JP2024002085A - Inorganic metal compound film-forming composition, method for manufacturing inorganic metal compound film using the same, and method for reducing volume shrinkage of inorganic metal compound film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an inorganic metal compound film-forming composition that provides an inorganic metal compound film with suppressed volumetric shrinkage when heated at temperatures below 400°C, a method for manufacturing an inorganic metal compound film using the same, and method for reducing volume shrinkage of an inorganic metal compound film.

SOLUTION: In an inorganic metal compound film-forming composition containing inorganic metal compound particles, a dispersant, and a solvent, at least one selected from the group consisting of metal nitride particles, metal carbide particles, metal boride particles, metal carbonitride particles, and metal boronitride particles the size of which are 50 nm or less is used as inorganic metal compound particles, and in the solid content of the inorganic metal compound film-forming composition, the ratio of the mass of the inorganic component to the total mass of the inorganic component and the organic component is 25 mass% or more.

SELECTED DRAWING: None

COPYRIGHT: (C)2024,JPO&INPIT

Description

The present invention relates to an inorganic metal compound film-forming composition, a method for producing an inorganic metal compound film using the same, and a method for reducing the volume shrinkage rate of an inorganic metal compound film.

Generally, in etching processing in semiconductor device manufacturing, etc., a patterned resist film formed by photolithography using a resist material such as a photoresist or an electron beam resist is used as an etching mask.
In order to perform the etching process well, it is desirable that the etching rate of the etching mask be considerably lower than the etching rate of the object to be etched, as an etching rate for the same type of etchant.

However, when using a resist film formed using the above resist material as an etching mask, depending on the combination of the etchant and the object to be etched, the etching rate of the object to be etched and the etching rate of the etching mask may not be much different. There is.
In such cases, an etching mask called a hard mask is often used, which generally exhibits a low etching rate with respect to various etchants. As a hard mask, for example, a hard mask made of an inorganic metal compound film containing metal oxide nanoparticles such as zirconium oxide nanoparticles as inorganic metal compound particles is known (see Patent Document 1).

Special Publication No. 2020-503409

Conventional inorganic metal compound films are formed by heating a coating film made of a composition containing inorganic metal compound particles such as metal oxide nanoparticles. The present inventors investigated and found that conventional metal oxide films have large volumetric shrinkage when heated at low temperatures of 400°C or lower, resulting in poor in-plane uniformity when main firing is performed at high temperatures of 450°C. As a result, it was found that when the metal oxide film after main firing was used as a hard mask in dry etching, it was difficult to perform dry etching uniformly.

The present invention has been made in view of such conventional circumstances, and provides an inorganic metal compound film-forming composition that provides an inorganic metal compound film whose volume shrinkage is suppressed when heated at 400°C or less, and a composition using the same. The present invention aims to provide a method for manufacturing an inorganic metal compound film and a method for reducing the volumetric shrinkage rate of the inorganic metal compound film.

The present inventors have conducted extensive research to solve the above problems. As a result, in an inorganic metal compound film-forming composition containing inorganic metal compound particles, a dispersant, and a solvent, the size thereof is 50 nm or less, and metal nitride particles, metal carbide particles, and metal boride particles. , metal carbonitride particles, and metal boronitride particles are used as inorganic metal compound particles, and the inorganic content mass and the organic content in the solid content of the inorganic metal compound film-forming composition are It has been found that the above problem can be solved by setting the ratio of the inorganic component mass to the total mass to 25% by mass or more, and the present invention has been completed. Specifically, the present invention provides the following.

A first aspect of the present invention is an inorganic metal compound film-forming composition containing inorganic metal compound particles, a dispersant, and a solvent,
The size of the inorganic metal compound particles is 50 nm or less,
The inorganic metal compound particles are at least one selected from the group consisting of metal nitride particles, metal carbide particles, metal boride particles, metal carbonitride particles, and metal boronitride particles,
In the solid content of the inorganic metal compound film-forming composition, the ratio of the mass of the inorganic component to the total mass of the inorganic component and the organic component is 25% by mass or more.

A second aspect of the present invention includes a coating film forming step of forming a coating film made of the inorganic metal compound film-forming composition according to the first aspect;
a heating step of heating the coating film;
A method for producing an inorganic metal compound film, including:

A third aspect of the present invention is a method for forming a coating film made of an inorganic metal compound film-forming composition and reducing the volume shrinkage rate of the inorganic metal compound film obtained by heating the coating film, comprising:
configuring an inorganic metal compound film-forming composition to contain inorganic metal compound particles, a dispersant, and a solvent,
The size of the inorganic metal compound particles is 5 nm or less,
The inorganic metal compound contained in the inorganic metal compound particles is at least one selected from the group consisting of metal nitrides, metal carbides, and metal borides,
In this method, in the solid content of the inorganic metal compound film-forming composition, the ratio of the mass of the inorganic component to the total mass of the inorganic component and the organic component is 25% by mass or more.

According to the present invention, an inorganic metal compound film-forming composition that provides an inorganic metal compound film whose volume shrinkage is suppressed when heated at 400° C. or lower, a method for producing an inorganic metal compound film using the same, and an inorganic metal compound film. A method of reducing the volumetric shrinkage of a membrane can be provided.

<Inorganic metal compound film-forming composition>
The inorganic metal compound film-forming composition contains inorganic metal compound particles, a dispersant, and a solvent. The inorganic metal compound film-forming composition can provide an inorganic metal compound film whose volume shrinkage is suppressed when heated at 400° C. or lower.

In the solid content of the inorganic metal compound film-forming composition, the ratio of the inorganic component mass to the total of the inorganic component mass and the organic component mass is 25% by mass or more, preferably 30% by mass or more, and more preferably 40% by mass. % or more, more preferably 50% by mass or more, particularly preferably 60% by mass or more. When the ratio is within the above range, the ratio of the inorganic component mass can be set high, and as a result, the resulting inorganic metal compound film is likely to have volumetric shrinkage suppressed when heated at a low temperature of 400° C. or lower. The upper limit of the ratio is not particularly limited, and may be 90% by mass, 80% by mass, or 75% by mass.

[Inorganic metal compound particles]
The inorganic metal compound particles are not particularly limited as long as they are made of an inorganic metal compound and satisfy the predetermined requirements described below.
The inorganic metal compound particles may be primary particles, secondary particles, or tertiary particles. Primary particles consist of a single particle. Secondary particles are aggregates of primary particles. The tertiary particles are aggregates of primary particles and secondary particles, or aggregates of secondary particles.
Typically, the inorganic metal compound particles may be inorganic metal compound nanoclusters, which are aggregates of inorganic metal compound nanoparticles. An inorganic metal compound nanocluster is an aggregate composed of a plurality of surfaces formed from an inorganic metal compound.

The size of the inorganic metal compound particles is 50 nm or less, preferably 15 nm or less, and more preferably 10 nm or less. The lower limit of the size of the metal-free compound particles is not particularly limited. The size of the inorganic compound particles may be, for example, 2 nm or more, or 3 nm or more.
Since the inorganic metal compound film-forming composition contains inorganic metal compound particles of the above-mentioned size, the volume shrinkage of the metal compound film is well suppressed when heated at a low temperature of 400°C or less, and the volume shrinkage of the metal compound film is well suppressed at a high temperature of 450°C. High in-plane uniformity when fired. As a result, when the metal compound film after main firing is used as a hard mask in dry etching, it is easy to perform dry etching uniformly.

The size of the inorganic metal compound particles can be measured by a TEM method in which the inorganic metal compound particles are observed using a transmission electron microscope (TEM).
More specifically, after applying a dispersion of inorganic metal compound particles onto an observation plate, the dispersion on the plate is dried. Observe the dried plate using TEM.
In the obtained observation image, the size of 100 or more inorganic metal compound particles is measured. Here, the maximum value of the Feret diameter is defined as the size of the inorganic metal compound particles. The number average value of the measured sizes of 100 or more inorganic metal compound particles is defined as the size of the inorganic metal compound particles.

The inorganic metal compound particles may be crystalline or amorphous. Furthermore, the metal-free compound particles may include a crystalline portion and an amorphous portion. Since it is easy to form a patterned inorganic metal compound film with less distortion after etching, the inorganic metal compound particles preferably contain an amorphous portion, and are more preferably amorphous.
The shape of the inorganic metal compound particles is not particularly limited. The shape of the inorganic metal compound particles may be spherical, polyhedral, rod-like, flaky, irregular, or the like.

The metal element contained in the inorganic metal compound particles is not particularly limited. Note that boron, silicon, germanium, arsenic, antimony, and tellurium, which are often distinguished from metal elements as metalloid elements, are also treated as metal elements in this application.
Examples of the metal elements contained in the inorganic metal compound particles include zinc, yttrium, hafnium, zirconium, lanthanum, cerium, neodymium, gadolinium, holmium, lutetium, tantalum, titanium, silicon, boron, aluminum, antimony, tin, indium, and tungsten. , copper, vanadium, chromium, niobium, molybdenum, ruthenium, rhodium, rhenium, iridium, germanium, gallium, thallium, scandium, and magnesium.
From the viewpoint of etching selectivity, titanium, boron, and tungsten are preferred among these elements.

Preferred specific examples of the inorganic metal compound particles include titanium nitride particles, tungsten nitride particles, boron nitride particles, tungsten carbide particles, zirconium nitride particles, tungsten boride particles, tungsten carbonitride particles, and aluminum nitride particles. At least one selected from the group consisting of particles, tantalum nitride particles, tungsten boron carbide particles, and tungsten boron nitride particles.
Note that when the metal atoms contained in the inorganic metal compound particles can have multiple valences, multiple types of metal atom compounds may exist as inorganic metal compounds composed of the same type of metal element.
For example, tungsten nitride includes W ₂ N ₃ (hexagonal system), WN (hexagonal system), W ₃ N ₄ (cubic system), and the like.

The method for producing the inorganic metal compound particles is not particularly limited. Various known methods can be employed to produce the inorganic metal compound particles. The size of the inorganic metal compound particles can be adjusted, for example, by appropriately adjusting various synthesis conditions such as the ratio of raw materials used, temperature conditions, reaction time, and stirring speed.
Moreover, commercially available products can also be used as the inorganic metal compound particles.

The amount of the inorganic metal compound particles used is not particularly limited as long as the ratio of the inorganic component mass to the total of the inorganic component mass and the organic component mass in the solid content of the inorganic metal compound film-forming composition is 25% by mass or more. .
The amount of inorganic metal compound particles used is, for example, 60% by mass or more and 99.9% by mass or less, preferably 65% by mass or more and 95% by mass, based on the total of components other than the solvent in the inorganic metal compound film-forming composition. % by mass or less. When the amount of the inorganic metal compound used is within the above range, volume shrinkage of the obtained inorganic metal compound film is likely to be suppressed when heated at a low temperature of 400° C. or lower.

[Dispersant]
The inorganic metal compound film-forming composition contains a dispersant. As the dispersant, additives used for the purpose of dispersion stabilization in various known dispersions can be used without particular limitation. Preferred dispersants include capping agents, polymeric dispersants, and surfactants.
The amount of the dispersant used is, for example, 0.1% by mass or more and 40% by mass or less, preferably 5% by mass or more and 35% by mass, based on the total of components other than the solvent in the inorganic metal compound film-forming composition. It is as follows. Within the above range, as the dispersant, a capping agent, a polymeric dispersant, and a surfactant may be used alone, or in combination of two or three types. When the amount of the inorganic metal compound used is within the above range, volume shrinkage of the obtained inorganic metal compound film is likely to be suppressed when heated at a low temperature of 400° C. or lower.

The capping agent binds to the surface of the inorganic metal compound particles and stabilizes the dispersion of the inorganic metal compound particles due to a steric hindrance effect or the like.
The polymeric dispersant stabilizes the dispersion of the inorganic metal compound particles due to the steric hindrance effect when it is adsorbed to the inorganic metal compound particles or when it is free from the inorganic metal compound particles.
Surfactants improve the wettability between inorganic metal compound particles and solvent by lowering the surface tension of the solvent, and can be used in a state where they are adsorbed on the inorganic metal compound particles or when they are free from the inorganic metal compound particles. The dispersion of inorganic metal compound particles is stabilized by the steric hindrance effect, etc.

In addition, in this specification, compounds that can be bonded to the surface of an inorganic metal compound include polymeric dispersants, anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants. Compounds that do not fall under any of the above are referred to as "capping agents."
A "polymeric dispersant" is a dispersant having a polymer chain other than a polyalkylene oxide chain.
"Surfactant" corresponds to any of anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants. The surfactant may or may not be able to bind to the surface of the inorganic metal compound particles.

Preferably, the dispersant contains a capping agent, and also preferably a surfactant.
The capping agent and surfactant will be explained below.

[Capping agent]
In the inorganic metal compound film-forming composition, some or all of the inorganic metal compound particles may be covered with a capping agent. The capping agent includes at least one selected from the group consisting of alkoxysilane, phenol, alcohol, carboxylic acid, and carboxylic acid halide. When the inorganic metal compound film-forming composition contains a capping agent together with the inorganic metal compound particles, the resulting inorganic metal compound film is likely to be inhibited from shrinking in volume when heated at a low temperature of 400° C. or lower.

Specific examples of the capping agent include n-propyltrimethoxysilane, n-propyltriethoxysilane, n-octyltrimethoxysilane, n-octyltriethoxysilane, n-dodecyltrimethoxysilane, n-dodecyltriethoxysilane, n-Hexadecyltrimethoxysilane, n-hexadecyltriethoxysilane, n-octadecyltrimethoxysilane, n-octadecyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenethylphenyltrimethoxysilane, phenethylethyltriethoxy Silane, 3-{2-methoxy[poly(ethyleneoxy)]}propyltrimethoxysilane, 3-{2-methoxy[poly(ethyleneoxy)]}propyltriethoxysilane, 3-{2-methoxy[tri(ethyleneoxy)] oxy)]}propyltrimethoxysilane, 3-{2-methoxy[tri(ethyleneoxy)]}propyltriethoxysilane, vinyltrimethoxylane, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, 1- hexenyltrimethoxysilane, 1-hexenyltriethoxysilane, 1-octenyltrimethoxysilane, 1-octenyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxy Silane, 3-mercaptopropyltriethoxysilane, 3-acryloyloxypropyltrimethoxysilane, 3-acryloylpropyltriethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-isocyanatopropyl Alkoxysilanes such as trimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-glycidoxypropyltriethoxysilane; ethanol, n-propanol, isopropanol, n-butanol, Phenols such as n-heptanol, n-hexanol, n-octanol, oleyl alcohol, n-dodecyl alcohol, n-hexadecanol (cetanol), n-octadecanol, benzyl alcohol, phenol, and triethylene glycol monomethyl ether or alcohols; phosphonic acids such as laurylphosphonic acid and stearylphosphonic acid; mercaptans such as lauryl mercaptan and stearyl mercaptan; octanoic acid, acetic acid, propionic acid, 2-[2-(methoxyethoxy)ethoxy]acetic acid, oleic acid, Examples include acids such as lauric acid, benzoic acid, 2-acryloyloxyethylsuccinic acid, and 2-acryloyloxyethyl phthalic acid; and acid halides of these acids, such as acid chlorides of these acids, and preferably phenol. These are compounds listed as alcohols, alcohols, or acids.

The amount of the capping agent used is not particularly limited as long as the ratio of the inorganic component mass to the total of the inorganic component mass and the organic component mass in the solid content of the inorganic metal compound film-forming composition is 25% by mass or more.
The amount of the capping agent used is, for example, 10% by mass or more and 35% by mass or less, preferably 13% by mass or more and 31% by mass or less, based on the total of components other than the solvent in the inorganic metal compound film-forming composition. More preferably, it is 16% by mass or more and 30% by mass or less. When the amount of the capping agent used is within the above range, the proportion of the organic content will not become too high, and as a result, the resulting inorganic metal compound film will be able to suppress volumetric shrinkage when heated at a low temperature of 400°C or less. Cheap.

[Polymer-based dispersant]
As the polymeric dispersant, polymeric dispersants conventionally used for dispersing various inorganic particles, pigments, etc. can be used without particular limitation.
Polymeric dispersants include polyamide amines, polyamide amine salts, polycarboxylic acids, polycarboxylic acid salts, high molecular weight unsaturated acid esters, modified polyurethanes, modified polyesters, modified poly(meth)acrylates, and (meth)acrylics. Examples include polymers, naphthalene sulfonic acid formalin condensates, polyoxyethylene alkyl phosphates, polyoxyethylene alkyl amines, and pigment derivatives.
Polymeric dispersants can be classified into linear polymeric dispersants, terminally modified polymeric dispersants, grafted polymeric dispersants, and block polymeric dispersants based on their structures.

Specific examples of polymer dispersants include DISPERBYK-102, DISPERBYK-103, DISPERBYK-106, DISPERBYK-108, DISPERBYK-109, DISPERBYK-110, DISPERBYK-111, DISPERBYK-118, DI SPERBYK-140, DISPERBYK-142, DISPERBYK-145, DISPERBYK-161, DISPERBYK-162, DISPERBYK-163, DISPERBYK-164, DISPERBYK-167, DISPERBYK-168, DISPERBYK-170, DISPERBYK-1 71, DISPERBYK-174, DISPERBYK-180, DISPERBYK-182, DISPERBYK- 184, DISPERBYK-185, DISPERBYK-2000, DISPERBYK-2001, DISPERBYK-2008, DISPERBYK-2009, DISPERBYK-2013, DISPERBYK-2022, DISPERBYK-2025, DISPERBYK-2050, DISPERBYK-2055, DISPERBYK-2096, DISPERBYK-2150, DISPERBYK-2152, DISPERBYK-2155, DISPERBYK-2163, DISPERBYK-2164, DISPERBYK-2200, BYK-P104, BYK-P104S, BYK-P105, BYK-9076, BYK-9077, and B YK-220S (both manufactured by BIC Chemie) ) etc.

The amount of the polymeric dispersant used is not particularly limited as long as the ratio of the inorganic component mass to the total of the inorganic component mass and the organic component mass in the solid content of the inorganic metal compound film-forming composition is 25% by mass or more. .
The amount of the polymer dispersant used is, for example, 10% by mass or more and 35% by mass or less, preferably 18% by mass or more and 28% by mass, based on the total of components other than the solvent in the inorganic metal compound film-forming composition. It is as follows.

[Surfactant]
As the surfactant, surfactants conventionally blended into dispersions containing various inorganic particles, pigments, etc. can be used without particular limitation.
Furthermore, when the inorganic metal compound film-forming composition contains a surfactant, the coating properties, antifoaming properties, leveling properties, etc. of the inorganic metal compound film-forming composition can be improved.
As the surfactant, for example, silicone surfactants and fluorine surfactants are preferred.

Specific examples of silicone surfactants include BYK-077, BYK-085, BYK-300, BYK-301, BYK-302, BYK-306, BYK-307, BYK-310, BYK-320, BYK-322. , BYK-323, BYK-325, BYK-330, BYK-331, BYK-333, BYK-335, BYK-341, BYK-344, BYK-345, BYK-346, BYK-348, BYK-354, BYK -355, BYK-356, BYK-358, BYK-361, BYK-370, BYK-371, BYK-375, BYK-380, and BYK-390 (all manufactured by BYK Chemie).

Specific examples of fluorosurfactants include F-114, F-177, F-410, F-411, F-450, F-493, F-494, F-443, F-444, F-445. , F-446, F-470, F-471, F-472SF, F-474, F-475, F-477, F-478, F-479, F-480SF, F-482, F-483, F -484, F-486, F-487, F-172D, MCF-350SF, TF-1025SF, TF-1117SF, TF-1026SF, TF-1128, TF-1127, TF-1129, TF-1126, TF-1130 , TF-1116SF, TF-1131, TF-1132, TF-1027SF, TF-1441, and TF-1442 (manufactured by DIC); Polyfox series PF-636, PF-6320, PF-656, PF-6520 (manufactured by Omnova), etc.

The amount of the surfactant used is not particularly limited as long as the ratio of the inorganic component mass to the total of the inorganic component mass and the organic component mass in the solid content of the inorganic metal compound film-forming composition is 25% by mass or more.
The surfactant is, for example, 0.01% by mass or more and 0.15% by mass or less, preferably 0.05% by mass or more and 0.0% by mass or less, based on the total of components other than the solvent in the inorganic metal compound film-forming composition. .1% by mass or less.

[Base material]
The inorganic metal compound film-forming composition may contain a base material for the purpose of adjusting film-forming properties and coating properties. The base material may be used alone or in combination of two or more. The base material is not particularly limited, and polymers such as resins and non-polymers such as low-molecular compounds can be used.

The mass average molecular weight (hereinafter referred to as "Mw") of the base material is not particularly limited as long as it does not impede the object of the present invention, and is preferably 700 or more and 40,000 or less, more preferably 900 or more and 30,000 or less, Even more preferably it is 1000 or more and 20000 or less. When Mw is within the above range, film forming properties and coating properties tend to be good. Further, by using a polymer or non-polymer having an Mw of 4000 or less, the gap filling property for the uneven substrate tends to be good. In this specification, Mw is determined by gel permeation chromatography (GPC) in terms of polystyrene.

[Acrylic resin (a-IV)]
As the acrylic resin (a-IV), one containing a structural unit derived from (meth)acrylic acid and/or a structural unit derived from other monomers such as (meth)acrylic acid ester can be used. (Meth)acrylic acid is acrylic acid or methacrylic acid. As the monomer providing the structural unit in the acrylic resin (a-IV), a compound represented by the following formula (a-4-1) is typically preferably used.

In the above formula (a-4-1), R ^a9 is a hydrogen atom or a methyl group. R ^a10 is a hydrogen atom or a monovalent organic group. This organic group may contain a bond or substituent other than a hydrocarbon group such as a hetero atom. Further, this organic group may be linear, branched, or cyclic. R ^a11 is a group represented by -O- or -NR ^a12 -. R ^a12 is a hydrogen atom or an alkyl group having 1 or more and 6 or less carbon atoms.

Substituents other than hydrocarbon groups in the organic group of R ^a10 are not particularly limited as long as the effects of the present invention are not impaired, and include halogen atoms, hydroxyl groups, mercapto groups, sulfide groups, cyano groups, isocyano groups, and cyanato groups. , isocyanato group, thiocyanato group, isothiocyanato group, silyl group, silanol group, alkoxy group, alkoxycarbonyl group, carbamoyl group, thiocarbamoyl group, nitro group, nitroso group, carboxy group, carboxylate group, acyl group, acyloxy group, sulfino group group, sulfo group, sulfonato group, phosphino group, phosphinyl group, phosphono group, phosphonato group, hydroxyimino group, alkyl ether group, alkylthioether group, aryl ether group, arylthioether group, amino group (-NH ₂ , -NHR, -NRR': R and R' each independently represent a hydrocarbon group). The hydrogen atom included in the above substituent may be substituted with a hydrocarbon group. Moreover, the hydrocarbon group contained in the above-mentioned substituent may be linear, branched, or cyclic.

Further, the organic group as R ^a10 may have a reactive functional group such as an acryloyloxy group, a methacryloyloxy group, an epoxy group, or an oxetanyl group.
An acyl group having an unsaturated double bond or the like, such as an acryloyloxy group or a methacryloyloxy group, is used, for example, in at least a portion of the epoxy group in the acrylic resin (a-IV) containing a structural unit having an epoxy group. It can be produced by reacting unsaturated carboxylic acids such as acrylic acid and methacrylic acid.
After reacting at least a portion of the epoxy group with an unsaturated carboxylic acid, the group generated by the reaction may be reacted with a polybasic acid anhydride.

Specific examples of polybasic acid anhydrides include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, Trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, 3-methylhexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, 3-ethylhexahydrophthalic anhydride, 4-ethylhexa Examples include hydrophthalic anhydride, tetrahydrophthalic anhydride, 3-methyltetrahydrophthalic anhydride, 4-methyltetrahydrophthalic anhydride, 3-ethyltetrahydrophthalic anhydride, and 4-ethyltetrahydrophthalic anhydride.

In addition, by reacting a compound having an epoxy group and an unsaturated double bond with a structural unit derived from an unsaturated carboxylic acid such as acrylic acid or methacrylic acid, which the acrylic resin (a-IV) has. , an unsaturated double bond can be introduced into the acrylic resin (a-IV). As the compound having an epoxy group and an unsaturated double bond, for example, glycidyl (meth)acrylate or compounds represented by formulas (a-4-1a) to (a-4-1o) described below may be used. Can be done.

R ^a10 is preferably an alkyl group, an aryl group, a cycloalkyl group, a polycycloalkyl group, a cycloalkylalkyl group, a polycycloalkylalkyl group, an aralkyl group, or a heterocyclic group, and these groups include a halogen atom, a hydroxyl group, , an alkyl group, or a heterocyclic group, and an oxygen atom may be bonded to these groups to form an epoxy group. Further, when these groups contain an alkylene moiety, the alkylene moiety may be interrupted by an ether bond, a thioether bond, or an ester bond.

When the alkyl group is linear or branched, the number of carbon atoms is preferably 1 or more and 20 or less, more preferably 1 or more and 15 or less, particularly preferably 1 or more and 10 or less. Examples of suitable alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, sec -pentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl group, isononyl group, n-decyl group, Examples include isodecyl group.

Among cycloalkyl groups, polycycloalkyl groups, cycloalkylalkyl groups, polycycloalkylalkyl groups, and alicyclic group-containing groups other than these groups, suitable examples of alicyclic groups contained in these groups are: , cyclopentyl group, monocyclic alicyclic group such as cyclohexyl group, adamantyl group, norbornyl group, isobornyl group, tricyclononyl group, tricyclodecyl group, tetracyclododecyl group, bicyclo-[2.1.1] -hexyl group, bicyclo-[2.2.1]-heptyl group, bicyclo-[2.2.2]-octyl group, bicyclo-[3.3.0]-octyl group, bicyclo-[4.3. 0]-nonyl group, and polycycloalkyl groups such as bicyclo-[4.4.0]-decyl group.

Suitable compounds represented by formula (a4-1) and having as R ^a10 a cycloalkyl group, a polycycloalkyl group, a cycloalkylalkyl group, a polycycloalkylalkyl group, and an alicyclic group-containing group other than these groups Examples include compounds represented by the following formulas (a-4-1a) to (a-4-1h). Among these, compounds represented by the following formulas (a-4-1c) to (a-4-1h) are preferred, and compounds represented by the following formula (a-4-1c) or the following formula (a-4-1d) are preferred. The compounds represented are more preferred.

In the above formula, R ^a20 represents a hydrogen atom or a methyl group, R ^a21 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, and R ^a22 represents a hydrogen atom or a carbon atom number 1 ~5 alkyl group. R ^a21 is preferably a single bond, a linear or branched alkylene group, such as a methylene group, ethylene group, propylene group, tetramethylene group, ethylethylene group, pentamethylene group, or hexamethylene group. As R ^a22 , for example, a methyl group or an ethyl group is preferable.

It is preferable to contain an acrylic resin containing a structural unit derived from polycycloalkyl (meth)acrylate (A-1) and/or a structural unit derived from aralkyl (meth)acrylate (A-2). When the acrylic resin contains a structural unit derived from (A-1), for example, it is represented by any of the above formulas (a-4-1c) to (a-4-1h), and R ^a21 is a single bond. From the viewpoint of the effects of the present invention, it is preferable that the compound contains a structural unit derived from (A-1), which is a compound having the following.

Specific examples of the compound represented by formula (a-4-1) in the case where the compound represented by formula (a-4-1) has a chain group having an epoxy group as R ^a10 , Examples include (meth)acrylic acid epoxyalkyl esters such as glycidyl (meth)acrylate, 2-methylglycidyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, and 6,7-epoxyheptyl (meth)acrylate. .

Further, the compound represented by formula (a-4-1) may be an alicyclic epoxy group-containing (meth)acrylic ester. The alicyclic group constituting the alicyclic epoxy group may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include cycloalkyl groups such as a cyclopentyl group and a cyclohexyl group. Examples of the polycyclic alicyclic group include polycycloalkyl groups such as norbornyl group, isobornyl group, tricyclononyl group, tricyclodecyl group, and tetracyclododecyl group.

Specific examples when the compound represented by formula (a-4-1) is a (meth)acrylate containing an alicyclic epoxy group include the following formulas (a-4-1i) to (a-4- Examples include compounds represented by 1m).

Other specific examples of the compound represented by formula (a-4-1) include (meth)acrylic acid, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxy -3-phenoxypropyl (meth)acrylate, 2-(meth)acryloyloxyethylsuccinic acid, 2-(meth)acryloyloxyethyl phthalic acid, 2-(meth)acryloyloxyethyl-2-hydroxyethylphthalic acid, Mono 2-(meth)acryloyloxyethyl acid phosphate, di-2-(meth)acryloyloxyethyl acid phosphate, 2-hydroxybutyl(meth)acrylate, 2-(meth)acryloyloxyethyl hexahydrophthalic acid, glycerin Di(meth)acrylate, 2-hydroxy-3 phenoxypropyl (meth)acrylate, bisphenol A diglycidyl ether (meth)acrylic acid adduct, O-phenylphenol glycidyl ether (meth)acrylate, 1,4-butanediol diglycidyl Ether di(meth)acrylate, 1,6-hexanediol diglycidyl ether di(meth)acrylate, dipropylene glycol diglycidyl ether di(meth)acrylate, pentaerythritol polyglycidyl ether (meth)acrylate, 1,3-propanediol diglycidyl ether (meth)acrylate, cyclohexanedimethanol diglycidyl ether (meth)acrylate, 1,6-hexanediol diglycidyl ether (meth)acrylate, glycerin polyglycidyl ether (meth)acrylate, ethylene glycol diglycidyl ether (meth)acrylate Acrylate, polyethylene glycol diglycidyl ether (meth)acrylate, dipropylene glycol diglycidyl ether (meth)acrylate, polypropylene glycol diglycidyl ether (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 1-acryloyloxyethyl (meth) Examples include (meth)acrylic monomers such as acrylate, 1,2,3-propanetriol 1,3-di(meth)acrylate, and 2-carboxyethyl (meth)acrylate.

From the viewpoint of the effect of the present invention, preferably (meth)acrylic acid, 2-(meth)acryloyloxyethylsuccinic acid, 2-(meth)acrylic acid, and 2-(meth)acrylic acid are preferred as compounds providing structural units in the acrylic resin (a-IV). ) Acryloyloxyethyl phthalic acid, 2-(meth)acryloyloxyethyl-2-hydroxyethylphthalic acid, alkyl (meth)acrylate having 1 to 5 carbon atoms, polycycloalkyl (meth)acrylate (A-1), or aralkyl (meth)acrylate (A-2). Examples of the polycycloalkyl (meth)acrylate (A-1) include compounds represented by any of the above formulas (a-4-1c) to (a-4-1h) and having a single bond as R ^a21. Examples of the aralkyl (meth)acrylate (A-2) include benzyl (meth)acrylate.

In the acrylic resin (a-IV), the amount of structural units derived from the above-mentioned preferred compound is not particularly limited as long as it does not impede the object of the present invention, and is, for example, 10% by mass based on the amount of all structural units. or more, and preferably 30% by mass or more. The upper limit may be set appropriately, and may be, for example, 100% by mass or less, or 90% by mass or less.

Further, the acrylic resin (a-IV) may be one obtained by polymerizing monomers other than (meth)acrylic acid ester. Examples of such monomers include (meth)acrylamides, unsaturated carboxylic acids, allyl compounds, vinyl ethers, vinyl esters, and styrenes, with vinyl ethers and styrenes being preferred. These monomers can be used alone or in combination of two or more.

(Meth)acrylamides include (meth)acrylamide, N-alkyl(meth)acrylamide, N-aryl(meth)acrylamide, N,N-dialkyl(meth)acrylamide, N,N-aryl(meth)acrylamide, N- -Methyl-N-phenyl (meth)acrylamide, N-hydroxyethyl-N-methyl (meth)acrylamide, and the like.

Examples of unsaturated carboxylic acids include monocarboxylic acids such as crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, and itaconic acid; anhydrides of these dicarboxylic acids; and the like.

Examples of allyl compounds include allyl esters such as allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, and allyl lactate; allyloxyethanol; etc. Can be mentioned.

Examples of vinyl ethers include hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, and hydroxyethyl vinyl ether. , diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether, and other alkyl vinyl ethers; vinyl phenyl ether, vinyl tolyl ether, vinyl chlorophenyl ether, vinyl-2,4-dichlorophenyl ether , vinyl aryl ethers such as vinyl naphthyl ether, vinyl anthrani ether, and the like.

Vinyl esters include vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl valerate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxy acetate, vinyl butoxy acetate, and vinyl phenyl. Examples include acetate, vinyl acetoacetate, vinyl lactate, vinyl-β-phenylbutyrate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, vinyl naphthoate, and the like.

Styrenes include styrene; methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, isopropylstyrene, butylstyrene, hexylstyrene, cyclohexylstyrene, decylstyrene, benzylstyrene, chloromethylstyrene, trifluoromethylstyrene, ethoxy Alkyl styrenes such as methylstyrene and acetoxymethylstyrene; alkoxystyrenes such as methoxystyrene, 4-methoxy-3-methylstyrene and dimethoxystyrene; chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, Halostyrenes such as dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethylstyrene, and 4-fluoro-3-trifluoromethylstyrene; and the like.

Since the inorganic metal compound film-forming composition contains inorganic metal compound particles, it can provide the etching resistance necessary for substrate processing even if the base material is an acrylic resin. As such, a polymer containing an aromatic ring, a non-polymer containing an aromatic ring, or both thereof may be additionally used.

Examples of the non-polymer containing an aromatic ring include compounds (X) having a bisphenylfluorene skeleton, a bisnaphthylfluorene skeleton, a methylene dinaphthalene skeleton, a tetrabenzonaphthalene skeleton, or a calixarene skeleton. These compounds may have a substituent, and examples of the substituent include an acryloyl group, a methacryloyl group, a vinyloxy group, a styryl group, an allyl group, a propargyl group, a diglycidylamino group, and a dipropargylamino group. A polymerizable group or an organic group containing a polymerizable group is preferable from the viewpoint of curability and the like.

As a polymer containing an aromatic ring,
- A resin having a repeating structure of the skeleton constituting the compound (X),
・Resin having a benzene skeleton, naphthalene skeleton, biphenyl skeleton, and/or anthracene skeleton as a repeating structure,
- Condensate of compound (X),
etc. The condensate can be produced by reacting compound (X) with one or more selected from the group consisting of aldehydes, compounds having an alkoxy group, compounds having an alkanoyloxy group, trioxanes, and fluorenones. can get. Further, as the polymer containing an aromatic ring, a known novolak resin or the like may be used.

[Novolac resin (a-II)]
As the novolak resin (a-II), various novolak resins conventionally blended into photosensitive compositions can be used. The novolac resin (a-II) is preferably one obtained by addition condensation of an aromatic compound having a phenolic hydroxyl group (hereinafter simply referred to as "phenols") and an aldehyde under an acid catalyst.

(Phenols)
Examples of phenols used in producing the novolak resin (a-II) include phenol; cresols such as o-cresol, m-cresol, and p-cresol; 2,3-xylenol, 2,4-xylenol; , 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol and other xylenol; o-ethylphenol, m-ethylphenol, p-ethylphenol and other ethylphenols; 2 - Alkylphenols such as isopropylphenol, 3-isopropylphenol, 4-isopropylphenol, o-butylphenol, m-butylphenol, p-butylphenol, and p-tert-butylphenol; 2,3,5-trimethylphenol, and 3,4 , 5-trimethylphenol; polyhydric phenols such as resorcinol, catechol, hydroquinone, hydroquinone monomethyl ether, pyrogallol, and phloroglycinol; alkyl polyhydric phenols such as alkylresorcinol, alkylcatechol, and alkylhydroquinone. (Each alkyl group has 1 to 4 carbon atoms.); α-naphthol; β-naphthol; hydroxydiphenyl; and bisphenol A. These phenols may be used alone or in combination of two or more.

(Aldehydes)
Examples of aldehydes used in producing the novolak resin (a-II) include formaldehyde, paraformaldehyde, furfural, benzaldehyde, nitrobenzaldehyde, and acetaldehyde. These aldehydes may be used alone or in combination of two or more.

(acid catalyst)
Examples of acid catalysts used in producing the novolak resin (a-II) include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and phosphorous acid; formic acid, oxalic acid, acetic acid, diethyl sulfate, and Examples include organic acids such as para-toluenesulfonic acid; and metal salts such as zinc acetate. These acid catalysts may be used alone or in combination of two or more.

The amount of the base material used is not particularly limited, and is, for example, 0.5% by mass or more and 35% by mass or less, preferably 1% by mass, based on the total of components other than the solvent in the inorganic metal compound film-forming composition. It is 25% by mass or less, more preferably 2% by mass or more and 15% by mass or less. When the amount of the base material used is within the above range, the proportion of the organic content will not be too high, and as a result, the resulting inorganic metal compound film will be able to suppress volumetric shrinkage when heated at a low temperature of 400°C or less. Cheap.

In the solid content of the inorganic metal compound film-forming composition, the mass ratio of the inorganic metal compound particles to the total of the inorganic metal compound particles and the base material is, for example, 45% by mass or more, preferably 50% by mass or more. , more preferably 60% by mass or more, and even more preferably 65% by mass or more. The upper limit of the above mass ratio is, for example, 95% by mass or less, preferably 90% by mass or less.

[solvent]
The inorganic metal compound film-forming composition contains a solvent for the purpose of adjusting coating properties and viscosity. As the solvent, typically an organic solvent is used. The type of organic solvent is not particularly limited as long as it can uniformly dissolve or disperse the components contained in the inorganic metal compound film-forming composition.

Suitable examples of organic solvents that can be used as solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, Diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol Mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether (Poly)alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, etc. (Poly)alkylene glycol monoalkyl ether acetates; Other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and tetrahydrofuran; Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone; 2-hydroxy Lactic acid alkyl esters such as methyl propionate and ethyl 2-hydroxypropionate; ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3 - Ethyl ethoxypropionate, ethyl ethoxy acetate, ethyl hydroxyacetate, 2-hydroxy-3-methyl moiety methyl carbonate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl formate, isopentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, Other esters such as ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, and ethyl 2-oxobutanoate; Aromatic hydrocarbons such as toluene and xylene; N-methylpyrrolidone, N,N- Examples include amides such as dimethylformamide and N,N-dimethylacetamide. These organic solvents can be used alone or in combination of two or more.

The amount of solvent used in the inorganic metal compound film-forming composition is not particularly limited. From the viewpoint of coating properties of the inorganic metal compound film-forming composition, the amount of the solvent used is, for example, 30% by mass or more and 99.9% by mass or less, based on the entire inorganic metal compound film-forming composition. Preferably it is 50% by mass or more and 98% by mass or less.

[Other ingredients]
The inorganic metal compound film-forming composition according to the present invention may optionally contain a dispersant other than the above-mentioned dispersant, a thermal polymerization inhibitor, an antifoaming agent, a silane coupling agent, a coloring agent (pigment, Additives such as dyes), inorganic fillers, organic fillers, crosslinking agents, and acid generators can be included. Conventionally known additives can be used for any of the additives. Examples of thermal polymerization inhibitors include hydroquinone and hydroquinone monoethyl ether, and examples of antifoaming agents include silicone-based and fluorine-based compounds.

The method for producing the inorganic metal compound film-forming composition according to the present invention is not particularly limited, and for example, the slurry obtained by treating inorganic metal compound particles with a dispersant such as a capping agent in the presence of a solvent Examples include a method of adding a base material, optionally a solvent, and optionally other components. Specifically, the inorganic metal compound film-forming composition according to the present invention can be produced, for example, as shown in Examples below.

<Method for manufacturing inorganic metal compound film>
The method for producing an inorganic metal compound film includes a coating film forming step of forming a coating film made of an inorganic metal compound film-forming composition, and a heating step of heating the coating film.

The coating film can be formed, for example, by applying an inorganic metal compound film-forming composition onto a substrate such as a semiconductor substrate. Coating methods include contact transfer coating devices such as roll coaters, reverse coaters, and bar coaters, and non-contact coating devices such as spinners (rotary coating devices, spin coaters), dip coaters, spray coaters, slit coaters, and curtain flow coaters. A method using a coating device may be mentioned. In addition, after adjusting the viscosity of the inorganic metal compound film-forming composition to an appropriate range, the inorganic metal compound film-forming composition is applied by a printing method such as an inkjet method or a screen printing method to form a desired shape. A patterned coating film may be formed.

The substrate preferably includes a metal film, a metal carbide film, a metal oxide film, a metal nitride film, or a metal oxynitride film. Examples of metals constituting the substrate include silicon, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, aluminum, indium, gallium, arsenic, palladium, iron, tantalum, iridium, molybdenum, and alloys thereof. , silicon, germanium, and gallium. Further, the surface of the substrate may have an uneven shape, and the uneven shape may be a patterned organic material.

Then, if necessary, volatile components such as solvents are removed and the coating film is dried. The drying method is not particularly limited, and examples include a method of drying on a hot plate at a temperature of 80° C. or higher and 140° C. or lower, preferably 90° C. or higher and 130° C. or lower, for a period of 60 seconds or more and 150 seconds or less. . Before heating with a hot plate, vacuum drying may be performed at room temperature using a vacuum drying device (VCD).

After forming the coating film in this manner, the coating film is heated. The temperature at which heating is performed is not particularly limited, and is preferably 400°C or higher, more preferably 420°C or higher, and even more preferably 430°C or higher. The upper limit may be set appropriately, for example, 600° C. or lower, and preferably 550° C. or lower in terms of etching rate control during dry etching or in-plane uniformity. The heating time is typically preferably 30 seconds or more and 150 seconds or less, more preferably 60 seconds or more and 120 seconds. The heating step may be performed at a single heating temperature, or may include multiple stages at different heating temperatures.

The inorganic metal compound film formed as described above is suitably used as, for example, a metal hard mask or pattern reversal material.

<Method for reducing the volumetric shrinkage rate of an inorganic metal compound film>
The method for reducing the volumetric shrinkage rate of an inorganic metal compound film according to the present invention is as described above; in other words, a coating film made of an inorganic metal compound film-forming composition is formed, and the coating film is A method for reducing the volume shrinkage of an inorganic metal compound film obtained by heating, the method comprising configuring the inorganic metal compound film-forming composition to be the above-mentioned inorganic metal compound film-forming composition. It is something that By this method, the volumetric shrinkage rate of the inorganic metal compound film can be reduced when heated at 400°C or lower, and in-plane uniformity can be maintained when heated at 400°C or higher, particularly 450°C or higher. The inorganic metal compound film-forming composition is as described above.

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples.

[Examples 1 to 10 and Comparative Example 1]
In Examples 1 to 10 and Comparative Example 1, inorganic metal compound particles of the type and size listed in Table 1 were treated with the dispersant listed in Table 1, and then the inorganic metal compound particles were treated with a solid content of 48. The mixture was dispersed in PGMEA (propylene glycol monomethyl ether acetate) to obtain an inorganic metal compound film-forming composition in an amount of % by mass. The size of the inorganic metal compound particles is a value measured by the method described above, and does not include the dispersant portion.

In Examples 1 to 10 and Comparative Example 1, the following A to C were used as dispersants.
A: DISPERBYK-111
B: 3-{2-methoxy[tri(ethyleneoxy)]}propyltrimethoxysilane C: Cetanol

Regarding the inorganic metal compound film-forming compositions of each Example and each Comparative Example, the proportion of the inorganic component mass was calculated by the following method. The results are shown in Table 1.
[Calculation of proportion of inorganic mass]
The inorganic metal compound film-forming composition was placed on a platinum sample pan and measured by TG-DTA. The mass when the temperature was raised from room temperature to 200°C at a rate of 10°C/min and maintained at 200°C for 5 minutes was defined as the solid content mass. Next, the temperature was raised from 200°C to 710°C at a rate of 10°C/min, and the mass when reaching 710°C was defined as the inorganic mass.
From these measurement results, the formula:
The organic content weight was calculated by organic content weight = solid content weight - inorganic content weight.
The following formula:
Ratio of mass of inorganic components (mass%) = mass of inorganic components / (mass of inorganic components + mass of organic components) × 100
Accordingly, the ratio (mass %) of the inorganic component mass to the total of the inorganic component mass and the organic component mass was calculated.

<Shrinkage rate evaluation>
The inorganic metal compound film-forming composition was dropped onto a 6-inch silicon wafer, accelerated to 500 rpm in 2 seconds, and then spin coated at 500 rpm for 10 seconds. Thereafter, using a hot plate, pre-baking was performed at 100° C. for 120 seconds, and post-baking was performed at a firing temperature of 450° C. for 90 seconds to obtain an inorganic metal compound film. Note that "room temperature" below means that the product was left to stand at room temperature for 90 seconds, meaning that no post-bake was actually performed.

The cross section of the obtained inorganic metal compound film was observed with a SEM, and the film thickness was measured. When the film thickness when the firing temperature was set to room temperature was taken as 100%, the ratio of the film thickness at the firing temperature of 450° C. to the film thickness at room temperature was defined as the shrinkage rate. Based on the measured shrinkage percentage values, the shrinkage percentage was evaluated according to the following criteria.
A: The shrinkage rate is less than 10%.
B: Shrinkage rate is 10% or more and less than 20%.
C: Shrinkage rate is 20% or more.

<Evaluation of unevenness>
The cross section of the formed inorganic metal compound film was observed with a scanning electron microscope at a magnification of 250×10 ³ times, and the unevenness of the inorganic metal compound film was evaluated according to the following criteria.
A: The surface of the formed inorganic metal compound film has a smooth curve, and the minimum radius of curvature of the surface curve is 1000 nm or more.
B: The surface of the formed inorganic metal compound film has a smooth curve, and the minimum radius of curvature of the surface curve is 500 nm or more and less than 1000 nm.
C: The surface contour of the formed inorganic metal compound film includes irregularities that are not smooth, and the minimum radius of curvature in the surface contour is 10 nm or more and less than 500 nm.
D: The surface contour of the formed inorganic metal compound film includes irregularities that are not smooth, and the minimum radius of curvature in the surface contour is less than 10 nm.

As can be seen from Table 1, the inorganic metal compound particles have a size of 50 nm or less and are selected from the group consisting of metal nitride particles, metal carbide particles, metal boride particles, metal carbonitride particles, and metal boronitride particles. The inorganic metal compound film-forming composition of the example containing the following gave an inorganic metal compound film in which volumetric shrinkage upon heating at 400° C. or lower was suppressed.
On the other hand, the inorganic metal compound film-forming composition of the comparative example containing inorganic metal compound particles having a size of more than 50 nm did not provide an inorganic metal compound film in which volumetric shrinkage was suppressed.

Claims (8)

An inorganic metal compound film-forming composition containing inorganic metal compound particles, a dispersant, and a solvent,
The size of the inorganic metal compound particles is 50 nm or less,
The inorganic metal compound particles are at least one selected from the group consisting of metal nitride particles, metal carbide particles, metal boride particles, metal carbonitride particles, and metal boronitride particles,
In the solid content of the inorganic metal compound film-forming composition, the ratio of the mass of the inorganic component to the total mass of the inorganic component and the mass of the organic component is 25% by mass or more. The inorganic metal compound film-forming composition according to claim 1, wherein the dispersant includes one or more selected from the group consisting of a capping agent, a polymeric dispersant, and a surfactant. The metals contained in the inorganic metal compound particles include zinc, yttrium, hafnium, zirconium, lanthanum, cerium, neodymium, gadolinium, holmium, lutetium, tantalum, titanium, silicon, boron, aluminum, antimony, tin, indium, tungsten, and copper. , vanadium, chromium, niobium, molybdenum, ruthenium, rhodium, rhenium, iridium, germanium, gallium, thallium, scandium, and magnesium. Compound film-forming composition. The inorganic metal compound particles include titanium nitride particles, tungsten nitride particles, boron nitride particles, tungsten carbide particles, zirconium nitride particles, tungsten boride particles, tungsten carbonitride particles, aluminum nitride particles, and tantalum nitride particles. The inorganic metal compound film-forming composition according to claim 1 or 2, which is at least one selected from the group consisting of particles, tungsten boron carbide particles, and tungsten boron nitride particles. A coating film forming step of forming a coating film made of the inorganic metal compound film-forming composition according to claim 1 or 2;
a heating step of heating the coating film;
A method for producing an inorganic metal compound film, comprising: The manufacturing method according to claim 5, wherein the heating temperature in the heating step is 400°C or higher. The manufacturing method according to claim 5, wherein the inorganic metal compound film is a metal hard mask. A method of reducing the volume shrinkage of an inorganic metal compound film obtained by forming a coating film made of an inorganic metal compound film-forming composition and heating the coating film, the method comprising:
configuring the inorganic metal compound film-forming composition to contain inorganic metal compound particles, a dispersant, and a solvent,
The size of the inorganic metal compound particles is 50 nm or less,
The inorganic metal compound contained in the inorganic metal compound particles is at least one selected from the group consisting of metal nitrides, metal carbides, and metal borides,
In the solid content of the inorganic metal compound film-forming composition, the ratio of the mass of the inorganic component to the total mass of the inorganic component and the organic component is 25% by mass or more.