6. A chemical mechanical polishing method comprising: chemically mechanically polishing the object to be polished using the chemical mechanical polishing aqueous dispersion according to any one of claims 1 to 5.

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