JP2017190413A - Polisher, storage liquid for polisher and polishing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polisher that can remove resin at a high polishing rate while preventing polishing scratches.SOLUTION: A polisher for resin polishing contains an abrasive grain and water. The abrasive grain has a positive charge in the polisher. The abrasive grain includes a particle attached with at least one selected from the group consisting of an aluminum compound and an aluminum ion (excluding a particle composed of alumina). The polisher has the pH of 3.0-7.0.SELECTED DRAWING: None

Description

  The present invention relates to an abrasive, a storage solution for an abrasive, and a polishing method.

  In recent years, new microfabrication techniques have been developed along with higher integration and higher performance of semiconductor integrated circuits (hereinafter referred to as “LSI”). Chemical mechanical polishing (hereinafter, referred to as “CMP” in some cases) is one such technique, and LSI manufacturing processes (particularly, planarization of interlayer insulating materials, formation of metal plugs, formation of embedded wiring in the multilayer wiring forming process) Etc.) are frequently used.

  By the way, various resins are expected to be used in various applications such as semiconductor packages; insulating materials (insulating films, etc.); wiring boards (eg, printed wiring boards), circuit boards, etc. In some cases, an excessive portion in the object to be polished is removed by polishing. However, resins having excellent heat resistance, mechanical strength, dimensional stability, insulating properties, etching resistance, etc. (for example, polybenzoxazole, polybenzoxazole precursors and polyimide) are very difficult to polish and remove. is there. On the other hand, in order to remove such a resin, a method of physically removing it using abrasive grains having high hardness has been proposed (see, for example, Patent Documents 1 and 2 below).

US Patent Application Publication No. 2014/209656 JP 2010-135472 A Japanese Patent No. 5328179

  However, in the conventional method using abrasive grains having high hardness, there is a concern that a large number of polishing scratches (scratches; scratches appearing on the polished surface after polishing; the same applies hereinafter) occur on the surface to be polished. Therefore, it is required for resin polishing abrasives to remove the resin at a good polishing rate while suppressing the generation of polishing flaws.

  An object of the present invention is to provide an abrasive capable of removing a resin at a good polishing rate while suppressing the generation of polishing flaws. Another object of the present invention is to provide an abrasive storage solution for obtaining the abrasive. Furthermore, this invention aims at providing the grinding | polishing method using the said abrasive | polishing agent.

  As a result of intensive studies, the inventors have found that particles (made of alumina) to which at least one selected from the group consisting of an aluminum compound and aluminum ions is attached in an abrasive having a pH of 3.0 to 7.0. It has been found that the above-mentioned problems can be solved by using abrasive grains that contain a positive charge.

  That is, the abrasive for polishing a resin according to the present invention is an abrasive containing abrasive grains and water, the abrasive grains having a positive charge in the abrasive, and the abrasive grains are an aluminum compound and It contains particles (excluding particles made of alumina) to which at least one member selected from the group consisting of aluminum ions is attached, and the pH of the abrasive is 3.0 to 7.0.

  According to the abrasive | polishing agent which concerns on this invention, resin can be removed with a favorable grinding | polishing speed | rate, suppressing generation | occurrence | production of an abrasion flaw. In particular, according to the polishing agent of the present invention, it is possible to remove polybenzoxazole, a polybenzoxazole precursor, and polyimide at a good polishing rate while suppressing generation of polishing flaws.

  By the way, in order to remove polyimide, a method using a strong alkali has been proposed (for example, see Patent Document 3). However, since such a method uses strong alkali, there is a concern in terms of safety to the human body. On the other hand, according to the abrasive | polishing agent which concerns on this invention, even if it is a case where a strong alkali is not used, resin can be removed with a favorable grinding | polishing speed | rate, suppressing generation | occurrence | production of an abrasion flaw.

  The abrasive preferably contains colloidal silica. In this case, polishing scratches can be easily reduced while maintaining a high polishing rate of the resin.

  The pH of the abrasive according to the present invention is preferably 3.0 to 5.0. In this case, it is possible to obtain a better polishing rate of the resin and to suppress agglomeration of abrasive grains.

  The abrasive according to the present invention may further contain an insulating material polishing inhibitor. In this case, the resin can be selectively removed with respect to the insulating material (excluding the resin).

  The abrasive according to the present invention may further contain an anticorrosive.

  The abrasive according to the present invention may further contain an oxidizing agent.

  The abrasive according to the present invention may further contain a pH adjuster.

  The abrasive according to the present invention may further contain a surfactant. In this case, the polishing rate of the material to be polished can be easily adjusted, and polishing scratches can be easily reduced.

  The abrasive storage solution according to the present invention is an abrasive storage solution for obtaining the abrasive according to the present invention, and the abrasive can be obtained by diluting with water. In this case, the cost, space, etc. required for transportation and storage of the abrasive can be reduced.

  The polishing method according to the present invention removes by polishing at least a part of the resin using the abrasive according to the present invention or the abrasive obtained by diluting the abrasive storage liquid according to the present invention with water. The process of carrying out is provided. According to such a polishing method, the resin can be removed at a good polishing rate.

  In the polishing method according to the present invention, the resin preferably contains at least one selected from the group consisting of polybenzoxazole, a precursor of polybenzoxazole, and polyimide.

  According to the present invention, the resin can be removed at a good polishing rate while suppressing the generation of polishing flaws. In particular, according to the present invention, it is possible to remove polybenzoxazole, a polybenzoxazole precursor and polyimide at a good polishing rate while suppressing generation of polishing flaws. Further, according to the present invention, even when a strong alkali is not used, the resin can be removed at a good polishing rate while suppressing generation of polishing flaws.

  ADVANTAGE OF THE INVENTION According to this invention, use of the abrasive | polishing agent or the storage liquid for abrasive | polishing agents for grinding | polishing of resin can be provided. ADVANTAGE OF THE INVENTION According to this invention, use of the abrasive | polishing agent or the storage liquid for abrasive | polishing agents for grinding | polishing of resin containing at least 1 type chosen from the group which consists of a polybenzoxazole, the precursor of polybenzoxazole, and a polyimide can be provided. ADVANTAGE OF THE INVENTION According to this invention, use of the abrasive | polishing agent or the storage liquid for abrasive | polishing agents for the grinding | polishing which removes at least one part of resin can be provided by carrying out chemical mechanical polishing of the base | substrate which has resin. ADVANTAGE OF THE INVENTION According to this invention, use of the abrasive | polishing agent or the storage liquid for abrasive | polishing agents for grinding | polishing of the to-be-polished surface containing resin and a metal material can be provided. ADVANTAGE OF THE INVENTION According to this invention, use of the abrasive | polishing agent or the storage liquid for abrasive | polishing agents for the selective grinding | polishing of resin with respect to an insulating material (except resin) can be provided. The present invention can provide the use of an abrasive or a stock solution for an abrasive for polishing a resin of a wiring board. The present invention can provide the use of an abrasive or an abrasive stock solution for polishing a resin on a circuit board.

<Definition>
In this specification, the term “process” includes not only an independent process but also a process in which an intended action of the process is achieved although it cannot be clearly distinguished from other processes.

  In the present specification, “to” indicates a range including numerical values described before and after that as a minimum value and a maximum value, respectively. In the numerical ranges described stepwise in the present specification, the upper limit value or lower limit value of a numerical range of a certain step may be replaced with the upper limit value or lower limit value of the numerical range of another step. In the numerical range described in this specification, the upper limit value or the lower limit value of the numerical range may be replaced with the values shown in the examples.

  In this specification, “A or B” may include either one of A and B, or may include both.

  In the present specification, the content of each component in the composition is the total amount of the plurality of substances present in the composition unless there is a specific notice when there are a plurality of substances corresponding to each component in the composition. means.

  In this specification, “removal rate” means a rate at which a material to be polished is removed per unit time.

  In this specification, “dilute the abrasive stock solution X times” means that when the abrasive is obtained by adding water to the abrasive stock solution, the mass of the abrasive is the mass of the abrasive stock solution. Means a dilution that is X times the. For example, to obtain an abrasive by adding the same amount of water to the mass of the abrasive stock solution is defined as diluting the abrasive stock solution twice.

  Hereinafter, embodiments of the present invention will be described.

<Abrasive>
The polishing slurry for resin according to the present embodiment (hereinafter sometimes simply referred to as “polishing agent”) is a composition that touches the surface to be polished during polishing, and is, for example, a polishing slurry for CMP.

  The abrasive | polishing agent which concerns on this embodiment is an abrasive | polishing agent for grind | polishing the base | substrate which has resin, for example, and removing at least one part of resin. The abrasive | polishing agent which concerns on this embodiment is an abrasive | polishing agent containing an abrasive grain and water, the said abrasive grain has a positive charge in the said abrasive | polishing agent, and the said abrasive grain consists of an aluminum compound and aluminum ion. It includes particles (excluding particles made of alumina) to which at least one selected from the above adheres. The polishing agent has a pH of 3.0 to 7.0. The abrasive | polishing agent which concerns on this embodiment may be used in order to grind | polish metal materials (For example, wiring metals, such as a copper-type metal and a cobalt-type metal; barrier metal) with resin. Moreover, the abrasive | polishing agent which concerns on this embodiment may be used in order to grind | polish resin selectively with respect to insulating materials (except resin, for example, inorganic insulating materials, such as a silicon oxide, and the same hereafter).

(resin)
As the resin to be polished, polybenzoxazole (PBO), PBO precursor, polyimide (PI), phenol resin, epoxy resin, acrylic resin, methacrylic resin, novolac resin, unsaturated polyester, polyester (unsaturated polyester) Excluded), polyamideimide, polyallyl ether, and heterocyclic-containing resins (excluding the resins exemplified above). The object to be polished may be a resin mainly composed of these. Examples of the “heterocycle-containing resin” include a pyrrole ring-containing resin, a pyridine ring-containing resin, and an imidazole ring-containing resin. The method for forming the resin is not particularly limited, and examples thereof include a vapor deposition method and a spine coating method. The shape of the resin is not particularly limited, but is, for example, a film shape (resin film). Among these resins, at least one selected from the group consisting of polybenzoxazole, a precursor of polybenzoxazole and polyimide is preferable from the viewpoint of excellent heat resistance, mechanical strength, dimensional stability, insulating properties, and etching resistance. Moreover, the abrasive | polishing agent which concerns on this embodiment can be used also for grinding | polishing of a wiring board or a circuit board.

  Hereinafter, components and the like contained in the abrasive according to this embodiment will be described in detail.

(Abrasive grains)
The abrasive | polishing agent which concerns on this embodiment contains an abrasive grain. The abrasive grains include particles to which at least one aluminum component selected from the group consisting of an aluminum compound and aluminum ions is attached, and the aluminum component is attached to the particles in an abrasive. As the particles to which the aluminum component is adhered, particles made of alumina are excluded. The aluminum component may be attached to at least a part of the surface of the particle. Examples of the aluminum compound include alumina and aluminum hydroxide. The abrasive has a positive charge in the abrasive. When the abrasive contains such abrasive grains, a good polishing rate of the resin can be obtained while suppressing generation of polishing flaws.

  When removing the resin by polishing (CMP or the like), the abrasive grains electrostatically act on the resin by using abrasive grains having a positive charge in an abrasive having a pH of 3.0 to 7.0. For this reason, it is considered that the resin polishing rate tends to be high. However, with abrasive grains having only a positive charge (abrasive grains not having an aluminum component), the resin cannot be removed at a good polishing rate. Since the aluminum component acts on the chemical bond of the resin (PBO, polyimide, etc.) due to the aluminum component adhering to the particles, it is considered that the resin can be removed at a good polishing rate.

  Examples of the constituent material of the abrasive grains include at least one selected from the group consisting of silica, ceria, cerium hydroxide, resin, and modified products thereof. The content of the constituent material in the abrasive grains is preferably 50% by mass or more, more preferably 75% by mass or more, still more preferably 90% by mass or more, and particularly preferably 95% by mass or more, based on the total mass of the abrasive grains. . The abrasive grains may be in an aspect made of the constituent material (an aspect in which substantially 100% by mass of the abrasive grains is the constituent material).

  Examples of silica include colloidal silica and fumed silica. Among these, colloidal silica is preferable from the viewpoint of easily reducing polishing scratches while maintaining a high resin polishing rate. As said colloidal silica, a commercial item can be obtained easily.

  The modified Mohs hardness of the material contained in the abrasive grains is preferably 12 or less, more preferably 10 or less, still more preferably 9 or less, and particularly preferably 8 or less. The corrected Mohs hardness of the abrasive grains is preferably 12 or less, more preferably 10 or less, still more preferably 9 or less, and particularly preferably 8 or less.

  Examples of the modified product include those obtained by modifying the surface of abrasive grains such as silica, ceria and cerium hydroxide with an alkyl group, and composite abrasive grains obtained by attaching other abrasive grains to the surface of the abrasive grains. The method for modifying the surface of the abrasive grains with an alkyl group is not particularly limited, and examples thereof include a method of reacting a hydroxyl group (hydroxyl group) present on the surface of the abrasive grain with an alkoxysilane having an alkyl group. . The alkoxysilane having an alkyl group is not particularly limited, but monomethyltrimethoxysilane, dimethyldimethoxysilane, trimethylmonomethoxysilane, monoethyltrimethoxysilane, diethyldimethoxysilane, triethylmonomethoxysilane, monomethyltriethoxysilane, dimethyl Examples include diethoxysilane and trimethylmonoethoxysilane. There is no restriction | limiting in particular as a reaction method, For example, although it reacts even if it puts the abrasive | polishing agent containing an abrasive grain and alkoxysilane at room temperature, you may heat in order to accelerate reaction.

  There is no particular limitation on the method for obtaining abrasive particles containing particles to which an aluminum component is adhered and having a positive charge. For example, a method of reacting an aluminum component with particles (a method of coating the surface of particles with an aluminum component, etc.) ). Moreover, you may use the abrasive grain marketed as an abrasive grain containing the particle | grains which modified the aluminum component.

  Whether or not the abrasive has a positive charge in the abrasive can be determined by measuring the zeta potential of the abrasive in the abrasive. When the zeta potential of the abrasive grains in the abrasive is measured and the numerical value exceeds 0 mV, it can be determined that the abrasive grains have a positive charge.

The zeta potential can be measured by, for example, trade name: DELSA NANO C manufactured by Beckman Coulter. The zeta potential (ζ [mV]) can be measured by the following procedure. First, in the zeta potential measurement device, the scattering intensity of the measurement sample is 1.0 × 10 ^{4 to} 5.0 × 10 ⁴ cps (where “cps” means counts per second, that is, counts per second, The sample is obtained by diluting the abrasive with pure water so that Then, the sample is put into a zeta potential measurement cell and the zeta potential is measured. In order to adjust the scattering intensity to the above range, for example, the abrasive is diluted so that the content of abrasive grains is adjusted to 1.7 to 1.8% by mass.

  The zeta potential is preferably 20 mV or more, more preferably 25 mV or more, further preferably 30 mV or more, and particularly preferably 35 mV or more from the viewpoint of obtaining a better polishing rate of the resin and good storage stability. The upper limit of the zeta potential is not particularly limited, but is 100 mV or less, for example.

  The average particle size of the abrasive grains is preferably 10 nm or more, more preferably greater than 10 nm, and even more preferably 20 nm or more, from the viewpoint that sufficient mechanical polishing power can be easily obtained and a higher polishing rate of the resin can be obtained. The average particle diameter of the abrasive grains is preferably 500 nm or less, more preferably 300 nm or less, and more preferably 200 nm from the viewpoint of obtaining good dispersion stability in the abrasive and further reducing the number of polishing scratches generated by polishing. The following are particularly preferred:

  The “average particle diameter” of the abrasive grains means the average secondary particle diameter of the abrasive grains. The average particle diameter is a value of D50 (median diameter of volume distribution, cumulative median value) obtained by measuring the abrasive with a dynamic light scattering particle size distribution analyzer (for example, product name: COULTER N4 SD manufactured by COULTER Electronics). Say.

  Specifically, the average particle diameter can be measured by the following procedure. First, 100 μL of abrasive (L represents liter; the same applies hereinafter) is weighed, and the content of abrasive grains is around 0.05% by mass (the transmittance (H) during measurement is 60 to 70%). ) To obtain a diluted solution. And an average particle diameter can be measured by throwing a dilution liquid into the sample tank of a dynamic light scattering type particle size distribution analyzer, and reading the value displayed as D50.

  From the viewpoint of obtaining an even better polishing rate of the resin, the abrasive particles are preferably particles in which primary particles are aggregated less than an average of less than 3 particles, and more preferably particles in which primary particles are aggregated less than an average of less than 2 particles. The upper limit of the degree of association of the abrasive grains varies depending on the average primary particle diameter of the abrasive grains used, and it is considered that the average secondary particle diameter only needs to be within the range described above. The degree of association can be obtained as an average secondary particle size and an average primary particle size and a ratio thereof (average secondary particle size / average primary particle size).

  The average primary particle size can be measured by a known transmission electron microscope (for example, trade name: H-7100FA manufactured by Hitachi, Ltd.). For example, a particle image is taken using the electron microscope, a biaxial average primary particle size is calculated for a predetermined number of arbitrary particles, and an average value thereof is obtained. When the particle size distribution is wide, the predetermined number should be a quantity that stabilizes the average value. When colloidal silica is used as the abrasive grains, since the particle diameters are generally uniform, the number of particles to be measured may be about 20 particles, for example.

  Specifically, a rectangle (circumscribed rectangle) that circumscribes the selected particle and is arranged so that its major axis is the longest is derived. And based on the major axis L and minor axis B of the circumscribed rectangle, the biaxial average primary particle size of one particle is calculated as “(L + B) / 2”. This operation can be performed on 20 arbitrary particles, and the average value of the obtained values can be used as the biaxial average primary particle size. This operation can also be automated by a computer program.

  The standard deviation of the average particle size distribution in the abrasive grains is preferably 10 nm or less, and more preferably 5 nm or less. In the measurement of the standard deviation of the average particle size distribution, for example, the abrasive grains in the abrasive can be put into COULTER N4SD manufactured by COULTER Electronics, and the standard deviation value can be obtained from the particle size distribution chart.

  The content of the abrasive grains is preferably 0.01% by mass or more based on the total mass of the abrasive from the viewpoint of obtaining sufficient mechanical polishing power and obtaining a higher polishing rate of the resin. More preferably, it is more preferably 0.5% by mass or more. The content of the abrasive grains is determined from the viewpoint of easily avoiding an increase in the viscosity of the abrasive, from the viewpoint of easily avoiding the aggregation of abrasive grains, from the viewpoint of easily reducing polishing scratches, and from the viewpoint of easy handling of the abrasive. 20 mass% or less is preferable on a mass basis, 15 mass% or less is more preferable, and 10 mass% or less is still more preferable.

(water)
The abrasive | polishing agent which concerns on this embodiment contains water. Water is used as a dispersion medium or solvent for other components. The water is preferably one containing as little impurities as possible in order to prevent the action of other components from being inhibited. Specifically, the water is preferably pure water, ultrapure water, or distilled water from which foreign ions are removed through a filter after removing impurity ions with an ion exchange resin.

(Additive)
The abrasive | polishing agent which concerns on this embodiment can contain an additive as components other than an abrasive grain and water. The additive can be used for the purpose of improving the dispersibility of the abrasive grains in the abrasive, improving the chemical stability of the abrasive, and improving the polishing rate. Examples of the additive include a pH adjuster, an anticorrosive, an oxidizing agent, a water-soluble polymer having an ether bond, an organic solvent, an insulating material polishing inhibitor, a surfactant, and an antifoaming agent. The content of the additive in the abrasive can be arbitrarily determined as long as the characteristics of the abrasive are not impaired.

[Abrasive pH and pH adjuster]
The pH of the abrasive according to this embodiment is 3.0 to 7.0 from the viewpoint of removing the resin at a good polishing rate while suppressing the generation of polishing flaws. The pH of the abrasive is preferably less than 7.0, from the viewpoint of further improving the polishing rate of the resin, and from the viewpoint of suppressing the aggregation of the abrasive grains and obtaining good dispersion stability of the abrasive grains. The following is more preferable, 6.0 or less is further preferable, and 5.0 or less is particularly preferable. The pH of the abrasive is preferably 3.5 or more, more preferably 4.0 or more, from the viewpoint that a sufficient mechanical polishing force is easily obtained and the polishing rate of the resin is further improved. From these viewpoints, the pH of the abrasive is preferably 3.5 to 7.0, more preferably 3.5 to 6.5, still more preferably 3.5 to 5.0, and 4.0 to 5.0. Is particularly preferred. The pH of the abrasive may be 3.0 to 5.0. The pH is defined as the pH at a liquid temperature of 25 ° C.

  The pH of the abrasive can be measured by a pH meter using a general glass electrode. Specifically, for example, trade name: Model (F-51) manufactured by HORIBA, Ltd. can be used. For example, phthalate pH standard solution (pH: 4.01), neutral phosphate pH standard solution (pH: 6.86), and borate pH standard solution (pH: 9.18) The pH value can be obtained by using the standard solution and calibrating the pH meter at three points, and then measuring the value after the pH meter electrode is placed in an abrasive and stabilized for 2 minutes or more. At this time, the liquid temperature of the standard buffer and the abrasive is, for example, 25 ° C.

  The abrasive according to the present embodiment may contain a pH adjuster (pH adjuster component). By using a pH adjuster, the pH of the abrasive can be easily adjusted. Examples of the pH adjuster include an acid component (acidic component); a base component (for example, a weak base component such as ammonia) and the like.

  The acid component is at least selected from the group consisting of an organic acid component and an inorganic acid component, from the viewpoint of further improving the dispersibility and stability of the aqueous dispersion and the polishing rate of the resin, wiring metal, and barrier metal. One type is preferred.

  Examples of the organic acid component include organic acids (excluding amino acids), organic acid esters, organic acid salts, amino acids and the like. Examples of organic acids include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, 2-methylbutyric acid, n-hexanoic acid, 3,3-dimethylbutyric acid, 2-ethylbutyric acid, 4-methylpentanoic acid, n-heptanoic acid, 2-methylhexanoic acid, n-octanoic acid, 2-ethylhexanoic acid, benzoic acid, glycolic acid, salicylic acid, glyceric acid, oxalic acid, malonic acid, succinic acid, 3-methylphthalic acid, 4-methylphthalic acid, 3-aminophthalic acid Acid, 4-aminophthalic acid, 3-nitrophthalic acid, 4-nitrophthalic acid, glutaric acid, adipic acid, pimelic acid, maleic acid, phthalic acid, isophthalic acid, malic acid, tartaric acid, citric acid, p-toluenesulfonic acid, p -Phenolsulfonic acid, methylsulfonic acid, lactic acid, itaconic acid, maleic acid, quinaldic acid, adipic acid, pimelic acid, etc. It is. Examples of the organic acid ester include esters of the organic acid. Examples of the organic acid salt include ammonium salts, alkali metal salts, alkaline earth metal salts and halides of the organic acids. Examples of amino acids include alanine, arginine, asparagine, aspartic acid, cysteine, glutamine, glutamic acid, glycine, histidine, isoleucine, leucine, lysine, methionine, phenylalanine, proline, serine, threonine, tryptophan, tyrosine, valine and the like.

  Examples of the inorganic acid component include inorganic acids, ammonium salts of the inorganic acids, ammonium persulfate, ammonium nitrate, ammonium chloride, and chromic acid. Examples of the inorganic acid include hydrochloric acid, sulfuric acid, nitric acid and the like.

  For example, when the object to be polished (substrate to be polished) is a silicon substrate including an integrated circuit element, contamination with alkali metal, alkaline earth metal, halide, etc. is not desirable. Salts other than alkali metal salts, alkaline earth metal salts and halides are preferred.

  As the acid component, from the viewpoint of effectively suppressing the etching rate while maintaining a practical polishing rate, acetic acid, malonic acid, malic acid, tartaric acid, citric acid, salicylic acid, adipic acid, phthalic acid, glycolic acid and At least one selected from the group consisting of succinic acid is preferred. An acid component can be used individually by 1 type or in combination of 2 or more types.

  The content of the acid component is preferably 0.001% by mass or more and 0.002% by mass based on the total mass of the abrasive from the viewpoint of obtaining a better polishing rate of the resin, the wiring metal and the barrier metal. The above is more preferable, 0.005 mass% or more is further preferable, 0.01 mass% or more is particularly preferable, 0.05 mass% or more is very preferable, and 0.1 mass% or more is very preferable. The content of the acid component is preferably 20% by mass or less, more preferably 10% by mass or less, and more preferably 5% by mass or less, based on the total mass of the abrasive, from the viewpoint of suppressing etching and reducing roughness of the surface to be polished. Is more preferable.

[Anticorrosive]
The abrasive according to this embodiment may contain an anticorrosive agent (anticorrosive component, metal anticorrosive agent). The anticorrosive can form a protective film against the wiring metal (copper metal, cobalt metal, etc.), thereby suppressing the etching of the wiring metal and easily reducing the roughness of the surface to be polished.

  There is no restriction | limiting in particular as an anticorrosive agent, Any conventionally well-known component can be used as a compound which has the anticorrosive action with respect to a metal material. Specifically, as the anticorrosive agent, at least one selected from the group consisting of triazole compounds, pyridine compounds, pyrazole compounds, pyrimidine compounds, imidazole compounds, guanidine compounds, thiazole compounds, tetrazole compounds, triazine compounds and hexamethylenetetramine is used. be able to. Here, “compound” is a general term for compounds having the skeleton, and for example, “triazole compound” means a compound having a triazole skeleton. An anticorrosive agent can be used individually by 1 type or in combination of 2 or more types.

  Examples of the triazole compound include 1,2,3-triazole, 1,2,4-triazole, 3-amino-1H-1,2,4-triazole, benzotriazole (BTA), 1-hydroxybenzotriazole, 1 -Dihydroxypropylbenzotriazole, 2,3-dicarboxypropylbenzotriazole, 4-hydroxybenzotriazole, 4-carboxy-1H-benzotriazole, 4-carboxy-1H-benzotriazole methyl ester (1H-benzotriazole-4-carboxylic acid) Acid methyl), 4-carboxy-1H-benzotriazole butyl ester (1H-benzotriazole-4-carboxylate butyl), 4-carboxy-1H-benzotriazole octyl ester (1H-benzotriazole-4-carboxylate) Octyl bonate), 5-hexylbenzotriazole, (1,2,3-benzotriazolyl-1-methyl) (1,2,4-triazolyl-1-methyl) (2-ethylhexyl) amine, tolyltriazole, Naphthotriazole, bis [(1-benzotriazolyl) methyl] phosphonic acid, 3H-1,2,3-triazolo [4,5-b] pyridin-3-ol, 1H-1,2,3-triazolo [ 4,5-b] pyridine, 1-acetyl-1H-1,2,3-triazolo [4,5-b] pyridine, 3-hydroxypyridine, 1,2,4-triazolo [1,5-a] pyrimidine 1,3,4,6,7,8-hexahydro-2H-pyrimido [1,2-a] pyrimidine, 2-methyl-5,7-diphenyl- [1,2,4] triazolo [1,5- a] Pyri Gin, 2-methylsulfanyl-5,7-diphenyl- [1,2,4] triazolo [1,5-a] pyrimidine, 2-methylsulfanyl-5,7-diphenyl-4,7-dihydro- [ 1,2,4] triazolo [1,5-a] pyrimidine and the like. A compound having a triazole skeleton and another skeleton in one molecule is classified as a triazole compound.

  Examples of pyridine compounds include pyridine, 8-hydroxyquinoline, prothionamide, 2-nitropyridin-3-ol, pyridoxamine, nicotinamide, iproniazide, isonicotinic acid, benzo [f] quinoline, 2,5-pyridinedicarboxylic acid, 4- Styrylpyridine, anabasine, 4-nitropyridine-1-oxide, pyridine-3-ethyl acetate, quinoline, 2-ethylpyridine, quinolinic acid, arecoline, citrazic acid, pyridine-3-methanol, 2-methyl-5-ethylpyridine , 2-fluoropyridine, pentafluoropyridine, 6-methylpyridin-3-ol, pyridine-2-ethyl acetate and the like.

  Examples of the pyrazole compound include pyrazole, 1-allyl-3,5-dimethylpyrazole, 3,5-di (2-pyridyl) pyrazole, 3,5-diisopropylpyrazole, 3,5-dimethyl-1-hydroxymethylpyrazole, 3 , 5-dimethyl-1-phenylpyrazole, 3,5-dimethylpyrazole, 3-amino-5-hydroxypyrazole, 4-methylpyrazole, N-methylpyrazole, 3-aminopyrazole, 3-aminopyrazole and the like.

  Pyrimidine compounds include pyrimidine, 1,3-diphenyl-pyrimidine-2,4,6-trione, 1,4,5,6-tetrahydropyrimidine, 2,4,5,6-tetraaminopyrimidine sulfate, 2, 4,5-trihydroxypyrimidine, 2,4,6-triaminopyrimidine, 2,4,6-trichloropyrimidine, 2,4,6-trimethoxypyrimidine, 2,4,6-triphenylpyrimidine, 2,4 -Diamino-6-hydroxylpyrimidine, 2,4-diaminopyrimidine, 2-acetamidopyrimidine, 2-aminopyrimidine, 4-aminopyrazolo [3,4-d] pyrimidine and the like.

  Examples of imidazole compounds include imidazole, 1,1′-carbonylbis-1H-imidazole, 1,1′-oxalyldiimidazole, 1,2,4,5-tetramethylimidazole, 1,2-dimethyl-5-nitroimidazole. 1,2-dimethylimidazole, 1- (3-aminopropyl) imidazole, 1-butylimidazole, 1-ethylimidazole, 1-methylimidazole, benzimidazole and the like.

  Examples of the guanidine compound include guanidine, 1,1,3,3-tetramethylguanidine, 1,2,3-triphenylguanidine, 1,3-di-o-tolylguanidine, 1,3-diphenylguanidine, and the like. .

  Examples of the thiazole compound include thiazole, 2-mercaptobenzothiazole, 2,4-dimethylthiazole and the like.

  Examples of the tetrazole compound include tetrazole, 5-methyltetrazole, 5-amino-1H-tetrazole, 1- (2-dimethylaminoethyl) -5-mercaptotetrazole and the like.

  Examples of the triazine compound include triazine and 3,4-dihydro-3-hydroxy-4-oxo-1,2,4-triazine.

  The content of the anticorrosive is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, based on the total mass of the abrasive, from the viewpoint of easily suppressing corrosion and surface roughness of the metal material. 0.02% by mass or more is more preferable, 0.05% by mass or more is particularly preferable, and 0.1% by mass or more is extremely preferable. The content of the anticorrosive is preferably 10% by mass or less based on the total mass of the abrasive, from the viewpoint of reducing complex foreign substances between the metal material and the anticorrosive on the surface to be polished (for example, the surface to be polished of the substrate), 5.0 mass% or less is more preferable, and 0.5 mass% or less is still more preferable.

  As an anticorrosive agent, a viewpoint of suitably obtaining the effect of suppressing the etching of the wiring metal and easily reducing the roughness of the surface to be polished by forming a protective film on the wiring metal such as a copper-based metal and a cobalt-based metal. And at least one selected from the group consisting of a triazole compound, a pyridine compound, an imidazole compound, a tetrazole compound, a triazine compound, and hexamethylenetetramine is preferred. 3H-1,2,3-triazolo [4,5-b] pyridine- 3-ol, 1-hydroxybenzotriazole, 1H-1,2,3-triazolo [4,5-b] pyridine, benzotriazole, 3-hydroxypyridine, benzimidazole, 5-amino-1H-tetrazole, 3,4 -Dihydro-3-hydroxy-4-oxo-1,2,4-triazine and hexamethy At least one selected from the group consisting Ntetoramin is more preferable.

  The mass ratio of the content of the acid component to the content of the anticorrosive agent in the abrasive (acid component / anticorrosive) is preferably 10/1 to 1/5 from the viewpoint of favorably controlling the etching rate and the polishing rate. 7/1 to 1/5 is more preferable, 5/1 to 1/5 is still more preferable, and 5/1 to 1/1 is particularly preferable.

[Oxidant]
The abrasive according to this embodiment may contain an oxidant (oxidant component, metal oxidant). When the polishing agent contains an oxidizing agent, the polishing rate of a metal material (wiring metal, barrier metal, etc., for example, a metal layer) can be improved.

  Using a polishing agent containing an anticorrosive and an oxidizing agent, a substrate comprising a resin and a metal material coated with the resin (for example, a wiring metal such as a copper-based metal or a cobalt-based metal; a barrier metal) is polished. When the metal material is exposed after polishing the resin, the oxidant forms an oxide film on the metal material, and the anticorrosive forms a protective film on the oxide film, thereby etching the metal material. The metal material can be appropriately polished while sufficiently suppressing the above. Further, polishing scratches on the metal material can be easily suppressed.

  There is no restriction | limiting in particular as an oxidizing agent, It can select suitably from the oxidizing agent used normally. Specific examples of the oxidizing agent include hydrogen peroxide, peroxosulfate, potassium periodate, hypochlorous acid, and ozone water. Among these, hydrogen peroxide is preferable. In addition, the nitric acid which is the said acid component has the addition effect as an oxidizing agent. An oxidizing agent can be used individually by 1 type or in combination of 2 or more types.

  The content of the oxidizing agent is preferably 0.01% by mass or more based on the total mass of the abrasive from the viewpoint of easily preventing the metal material from being insufficiently oxidized and reducing the polishing rate of the metal material. More preferably, it is more preferably 0.1% by mass or more, particularly preferably 0.5% by mass or more, and most preferably 1% by mass or more. The content of the oxidizing agent is preferably 10% by mass or less, more preferably 8% by mass or less, based on the total mass of the abrasive, from the viewpoint that it is possible to easily suppress the occurrence of roughness on the surface to be polished and to easily suppress dishing. Preferably, 5 mass% or less is more preferable, and 3 mass% or less is especially preferable. In addition, when using the oxidizing agent generally available as aqueous solution like hydrogen peroxide water, content of an oxidizing agent can be adjusted so that content of the oxidizing agent contained in the said aqueous solution may become the said range in an abrasive | polishing agent.

(Water-soluble polymer having an ether bond)
The abrasive according to this embodiment may contain a water-soluble polymer having an ether bond. When the abrasive contains a water-soluble polymer having an ether bond, a better polishing rate of the resin can be obtained.

  The water-soluble polymer having an ether bond is not particularly limited as long as it is a polymer having an ether bond and is soluble or miscible in water, and examples thereof include polyethers and monoether compounds. The water-soluble polymer having an ether bond is preferably a polyether from the viewpoint of easily improving the polishing rate of the resin.

  Examples of the polyether include polysaccharide, polyalkylene glycol, polyglycerin, polyoxypropylene polyglyceryl ether, polyoxyethylene polyglyceryl ether, glycerin aliphatic ester, diglycerin aliphatic ester, aromatic glycol ether, aliphatic glycol ether, ester Glycol ether, propylene oxide adduct, gallic acid glycoside, phenol glycoside, polyphenol glycoside, sugar ester compound, polyoxyethylene glyceryl isostearate, polyoxyethylene glyceryl triisostearate, 1 , 4-di (2-hydroxyethoxy) benzene, 2,2-bis (4-polyoxyethylene-oxyphenyl) propane, 2,2-bis (4-polyoxypropyleneoxyphenyl) propyl Bread, ethylene glycol monophenyl ether, diethylene glycol monophenyl ether, polyoxyalkylene monophenyl ether, propylene glycol monophenyl ether, polyoxypropylene monomethyl phenyl ether, polyethylene glycol monomethyl ether, pentaerythritol polyoxyethylene ether, Examples include ethylene glycol monoallyl ether, polyoxyethylene monoallyl ether, dimethylol heptane EO adduct, diglycerin aliphatic ester, and alkyl glucoside. In the present specification, “polysaccharide” is defined as a substance polymerized by a glycosidic bond with a polymerization degree of 2 or more unless otherwise specified.

  Polysaccharides include sucrose, lactulose, lactose, trehalose, maltose, cellobiose, cordobiose, nigerose, isomaltose, isotrehalose, neotrehalose, sophorose, laminaribiose, gentibiose, tulanose, maltulose, palatinose, gentiobiose, mannobiose , Melibiose, melibiurose, neolactose, galactosucrose, silabiose, rutinose, rutinose, vicyanose, xylobiose, primeverose, trehalosamine, maltitol, cellobionic acid, lactosamine, lactosediamine, lactobionic acid, lactitol, hyalobiuronic acid, sucralose, nigerotriose Maltotriose, melezitose, maltotriurose, rafino , Kestose, nystose, nigerotetraose, stachyose, amylose, dextran, dextrin, maltodextrin, cluster dextrin, cycloawaodrine, laminaran, callose, PGA, pectin, glucomannan, gellan gum, curdlan, psyllium, locust bean gum , Pullulan, alginic acid, tamarind, carrageenan, CMC, xanthan gum, gum arabic, guar gum, pectin, soy polysaccharide, fructan, glycogen, α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, isomaltoligosaccharide, galactooligosaccharide, Xylooligosaccharides, soybean oligosaccharides, nigerooligosaccharides, dairy oligosaccharides, fructooligosaccharides and the like can be mentioned.

  Examples of the α-glucose polymer include amylose, dextran, dextrin, maltodextrin, cluster dextrin, α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, maltose, isomaltose, maltotriose, stachyose and the like.

(Organic solvent)
The abrasive according to this embodiment may contain an organic solvent. When the abrasive contains an organic solvent, the polishing rate of the resin and the wettability of the abrasive can be further improved. Although there is no restriction | limiting in particular as an organic solvent, A liquid solvent is preferable at 20 degreeC. From the viewpoint of highly concentrating the abrasive, the solubility of the organic solvent in 100 g of water (20 ° C.) is preferably 30 g or more, more preferably 50 g or more, and even more preferably 100 g or more. An organic solvent can be used individually by 1 type or in combination of 2 or more types.

  Examples of the organic solvent include carbonate esters, lactones, glycols, and derivatives of glycols. Examples of the carbonic acid esters include ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, and methyl ethyl carbonate. Examples of lactones include butyrolactone and propyllactone. Examples of glycols include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, and tripropylene glycol. Examples of the derivatives of glycols include glycol monoethers and glycol diethers. As glycol monoethers, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, triethylene glycol monomethyl ether, tripropylene glycol monomethyl ether, ethylene glycol monoethyl ether , Propylene glycol monoethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monoethyl ether, tripropylene glycol monoethyl ether, ethylene glycol monopropyl ether, propylene glycol monopropyl ether, polyethylene Glycol monopropyl ether, dipropylene glycol monopropyl ether, triethylene glycol monopropyl ether, tripropylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monobutyl ether, diethylene glycol monobutyl ether, dipropylene glycol monobutyl ether, triethylene glycol mono Examples include butyl ether and tripropylene glycol monobutyl ether. As glycol diethers, ethylene glycol dimethyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, triethylene glycol dimethyl ether, tripropylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol diethyl ether, diethylene glycol diethyl ether, dipropylene glycol Diethyl ether, triethylene glycol diethyl ether, tripropylene glycol diethyl ether, ethylene glycol dipropyl ether, propylene glycol dipropyl ether, diethylene glycol dipropyl ether, dipropylene glycol dipropyl ether, trie Glycol dipropyl ether, tripropylene glycol dipropyl ether, ethylene glycol dibutyl ether, propylene glycol dibutyl ether, diethylene glycol dibutyl ether, dipropylene glycol dibutyl ether, triethylene glycol dibutyl ether, tripropylene glycol dibutyl ether and the like. As the organic solvent, at least one selected from the group consisting of glycols and derivatives of glycols is preferable from the viewpoint of low surface tension, and glycol monoethers are more preferable from the viewpoint of lower surface tension.

  The content of the organic solvent is preferably 0.500% by mass or more and more preferably 1.000% by mass or more based on the total mass of the abrasive from the viewpoint of suppressing the wettability of the abrasive to the resin. . From the viewpoint of excellent dispersion stability, the content of the organic solvent is preferably 20.000% by mass or less, more preferably 15.000% by mass or less, and further preferably 10.000% by mass or less, based on the total mass of the abrasive. preferable.

[Insulating material polishing inhibitor]
The abrasive according to this embodiment may contain an insulating material polishing inhibitor (insulating material polishing inhibitor component, for example, an inorganic insulating film polishing inhibitor) as a component that suppresses polishing of the insulating material. When the abrasive contains the insulating material polishing inhibitor, the polishing rate of the insulating material can be suppressed, and the resin can be selectively removed with respect to the insulating material.

  Examples of the insulating material polishing inhibitor include allylamine polymers. In the present specification, the “allylamine polymer” is defined as a polymer having a structural unit obtained by polymerizing a monomer containing an allylamine compound. In this specification, an “allylamine compound” is defined as a compound having an allyl group and an amino group. The allylamine polymer may have a structural unit obtained by polymerizing only an allylamine compound, and has a structural unit obtained by copolymerizing an allylamine compound and a compound other than the allylamine compound. It may be.

  The insulating material polishing inhibitor can be used alone or in combination of two or more.

  The weight average molecular weight (Mw) of the insulating material polishing inhibitor (allylamine polymer or the like) is preferably 500 or more, more preferably 800 or more, and still more preferably 1000 or more, from the viewpoint of easily suppressing the polishing rate of the insulating material. The weight average molecular weight of the insulating material polishing inhibitor (allylamine-based polymer or the like) is preferably 300000 or less, more preferably 200000 or less, from the viewpoint of suppressing the viscosity from becoming excessively high and obtaining good storage stability. 150,000 or less is more preferable. The weight average molecular weight of the insulating material polishing inhibitor (such as an allylamine polymer) can be measured using GPC under the same conditions as the weight average molecular weight of the water-soluble polymer having an ether bond.

  The content of the insulating material polishing inhibitor is preferably 0.001% by mass or more, more preferably 0.003% by mass or more, based on the total mass of the abrasive, from the viewpoint of easily suppressing the polishing rate of the insulating material. 0.004 mass% or more is more preferable, and 0.005 mass% or more is particularly preferable. The content of the insulating material polishing inhibitor is 0.400 on the basis of the total mass of the polishing agent from the viewpoint of easily suppressing a decrease in the polishing rate of the resin and easily maintaining a high polishing rate ratio of the resin to the insulating material. % By mass or less is preferable, 0.300% by mass or less is more preferable, 0.200% by mass or less is further preferable, and 0.100% by mass or less is particularly preferable.

  The mass ratio of the insulating material polishing inhibitor content to the abrasive content (insulating material polishing inhibitor / abrasive grain) is 0.002 or more from the viewpoint of easily removing the resin from the insulating material. Preferably, 0.003 or more is more preferable, and 0.005 or more is still more preferable. The mass ratio of the insulating material polishing inhibitor content to the abrasive content is preferably 0.400 or less, more preferably 0.300 or less, more preferably 0.200, from the viewpoint of easy removal of the resin at a good polishing rate. The following is more preferable.

[Surfactant]
The abrasive may contain a surfactant (surfactant component). When the polishing agent contains a surfactant, the polishing rate of the material to be polished can be easily adjusted and polishing scratches can be easily reduced.

  Examples of the surfactant include a water-soluble anionic surfactant, a water-soluble nonionic surfactant, and a water-soluble cationic surfactant. Examples of the water-soluble anionic surfactant include ammonium lauryl sulfate, polyoxyethylene lauryl ether ammonium sulfate, alkyl phosphate ester salt, polyoxyethylene alkyl ether phosphate, lauroyl sarcosine salt and the like. Examples of the water-soluble nonionic surfactant include polyoxyethylene lauryl ether and polyethylene glycol monostearate. Water-soluble cationic surfactants include hexadecyl trimethyl ammonium salt, myristyl trimethyl ammonium salt, lauryl trimethyl ammonium salt, stearyl trimethyl ammonium salt, cetyl trimethyl ammonium salt, stearyl trimethyl ammonium salt, distearyl dimethyl ammonium salt, alkylbenzyl Examples thereof include dimethylammonium salt, alkylbenzyldimethylammonium salt, coconutamine acetate, stearylamine acetate and the like. Among these, as the surfactant, a water-soluble anionic surfactant is preferable. In particular, it is more preferable to use at least one water-soluble anionic surfactant such as a polymer dispersant obtained by using an ammonium salt or a tetramethylammonium salt as a copolymerization component. Surfactant can be used individually by 1 type or in combination of 2 or more types. The content of the surfactant is, for example, 0.0001 to 0.1% by mass based on the total mass of the abrasive.

(Other)
The blending method of each component contained in the abrasive and the dilution method of the abrasive are not particularly limited. For example, each component can be dispersed or dissolved by stirring with a blade-type stirrer or ultrasonic dispersion. The mixing order of each component with respect to water is not limited.

  The abrasive according to this embodiment may be stored as a one-part abrasive containing at least abrasive grains and water, and has a slurry (first liquid) and an additive liquid (second liquid). It may be stored as a multi-liquid abrasive. In a multi-liquid type abrasive | polishing agent, the structural component of the said abrasive | polishing agent is divided into a slurry and an additive liquid so that slurry and an additive liquid may be mixed and it may become the said abrasive | polishing agent. The slurry includes at least abrasive grains and water, for example. The additive liquid contains at least water, for example. Additives such as pH adjusters, anticorrosives, oxidizing agents, water-soluble polymers with ether bonds, organic solvents, insulating material polishing inhibitors, surfactants, antifoaming agents, etc. are added to the slurry and additive liquids. It is preferably included. The constituents of the abrasive may be stored in three or more liquids.

  In the multi-liquid abrasive, the slurry and additive liquid may be mixed immediately before or during polishing to prepare the abrasive. The slurry and additive liquid in the multi-liquid type abrasive may be respectively supplied onto the polishing surface plate, and the surface to be polished may be polished using an abrasive obtained by mixing the slurry and the additive liquid on the polishing surface plate. .

<Abrasive stock solution>
The storage solution for abrasive | polishing agent which concerns on this embodiment is a storage solution for obtaining the said abrasive | polishing agent, and the said abrasive | polishing agent is obtained by diluting the storage solution for abrasive | polishing agents with water. The abrasive stock solution is stored with the amount of water reduced compared to the time of use, and is diluted with water before use or at the time of use and used as the abrasive. The abrasive stock solution is different from the abrasive in that the water content is less than that of the abrasive. The dilution factor is, for example, 1.5 times or more.

<Polishing method>
The polishing method according to this embodiment includes a polishing step in which at least a part of the resin is polished (CMP or the like) and removed using an abrasive. In the polishing step, the surface to be polished containing resin can be polished. In the polishing step, at least a part of the resin can be removed by polishing a substrate having resin using an abrasive. The base may have, for example, a resin formed on a substrate having concave and convex portions on the surface. The substrate may be, for example, a wiring board or a circuit board. The polishing method according to the present embodiment may include a step of preparing a substrate having a resin before the polishing step. The resin preferably contains at least one selected from the group consisting of polybenzoxazole, a precursor of polybenzoxazole, and polyimide.

  The polishing step may be a step of polishing and removing at least part of the resin using a one-component abrasive, and polishing obtained by mixing a slurry and an additive solution in a multi-component abrasive. It may be a step of polishing and removing at least a part of the resin using an agent, and polishing at least a part of the resin using an abrasive obtained by diluting the stock solution for abrasive with water. It may be a step of removing.

  In the polishing step, a substrate provided with a metal material and / or an insulating material in addition to the resin may be polished. In this case, in the polishing step, for example, the polishing may be stopped when the resin is polished and a metal material (wiring metal, barrier metal, etc.) or an insulating material is exposed. In the polishing step, these materials may be simultaneously polished by polishing a surface to be polished containing a resin and a metal material (wiring metal, barrier metal, etc.) and / or at least a part of an insulating material.

  When a multi-liquid abrasive is used, the polishing method according to the present embodiment includes an abrasive preparation step of obtaining an abrasive by mixing the slurry and additive liquid in the multi-liquid abrasive before the polishing step. May be. When using the storage solution for abrasive | polishing agent, the grinding | polishing method which concerns on this embodiment may be equipped with the abrasive | polishing agent preparation process which dilutes the storage liquid for abrasive | polishing agent with water before a grinding | polishing process.

  In the polishing step, for example, the surface to be polished of the substrate is pressed against the polishing cloth (polishing pad) of the polishing surface plate, and an abrasive is supplied between the surface to be polished and the polishing cloth, so that the back surface of the substrate (surface to be polished) The surface to be polished can be polished by moving the substrate relative to the polishing surface plate while applying a predetermined pressure to the surface opposite to the surface.

  As the polishing apparatus, for example, a general polishing apparatus having a surface plate to which a motor capable of changing the number of rotations and the like, and a polishing cloth can be attached, and a holder for holding the substrate can be used. Although there is no restriction | limiting in particular as abrasive cloth, A general nonwoven fabric, a polyurethane foam, a porous fluororesin, etc. can be used. The polishing conditions are not particularly limited, but the rotation speed of the surface plate is preferably a low rotation of 200 times / min or less so that the substrate does not jump out. For example, during polishing, an abrasive is continuously supplied to the polishing cloth with a pump or the like. Although there is no restriction | limiting in the supply amount of an abrasive | polishing agent, It is preferable that the surface of an abrasive cloth is always covered with an abrasive | polishing agent and the product produced by progress of grinding | polishing is discharged | emitted continuously.

  In order to perform polishing with the surface state of the polishing cloth always the same, the polishing method according to the present embodiment preferably includes a conditioning process of the polishing cloth before the polishing process. For example, using a dresser with diamond particles, the polishing pad can be conditioned with a liquid containing at least water. The polishing method according to this embodiment preferably includes a substrate cleaning step after the polishing step. The substrate after polishing is preferably washed in running water, and then dried after removing water droplets adhering to the substrate using spin drying or the like. In addition, while a commercially available cleaning liquid is poured on the surface of the substrate, a brush made of polyvinyl alcohol resin is rotated, and the brush is pressed against the substrate with a certain pressure to remove deposits on the substrate by a known cleaning method. It is more preferable to dry after washing.

  According to the abrasive | polishing agent which concerns on this embodiment, the base | substrate which has resin can be grind | polished and at least one part of resin can be removed. As an application using such a feature, for example, a resin polishing application used in a rewiring process can be cited.

  From the viewpoint of shortening the polishing time, the resin polishing rate is preferably 300 nm / min or more, more preferably 500 nm / min or more, and still more preferably 1000 nm / min or more. The polishing rate of the resin is preferably 5000 nm / min or less from the viewpoint that the excessive polishing of the concave portion of the resin is suppressed and the flatness is further improved, and the polishing time is easy to adjust. 3000 nm / min or less is more preferable.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in more detail, this invention is not limited to these Examples, unless it deviates from the technical idea of this invention. For example, the material of the abrasive and the blending ratio thereof may be other than the types and ratios described in this example, and the composition and structure of the polishing target may be other than those described in this example.

<Preparation of abrasive>
Example 1
Colloidal silica 1 (abrasive grains to which aluminum component (aluminum hydroxide) was attached. Average particle diameter (D50): 30 nm) X mass parts of ultrapure water was poured into 5.00 mass parts to obtain 100 mass parts of an abrasive. . The colloidal silica 1 was supplied using a colloidal silica dispersion containing 5.0% by mass of acetic acid as a dispersant with respect to the total mass of the colloidal silica. In addition, the compounding quantity (X mass part) of ultrapure water was adjusted and calculated so that an abrasive | polishing agent might be 100 mass parts.

(Examples 2-7, Comparative Examples 1-3, 7)
An abrasive was prepared in the same manner as in Example 1 except that the types and contents of the abrasive grains, anticorrosive, oxidizing agent and pH adjuster were changed as shown in Tables 1 and 2. The amount of each component in Table 1 and Table 2 is the content (unit: mass%) based on the total mass of the abrasive. Colloidal silica 2 of Comparative Example 7 is colloidal silica (average particle diameter (D50): 30 nm) to which no aluminum component is attached.

(Comparative Examples 4-6)
The abrasive grain of Table 2 was put into a 1.00 mass part container. Next, X parts by mass of ultrapure water was poured, and then the pH was adjusted with acetic acid to obtain 100 parts by mass of an abrasive. In addition, the compounding quantity (X mass part) of ultrapure water was adjusted and calculated so that an abrasive | polishing agent might be 100 mass parts. Colloidal silica 2 of Comparative Example 4 is colloidal silica (average particle diameter (D50): 30 nm) to which no aluminum component is attached. Colloidal silica 3 of Comparative Example 5 is colloidal silica (average particle diameter (D50): 70 nm) to which an amine compound is attached. The α-alumina of Comparative Example 6 is a particle made of alumina.

<Measurement of pH of abrasive>
The pH of the abrasive was measured under the following conditions. The results are shown in Tables 1 and 2.
Measurement temperature: 25 ± 5 ° C
Measuring device: Product name of Horiba, Ltd .: Model (F-51)
Measurement method: phthalate pH standard solution (pH: 4.01), neutral phosphate pH standard solution (pH: 6.86), and borate pH standard solution (pH: 9.18) After the pH meter was calibrated at three points using the pH standard solution, the pH meter electrode was placed in an abrasive and the pH after stabilizing for 2 minutes or more was measured with the measuring device.

<Measurement of zeta potential>
The zeta potential of the abrasive grains in the abrasive was measured as follows. As the zeta potential measuring device, trade name: DELSA NANO C manufactured by Beckman Coulter, Inc. was used. The sample was obtained by diluting the abrasive with pure water so that the scattering intensity of the measurement sample was 1.0 × 10 ^{4 to} 5.0 × 10 ⁴ cps in a zeta potential measurement device. Thereafter, the obtained sample was put in a cell for measuring zeta potential, and zeta potential was measured. In all examples, the surface of the abrasive grains was positively charged in the abrasive. The results are shown in Tables 1 and 2.

<Evaluation of polishing characteristics>
(Evaluation of polishing rate and scratches)
As a substrate having a film to be polished, a substrate obtained by forming a polybenzoxazole film (PBO film) having a thickness of 8000 nm on a silicon substrate and a polyimide film (PI film) having a thickness of 8000 nm are formed on the silicon substrate. The obtained base and a base obtained by forming a 1000 nm thick copper film (Cu film) on a silicon substrate were used. Using the polishing agent prepared above, the film to be polished was subjected to chemical mechanical polishing for 60 seconds under the following polishing conditions. The copper film was polished in Examples 1 to 4, 7 and Comparative Example 7.

[Polishing conditions]
Polishing device: single-side polishing machine (Applied Materials, trade name: Reflexion LK)
Polishing cloth: Polishing cloth made of suede foam polyurethane resin Surface plate rotation speed: 123 times / min
Head rotation speed: 117 times / min
Polishing pressure: 21 kPa
Abrasive supply amount: 300 mL / min

  A sponge brush (made of polyvinyl alcohol resin) was pressed against the surface to be polished of the substrate polished under the above polishing conditions, and the substrate and the sponge brush were rotated while supplying distilled water to the surface to be polished, and washed for 60 seconds. Next, the sponge brush was removed, and distilled water was supplied to the polished surface of the substrate for 60 seconds. Finally, the substrate was dried by spinning off the distilled water by rotating the substrate at a high speed.

  The polishing rate was calculated from the difference in film thickness obtained by measuring the film thickness of the film to be polished before and after polishing. A film thickness measuring device (manufactured by Dainippon Screen Mfg. Co., Ltd., trade name: Lambda Ace, VL-M8000LS) was used to measure the film thickness of the PBO film and the PI film. A metal film thickness measuring device (manufactured by Hitachi Kokusai Electric Co., Ltd., trade name: VR-120 / 08S) was used for measuring the film thickness of the copper film. Tables 1 and 2 show the measurement results of the polishing rate.

  The number of polishing scratches was evaluated by observing the polished surface of the PBO film after polishing with an optical microscope. The case where no polishing flaw was observed was evaluated as “A”, and the case where a polishing flaw was observed was evaluated as “B”. The results are shown in Tables 1 and 2.

(Evaluation of copper etching rate (Cu-ER))
In Examples 1 to 7 and Comparative Examples 1 to 3 and 7, the copper etching rate (Cu etching rate) was evaluated.

  First, a blanket substrate (a) having a copper film with a thickness of 500 nm formed by a CVD method on a silicon substrate having a diameter of 8 inches was prepared. The blanket substrate (a) was cut into 20 mm square chips to prepare evaluation chips (b).

In a thermostatic bath at 60 ° C., the evaluation chip (b) was immersed for 1 minute in a beaker containing 50 g of the abrasive. The evaluation chip (b) after immersion was taken out and thoroughly washed with pure water. Thereafter, nitrogen gas was blown to remove moisture on the chip, and the chip was dried. The resistance of the evaluation chip (b) after drying was measured with a resistivity meter, and converted into the thickness of the copper film after immersion by the following formula (1). Formula (1) is a conversion formula obtained based on a calibration curve obtained from information on resistance values respectively corresponding to the thicknesses of the blanket substrate (a).
Thickness [nm] of copper film after immersion = 1.83 × 10000 / resistance value of evaluation chip (b) [mΩ] (1)

And Cu etching rate was calculated | required from following formula (2) from the thickness (thickness of the copper film after immersion, and thickness of the copper film before immersion) of the obtained copper film. Tables 1 and 2 show the measurement results of the Cu etching rate.
Etching rate of copper (Cu etching rate) [nm / min] = (thickness of copper film before immersion [nm] −thickness of copper film after immersion [nm]) / 1 minute (2)

  As shown in Table 1 and Table 2, when Examples and Comparative Examples are compared with each other, the abrasive grains containing particles having an aluminum component attached thereto and having a positive charge and water are contained, and the pH is 3.0. It can be seen that by using an abrasive of ˜7.0, there are few polishing scratches and a good polishing rate of the resin can be obtained. In each Example such as Example 7 using an abrasive containing an anticorrosive and an oxidizing agent (hydrogen peroxide), the metal material (copper) is appropriately polished while polishing the resin at a good polishing rate. You can see that

Claims (11)

An abrasive containing abrasive grains and water,
The abrasive has a positive charge in the abrasive;
The abrasive grains include particles (excluding particles made of alumina) to which at least one selected from the group consisting of an aluminum compound and aluminum ions is attached,
A polishing agent for resin polishing, wherein the polishing agent has a pH of 3.0 to 7.0.   The abrasive | polishing agent of Claim 1 in which the said abrasive grain contains colloidal silica.   The abrasive | polishing agent of Claim 1 or 2 whose pH is 3.0-5.0.   The abrasive | polishing agent as described in any one of Claims 1-3 which further contains an insulating material polish inhibitor.   The abrasive | polishing agent as described in any one of Claims 1-4 which further contains a corrosion inhibitor.   The abrasive | polishing agent as described in any one of Claims 1-5 which further contains an oxidizing agent.   The abrasive | polishing agent as described in any one of Claims 1-6 which further contains a pH adjuster.   The abrasive | polishing agent as described in any one of Claims 1-7 which further contains surfactant. An abrasive stock solution for obtaining the abrasive according to any one of claims 1 to 8,
A storage solution for abrasives, which is obtained by diluting with water.   Polishing at least a part of the resin by using the abrasive according to any one of claims 1 to 8 or the abrasive obtained by diluting the storage liquid for abrasive according to claim 9 with water. A polishing method, comprising a step of removing it.   The polishing method according to claim 10, wherein the resin contains at least one selected from the group consisting of polybenzoxazole, a precursor of polybenzoxazole, and polyimide.