JP2010036290A - Aqueous dispersing element for chemical mechanical polishing to be used for manufacturing circuit board, method of manufacturing circuit board, circuit board, and multilayer circuit board - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an aqueous dispersing element for chemical mechanical polishing, suitably used for forming the circuit board provided with a wiring layer including copper or copper alloy in a resin substrate, with high speed to polish the copper or copper alloy, excellent step eliminating property and excellent flatness of the obtained circuit board. <P>SOLUTION: The aqueous dispersing element is used for forming the circuit board provided with the wiring layer including copper or copper alloy in the resin substrate. The aqueous dispersing element contains (A) organic acid, (B) nitrogen-containing heterocyclic compound, (C) oxidant, (D1) first abrasive grain having a primary particle size of 20 to 70 nm and (D2) second abrasive grain having a primary particle size of 80 to 150 nm. Concentration of the (A) organic acid with respect to the aqueous dispersing element is 3 to 15 mass%, a ratio (N1/N2) of a particle number N1 of (D1) the first abrasive grain to a particle number N2 of (D2) the second abrasive grain is 3 to 50, and a pH value is 1 to 5. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an aqueous dispersion for chemical mechanical polishing used for manufacturing a circuit board, a method for manufacturing a circuit board using the aqueous dispersion, a circuit board, and a multilayer circuit board.

  In recent years, electronic devices have been miniaturized, and further miniaturization and multilayering are required for semiconductor devices constituting the electronic devices and circuit boards for mounting the semiconductor devices. A multilayer circuit board (multilayered circuit board) generally has a three-dimensional wiring structure in which a plurality of circuit boards on which wiring patterns are formed are stacked. When the thickness of the multilayer circuit board or the circuit board is not uniform or the flatness is insufficient, problems such as poor connection may occur when the semiconductor device is mounted. Therefore, the circuit boards of the respective layers constituting the multilayer circuit board have a uniform thickness and a flat surface so that unevenness and bending do not occur when the multilayer circuit board is laminated to form a multilayer circuit board. Need to be formed.

  One of the causes of impairing the flatness of the circuit board is the unevenness of the wiring pattern. Such irregularities often occur when a circuit board is manufactured. As a method of manufacturing a circuit board having a wiring pattern, for example, a recess corresponding to a desired wiring pattern is formed on the surface of the board, a conductive layer is formed on the entire surface by plating, and then the surface side of the board is polished. There is a method in which the conductive layer remains only in the recess. In such a manufacturing method, in the plating step, the thinner the line width of the wiring pattern, the thicker the plating thickness of that part may be, and the distribution of the current during plating occurs due to the density of the wiring of the wiring pattern. Depending on the distribution, the thickness may become non-uniform. For this reason, variations in the initial plating thickness have an effect on the subsequent polishing process, and as a result, the flatness of the circuit board may be impaired. Further, when the circuit board is formed by polishing, a phenomenon called dishing in which the polished surface of the wiring pattern formed on the circuit board becomes concave may occur.

  The polishing step is performed by buffing, for example. Patent Document 1 discloses a polishing method using a roll buff, but uses a roll buff formed by combining hard abrasive grains with a binder to form a cylinder. For this reason, such a polishing method has the disadvantages that the thickness of the circuit board is likely to be uneven, and that the surface of the conductive layer is easily damaged (flatness is impaired). Also, a method using a slurry in buffing has been proposed (see, for example, Patent Document 2). However, this method also has a large difference in polishing speed depending on the material of the surface to be polished, and the technical level is such that extremely high thickness uniformity and surface flatness can be obtained like a circuit board used for a multilayer circuit board. Not yet reached.

When the conductive layer is formed by plating, the conductive layer is deposited along the unevenness of the substrate surface, so that the upper surface of the conductive layer has a concave shape above the recess. When a conductive layer having such a step is polished, the conductive layer may be removed while maintaining the shape of the step. In particular, when an attempt is made to remove the conductive layer formed outside the recess by a general polishing method, there is a disadvantage that the conductive layer inside the recess is simultaneously removed.
JP 2002-134920 A JP2003-257910A

  When the polishing process is performed by chemical mechanical polishing, the flatness is better than other polishing methods. However, the conventional chemical mechanical polishing has a low polishing rate. In particular, in order to form a circuit board, since the amount of wiring material to be removed is large, it is necessary to greatly improve the polishing rate of chemical mechanical polishing. Further, when there is a step on the surface of the wiring layer after plating, it is necessary to polish the chemical mechanical polishing so that the step is eliminated earlier than the surface to be polished reaches the surface of the resin substrate.

  As described above, the performance of the chemical mechanical polishing aqueous dispersion used for chemical mechanical polishing of the circuit board includes increasing the flatness of the surface to be polished, increasing the polishing rate, and making the step as fast as possible during polishing. It is required to eliminate (step difference elimination) at the same time.

  One of the objects of the present invention is an aqueous dispersion for chemical mechanical polishing suitably used for forming a circuit board in which a wiring layer containing copper or a copper alloy is provided on a resin substrate, the copper or copper alloy It is an object to provide an aqueous dispersion for chemical mechanical polishing that has a high polishing rate, excellent step resolution, and good flatness of the resulting circuit board.

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

  One of the objects of the present invention is to provide a circuit board with good flatness and a multilayer circuit board with good flatness in which a plurality of circuit boards are stacked.

The chemical mechanical polishing aqueous dispersion according to the present invention comprises:
A chemical mechanical polishing aqueous dispersion used for forming a circuit board provided with a wiring layer containing copper or a copper alloy on a resin substrate,
(A) an organic acid;
(B) a nitrogen-containing heterocyclic compound;
(C) an oxidizing agent;
(D1) a first abrasive grain having a primary particle diameter of 20 to 70 nm;
(D2) a second abrasive grain having a primary particle diameter of 80 to 150 nm,
Including
The concentration of the (A) organic acid with respect to the chemical mechanical polishing aqueous dispersion is 3 to 15% by mass,
The ratio (N1 / N2) of the particle number N1 of the (D1) first abrasive grains and the particle number N2 of the (D2) second abrasive grains is 3 to 50,
The pH value is 1-5.

In the chemical mechanical polishing aqueous dispersion according to the present invention,
The (D1) first abrasive grains may be silica particles.

In the chemical mechanical polishing aqueous dispersion according to the present invention,
The (D2) second abrasive grains can be any one of silica particles, calcium carbonate particles, organic polymer particles, and organic-inorganic composite particles.

In the chemical mechanical polishing aqueous dispersion according to the present invention,
The (D1) first abrasive grains and the (D2) second abrasive grains may be silica particles.

In the chemical mechanical polishing aqueous dispersion according to the present invention,
The silica particles may be at least one selected from colloidal silica and fumed silica.

In the chemical mechanical polishing aqueous dispersion according to the present invention,
The (A) organic acid may be at least one selected from citric acid, glycine, malic acid, tartaric acid, and oxalic acid.

In the chemical mechanical polishing aqueous dispersion according to the present invention,
The (B) nitrogen-containing heterocyclic compound may be at least one selected from benzotriazole, triazole, imidazole, and carboxybenzotriazole.

In the chemical mechanical polishing aqueous dispersion according to the present invention,
The (C) oxidizing agent may be hydrogen peroxide.

A method for manufacturing a circuit board according to the present invention includes:
A step of performing chemical mechanical polishing using the above-described chemical mechanical polishing aqueous dispersion.

  The circuit board according to the present invention is manufactured by the above-described manufacturing method.

  A multilayer circuit board according to the present invention includes a plurality of circuit boards described above.

  According to the chemical mechanical polishing aqueous dispersion, a circuit board in which a wiring layer containing copper or a copper alloy is provided on a resin board can be polished uniformly over the entire circuit board and with a flat surface. Furthermore, according to the above-mentioned chemical mechanical polishing aqueous dispersion, the polishing rate of copper or copper alloy can be made extremely high on the order of μm / min, and the step resolution can be improved, that is, the time required to eliminate the step. Can be shortened. Further, according to the method for manufacturing a circuit board, the circuit board can be manufactured flat and with high throughput. The circuit board and the multilayer circuit board have a uniform thickness over the entire board and have a flat surface. According to the chemical mechanical polishing aqueous dispersion according to the present invention, it is possible to easily provide a circuit board or a multilayer circuit board that is less prone to problems such as poor connection when a semiconductor device or the like is mounted.

  Hereinafter, preferred embodiments according to the present invention will be described in detail. In addition, this invention is not limited to the following embodiment, Various modifications implemented in the range which does not change the summary of this invention are also included.

1. Chemical mechanical polishing aqueous dispersion The chemical mechanical polishing aqueous dispersion according to this embodiment includes (A) an organic acid, (B) a nitrogen-containing heterocyclic compound, (C) an oxidizing agent, and (D1) first. And (D2) second abrasive grains.

  Hereinafter, each component contained in the chemical mechanical polishing aqueous dispersion according to this embodiment will be described in detail. Hereinafter, the substances (A) to (D2) may be abbreviated as components (A) to (D2), respectively.

1.1. Organic Acid The chemical mechanical polishing aqueous dispersion according to this embodiment contains (A) an organic acid. (A) One of the functions of the organic acid is to improve the polishing rate when the chemical mechanical polishing aqueous dispersion is applied to polishing of the wiring layer containing copper or copper alloy on the resin substrate. . As the organic acid (A) used in the chemical mechanical polishing aqueous dispersion of the present embodiment, an organic acid having a coordination ability with respect to the surface of the wiring material containing ions or copper or a copper alloy containing the wiring material element is used. Is preferred. (A) The organic acid is more preferably an organic acid having chelate coordination ability.

  Examples of the organic acid used in the chemical mechanical polishing aqueous dispersion of this embodiment include tartaric acid, fumaric acid, glycolic acid, phthalic acid, maleic acid, formic acid, acetic acid, oxalic acid, citric acid, malic acid, malonic acid, and glutaric acid. Examples include acid, succinic acid, benzoic acid, quinolinic acid, quinaldic acid, and amidosulfuric acid. In addition, as the organic acid used in the present invention, amino acids such as glycine, alanine, aspartic acid, glutamic acid, lysine, arginine, tryptophan, aromatic amino acids, and heterocyclic amino acids can also be suitably used. These organic acids can be dissociated into at least one proton (hydrogen ion) and a counter anion (parent ion) in the chemical mechanical polishing aqueous dispersion. The chemical mechanical polishing aqueous dispersion of the present embodiment may contain the above-mentioned organic acid alone, or may contain two or more of the above-mentioned organic acids. Among these organic acids, since the effect of improving the polishing rate of the chemical mechanical polishing aqueous dispersion is high, at least one selected from citric acid, glycine, malic acid, tartaric acid and oxalic acid is particularly preferable. .

  The organic acid used in the chemical mechanical polishing aqueous dispersion of the present embodiment is dissolved in the chemical mechanical polishing aqueous dispersion, and a cation derived from another component optionally added, such as an ammonium ion, It may be paired with potassium ions or the like. In this case, a salt is formed when the chemical mechanical polishing aqueous dispersion is dried. In this case, the paired cation may be monovalent or more.

  The content of the (A) organic acid in the chemical mechanical polishing aqueous dispersion of this embodiment is 3 to 15% by mass with respect to the mass of the chemical mechanical polishing aqueous dispersion in use as the whole (A) organic acid. It is. The content of (A) the organic acid is more preferably 3.5 to 12% by mass, and particularly preferably 4 to 10.5% by mass. (A) If the content of the organic acid 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 step. On the other hand, when the content of the organic acid (A) exceeds the above range, the chemical etching effect increases, corrosion of the wiring layer occurs, the level difference elimination deteriorates, and the flatness of the polished surface is impaired. Sometimes.

1.2. Nitrogen-containing heterocyclic compound The chemical mechanical polishing aqueous dispersion according to this embodiment contains (B) a nitrogen-containing heterocyclic compound. (B) One of the functions of the nitrogen-containing heterocyclic compound is to form a water-insoluble complex with a metal such as copper and to protect the surface of the surface to be polished, thereby increasing the flatness of the surface to be polished. It is done. (B) As a nitrogen-containing heterocyclic compound, the nitrogen-containing heterocyclic compound which has a coordination ability with respect to the surface of the wiring material containing the ion which consists of a wiring material element, or copper or a copper alloy is preferable. (B) A nitrogen-containing heterocyclic compound having chelate coordination ability is more preferable as the nitrogen-containing heterocyclic compound.

  The (B) nitrogen-containing heterocyclic compound suitably used in the chemical mechanical polishing aqueous dispersion according to this embodiment is a compound containing at least one nitrogen as a hetero atom 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 heterocyclic 5-membered ring and a heterocyclic 6-membered ring having at least one nitrogen atom. Examples of the heterocyclic ring include a hetero five-membered ring such as a pyrrole structure, an imidazole structure, and a triazole structure, and a hetero six-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. Specifically, indole structure, isoindole structure, benzimidazole structure, benzotriazole structure, quinoline structure, isoquinoline structure, quinazoline structure, cinnoline structure, phthalazine structure, quinoxaline structure, acridine structure and the like can be mentioned. Among 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 nitrogen-containing heterocyclic compounds include aziridine, pyridine, pyrimidine, pyrrolidine, piperidine, pyrazine, triazine, pyrrole, imidazole, indole, quinoline, isoquinoline, benzoisoquinoline, purine, pteridine, triazole, triazolidine, benzotriazole, carboxy Examples thereof include benzotriazole, and further, derivatives having these skeletons can be exemplified.

  In the chemical mechanical polishing aqueous dispersion according to this embodiment, as the nitrogen-containing heterocyclic compound (B), the above nitrogen-containing heterocyclic compounds can be used singly or in combination of two or more. (B) The nitrogen-containing heterocyclic compound is particularly preferably at least one selected from benzotriazole, triazole, imidazole, and carboxybenzotriazole.

  The content of the (B) nitrogen-containing heterocyclic compound in the chemical mechanical polishing aqueous dispersion of the present embodiment is based on the mass of the chemical mechanical polishing aqueous dispersion in use as the whole (B) nitrogen-containing heterocyclic compound. , Preferably it is 0.05-2 mass%, More preferably, it is 0.1-1 mass%, Most preferably, it is 0.2-0.5 mass%. (B) If the content of the nitrogen-containing heterocyclic compound is less than the above range, the flatness of the polished surface may be impaired. (B) When content of a nitrogen-containing heterocyclic compound exceeds the said range, a polishing rate may fall.

1.3. Oxidizing agent The chemical mechanical polishing aqueous dispersion according to this embodiment contains (C) an oxidizing agent. (C) One of the functions of the oxidizing agent is to improve the polishing rate when the chemical mechanical polishing aqueous dispersion is applied to polishing of a circuit board on which a wiring layer containing copper and copper is formed. Can be mentioned. The reason for this is that (C) the oxidizing agent oxidizes the surface of copper or the like and promotes a complexing reaction with the components of the chemical mechanical polishing aqueous dispersion, thereby forming a fragile modified layer on the surface of copper or the like. It is thought that it is formed to facilitate polishing of copper or the like.

  Examples of the oxidizing agent (C) used in the chemical mechanical polishing aqueous dispersion of the present embodiment include hydrogen peroxide, peracetic acid, perbenzoic acid, organic peroxides such as tert-butyl hydroperoxide, potassium permanganate, and the like. Permanganic acid compounds, dichromic acid compounds such as potassium dichromate, halogen acid compounds such as potassium iodate, nitric acid compounds such as nitric acid and iron nitrate, perhalogenous compounds such as perchloric acid, and ammonium persulfate. Examples thereof include sulfates and heteropolyacids. Of these oxidizing agents, in view of oxidizing power, corrosiveness to resin substrates, and ease of handling, persulfates such as hydrogen peroxide, organic peroxide, or ammonium persulfate are preferred, and decomposition products are preferred. Particularly preferred is hydrogen peroxide which is harmless.

  The content of the (C) oxidizing agent in the chemical mechanical polishing aqueous dispersion of the present embodiment is preferably 1 to 30% by mass, more preferably based on the mass of the chemical mechanical polishing aqueous dispersion in use. It is 5-20 mass%, Most preferably, it is 5-15 mass%. (C) When content of an oxidizing agent is less than the said range, a chemical effect may become inadequate and a grinding | polishing speed | rate may fall, and it may require much time to complete | finish a grinding | polishing process. On the other hand, if the content of (E) the oxidizing agent exceeds the upper range, the surface to be polished may be corroded and flatness may be impaired.

1.4. First Abrasive Grain and Second Abrasive Grain The chemical mechanical polishing aqueous dispersion according to this embodiment includes (D1) first abrasive grains and (D2) second abrasive grains. (D1) The primary particle diameter of the first abrasive grains is 20 to 70 nm, and (D2) the primary particle diameter of the second abrasive grains is 80 to 150 nm. (D1) The primary particle diameter of the first abrasive grains is more preferably 30 to 65 nm, and further preferably 35 to 60 nm. (D2) The primary particle diameter of the second abrasive grains is more preferably 85 to 130 nm, and still more preferably 90 to 110 nm.

  Here, the primary particle diameter of the abrasive grains is a particle diameter obtained from a particle image of the primary particles observed with a transmission electron microscope. Further, when the abrasive grains are not spherical, it means an average value of the maximum length and the minimum length of the observed image. When the abrasive grains are organic-inorganic composite particles, the primary particle diameter is measured in units of one organic-inorganic composite particle. In addition, the average primary particle size of the abrasive grains is calculated by randomly selecting 500 particle images in a particle image obtained by observation with a transmission electron microscope, measuring the particle size of each selected particle, and calculating the average value. It is the value.

  The ratio (N1 / N2) of (D1) the number N1 of the first abrasive grains and (D2) the number N2 of the second abrasive grains contained in the chemical mechanical polishing aqueous dispersion is 3-50. . The ratio (N1 / N2) is more preferably 4 to 35, and still more preferably 5 to 25.

  Here, the ratio (N1 / N2) of (D1) the number N1 of the first abrasive grains and (D2) the number N2 of the second abrasive grains contained in the chemical mechanical polishing aqueous dispersion is, for example, It can be obtained as follows. First, the subject chemical mechanical polishing aqueous dispersion is observed with a transmission electron microscope. Next, 500 primary particles are randomly selected from the observed primary particles. And about each selected primary particle, a particle diameter is measured, respectively, and the particle diameter of each primary particle belongs to the range of the primary particle diameter of (D1) 1st abrasive grain or (D2) 2nd abrasive grain. Determine whether or not. And (D1) the number n1 of primary particles belonging to the primary particle diameter range of the first abrasive grains, and (D2) the number n2 of primary particles belonging to the primary particle diameter range of the second abrasive grains, Count. Then, a ratio (n1 / n2) between the number n1 and the number n2 is obtained. This ratio (n1 / n2) is a ratio of (D1) the number N1 of the first abrasive grains and (D2) the number N2 of the second abrasive grains contained in the target chemical mechanical polishing aqueous dispersion. It is approximately equal to (N1 / N2). In the above-described example of how to obtain the ratio (N1 / N2), the number of primary particles to be measured is 500. If the number is increased, the ratio (N1 / N2) can be obtained more accurately. Even when the number less than 500 is measured, for example, when the number is 100 or more, the ratio (N1 / N2) can be obtained approximately. When the abrasive grains are organic / inorganic composite particles, the primary particle diameter is measured in units of one organic / inorganic composite particle.

  (D1) As one of the functions of the first abrasive grains, the polishing rate is improved when the chemical mechanical polishing aqueous dispersion is applied to polishing of a circuit board on which a wiring layer containing copper and copper is formed. Can be mentioned. (D1) Since the primary particle diameter of the first abrasive grains is smaller than (D2) the primary particle diameter of the second abrasive grains, when the contents of both are the same, (D1) of the first abrasive grains The number of primary particles (D2) is larger than the number of primary particles of the second abrasive grains. Therefore, (D1) the first abrasive grains are more frequently in contact with the wiring layer to be polished. Therefore, (D1) the first abrasive grains have a greater contribution to the improvement of the polishing rate than (D2) the second abrasive grains.

  (D2) As one of the functions of the second abrasive grains, when the 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 level difference elimination property This increases the time required to eliminate the level difference. (D2) Since the primary particle diameter of the second abrasive grains is larger than (D1) the primary particle diameter of the first abrasive grains, (D1) mechanical polishing power in chemical mechanical polishing is higher than that of the first abrasive grains. The contribution to raising Therefore, (D2) the second abrasive grain has a greater ability to eliminate the step of the wiring layer to be polished. Therefore, (D2) the second abrasive grain has a large contribution to shortening the time until the step is eliminated compared to (D1) the first abrasive grain.

  When the ratio (N1 / N2) is less than the above range or exceeds the above range, the difference in the number of (D1) first abrasive grains and (D2) second abrasive grains increases, In some cases, the effect of improving the level difference elimination cannot be obtained.

  Moreover, (D1) When the primary particle diameter of the first abrasive grains is less than the upper range, the mechanical polishing power of the chemical mechanical polishing aqueous dispersion may be extremely reduced, and the polishing rate may be reduced. . (D1) When the primary particle diameter of the first abrasive grains exceeds the upper range, the number of particles decreases, and it is necessary to increase the amount of addition, which is not preferable. (D2) If the primary particle diameter of the second abrasive grains is less than the upper range, the step resolution is reduced, and the flatness of the circuit board may be impaired. (D2) If the primary particle diameter of the second abrasive grains exceeds the upper range, the storage stability may deteriorate, which is not preferable.

  Examples of the type of (D1) first abrasive grains and (D2) second abrasive grains include inorganic particles, organic particles, and organic-inorganic composite particles. The types of (D1) first abrasive grains and (D2) second abrasive grains may be the same or different. Examples of the inorganic particles include silica particles, alumina particles, titania particles, zirconia particles, ceria particles, calcium carbonate particles, and the like.

  The silica particles include fumed silica synthesized by the fumed method in which silicon chloride and the like are reacted with oxygen and hydrogen in the gas phase, silica synthesized by the sol-gel method synthesized by hydrolytic condensation from metal alkoxide, and purification. And colloidal silica synthesized by an inorganic colloid method or the like from which impurities have been removed. As the silica particles, colloidal silica synthesized by an inorganic colloid method in which impurities are removed by purification is preferable.

  The calcium carbonate particles are preferably high-purity calcium carbonate particles obtained by reacting carbon dioxide after purifying calcium hydroxide in water.

  Organic particles include polyethylene, polypropylene, poly-1-butene, olefin copolymers such as poly-4-methyl-1-pentene, polystyrene, styrene copolymers, polyvinyl chloride, polyacetal, saturated polyester, polyamide , Organic polymer particles such as polycarbonate, phenoxy resin, polymethyl methacrylate, (meth) acrylic resin, and acrylic copolymer.

  The organic / inorganic composite particles can be composed of the organic particles and the inorganic particles. The organic-inorganic composite particles may be any particles as long as 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, and the types and configurations of the particles are particularly limited. Not. Examples of the organic-inorganic composite particles include polycondensation of alkoxysilane, aluminum alkoxide, titanium alkoxide, etc. in the presence of polymer particles such as polystyrene and polymethyl methacrylate, and at least the surface of the polymer particles is polysiloxane, What a polycondensate, such as aluminoxane and a poly titanoxane, couple | bonds together can be used. The produced polycondensate may be directly bonded to the functional group of the polymer particles, or may be bonded via a silane coupling agent or the like. Further, silica particles, alumina particles, or the like can be used instead of alkoxysilane or the like. In this case, the organic-inorganic composite particles are formed such that silica particles are present on the surface of the polymer particles using a polycondensate such as polysiloxane, polyaluminoxane, polytitanoxane or the like as a binder. These may be held in entanglement with polysiloxane or the like, or may be chemically bonded to the polymer particles by a functional group such as a hydroxyl group which they have.

  The organic-inorganic composite particles that can be used in the chemical mechanical polishing aqueous dispersion according to this embodiment include an aqueous dispersion containing organic particles having different zeta potentials and inorganic particles, and these particles are separated by electrostatic force. What is combined is mentioned. The zeta potential of organic particles is often negative over the entire pH range or a wide range excluding the low pH range, but by making organic particles having a carboxyl group, a sulfonic acid group, etc., the negative potential is more reliably reduced. Organic particles having a zeta potential can be obtained. Moreover, it can also be set as the organic particle which has a positive zeta potential in a specific pH range by setting it as the organic particle which has an amino group etc. On the other hand, the zeta potential of inorganic particles is highly pH-dependent and has an isoelectric point at which this potential becomes 0, and the sign of the zeta potential is reversed before and after that. Therefore, by combining specific organic particles and inorganic particles and mixing them in a pH range in which the zeta potential has an opposite sign, the organic particles and the inorganic particles can be integrally combined by electrostatic force. Further, even when the zeta potential has the same sign during mixing, the organic particles and the inorganic particles can be integrated by changing the pH and changing the zeta potential to the opposite sign.

  Furthermore, as the above organic-inorganic composite particles, alkoxysilane, aluminum alkoxide, titanium alkoxide and the like are polycondensed as described above in the presence of particles integrally combined by electrostatic force, and at least on the surface of the particles, Further, a compound obtained by combining polysiloxane or the like can also be used.

  Of these, silica particles are particularly preferable as the first abrasive grains (D1). (D2) The second abrasive is preferably any one selected from silica particles, calcium carbonate particles, organic polymer particles, and organic-inorganic composite particles. Furthermore, both (D1) first abrasive grains and (D2) second abrasive grains are particularly preferably silica particles.

  The total content of the (D1) first abrasive grains and the (D2) second abrasive grains in the chemical mechanical polishing aqueous dispersion according to this embodiment is arbitrary, but the chemical mechanical polishing aqueous system in use is not limited. It is more preferable that it is 0.5-5 mass% with respect to the mass of a dispersion. The total content of (D1) first abrasive grains and (D2) second abrasive grains is more preferably 1 to 4.5 mass%, particularly preferably 1.5 to 4 mass%. When the total content of the component (D1) and the component (D2) 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 step. On the other hand, when the total content of the component (D1) and the component (D2) exceeds the above range, the flatness of the surface to be polished may be insufficient, the cost may be increased, and chemical mechanical polishing may be performed. The storage stability of the aqueous dispersion may not be ensured.

1.5. PH of aqueous dispersion for chemical mechanical polishing
In the chemical mechanical polishing aqueous dispersion according to this embodiment, the pH value of the chemical mechanical polishing aqueous dispersion 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 chemical mechanical polishing aqueous dispersion is more preferably 1.5 to 4.5, and still more preferably 2 to 4. When the pH value of the chemical mechanical polishing aqueous dispersion is less than the above range, the step-resolving property may be lowered or the flatness may be deteriorated. If the pH value of the chemical mechanical polishing aqueous dispersion exceeds the above range, the polishing rate may decrease.

  The pH value of the chemical mechanical polishing aqueous dispersion varies depending on the amount of each component described above. For this reason, the pH value is adjusted to be in the above range by selecting the type of each component or changing the blending amount. Further, depending on the type and amount of each component, the pH value may not fall within the above range. In that case, a pH adjuster or the like may be appropriately added to the chemical mechanical polishing aqueous dispersion to adjust the pH value within the above range.

1.6. pH adjuster The chemical mechanical polishing aqueous dispersion of the present embodiment may be mixed with a pH adjuster such as an acid, an alkali, or the like, if necessary. One of the functions of the pH adjuster is to adjust the chemical mechanical polishing aqueous dispersion to a desired pH. Thereby, the chemical mechanical polishing aqueous dispersion has a desired pH value, and it is possible to adjust the polishing rate, improve the flatness, eliminate the step difference, and suppress the corrosion of the wiring layer. The pH adjusting agent can be used when the pH of the chemical mechanical polishing aqueous dispersion is outside the range of 1 to 5, and the pH of the chemical mechanical polishing aqueous dispersion is in the range of 1 to 5. Sometimes it can be used to further adjust the pH.

  Examples of the pH adjuster include inorganic acids such as sulfuric acid and phosphoric acid as the acid, and alkali metal water such as sodium hydroxide, potassium hydroxide, rubidium hydroxide, and cesium hydroxide as the alkali. Examples thereof include oxides, organic alkali compounds such as TMAH and choline, and ammonia. An acid and an alkali may be mix | blended independently and multiple types may be mix | blended. By adding a pH adjuster, the pH is appropriately set so that the abrasive grains can exist stably while taking into consideration the electrochemical properties of the surface to be polished, the dispersibility and stability of the abrasive grains, and the polishing rate. can do. As a pH adjuster particularly suitable for the chemical mechanical polishing aqueous dispersion of the present embodiment, phosphoric acid may be mentioned from the viewpoint of improving the polishing rate.

1.7. Other Additives The chemical mechanical polishing aqueous dispersion according to this embodiment may contain various additives as necessary in addition to the above components. Examples of other additives include anticorrosives for wiring materials, antifoaming agents and antifoaming agents that reduce foaming of the slurry.

1.8. Effect As a result of the chemical mechanical polishing aqueous dispersion of the present embodiment having the above-described configuration, the thickness of the circuit board in which the wiring layer containing copper or copper alloy is provided on the resin board is uniform over the entire circuit board. In addition, the surface can be polished flat. Furthermore, according to the above-mentioned chemical mechanical polishing aqueous dispersion, the polishing rate of copper or copper alloy can be made extremely high on the order of μm / min, and the step resolution can be improved, that is, the time required to eliminate the step. Can be shortened.

  In particular, the chemical mechanical polishing aqueous dispersion of the present embodiment includes abrasive grains (first abrasive grains) having a primary particle diameter of 20 to 70 nm and abrasive grains (second abrasive grains) having a primary particle diameter of 80 to 150 nm. And the ratio (N1 / N2) of the number N1 of the first abrasive grains to the number N2 of the second abrasive grains is 3-50. As a result, the chemical mechanical polishing aqueous dispersion of the present embodiment mainly has the function of improving the polishing rate by the first abrasive grains, and mainly has the function of improving the level difference elimination by the second abrasive grains. Therefore, the content of the abrasive grains as a whole can be reduced, and the storage stability of the chemical mechanical polishing aqueous dispersion can be improved and the cost can be reduced.

2. Circuit board manufacturing method, circuit board, and multilayer circuit board A circuit board manufacturing method according to the present embodiment uses a chemical mechanical polishing aqueous dispersion described in "1. Chemical mechanical polishing aqueous dispersion". A step of polishing.

  The chemical mechanical polishing step is performed by introducing the above-described chemical mechanical polishing aqueous dispersion into a general chemical mechanical polishing apparatus. Hereafter, the manufacturing process of a circuit board is concretely demonstrated using drawing. 1 to 5 are cross-sectional views schematically showing an example of a manufacturing process of the circuit board 100 according to the present embodiment. The chemical mechanical polishing step in the method for manufacturing the circuit board 100 according to the present embodiment is a step for polishing a wiring layer made of copper or a copper alloy.

  As the resin substrate 10 used in the method for manufacturing the circuit board 100 according to the present embodiment, it suffices if the portion where the wiring layer is formed has insulation, for example, a film substrate, a plastic substrate can be used, and a glass substrate or the like. Can also be used. The resin substrate 10 may be a single-layer body or a laminate in which a resin layer is 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 a recess 12 by techniques such as photolithography and etching. The recess 12 is formed corresponding to the wiring layer of the circuit board 100. At least the surface of the resin substrate 10 on which the concave portion 12 is provided has electrical insulation.

  Next, as shown in FIG. 2, a barrier metal film 20 is formed so as to cover the surface of the resin substrate 10 and the bottom and inner wall surface of the recess 12. The barrier metal film 20 is provided as necessary. The barrier metal film 20 can be made of a material such as tantalum or tantalum nitride, for example. As a method for forming the barrier metal film 20, chemical vapor deposition (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 a metal film 30. The metal film 30 can be made of copper or a copper alloy. After the chemical mechanical polishing process, the metal film 30 remains in the recess 12 and forms a wiring layer of the circuit board 100. As a method for forming the metal film 30, physical vapor deposition (PVD) such as sputtering and vacuum deposition can be applied.

  Next, as shown in FIG. 4, the excess metal film 30 other than the portion buried in the recess 12 is removed by chemical mechanical polishing 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 normal cleaning method.

  Finally, as shown in FIG. 5, the surfaces of the barrier metal film 20 a and the metal film 30 other than the recess 12 are subjected to chemical mechanical polishing using another chemical mechanical polishing aqueous dispersion for the barrier metal film. To remove.

  The circuit board 100 is formed as described above. The circuit board 100 can have a wiring layer having an arbitrary shape. And the multilayer circuit board of this embodiment can be formed by laminating | stacking the some circuit board which has a wiring layer of a suitable shape. The multilayer circuit board can have a three-dimensional wiring structure by appropriately connecting the wiring layers of the circuit boards.

  In the chemical mechanical polishing step of the present embodiment, the metal film 30 is removed using the chemical mechanical polishing aqueous dispersion of the present embodiment. Therefore, the polishing rate is large, and the level difference elimination and the in-plane flatness of the polishing are good. It is difficult to cause selective polishing such as dishing. Therefore, according to the circuit board manufacturing method of the present 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 this embodiment has high in-plane flatness and small dishing. Therefore, the multilayer circuit board formed by stacking the circuit boards 100 of the present embodiment has a uniform thickness over the entire board and has a flat surface.

3. Examples and Comparative Examples Hereinafter, the present invention will be further described with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples and Comparative Examples.

3.1. Production of evaluation substrate 3.1.1. Preparation of flatness evaluation substrate Spinning WPR-1201 varnish (manufactured by JSR Corporation; photosensitive insulating resin composition) on a copper-clad laminate (substrate thickness: 0.6 mm, size: 10 cm square) whose surface has been roughened. It was coated and heated on a hot plate at 110 ° C. for 3 minutes to produce a uniform coating film having a thickness of 10 μm. Thereafter, using an aligner (MA-100 manufactured by Karl Suss), ultraviolet rays from a high-pressure mercury lamp were irradiated through a pattern mask having a wiring of L / S = 100 μm / 100 μm and a pad portion of 2 mm × 2 mm. The exposure of ultraviolet rays was performed so that the exposure amount at a wavelength of 350 nm was 3000 to 5000 J / m ² . Subsequently, it was heated at 110 ° C. for 3 minutes (PEB) on a hot plate, subjected to immersion development at 23 ° C. for 60 seconds using an aqueous 2.38 mass% tetramethylammonium hydroxide (TMAH) solution, and then 120 ° C. in a convection oven. * 2 hours of heating was performed to form a cured insulating resin film having a groove pattern on the copper-clad laminate. A copper seed layer was formed on the obtained cured cured resin film by electroless plating, and then a 10 μm copper plating layer was formed by electrolytic plating. In this way, a flatness evaluation substrate in which copper was embedded in the groove pattern was obtained. If this substrate is properly chemically and mechanically polished, if the copper outside the groove pattern is removed, a circuit substrate having a conductive layer line of 100 μm width and a conductive layer line of 2 mm width is formed.

3.1.2. Preparation of Copper Polishing Rate Evaluation Substrate A substrate with a 10 μm copper plating layer was obtained in the same manner as in “3.1.1. Preparation of flatness evaluation substrate” except that the insulating resin layer groove pattern was not formed.

3.2. Preparation of abrasive dispersion 3.2.1. Preparation of Water Dispersion Containing Colloidal Silica A water dispersion containing colloidal silica prepared a commercial product and a synthetic product prepared as follows. As commercial products, trade names PPS-45P and trade names PPS-80P (manufactured by Catalyst Kasei Kogyo Co., Ltd.) were used. Each colloidal silica was observed with a transmission electron microscope (TEM) and the average primary particle diameter was measured, and it was 55 nm and 105 nm.

  The synthetic product was prepared as follows. A flask having a volume of 2 liters was charged with 70 g of 25% by mass ammonia water, 40 g ion-exchanged water, 175 g ethanol, and 21 g tetraethoxysilane. And it heated up at 60 degreeC, stirring, after continuing stirring for 2 hours with this temperature, it cooled and obtained the colloidal silica / alcohol dispersion. At this time, for the purpose of changing the primary particle size of the colloidal silica, five types of aqueous dispersions were prepared by changing the blending amount of each component and the stirring speed. Next, an operation for removing the alcohol content was repeated several times while adding ion-exchanged water at a temperature of 80 ° C. with respect to each dispersion to remove the alcohol content in the dispersion, and the solid content was 8% by mass. Five types of aqueous colloidal silica dispersions were prepared. With respect to each dispersion, colloidal silica was observed with a TEM and the average primary particle size was measured and found to be 35 nm, 40 nm, 70 nm, 90 nm and 135 nm.

3.2.2. Preparation of aqueous dispersion containing composite particles First, an aqueous dispersion (a) and an aqueous dispersion (b) containing polymer particles were prepared as follows. 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), 5 parts by mass of 4-vinylpyridine, azo polymerization 2 parts by weight of an initiator (trade name “V50” manufactured by Wako Pure Chemical Industries, Ltd.) and 400 parts by weight of ion-exchanged water are put into a flask having a capacity of 2000 cm ³ and heated to 70 ° C. with stirring in a nitrogen gas atmosphere. Warm and polymerize for 6 hours. As a result, an aqueous dispersion (a) containing polymethyl methacrylate-based particles having an average particle diameter of 100 nm and having a functional group having an amino group cation and a polyethylene glycol chain was obtained. The polymerization yield was 95%. An aqueous dispersion (b) having an average particle diameter of polymer particles of 130 nm was prepared in the same manner as above except that the stirring speed was increased.

Next, each of the aqueous dispersion (a) and the aqueous dispersion (b) is diluted so that the polymethyl methacrylate-based particles are contained at 10% by mass, and the aqueous dispersion (c) and the aqueous dispersion (d) are obtained. Prepared. About 100 parts by mass of each of the aqueous dispersion (c) and the aqueous dispersion (d) was put into a flask having a capacity of 2000 cm ³ , 1 part by mass of methyltrimethoxysilane was added, and the mixture was stirred at 40 ° C. for 2 hours. Thereafter, the pH was adjusted to 2 with nitric acid to obtain an aqueous dispersion (e) and an aqueous dispersion (f). On the other hand, the pH of an aqueous dispersion containing 10% by mass of colloidal silica (manufactured by Nissan Chemical Co., Ltd., trade name “Snowtex O”) was adjusted to 8 with potassium hydroxide to obtain an aqueous dispersion (g). The zeta potential of the polymethyl methacrylate-based particles contained in the aqueous dispersion (e) and the aqueous dispersion (f) was +17 mV, and the zeta potential of the colloidal silica particles contained in the aqueous dispersion (g) was −40 mV. Thereafter, for each of the aqueous dispersion (e) and the aqueous dispersion (f), 50 parts by mass of the aqueous dispersion (g) was gradually added to 100 parts by mass over 2 hours, mixed, stirred for 2 hours, An aqueous dispersion (h) and an aqueous dispersion (i) containing particles having silica particles attached to methyl methacrylate particles were obtained. Then, after adding 2 parts of vinyltriethoxysilane to each aqueous dispersion and stirring for 1 hour, 1 part by weight of tetraethoxysilane was added, the temperature was raised to 60 ° C., and stirring was continued for 3 hours. By cooling, an aqueous dispersion (j) and an aqueous dispersion (k) containing composite particles were obtained. When the water dispersion (j) and the water dispersion (k) were each observed with a TEM and the primary particle diameter was measured, the average primary particle diameter of the composite particles contained in the water dispersion (j) was 130 nm. The average primary particle diameter of the composite particles contained in the aqueous dispersion (k) was 100 nm. In both cases, it was confirmed that the silica particles were adhered to 80% of the surface of the polymethyl methacrylate particles in the composite particles.

3.3. Preparation of aqueous dispersion for chemical mechanical polishing A polyethylene bottle having a capacity of 1 liter so that each of the aqueous dispersions described in the section “3.2. Preparation of Abrasive Dispersion” has the composition described in Table 1. It was thrown into. To this, the compounds shown in Table 1 were added so as to have respective contents, and stirred sufficiently. Thereafter, phosphoric acid, ammonia and potassium hydroxide were added to the dispersions indicated by ◯ in Table 1 as pH adjusters, and the pH was adjusted to the value shown in Table 1. Then, it filtered with the filter of the hole diameter of 5 micrometers, and obtained the aqueous dispersion for chemical mechanical polishing of Examples 1-7 and Comparative Examples 1-7. The ratio (N1 / N2) was determined as follows, and the results are shown in Table 1.

  The chemical mechanical polishing aqueous dispersions of each Example and each Comparative Example were each subjected to TEM observation. 500 primary particles were randomly selected from the observed primary particles. The diameter (primary particle diameter) of each selected primary particle was measured. Subsequently, the number of particles having a primary particle diameter of 20 to 70 nm (D1) (n1) and 80 to 150 nm (D2) (n2) was counted and recorded in Table 1. Then, the value of the ratio (n1 / n2) between the number n1 and the number n2 is obtained, and this value is contained in each chemical mechanical polishing aqueous dispersion (D1) The number N1 of the first abrasive grains and (D2) The ratio of the number N2 of the second abrasive grains (N1 / N2) is shown in Table 1.

3.4. Polishing of substrate A substrate with a copper film without a wiring pattern using the aqueous dispersions of Examples 1 to 7 and Comparative Examples 1 to 7 and a substrate for flatness evaluation in which copper is embedded in the above groove pattern are as follows: Polished with.
Polishing device: Lapmaster LM15
・ Polishing pad: IC1000 (made by Nitta Haas)
-Carrier head load: 280 hPa
・ Surface plate rotation speed: 90rpm
Abrasive supply amount: 100 ml / min The copper polishing rate was calculated from the polishing result of the substrate with a copper film without a wiring pattern, using the following calculation formula. The polishing rate of each example and comparative example is shown in Table 1.

Polishing speed (μm / min) = polishing amount (μm) / polishing time (min)
The polishing amount was calculated using the following equation, assuming that the density of copper was 8.9 g / cm ³ .

Polishing amount (μm) = (weight before polishing (g) −weight after polishing (g)) / substrate area (cm ² ) × copper density (g / cm ³ ) × 104
When the value of the polishing rate is 7 (μm / min) or more, it can be said that the polishing rate is good.

3.5. Evaluation of level difference elimination property The level difference elimination property was separately polished in the same manner as described in “3.4. Polishing of substrate” above. Every 6 seconds from the start of polishing, the step of the substrate is measured using a stylus type step gauge (manufactured by KLA-Tencor, model “P-10”), and the step on the surface of the copper film is 0.5 μm or less. At that time, it was determined that the step was eliminated, and the time from the start of polishing to the elimination of the step was recorded and evaluated. Table 1 shows the time required to eliminate the level difference for each example and each comparative example. The level difference resolving property can be said to be very good if the time required for level difference cancellation is within 1 minute.

3.6. Evaluation of dishing If an initial surplus film having a thickness T (nm) in which a wiring material is deposited in a recess or the like is polished at a polishing rate V (nm / min), the object is to polish by the time of T / V (min) originally. Should be able to be achieved. However, in the actual manufacturing process, excessive polishing (over polishing) exceeding T / V (min) is performed in order to remove the wiring material remaining in portions other than the recesses. At this time, the wiring portion may be excessively polished, resulting in a concave shape. Such a concave wiring shape is called “dishing” and is not preferable from the viewpoint of reducing the yield of manufactured products. Therefore, dishing was taken as an evaluation item in each example and comparative example.

  Evaluation of dishing was performed using the above-mentioned flatness evaluation board | substrate using the stylus type level | step difference meter (The product made by KLA-Tencor, model "P-10"). The polishing time in the dishing evaluation is a value obtained by dividing the initial excess copper film having a thickness T (nm) by the polishing rate V (nm / min) obtained in “3.4. Polishing of Substrate” (T / V) (minutes) multiplied by 1.5 (minutes).

  In the item of dishing in the evaluation items in Table 1, the amount of depression of the copper wiring measured by the surface roughness meter was described as the dishing value (μm). The dishing values are shown in Table 1 for 100 μm wide lines and 2 mm wide lines formed on the flatness evaluation substrate. For reference, the difference in dishing value between the 100 μm width line and the 2 mm width line is also shown in Table 1. The dishing value is good when it is 1.5 (μm) or less for a line of 100 μm width, and good when it is 2.0 (μm) or less for a line of 2 mm width.

3.7. Storage Stability Evaluation of the storage stability of the chemical mechanical polishing aqueous dispersions of each Example and each Comparative Example was carried out by preparing the chemical mechanical polishing aqueous dispersions and then allowing them to stand at room temperature and normal pressure for 60 days. It implemented by observing each dispersion | distribution after placement visually. As an index for evaluating the storage stability, ◎ when there is no change immediately after preparation, ◯ when a slight precipitate is observed, and × when the separation of the components occurs or the supernatant region occurs, The results are shown in Table 1.

3.8. Evaluation Results According to the results of Table 1, in the chemical mechanical polishing aqueous dispersions of Examples 1 to 7, the copper polishing rate was 7.2 μm / min or more and was sufficiently high. And the chemical mechanical polishing aqueous dispersions of Examples 1 to 7 had a time difference elimination within 1 minute and had extremely good level difference elimination. Moreover, it was found that the chemical mechanical polishing aqueous dispersions of Examples 1 to 7 had a good overpolish margin because the dishing of 100 μm wiring was as small as 1.2 μm or less. Further, it was found that the dishing of the 2 mm wiring is as small as 1.7 μm or less and has a good overpolish margin even for the wiring having a large width. Note that the difference in dishing between the 100 μm line and the 2 mm line is 0.5 μm or less, and it was found that the line width dependence of dishing is small. Moreover, the chemical mechanical polishing aqueous dispersions of Examples 1 to 7 all had good storage stability.

  On the other hand, as shown in Table 1, Comparative Example 1 in which the ratio (N1 / N2) exceeded the upper limit of 3 to 50 was insufficient for a long time of 1.6 minutes until the step was eliminated. Further, in Comparative Example 2 in which the ratio (N1 / N2) is less than the lower limit of 3 to 50, the polishing rate was as small as 5.1 μm / min, and the time until the step was eliminated was as long as 1.4 minutes and was poor. . Similarly, in Comparative Example 3 in which the ratio (N1 / N2) is less than the lower limit of 3 to 50, the polishing rate and the time required to eliminate the step are in a favorable range due to the increase in the content of abrasive grains. It was bad. In Comparative Example 4 (1.5% by mass) in which the content of the component (A) is less than the range of 3 to 15% by mass, the polishing rate is very low, and the time until the step is eliminated is as long as 3.5 minutes. It was bad. In Comparative Example 5 (21 mass%) in which the content of the component (A) exceeded the range of 3 to 15 mass%, dishing was poor. In Comparative Example 6 (pH = 0.5) in which the pH value was outside the lower limit of the range of 1 to 5, the time required to eliminate the step was long and dishing was extremely large. In Comparative Example 7 (pH = 6) in which the pH value deviated from the upper limit of the range of 1 to 5, the polishing rate was low, and the time until the step was eliminated was also poor. In addition, about Comparative Example 3 and Comparative Examples 5-7, the storage stability was also inferior.

  As described above, the chemical mechanical polishing aqueous dispersions of the respective examples can polish a metal film containing copper or a copper alloy on a resin substrate at a high polishing rate, and have excellent step resolution and in-plane uniformity of the substrate. It has been found that it is possible to ensure the thickness and to suppress the variation in flatness within the polished surface.

It is sectional drawing which shows typically the process of the manufacturing method of the circuit board of this embodiment. It is sectional drawing which shows typically the process of the manufacturing method of the circuit board of this embodiment. It is sectional drawing which shows typically the process of the manufacturing method of the circuit board of this embodiment. It is sectional drawing which shows typically the process of the manufacturing method of the circuit board of this embodiment. It is sectional drawing which shows typically the example of the circuit board manufactured by the manufacturing method of the circuit board of this embodiment.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 ... Resin board | substrate, 12 ... Recessed part, 20 ... Barrier metal film, 30 ... Metal film

Claims (11)

A chemical mechanical polishing aqueous dispersion used for forming a circuit board provided with a wiring layer containing copper or a copper alloy on a resin substrate,
(A) an organic acid;
(B) a nitrogen-containing heterocyclic compound;
(C) an oxidizing agent;
(D1) a first abrasive grain having a primary particle diameter of 20 to 70 nm;
(D2) a second abrasive grain having a primary particle diameter of 80 to 150 nm,
Including
The concentration of the (A) organic acid with respect to the chemical mechanical polishing aqueous dispersion is 3 to 15% by mass,
The ratio (N1 / N2) of the particle number N1 of the (D1) first abrasive grains and the particle number N2 of the (D2) second abrasive grains is 3 to 50,
The aqueous dispersion for chemical mechanical polishing having a pH value of 1 to 5. In claim 1,
(D1) The chemical mechanical polishing aqueous dispersion, wherein the first abrasive grains are silica particles. In claim 1 or claim 2,
(D2) The second abrasive grain is an aqueous dispersion for chemical mechanical polishing, which is any one of silica particles, calcium carbonate particles, organic polymer particles, and organic-inorganic composite particles. In any one of Claims 1 thru | or 3,
The (D1) first abrasive grains and the (D2) second abrasive grains are silica-based aqueous dispersions for chemical mechanical polishing. In any one of Claims 2 thru | or 4,
The silica particle is an aqueous dispersion for chemical mechanical polishing, which is at least one selected from colloidal silica and fumed silica. In any one of Claims 1 thru | or 5,
The chemical acid polishing aqueous dispersion, wherein the organic acid (A) is at least one selected from citric acid, glycine, malic acid, tartaric acid and oxalic acid. In any one of Claims 1 thru | or 6,
The chemical mechanical polishing aqueous dispersion, wherein the (B) nitrogen-containing heterocyclic compound is at least one selected from benzotriazole, triazole, imidazole, and carboxybenzotriazole. In any one of Claims 1 thru | or 7,
The chemical mechanical polishing aqueous dispersion, wherein (C) the oxidizing agent is hydrogen peroxide.   A method for manufacturing a circuit board, comprising a step of performing chemical mechanical polishing using the chemical mechanical polishing aqueous dispersion according to claim 1.   A circuit board manufactured by the manufacturing method according to claim 9.   A multilayer circuit board in which a plurality of the circuit boards according to claim 10 are laminated.

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