KR101564469B1 - Chemical mechanical polishing aqueous dispersion for manufacturing circuit board circuit board manufacturing method circuit board and multilayer circuit board - Google Patents

Abstract

An object of the present invention is to provide an aqueous dispersion for chemical mechanical polishing which is preferably used for forming a circuit board on which a wiring layer comprising copper or a copper alloy is formed on a resin substrate and which has a sufficiently high polishing rate for copper or copper alloy, And an object of the present invention is to provide an aqueous dispersion for chemical mechanical polishing having a good flatness of the obtained circuit board.

The aqueous dispersion for chemical mechanical polishing according to the present invention is an aqueous dispersion for chemical mechanical polishing used for forming a circuit board on which a wiring layer comprising copper or a copper alloy is formed on a resin substrate, (B1) at least one of a surfactant and a water-soluble polymer compound, (C1) an oxidizing agent, and (D1) abrasive grains, wherein the concentration of the component (A1) in the aqueous dispersion for chemical mechanical polishing _A1 at M (mass%) and the (D1) _D1 M concentration (mass%) of components, having a relationship M _A1 / M _D1 = 1 to 30, a value of pH 8 to 12.

Aqueous dispersion for chemical mechanical polishing, organic acid, oxidizing agent, abrasive, circuit board

Description

TECHNICAL FIELD [0001] The present invention relates to a chemical mechanical polishing aqueous dispersion for use in the production of a circuit board, a method for producing a circuit board, a circuit board and a multilayer circuit board,

TECHNICAL FIELD The present invention relates to an aqueous dispersion for chemical mechanical polishing used in the production of a circuit board, a method for producing a circuit board using the aqueous dispersion, a circuit board and a multilayer circuit board.

BACKGROUND ART [0002] In recent years, miniaturization of electronic devices has been progressing, and further miniaturization and multilayering of a semiconductor device constituting the electronic device and a circuit board for mounting the semiconductor device are required. A multilayer circuit board (multilayered circuit board) generally has a plurality of circuit boards on which wiring patterns are formed, and has a three-dimensional wiring structure. If the thickness of the multilayer circuit board or the circuit board is not uniform or the flatness is insufficient, problems such as connection failure may occur when the semiconductor device is mounted. Therefore, the circuit boards of the respective layers constituting the multilayer circuit board need not only have a uniform thickness but also have a flat surface so as to prevent concavity and convexity from occurring when the multilayer circuit board is laminated. .

One of the reasons for impairing the flatness of the circuit board is the unevenness of the wiring pattern. Such unevenness often occurs when a circuit board is manufactured. As a method for producing a circuit board having a wiring pattern, for example, a method is known in which a concave portion corresponding to a desired wiring pattern is formed on the surface of a substrate, a conductive layer is formed on the entire surface by plating, There is a method in which the conductive layer remains only in the recessed portion. In such a manufacturing method, in the plating process, the thinner the line width of the wiring pattern, the thicker the plating thickness becomes, and the distribution in the current at the time of plating is generated due to the wiring density coarsening of the wiring pattern, The thickness may become uneven in some cases. Therefore, the fluctuation of the initial plating thickness affects the subsequent polishing step, and consequently, the flatness of the circuit board is sometimes deteriorated. In addition, when the circuit board is formed by polishing, there is a case where a dishing phenomenon occurs in which the polished surface of the wiring pattern formed on the circuit board becomes a concave shape.

The polishing step is performed, for example, by buff polishing. The following Patent Document 1 discloses a polishing method using a roll buff. However, a roll buff formed by combining hard abrasive grains with a bonding agent and forming a cylindrical shape is used. Therefore, in such a polishing method, the thickness of the circuit board tends to be uneven, and the surface of the conductive layer is easily damaged (flatness damage). A method of using a slurry in buff polishing has also been proposed (for example, see Patent Document 2 below). However, this method also has a large difference in polishing rate depending on the material of the polished surface to be polished, and it does not reach a level of technology that can achieve a very high thickness uniformity and surface flatness as a circuit board used for a multilayer circuit board Respectively.

[Patent Document 1] Japanese Unexamined Patent Publication No. 2002-134920

[Patent Document 2] Japanese Unexamined Patent Publication No. 2003-257910

When the polishing process is performed by chemical mechanical polishing, the flatness is improved as compared with other polishing methods. However, conventional chemical mechanical polishing has a low polishing rate. Particularly, in order to form a circuit board, since the amount of wiring material to be removed is large, it is necessary to remarkably improve the polishing speed of the chemical mechanical polishing. As described above, the performance of the chemical mechanical polishing aqueous dispersion used for polishing a circuit substrate by chemical mechanical polishing is required not only to increase the flatness of the polished surface, but also to increase the polishing rate.

One of the objects of the present invention is to provide an aqueous dispersion for chemical mechanical polishing which is preferably used for forming a circuit board on which a wiring layer comprising copper or a copper alloy is provided on a resin substrate and which has a sufficient polishing rate for copper or a copper alloy And which is excellent in planarity of the obtained circuit board.

One of the objects of the present invention is to provide a manufacturing method of a circuit board having good flatness, which includes a step of performing chemical mechanical polishing, and which has a sufficiently high polishing rate in the above process.

One of the objects of the present invention is to provide a circuit board having good flatness and a multilayer circuit board having a plurality of the circuit boards laminated and having good flatness.

The present invention has been made to solve at least some of the problems described above, and can be realized as the following aspects or application examples.

[Application Example 1]

One aspect of the chemical mechanical polishing aqueous dispersion according to the present invention is characterized in that,

An aqueous dispersion for chemical mechanical polishing used for forming a circuit board on which a wiring layer containing copper or a copper alloy is provided on a resin substrate,

(A1) at least one kind of salts of organic acids and organic acids,

(B1) at least one of a surfactant and a water-soluble polymer compound,

(C1) an oxidizing agent,

(D1) abrasive grain,

M _A1 / M _D1 = 1 to 30 in the concentration M _A1 (mass%) of the component (A1) and the concentration M _D1 (mass%) of the component (D1) relative to the chemical mechanical polishing aqueous dispersion Lt; / RTI &

and a pH value of 8 to 12.

[Application example 2]

In Application Example 1,

And further M _A1 = 5 to 15 (mass%).

[Application Example 3]

In Application Example 1,

The component (A1) may be glycine.

[Application example 4]

In Application Example 1,

The component (B1) may be at least one member selected from dodecylbenzenesulfonic acid, potassium dodecylbenzenesulfonate and ammonium dodecylbenzenesulfonate.

[Application Example 5]

In Application Example 1,

The component (C1) may be hydrogen peroxide.

[Application Example 6]

In Application Example 1,

The component (D1) may be at least one member selected from silica particles, calcium carbonate particles, organic polymer particles and organic-inorganic composite particles.

[Application Example 7]

An aspect of the method of manufacturing a circuit board according to the present invention is characterized in that,

And chemical mechanical polishing using the aqueous dispersion for chemical mechanical polishing according to any one of Application Examples 1 to 6.

[Application Example 8]

One embodiment of the circuit board according to the present invention is manufactured by the manufacturing method described in Application Example 7. [

[Application Example 9]

One aspect of the multilayer circuit board according to the present invention includes a plurality of the circuit boards described in Application Example 8 stacked.

[Application Example 10]

One aspect of the chemical mechanical polishing aqueous dispersion according to the present invention is characterized in that,

An aqueous dispersion for chemical mechanical polishing used for forming a circuit board on which a wiring layer containing copper or a copper alloy is provided on a resin substrate,

(A2) an organic acid,

(B2) a nitrogen-containing heterocyclic compound,

(C2) an oxidizing agent,

(D2) abrasive grains,

In the above (A2) the concentration M _A2 (% by weight) of the component and the (D2) concentration M _D2 (% by mass) of components for the aqueous dispersion for the chemical mechanical polishing, and the relationship M _A2 / M _D2 = 1 to 20 Lt; / RTI &

and a pH value of 1 to 5.

[Application Example 11]

In Application Example 10,

And M _A2 = 3 to 15 (mass%).

[Application Example 12]

In Application Example 10,

The (A2) organic acid may be at least one selected from citric acid, glycine, malic acid, tartaric acid and oxalic acid.

[Application Example 13]

In Application Example 10,

The nitrogen-containing heterocyclic compound (B2) may be at least one selected from benzotriazole, triazole, imidazole and carboxybenzotriazole.

[Application Example 14]

In Application Example 10,

The (C2) oxidizing agent may be hydrogen peroxide.

[Application Example 15]

In Application Example 10,

The abrasive (D2) may be any one of silica particles, calcium carbonate particles, organic polymer particles and organic-inorganic composite particles.

[Application Example 16]

An aspect of the method of manufacturing a circuit board according to the present invention is characterized in that,

And a step of performing chemical mechanical polishing using the aqueous dispersion for chemical mechanical polishing according to any one of Application Examples 10 to 15.

[Application Example 17]

One embodiment of the circuit board according to the present invention is manufactured by the manufacturing method described in Application Example 16. [

[Application Example 18]

In one aspect of the multilayer circuit board according to the present invention, a plurality of circuit boards described in Application Example 17 are laminated.

According to the chemical mechanical polishing aqueous dispersion, a circuit board provided with a wiring layer containing copper or a copper alloy on a resin substrate can be uniformly polished over the entire surface of the circuit board and its surface can be polished flat. Further, according to the aqueous dispersion for chemical mechanical polishing, the polishing rate of copper or copper alloy can be made very high on the order of 탆 / minute. In addition, according to the above-described method of manufacturing a circuit board, the circuit board can be manufactured with a flatness and a high throughput. Further, the circuit board and the multilayer circuit board have a uniform thickness over the entire substrate and have a flat surface. According to the aqueous dispersion for chemical mechanical polishing according to the present invention, it is possible to easily provide a circuit board or a multilayer circuit board on which problems such as poor connection and the like are less likely to occur when a semiconductor device or the like is mounted.

Hereinafter, preferred embodiments according to the present invention will be described in detail. Further, the present invention is not limited to the following embodiments, and includes various modifications embodied without departing from the gist of the present invention.

1. An aqueous dispersion for chemical mechanical polishing

1.1. First Embodiment

(B1) at least one of a surfactant and a water-soluble polymer compound, (C1) an oxidizing agent, (D1) at least one kind of surfactant and at least one water-soluble polymer compound, Includes abrasive grain.

Hereinafter, each component included in the chemical mechanical polishing aqueous dispersion according to the first embodiment will be described in detail. In addition, each of the following substances (A1) to (D1) may be omitted as the components (A1) to (D1).

1.1.1. (A1) salts of organic and organic acids

The chemical mechanical polishing aqueous dispersion according to the first embodiment contains at least one of (A1) a salt of an organic acid and an organic acid. One of the functions of the component (A1) is to improve the polishing rate when a chemical mechanical polishing aqueous dispersion is applied to a resin substrate for a wiring layer containing copper or a copper alloy. As the component (A1) used in the chemical mechanical polishing aqueous dispersion according to the first embodiment, an organic acid having a coordinating ability or an organic acid having an ability to coordinate with respect to a surface of a wiring material containing ions of a wiring material element or copper or a copper alloy, Salts of organic acids are preferred. The component (A1) is more preferably a salt of an organic acid or an organic acid having a chelate coordinating ability.

Examples of the organic acid used in the chemical mechanical polishing aqueous dispersion according to the first embodiment include organic acids such as tartaric acid, fumaric acid, glycolic acid, phthalic acid, maleic acid, formic acid, acetic acid, oxalic acid, citric acid, malic acid, malonic acid, glutaric acid, Benzoic acid, quinolinic acid, quinaldic acid, amide sulfuric acid, and the like. As the organic acid used in the present invention, amino acids such as glycine, alanine, aspartic acid, glutamic acid, lysine, arginine, tryptophan, aromatic amino acid and heterocyclic amino acid can also be preferably used. The salts of these organic acids and organic acids can be dissociated into anions paired with one or more protons (hydrogen ions) in the aqueous dispersion for chemical mechanical polishing. Among these organic acids, glycine is particularly preferable in that the effect of improving the polishing rate of the aqueous dispersion for chemical mechanical polishing is high.

Examples of the salt of the organic acid used in the aqueous dispersion for chemical mechanical polishing according to the first embodiment include salts of the aforementioned organic acids. The salt of the organic acid can be dissociated into a pair of ions in an aqueous dispersion for chemical mechanical polishing. In a salt of a divalent or higher organic acid, the cations forming the pair may be monovalent or more. Examples of preferable organic acid salts for the chemical mechanical polishing aqueous dispersion of the present embodiment include potassium salts, ammonium salts and sodium salts of the above organic acids. As the salt of the organic acid contained in the aqueous dispersion for chemical mechanical polishing according to the present embodiment, a cation derived from another component optionally added in the state where the organic acid is dissolved in the aqueous dispersion for chemical mechanical polishing, for example, ammonium Ion, potassium ion and the like, and the salt formed when the aqueous dispersion for chemical mechanical polishing is dried. Specific examples of the salt of the organic acid which is preferable for the chemical mechanical polishing aqueous dispersion of the present embodiment include potassium amide sulfate, ammonium amide sulfate, sodium amide sulfate and the like.

In the aqueous dispersion for chemical mechanical polishing according to the first embodiment, the above-mentioned salts of organic acids or organic acids may be contained singly or two or more salts of organic acids and organic acids may be contained.

The content of the component (A1) in the chemical mechanical polishing aqueous dispersion according to the first embodiment may be arbitrary as long as it satisfies the quantitative relationship between the component (A1) and the component (D1) And more preferably 5 to 15% by mass with respect to the mass of the aqueous dispersion for chemical mechanical polishing at the time of use. That is, the concentration M _A1 of the component (A1) in the aqueous dispersion for chemical mechanical polishing is preferably 5 to 15 mass%, more preferably 7 to 13 mass%, and particularly preferably 8 to 12 mass% to be. If the content of the component (A1) is less than the above range, a sufficient polishing rate may not be obtained, and it may take a long time to complete the polishing process. On the other hand, if the content of the component (A1) exceeds the above range, the chemical etching effect becomes large, so that corrosion of the wiring layer occurs or flatness of the surface to be polished may be impaired.

1.1.2. (B1) Surfactant and water-soluble polymer compound

The chemical mechanical polishing aqueous dispersion according to the first embodiment contains at least one of (B1) a surfactant and a water-soluble polymer compound. One of the functions of the component (B1) is to impart viscosity to the chemical mechanical polishing aqueous dispersion to stabilize the polishing performance and to improve the flatness of the surface to be polished. That is, the viscosity of the aqueous dispersion for chemical mechanical polishing can be controlled according to the content of the component (B1). Further, by controlling the viscosity of the aqueous dispersion for chemical mechanical polishing, the polishing performance of the aqueous dispersion for chemical mechanical polishing can be controlled.

Examples of the surfactant that can be preferably used in the aqueous dispersion for chemical mechanical polishing according to the first embodiment include a nonionic surfactant, an anionic surfactant, and a cationic surfactant. The nonionic surfactant includes, for example, a nonionic surfactant having a triple bond. Specific examples thereof include acetylene glycol and its ethylene oxide adducts, and acetylene alcohol. Examples of the nonionic surfactant include silicone surfactants, cyclodextrins and derivatives thereof, and the like. Examples of the cationic surfactant include an aliphatic amine salt and an aliphatic ammonium salt. Examples of the anionic surfactant include an aliphatic soap, a sulfuric acid ester salt, and a phosphoric acid ester salt.

Among them, an anionic surfactant is preferable as the surfactant for the chemical mechanical polishing aqueous dispersion according to the present embodiment. Examples of the anionic surfactant include derivatives of succinic acid such as alkenylsuccinic acid, high-class organic acids and salts thereof such as stearic acid and oleic acid, and high-quality sulfonic acids and salts thereof such as alkylbenzenesulfonic acid, alkylnaphthalenesulfonic acid and -olefin sulfonic acid. Examples of salts of alkenylsuccinic acid include dipotassium alkenylsuccinate (trade name "Latex ASK" available from Kao Corporation). As the alkylbenzenesulfonic acid, dodecylbenzenesulfonic acid is particularly preferable. The salt of the sulfonic acid is preferably an ammonium salt, a potassium salt or a sodium salt. Preferable specific examples of the alkylbenzenesulfonic acid salt include ammonium dodecylbenzenesulfonate and potassium dodecylbenzenesulfonate.

Examples of water-soluble polymer compounds that can be preferably used in the aqueous dispersion for chemical mechanical polishing according to the first embodiment include water-soluble high molecular compounds such as polyvinyl pyrrolidone (PVP) and polyvinyl methyl ether, polyacrylic acid (PAA) A water-soluble polymer compound having a carboxylic acid group such as methacrylic acid, a copolymer of acrylic acid and methacrylic acid, a polymeric compound having a carboxylic acid group such as polymaleic acid and salts thereof, a water-soluble polymer compound having a sulfonic acid group such as polyisoprenesulfonic acid and salts thereof, And water-soluble polymer compounds having hydroxyl groups such as hydroxyethylcellulose, polyvinyl alcohol, and the like.

When the water-soluble polymer compound used in the chemical mechanical polishing aqueous dispersion according to the first embodiment is PVP, the value measured by weight average molecular weight (Mw) in terms of polyethylene glycol as measured by aqueous GPC (gel permeation chromatography) It is preferable to use PVP exceeding 20,000,000. PVP having a molecular weight of more than 20,000, preferably 150,000 or less, more preferably 300,000 to 1,500,000, still more preferably 500,000 to 1,200,000, and particularly preferably 650,000 to 1,120,000 may be used. When the weight average molecular weight of PVP is within the above range, the effect of reducing the friction during polishing is enhanced, and the wiring layer including copper and copper can be more stably polished. Further, it is possible to suppress dishing or the like of the wiring layer including copper and copper. If the weight average molecular weight is smaller than the above lower limit, the above effect is liable to become insufficient, which is not preferable. On the other hand, if the weight average molecular weight is too large, the polishing rate tends to decrease and cohesion of abrasive grains tends to occur, and scratches on the wiring layer including copper and copper may increase due to agglomerated abrasive grains .

In the chemical mechanical polishing aqueous dispersion according to the first embodiment, the above-mentioned surfactant and the water-soluble polymer compound may be used singly or in combination of two or more as the component (B1).

The content of the component (B1) in the aqueous dispersion for chemical mechanical polishing according to the first embodiment is preferably 0.01 to 1 (mass%) based on the mass of the aqueous dispersion for chemical mechanical polishing at the time of use By mass, more preferably 0.05 to 0.5% by mass, and particularly preferably 0.1 to 0.3% by mass. If the content of the component (B1) is less than the above range, the viscosity of the aqueous dispersion for chemical mechanical polishing is too low, so that the pressure on the polishing pad can not be efficiently and uniformly transmitted to the surface to be polished. The polishing performance of the aqueous dispersion for chemical mechanical polishing may fluctuate and the flatness may be impaired. In addition, since the viscosity of the aqueous dispersion for chemical mechanical polishing is lowered, it flows out between the substrate to be polished and the polishing pad before the aqueous dispersion for chemical mechanical polishing functions effectively, and in particular, There is a case where the amount of abrasive aqueous dispersion is varied. On the other hand, if the content of the component (B1) exceeds the above range, the effect of improving the flatness with respect to the content may become insufficient and sufficient flatness may not be obtained. The polishing rate may decrease or the viscosity of the aqueous dispersion for chemical mechanical polishing Becomes too high, the abrasive friction heat rises and the in-plane uniformity may deteriorate. When the content of the component (B1) exceeds the above range, bubbles tend to be formed in the aqueous dispersion for chemical mechanical polishing, so that the handling property may be deteriorated.

1.1.3. (C1) oxidizing agent

The chemical mechanical polishing aqueous dispersion according to the first embodiment contains (C1) an oxidizing agent. (C1) One of the functions of the oxidizing agent is to improve the polishing rate when a chemical mechanical polishing aqueous dispersion is applied to the polishing of a circuit board on which a wiring layer containing copper and copper is formed. The reason is that (C1) the oxidizing agent oxidizes the surface of copper or the like to accelerate the complex reaction with the components of the chemical mechanical polishing aqueous dispersion, thereby forming a weakly modified layer on the surface of copper or the like, I think it is easy.

Examples of the oxidizing agent (C1) used in the chemical mechanical polishing aqueous dispersion according to the first embodiment include hydrogen peroxide, organic peroxides such as peracetic acid, perbenzoic acid and tert-butyl hydroperoxide, permanganic acid compounds such as potassium permanganate, And potassium iodate; nitric acid compounds such as nitric acid and iron nitrate; perhalogenated acid compounds such as perchloric acid; persulfates such as ammonium persulfate; and heteropolyacids. Among these oxidizing agents, hydrogen peroxide, organic peroxides or persulfates such as ammonium persulfate are preferable and hydrogen peroxide in which the decomposition products are harmless are particularly preferable in consideration of the oxidizing power, the corrosiveness to the resin substrate, and ease of handling.

The content of the (C1) oxidizing agent in the aqueous dispersion for chemical mechanical polishing according to the first embodiment is preferably 0.5 to 5% by mass with respect to the mass of the aqueous dispersion for chemical mechanical polishing at the time of use, 1 to 4% by mass, and particularly preferably 1.5 to 3% by mass. If the content of the (C1) oxidizing agent is less than the above range, the chemical effect becomes insufficient and the polishing rate may be lowered, and it may take a long time to complete the polishing process. On the other hand, if the content of the oxidizing agent (C1) exceeds the above range, the surface to be polished may be corroded and the flatness may be impaired.

1.1.4. (D1) abrasive grain

The chemical mechanical polishing aqueous dispersion according to the first embodiment includes (D1) abrasive grains. (D1) Examples of the abrasive include inorganic particles, organic particles and organic-inorganic composite particles.

Examples of the inorganic particles include silica particles, alumina particles, titania particles, zirconia particles, ceria particles, and calcium carbonate particles.

Examples of the silica particles include fumed silica synthesized by a fumed method in which silicon chloride or the like is reacted with gaseous hydrogen in vapor phase, silica synthesized by a sol-gel method synthesized by hydrolysis and condensation from metal alkoxide, And colloidal silica synthesized by an inorganic colloid method or the like removed. Particularly, as the silica particles, colloidal silica synthesized by an inorganic colloid method in which impurities are removed by purification is preferable.

When (D1) silica particles are used as the abrasive grains in the chemical mechanical polishing aqueous dispersion according to the first embodiment, it is preferable to use colloidal silica having an average particle diameter of 200 nm or less because the flatness is improved.

As the calcium carbonate particles, high-purity calcium carbonate particles obtained by purifying calcium hydroxide in water and reacting with carbon dioxide gas are preferable.

Examples of the organic particles include olefin-based copolymers such as polyethylene, polypropylene, poly-1-butene and poly-4-methyl-1-pentene; polystyrene; styrene copolymers; polyvinyl chloride; polyacetals; saturated polyesters; polyamides , Polycarbonate, phenoxy resin, polymethyl methacrylate, (meth) acrylic resin and acrylic copolymer.

The organic-inorganic composite particles may include the above-mentioned organic particles and the above-mentioned inorganic particles. The organic-inorganic composite particles are not particularly limited as long as the organic particles and the inorganic particles are integrally formed so as not to be separated easily during the chemical mechanical polishing process. Examples of the organic-inorganic composite particles include polycondensation of alkoxysilanes, aluminum alkoxides, titanium alkoxides, and the like in the presence of polymer particles such as polystyrene and polymethyl methacrylate to form polysiloxane, polyaluminum And a polycondensate such as polyoxyethylene, polyoxyethylene, polyoxyethylene, polyoxyethylene, polyoxyethylene, polyoxyethylene, polyoxyethylene, polyoxyethylene, polyoxyethylene, The resulting polycondensate may be bonded directly to the functional group of the polymer particles, or may be bonded via a silane coupling agent or the like. In place of alkoxysilane, silica particles, alumina particles and the like may also be used. In this case, the organic-inorganic composite particles are formed such that silica particles or the like are present on the surface of the polymer particles using a polycondensate such as polysiloxane, polyaluminoxane, or polytitanic acid as a binder. They may be entangled with a polysiloxane or the like, or they may be chemically bonded to polymer particles by functional groups such as a hydroxyl group.

The organic-inorganic composite particles that can be used in the aqueous dispersion for chemical mechanical polishing according to the first embodiment are those which have a zeta potential different from that of the water-dispersible organic compound, And the like. The zeta potential of the organic particles is often negative over a wide range except the entire pH range or low pH range. However, by making the organic particles having a carboxyl group, a sulfonic acid group and the like more reliable, the organic particles having negative zeta potential . Further, organic particles having a positive zeta potential in a specific pH range can be made into organic particles having an amino group or the like. On the other hand, the zeta potential of the inorganic particles is high in pH dependency and has an isoelectric point at which this potential becomes zero, and the sign of the zeta potential is reversed before and after the isoelectric point. Therefore, by combining specific organic particles and inorganic particles and mixing them in a pH region where their zeta potentials are opposite signs, the organic particles and the inorganic particles can be integrated into one body by electrostatic force. In addition, even when the zeta potential is the same in mixing, the zeta potential is reversed by changing the pH after that, so that the organic particles and the inorganic particles can be integrated.

The organic-inorganic composite particles may be prepared by polycondensing alkoxysilanes, aluminum alkoxides, titanium alkoxides, and the like, as described above, in the presence of particles integrally compounded by electrostatic force, May be used in combination.

Among the above abrasive grains, the abrasive grains to be used in the chemical mechanical polishing aqueous dispersion according to the first embodiment are preferably at least one selected from silica particles, calcium carbonate particles, organic polymer particles and organic-inorganic composite particles.

The average particle diameter of the (D1) abrasive grain used in the present invention is preferably 20 to 500 nm. The average particle diameter can be measured by a laser scattering diffractometer, or by observation with a transmission electron microscope. When the average particle diameter is less than 20 nm, there are cases in which an aqueous dispersion for chemical mechanical polishing having a sufficiently high polishing rate can not be obtained. If the average particle diameter exceeds 500 nm, stable aqueous dispersion may not be easily obtained due to precipitation and separation of the abrasive grains. The average particle diameter of the abrasive grains may be in the above range, more preferably 30 to 400 nm, and particularly preferably 40 to 300 nm. When the average particle diameter is within this range, a stable chemical mechanical polishing aqueous dispersion having a high polishing rate, sufficiently suppressing dishing and hardly causing sedimentation and separation of particles can be obtained.

The content of the component (D1) in the aqueous dispersion for chemical mechanical polishing according to the first embodiment may be arbitrary as long as it satisfies the quantitative relationship between the component (A1) and the component (D1) described below, And more preferably 0.5 to 5% by mass with respect to the mass of the polishing aqueous dispersion. That is, the concentration M _D1 of the component (D1) is more preferably 0.5 to 5% by mass in the chemical mechanical polishing aqueous dispersion. The content of the component (D1) is more preferably from 1 to 4.5% by mass, and particularly preferably from 1.5 to 4% by mass. If the content of the component (D1) is less than the above range, a sufficient polishing rate may not be obtained, and it may take a long time to complete the polishing process. On the other hand, when the content of the abrasive grains exceeds the above range, the flatness of the surface to be polished sometimes becomes insufficient, and in some cases, the cost becomes high and the storage stability of the aqueous dispersion for chemical mechanical polishing may not be secured .

1.1.5. Quantitative relationship between the components (A1) and (D1) of the aqueous dispersion for chemical mechanical polishing

The chemical mechanical polishing aqueous dispersion according to the first embodiment, (A1) at a concentration M _A1 (% by weight), and (D1) the concentration M _D1 (% by mass) of components of the component, M _A1 / M _D1 = 1 to Lt; / RTI > Here, M _A1 and M _D1 are the concentrations of the component (A1) and the component (D1), respectively, and refer to the ratio of the mass of the components (A1) and (D1) to the total mass of the chemical mechanical polishing aqueous dispersion . The ratio M _A1 / M _D1 of the concentration M _A1 of the component (A1) and the concentration M _D1 of the component (D1) is more preferably M _A1 / M _D1 = 2 to 20 and M _A1 / M _D1 = 3 to 10 More preferable. If the ratio M _A1 / M _D1 is less than the above range, dishing of the wiring layer tends to become large, which is not preferable. If the ratio M _A1 / M _D1 is less than the above range, (D1) the abrasive component becomes relatively large and the mechanical polishing is excessively performed on the resin substrate, the resin substrate as the object to be polished may contain copper or a copper alloy The surface to be polished of the circuit board provided with the wiring layer is roughened. In addition, a stable chemical mechanical polishing aqueous dispersion may not be obtained in some cases. When the ratio M _A1 / M _D1 exceeds the above range, the flatness of the surface to be polished may become insufficient. In addition, corrosion to the wiring metal sometimes occurs, which is not preferable.

1.1.6. PH of aqueous dispersion for chemical mechanical polishing

In the chemical mechanical polishing aqueous dispersion according to the first embodiment, the pH value of the aqueous dispersion for chemical mechanical polishing is 8 to 12. Here, pH refers to a hydrogen ion index, and the value can be measured using a commercially available pH meter or the like. The pH value of the aqueous dispersion for chemical mechanical polishing is preferably 8.5 to 11.5, more preferably 9 to 11. If the pH value of the aqueous dispersion for chemical mechanical polishing is less than the above range, the polishing rate may be lowered. If the pH value of the aqueous dispersion for chemical mechanical polishing exceeds the above range, dissolution of the abrasive grains may occur and the flatness of the surface to be polished may deteriorate.

The pH value of the aqueous dispersion for chemical mechanical polishing varies depending on the blending amount of the components (A1) to (D1). Therefore, the kind of each component is selected or the amount of blending is changed so as to be in the range of the pH value described above. Depending on the kinds and blending amounts of the components (A1) to (D1), the pH may not be within the above range. In this case, a pH adjuster or the like may be appropriately added to the chemical mechanical polishing aqueous dispersion to adjust the pH value to fall within the above range.

1.1.7. pH adjuster

In the aqueous dispersion for chemical mechanical polishing according to the first embodiment, a pH adjuster such as an acid or an alkali may be added as necessary. One of the functions of the pH adjuster is to adjust the pH of the aqueous dispersion for chemical mechanical polishing to a desired pH. Thus, the aqueous dispersion for chemical mechanical polishing has a desired pH value, whereby the polishing rate can be adjusted, the flatness can be improved, and the corrosion of the wiring layer can be suppressed. The pH adjuster can be used not only when the pH of the aqueous dispersion for chemical mechanical polishing is out of the range of 8 to 12 but also when the pH of the aqueous dispersion for chemical mechanical polishing is in the range of 8 to 12, Can be used to adjust.

Examples of the pH adjuster include inorganic acids such as sulfuric acid and phosphoric acid. Examples of the alkali include hydroxides of alkali metals such as sodium hydroxide, potassium hydroxide, rubidium hydroxide and cesium hydroxide, tetramethylammonium hydroxide, Organic alkali compounds and ammonia. The acid and the alkali may be compounded singly or plural kinds may be compounded. By adding a pH adjusting agent, the pH can be appropriately set so that the abrasive grains can stably exist, taking into consideration the electrochemical properties of the surface to be polished, the dispersibility of the abrasive grains, the stability, and the polishing rate. A particularly preferable pH adjuster for the aqueous dispersion for chemical mechanical polishing according to the present embodiment is ammonia from the viewpoint of improving the polishing rate.

1.1.8. Other additives

In the chemical mechanical polishing aqueous dispersion according to the first embodiment, in addition to the above-described components, various additives may be added as required. Examples of other additives include anticorrosive agents for wiring materials, suppressing agents for reducing the generation of bubbles in the slurry, antifoaming agents and the like.

1.2. Second Embodiment

The chemical mechanical polishing aqueous dispersion according to the second embodiment comprises (A2) an organic acid, (B2) a nitrogen-containing heterocyclic compound, (C2) an oxidizing agent, and (D2) abrasive grains. In addition, each of the following substances (A2) to (D2) may be omitted as the components (A2) to (D2).

1.2.1. (A2) Organic acid

The chemical mechanical polishing aqueous dispersion according to the second embodiment contains (A2) an organic acid. (A2) One of the functions of the organic acid is to improve the polishing rate when a chemical mechanical polishing aqueous dispersion is applied to the resin substrate for the polishing of a wiring layer containing copper or a copper alloy. As the organic acid (A2) used in the chemical mechanical polishing aqueous dispersion according to the second embodiment, an organic acid having a coordinating ability is preferably added to the surface of a wiring material containing ions of a wiring material element or copper or a copper alloy desirable. The organic acid (A2) is more preferably an organic acid having a chelate coordinating ability.

Examples of the organic acid used in the chemical mechanical polishing aqueous dispersion according to the second embodiment include organic acids such as tartaric acid, fumaric acid, glycolic acid, phthalic acid, maleic acid, formic acid, acetic acid, oxalic acid, citric acid, malic acid, malonic acid, glutaric acid, Benzoic acid, quinolinic acid, quinaldic acid, amide sulfuric acid, and the like. As the organic acid used in the present invention, amino acids such as glycine, alanine, aspartic acid, glutamic acid, lysine, arginine, tryptophan, aromatic amino acid and heterocyclic amino acid can also be preferably used. These organic acids can be dissociated into anions (proton ions) paired with one or more protons (hydrogen ions) in the aqueous dispersion for chemical mechanical polishing. In the aqueous dispersion for chemical mechanical polishing according to the second embodiment, the above-described organic acid may be contained singly or two or more of the above-mentioned organic acids may be contained. Of these organic acids, at least one selected from citric acid, glycine, malic acid, tartaric acid and oxalic acid is particularly preferable in that the effect of improving the polishing rate of the aqueous dispersion for chemical mechanical polishing is high.

The organic acid used in the aqueous dispersion for chemical mechanical polishing according to the second embodiment is preferably a cation derived from other components optionally added in the state of being dissolved in the aqueous dispersion for chemical mechanical polishing such as ammonium ion, And in this case, a salt is formed when the aqueous dispersion for chemical mechanical polishing is dried. In this case, the cations forming the pair may be monovalent or more.

The content of the organic acid (A2) in the aqueous dispersion for chemical mechanical polishing according to the second embodiment is preferably in the range of 3 to 15 mass% based on the mass of the aqueous dispersion for chemical mechanical polishing (A2) %, More preferably 3.5 to 12 mass%, and particularly preferably 4 to 10.5 mass%. If the content of the organic acid (A2) is less than the above range, a sufficient polishing rate may not be obtained, and it may take a long time to complete the polishing process. On the other hand, if the content of the organic acid (A2) exceeds the above range, the chemical etching effect becomes large, so that corrosion of the wiring layer occurs and the flatness of the surface to be polished may be impaired.

1.2.2. (B2) a nitrogen-containing heterocyclic compound

The chemical mechanical polishing aqueous dispersion according to the second embodiment contains (B2) a nitrogen-containing heterocyclic compound. One of functions of the nitrogen-containing heterocyclic compound (B2) is to form a water-insoluble complex with a metal such as copper to protect the surface of the surface to be polished, thereby improving the flatness of the polished surface to be polished. The nitrogen-containing heterocyclic compound (B2) is preferably a nitrogen-containing heterocyclic compound having a coordinating ability with respect to a surface of a wiring material containing ions of a wiring material element or copper or a copper alloy. The nitrogen-containing heterocyclic compound (B2) is more preferably a nitrogen-containing heterocyclic compound having a chelate coordinating ability.

The nitrogen-containing heterocyclic compound (B2) preferably used in the aqueous dispersion for chemical mechanical polishing according to the second embodiment is a compound containing at least one nitrogen as a heteroatom among the heterocyclic compounds. The nitrogen-containing heterocyclic compound is an organic compound containing at least one heterocyclic ring selected from the group consisting of a complex 5-membered ring having at least one nitrogen atom and a heterocyclic 6-membered ring. Examples of the heterocycle include a complex five-membered ring such as a pyrrole structure, an imidazole structure, and a triazole structure, and a complex 6-membered ring such as a pyridine structure, a pyrimidine structure, a pyridazine structure, and a pyrazine structure. The heterocyclic ring may form a condensed ring. Specific examples thereof include an indole structure, an isoindole structure, a benzoimidazole structure, a benzotriazole structure, a quinoline structure, an isoquinoline structure, a quinazoline structure, a cinnoline structure, a phthalazine structure, a quinoxaline structure, . Of the heterocyclic compounds having such a structure, a heterocyclic compound having a pyridine structure, a quinoline structure, a benzimidazole structure, or a benzotriazole structure is preferable. Specific examples of the nitrogen-containing heterocyclic compound include aziridine, pyridine, pyrimidine, pyrrolidine, piperidine, pyrazine, triazine, pyrrole, imidazole, indole, quinoline, isoquinoline, benzoisoquinoline, Triazine, triazolidine, benzotriazole, carboxybenzotriazole, and the like, and further derivatives having these skeletons can be exemplified.

In the chemical mechanical polishing aqueous dispersion according to the second embodiment, the nitrogen-containing heterocyclic compound (B2) may be used singly or in combination of two or more species as the nitrogen-containing heterocyclic compound. As the nitrogen-containing heterocyclic compound (B2), at least one selected from benzotriazole, triazole, imidazole and carboxybenzotriazole is particularly preferable.

The content of the (B2) nitrogen-containing heterocyclic compound in the aqueous dispersion for chemical mechanical polishing according to the second embodiment is preferably in the range of Is preferably 0.05 to 2% by mass, more preferably 0.1 to 1% by mass, and particularly preferably 0.2 to 0.5% by mass. If the content of the (B2) nitrogen-containing heterocyclic compound is less than the above range, the flatness of the polished surface may be impaired. If the content of the (B2) nitrogen-containing heterocyclic compound exceeds the above range, the polishing rate may be lowered.

1.2.3. (C2) oxidizing agent

The chemical mechanical polishing aqueous dispersion according to the second embodiment contains (C2) an oxidizing agent. As the (C2) oxidizing agent, the oxidizing agent described in the section "1.1.3 (C1) oxidizing agent" can be used. The function of the oxidizing agent (C2) in the second embodiment is also the same as the function described in the section "1.1.3. (C1) oxidizing agent".

The content of the (C2) oxidizing agent in the aqueous dispersion for chemical mechanical polishing according to the second embodiment is preferably 1 to 30% by mass with respect to the mass of the aqueous dispersion for chemical mechanical polishing at the time of use, 5 to 20% by mass, and particularly preferably 5 to 15% by mass. If the content of the (C2) oxidizing agent is less than the above range, the chemical effect becomes insufficient and the polishing rate may be lowered, which may require a long time to complete the polishing process. On the other hand, if the content of the (C2) oxidizing agent exceeds the upper range, there is a case where the polished surface is corroded to impair the flatness, and the polishing rate may be lowered in some cases.

1.2.4. (D2) abrasive grain

The chemical mechanical polishing aqueous dispersion according to the second embodiment contains (D2) abrasive grains. (D2) The abrasives described in the section 1.1.4. (D1) abrasives can be used. The function and the content of the (D2) abrasive grain in the second embodiment are the same as those described in the above section 1.1.4 (D1) abrasive grain.

1.2.5. Quantitative relationship between the components (A2) and (D2) of the aqueous dispersion for chemical mechanical polishing

The chemical mechanical polishing aqueous dispersion according to the second embodiment, (A2) at a concentration M _A2 (% by weight) and (D2) concentration M _D2 (% by mass) of components of the component, M _A2 / M _D2 = 1 to 20 < / RTI > Here, M _A2 and M _D2 refer to the ratio of the mass of the component (A) and the mass of the component (D2) to the total mass of the aqueous dispersion for chemical mechanical polishing. The ratio M _A2 / M _D2 of the concentration M _A2 of the component (A2) to the concentration M _D2 of the component (D2) is more preferably M _A2 / M _D2 = 1 to 10, and M _A2 / M _D2 = desirable. When the ratio M _A2 / M _D2 is less than the above range, dishing of the wiring layer tends to become large, which is not preferable. If the ratio M _A2 / M _D2 is less than the above range, the abrasive component (D2) becomes relatively large and the mechanical polishing on the resin substrate is excessively performed. Therefore, the resin substrate, which is the object to be polished, The surface to be polished of the circuit board provided with the wiring layer is roughened. In addition, a stable chemical mechanical polishing aqueous dispersion may not be obtained in some cases. If the ratio M _A2 / M _D2 exceeds the above range, the flatness of the polished surface may be insufficient. In addition, corrosion to the wiring metal sometimes occurs, which is not preferable.

1.2.6. PH of aqueous dispersion for chemical mechanical polishing

In the chemical mechanical polishing aqueous dispersion according to the second embodiment, the pH value of the aqueous dispersion for chemical mechanical polishing is 1 to 5. Here, pH refers to a hydrogen ion index, and the value can be measured using a commercially available pH meter or the like. The pH value of the aqueous dispersion for chemical mechanical polishing is preferably 1.5 to 4.5, more preferably 2 to 4. If the pH value of the aqueous dispersion for chemical mechanical polishing is less than the above range, the flatness of the surface to be polished may be deteriorated. If the pH value of the aqueous dispersion for chemical mechanical polishing exceeds the above range, the polishing rate may be lowered.

The pH value of the aqueous dispersion for chemical mechanical polishing varies depending on the blending amount of the components (A2) to (D2). Therefore, the kind of each component is selected or the amount of blending is changed so as to be in the range of the pH value described above. Depending on the kinds and blending amounts of the components (A2) to (D2), the pH may not be within the above range. In this case, a pH adjuster or the like may be appropriately added to the chemical mechanical polishing aqueous dispersion to adjust the pH value to fall within the above range.

1.2.7. pH adjuster

In the aqueous dispersion for chemical mechanical polishing according to the second embodiment, a pH adjuster such as an acid or an alkali may be added as necessary. As the pH adjusting agent, the pH adjusting agent described in the above section 1.1.7, "pH adjusting agent" can be used. The function of the pH adjuster in the second embodiment is also the same as the function described in the section of "1.1.7.

1.2.8. Other additives

The chemical mechanical polishing aqueous dispersion according to the second embodiment may contain various additives in addition to the above-described components, if necessary. Examples of other additives include anticorrosive agents for wiring materials, suppressing agents for reducing the generation of bubbles in the slurry, antifoaming agents and the like.

2. Method for manufacturing circuit board, circuit board and multi-layer circuit board

The method for producing a circuit board according to the third embodiment has a step of performing chemical mechanical polishing using the aqueous dispersion for chemical mechanical polishing described in "1. Aqueous dispersion for chemical mechanical polishing ".

The chemical mechanical polishing process is carried out by introducing the above-mentioned aqueous dispersion for chemical mechanical polishing into a general chemical mechanical polishing apparatus. Hereinafter, the manufacturing process of the circuit board will be described in detail with reference to the drawings. 1 to 5 are cross-sectional views schematically showing an example of a manufacturing process of the circuit board 100 according to the third embodiment. The chemical mechanical polishing process in the method for manufacturing the circuit board 100 according to the third embodiment is a process for polishing a wiring layer including copper or a copper alloy in particular.

As the resin substrate 10 to be used in the method of manufacturing the circuit board 100 according to the third embodiment, it is preferable that the resin substrate 10 has insulation at a portion where the wiring layer is formed. For example, a film substrate or a plastic substrate can be used, A glass substrate or the like can also be used. The resin substrate 10 may be a single layer or a laminate having a resin layer formed on a substrate made of another material such as silicon.

As shown in Fig. 1, first, a resin substrate 10 is prepared. The resin substrate 10 is provided with recessed portions 12 by techniques such as photolithography and etching. The concave portion 12 is formed corresponding to the wiring layer of the circuit board 100. At least the side of the resin substrate 10 on which the concave portion 12 is provided has electrical insulation.

2, the barrier metal film 20 is formed so as to cover the surface of the resin substrate 10, the bottom of the concave portion 12, and the inner wall surface. The barrier metal film 20 is provided if necessary. The barrier metal film 20 may include a material such as tantalum or tantalum nitride, for example. As a method for forming the barrier metal film 20, a chemical vapor deposition method (CVD) can be applied.

Next, as shown in Fig. 3, a metal for wiring is deposited so as to cover the surface of the barrier metal film 20 to form the metal film 30. Next, as shown in Fig. The metal film 30 may include copper or a copper alloy. The metal film 30 remains in the concave portion 12 after the chemical mechanical polishing process, thereby forming a wiring layer of the circuit board 100. [ As the film formation method of the metal film 30, physical vapor deposition (PVD) such as sputtering or vacuum deposition can be applied.

Then, as shown in Fig. 4, an extra metal film 30 other than the portion buried in the recess 12 is chemically mechanically polished by using the chemical mechanical polishing aqueous dispersion according to the present embodiment . When the barrier metal film 20 is provided, the above method is continued until the barrier metal film 20 is exposed. After chemical mechanical polishing, it is preferable to remove abrasive grains remaining on the surface to be polished. The removal of the abrasive grains can be performed by a conventional cleaning method.

Finally, as shown in Fig. 5, the surface of the barrier metal film 20a and the metal film 30 formed in addition to the concave portion 12 is chemically mechanically polished using another chemical mechanical polishing aqueous dispersion for the barrier metal film .

The circuit board 100 is formed as described above. The circuit board 100 may have a wiring layer of arbitrary shape. Further, a multilayer circuit board can be formed by laminating a plurality of circuit boards having wiring layers of appropriate shapes. In the multilayer circuit board, the wiring layers of the respective circuit boards are suitably electrically connected and can have a three-dimensional wiring structure.

Since the chemical mechanical polishing process of the third embodiment uses the aqueous dispersion for chemical mechanical polishing according to the first or second embodiment to remove the metal film 30, the polishing rate is high and the in-plane flatness of the polishing is good And selective polishing such as dishing is unlikely to occur. Therefore, according to the circuit board manufacturing method of the third embodiment, the circuit board 100 having excellent in-plane flatness can be manufactured with high throughput.

The circuit board 100 manufactured by the manufacturing method of the third embodiment has a high in-plane flatness and a small dishing. Therefore, the multilayer circuit board formed by stacking the circuit boards 100 has a uniform thickness over the entire substrate, and has a flat surface.

3. Examples and Comparative Examples

Hereinafter, the present invention will be described by Examples and Comparative Examples, but the present invention is not limited to these Examples and Comparative Examples.

3.1. Manufacture of Evaluation Board

3.1.1. Fabrication of Substrate for Flatness Evaluation

WPR-1201 varnish (manufactured by JSR Kabushiki Kaisha; photosensitive resin composition) was spin-coated on a copper clad laminate (substrate thickness: 0.6 mm, size: 10 cm side) The plate was heated at 110 DEG C for 3 minutes to prepare a uniform coating film having a thickness of 10 mu m. Thereafter, using an aligner ("MA-100" manufactured by Karl Suss Co.), a pattern mask having a wiring of L / S = 100 mu m / 100 mu m and a pad portion of 2 mm x 2 mm Ultraviolet rays were irradiated. The ultraviolet ray exposure was performed such that an exposure amount at a wavelength of 350 nm was 3,000 to 5,000 J / m 2. Subsequently, the substrate was heated (PEB) at 110 DEG C for 3 minutes on a hot plate, immersed in a 2.38 mass% aqueous solution of tetramethylammonium hydroxide (TMAH) at 23 DEG C for 60 seconds, heated in a convection oven at 120 DEG C x2 For a period of time to form an insulating resin cured film having a groove pattern on the copper clad laminate. A copper seed layer was formed on the obtained insulating resin cured film by electroless plating, and thereafter a copper plating layer of 10 탆 was formed by electrolytic plating. Thus, a substrate for flatness evaluation in which copper was embedded in the groove pattern was obtained. This substrate is subjected to chemical mechanical polishing to remove copper other than the groove pattern, thereby forming a circuit board having a conductive layer line having a width of 100 占 퐉 and a conductive layer line having a width of 2 mm.

3.1.2. Preparation of substrate for copper polishing rate evaluation

A substrate with a copper plating layer of 10 占 퐉 was obtained in the same manner as in "3.1.1. Production of a flatness evaluation substrate" except that the groove pattern formation of the insulating resin layer was not performed.

3.2. Preparation of abrasive dispersion

3.2.1. Preparation of water dispersion containing fumed silica particles

2 kg of fumed silica particles (manufactured by Nippon Aerosil K.K., trade name "Aerosil # 90") was dispersed in 6.7 kg of ion-exchanged water by an ultrasonic dispersing machine, and the resultant was filtered with a filter having an air diameter of 5 μm to obtain a fumed silica- Was prepared.

3.2.2. Preparation of water dispersion containing colloidal silica

70 g of 25% by mass aqueous ammonia, 40 g of ion-exchanged water, 175 g of ethanol and 21 g of tetraethoxysilane were introduced into a flask having a capacity of 2 liters, and the mixture was heated to 60 DEG C with stirring at 180 rpm, Followed by cooling to obtain a colloidal silica / alcohol dispersion having an average particle diameter of 70 nm. Subsequently, the operation of removing the alcohol component while adding ion-exchanged water to the dispersion at a temperature of 80 캜 by an evaporator was repeated several times, and the alcohol component in the dispersion was removed to obtain a water dispersion having a solid content of 8 mass% .

3.3. Preparation of aqueous solution of component (B1)

An aqueous solution of polyvinylpyrrolidone was prepared as follows, and another aqueous solution of dodecylbenzenesulfonic acid, dipotassium alkenylsuccinate, polyvinyl alcohol and oleic acid was prepared by dissolving a predetermined amount in ion-exchanged water.

60 g of degassed N-vinyl-2-pyrrolidone and 240 g of degassed water were charged into a 500-mL flask. This was heated to 60 DEG C under stirring in a nitrogen stream, and 0.3 g of a 10 mass% aqueous sodium sulfite solution and 0.3 g of a 10 mass% aqueous solution of t-butyl hydroperoxide were added. Stirring was continued at 60 캜 for 3 hours, and then 1.8 g of a 10 mass% sodium sulfite aqueous solution and 1.2 g of a 10 mass% aqueous solution of t-butyl hydroperoxide were added and stirring was further continued for 3 hours. This reaction mixture was diluted with ion-exchange water to obtain a 20 mass% aqueous solution of polyvinylpyrrolidone. The weight average of the polyvinylpyrrolidone thus prepared as measured by water-based gel permeation chromatography using 0.1 mol / L aqueous solution of NaCl / acetonitrile = 80/20 (vol / vol) as an eluent The molecular weight (Mw) was 1,000,000. The K value obtained by the Fikentscher method was 95.

3.4. Preparation of aqueous dispersion for chemical mechanical polishing

A predetermined amount of the water dispersion described in "3.2 Preparation of abrasive dispersion" was added to a bottle made of polyethylene having a volume of 1 L and the compounds described in the following Table 1 or Table 2 were added to the respective contents And sufficiently stirred. Thereafter, a pH adjuster was added to adjust the pH to the values shown in Table 1 or Table 2. Thereafter, the resultant was filtered with a filter having an opening diameter of 5 탆 to obtain an aqueous dispersion for chemical mechanical polishing of Examples 1 to 18 and Comparative Examples 1 to 8.

3.5. Abrasion of the substrate

Using the aqueous dispersion for chemical mechanical polishing of Examples 1 to 18 and Comparative Examples 1 to 8, a copper-film-attached substrate without a wiring pattern and a flatness-evaluation substrate with copper embedded in the groove pattern described above were subjected to the following conditions Polishing.

ㆍ Polishing apparatus: Lapmaster LM15

ㆍ Polishing pad: IC1000 (manufactured by Nitta Hass Co.)

ㆍ Carrier head load: 280 hPa

ㆍ Number of revolutions of table: 90 rpm

ㆍ Feed rate of abrasive: 100 ml / min

The polishing rate of copper was calculated from the polishing result of the copper film-attached substrate having no wiring pattern using the following equation (1). The polishing rates of the respective Examples and Comparative Examples are shown in Table 1 or Table 2.

Polishing speed (占 퐉 / minute) = polishing amount (占 퐉) / polishing time (minute)

The polishing amount was calculated using the following equation (2), with the density of copper being 8.9 g / cm < 3 >.

(G / cm < 3 >)) x 10 < ⁴ >

When the value of the polishing rate is 5 (탆 / minute) or more, it can be said that the polishing rate is good.

3.6. Evaluation of dishing

When the initial excess film having a thickness T (nm) obtained by depositing a wiring material on a concave portion or the like is polished at a polishing rate V (nm / minute), the object can be achieved by polishing for a time of T / V (minute). However, in an actual manufacturing process, excess polishing (overpolish) exceeding T / V (minute) is performed in order to remove the wiring material remaining in a portion other than the recess. At this time, the wiring portion is excessively polished, resulting in a concave shape. This concave wiring shape is called "dishing" and is not preferable from the viewpoint of lowering the yield of the manufactured product. Therefore, in each of the examples and the comparative examples, dishing was used as an evaluation item.

The evaluation of the dishing was carried out using the above-described flatness evaluation substrate, using a needle contact type step system (manufactured by KLA-Tencor, type "P-10"). The polishing time in the evaluation of the dishing is a value (T / V) (minute) obtained by dividing the initial surplus copper film having the thickness T (nm) by the polishing rate V (nm / min) obtained in "3.5. Polishing of the substrate" Was multiplied by 1.5 (min).

In the column of dishing in the evaluation items in Table 1 or Table 2, the amount of the concave portion of the copper wiring measured by the surface roughness meter was described as a dicing value (탆). In the table, "* 1" indicates a case where the wiring is lost and measurement is impossible. The dicing values are shown in Table 1 for each of a 100 탆 wide line and a 2 mm wide line formed on the flatness evaluation substrate. For reference, the differences in the dicing values in the lines of 100 占 퐉 width and 2mm width are also shown in Table 1. The value of dishing is good when it is 1.5 (mu m) or less in a line of 100 mu m width, and is good when it is 2.0 mu m or less in a line of 2 mm width.

3.7. Storage stability

The evaluation of the storage stability of the aqueous dispersion for chemical mechanical polishing of each of the examples and comparative examples was carried out as follows. After the aqueous dispersion for chemical mechanical polishing was prepared, the dispersion was allowed to stand at normal temperature and normal pressure and allowed to stand for 60 days. . As the index of the evaluation of the storage stability, ⊚ indicates no change immediately after the preparation, ∘ indicates that the precipitate was observed to some extent, and X indicates that the separation of the components occurred or the supernatant region occurred. The results are shown in Table 1 or Table 2 .

3.8. Evaluation results

According to the results shown in Table 1, the polishing rates of copper in the aqueous dispersions for chemical mechanical polishing of Examples 1 to 9 were all sufficiently high at 6.8 탆 / min or more. It was also found that the dishing of the 100 占 퐉 wiring is as small as 1.5 占 퐉 or less and has a good overpopisition margin. It has also been found that the dishing of the 2 mm wiring is small at 2.2 탆 or less and has a good overpoping margin even for a wiring having a large width. In addition, the difference in dishing between the 100 탆 line and the 2 탆 line was 0.7 탆 or less, and it was found that the line width dependence of the dishing was small. In addition, the aqueous dispersion for chemical mechanical polishing of Examples 1 to 9 had good storage stability.

On the other hand, as shown in Table 1, in Comparative Example 1 (M _A1 / M _D1 = 0.7) having no relationship of M _A1 / M _D1 = 1 to 30, dishing was large and poor. In Comparative Example 4 (M _A1 / M _D1 = 36) in which the relationship of M _A1 / M _D1 = 1 to 30 was not satisfied, dishing was very large and poor because the wiring was lost. In Comparative Example 2 (pH = 6.3) in which the pH value was outside the lower limit of the range of 8 to 12, the polishing rate was small and poor. In Comparative Example 3 (pH = 13.5) in which the pH value was outside the upper limit of the range of 8 to 12, the dishing was very large and poor. In addition, for Comparative Examples 1, 3 and 4, storage stability was insufficient.

According to the results shown in Table 2, in the aqueous dispersion for chemical mechanical polishing of Examples 10 to 18, the polishing rate of copper was sufficiently high at all of 6.6 占 퐉 / min or more. It was also found that the dishing of the 100 占 퐉 wiring was small at 1.4 占 퐉 or less and had a good overpopisis margin. It was also found that the dishing of the 2 mm wiring was small at 2.0 占 퐉 or less and had a good overpoping margin even for a wiring having a large width. In addition, the difference in dishing between the 100 탆 line and the 2 탆 line was 1.0 탆 or less, and it was found that the line width dependency of the dishing was small. In addition, the aqueous dispersion for chemical mechanical polishing of Examples 10 to 18 had good storage stability.

On the other hand, as shown in Table 2, in Comparative Example 5 (M _A2 / M _D2 = 0.5) in which M _A2 / M _D2 = 1 to 20 did not have a relationship, dishing of 2 mm wiring was large and poor. In Comparative Example 6 (M _A2 / M _D2 = 25) in which M _A2 / M _D2 = 1 to 20, the dishing of both 100 μm wiring and 2 mm wiring was large and poor. In Comparative Example 7 (pH = 0.5) in which the pH value was out of the lower limit of the range of 1 to 5, dishing was very large and bad because the wiring was lost. In Comparative Example 8 (pH = 5.5) in which the pH value was outside the upper limit in the range of 1 to 5, the polishing rate was insufficient. In addition, with respect to Comparative Example 1, storage stability was also insufficient.

As described above, the chemical mechanical polishing aqueous dispersion according to the embodiment can polish a metal film containing copper or a copper alloy on a resin substrate at a high polishing rate, to secure the in-plane uniformity of the substrate, It has been found that the suppression of the fluctuation of the flatness can be realized.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a cross-sectional view schematically showing a step of a circuit board manufacturing method of the present embodiment.

2 is a cross-sectional view schematically showing a step of the circuit board manufacturing method of the present embodiment.

3 is a cross-sectional view schematically showing a step of a circuit board manufacturing method of the present embodiment.

4 is a cross-sectional view schematically showing the steps of the circuit board manufacturing method of this embodiment.

5 is a cross-sectional view schematically showing an example of a circuit board manufactured by the circuit board manufacturing method of the present embodiment.

BRIEF DESCRIPTION OF THE DRAWINGS FIG.

10 ... Resin Substrate, 12 ... Concave, 20 ... Barrier metal membrane, 30 ... Metal film

Claims (18)

An aqueous dispersion for chemical mechanical polishing used for forming a circuit board on which a wiring layer containing copper or a copper alloy is provided on a resin substrate, (A1) 5 to 15% by mass of at least one of organic acid and organic acid salts, (B1) 0.01 to 1% by mass of at least one selected from dodecylbenzenesulfonic acid, potassium dodecylbenzenesulfonate and ammonium dodecylbenzenesulfonate, (C1) 0.5 to 5% by mass of an oxidizing agent, (D1) 0.5 to 5 mass% Lt; / RTI > M _A1 / M _D1 = 1 to 30 in the concentration M _A1 (mass%) of the component (A1) and the concentration M _D1 (mass%) of the component (D1) relative to the chemical mechanical polishing aqueous dispersion Lt; / RTI & and a pH value of 8 to 12. The chemical mechanical polishing aqueous dispersion according to claim 1, The method according to claim 1, Further comprising M _A1 = 5 to 15 (mass%). The method according to claim 1, Wherein the component (A1) is glycine. delete The method according to claim 1, Wherein the component (C1) is hydrogen peroxide. The method according to claim 1, Wherein the component (D1) is at least one member selected from silica particles, calcium carbonate particles, organic polymer particles and organic-inorganic composite particles. A method for producing a circuit board having a step of performing chemical mechanical polishing using the aqueous dispersion for chemical mechanical polishing according to any one of claims 1 to 3, 5 and 6. delete delete An aqueous dispersion for chemical mechanical polishing used for forming a circuit board on which a wiring layer containing copper or a copper alloy is provided on a resin substrate, (A2) 3 to 15% by mass of an organic acid, (B2) 0.05 to 2% by mass of a nitrogen-containing heterocyclic compound, (C2) an oxidizing agent in an amount of 1 to 30% by mass, (D2) 0.5 to 5 mass% Lt; / RTI > In the above (A2) the concentration M _A2 (% by weight) of the component and the (D2) concentration M _D2 (% by mass) of components for the aqueous dispersion for the chemical mechanical polishing, and the relationship M _A2 / M _D2 = 1 to 20 Lt; / RTI & wherein the pH value of the aqueous dispersion is 1 to 5. 11. The method of claim 10, Further comprising M _A2 = 3 to 15 (% by mass). 11. The method of claim 10, Wherein the (A2) organic acid is at least one selected from citric acid, glycine, malic acid, tartaric acid and oxalic acid. 11. The method of claim 10, Wherein the nitrogen-containing heterocyclic compound (B2) is at least one selected from benzotriazole, triazole, imidazole and carboxybenzotriazole. 11. The method of claim 10, Wherein the oxidizing agent (C2) is hydrogen peroxide. 11. The method of claim 10, Wherein the abrasive (D2) is any one of silica particles, calcium carbonate particles, organic polymer particles and organic-inorganic composite particles. A method for producing a circuit board having a step of performing chemical mechanical polishing using the aqueous dispersion for chemical mechanical polishing according to any one of claims 10 to 15. delete delete

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