JP4603818B2 - Film-forming coating solution, insulating film obtained using the coating solution, and electronic device having the same - Google Patents

Description

  The present invention relates to a coating liquid for forming an insulating film, and more particularly relates to a material for forming an insulating film having good dielectric constant, heat resistance, and mechanical strength for use in electronic devices, and further, an insulating film obtained using the coating liquid. The present invention relates to an electronic device.

In recent years, in the field of electronic materials, with the progress of higher integration, more functions, and higher performance, circuit resistance and capacitor capacity between wirings have increased, leading to an increase in power consumption and delay time. In particular, an increase in delay time is a major factor in reducing the signal speed of the device and the occurrence of crosstalk. Therefore, in order to reduce the delay time and speed up the device, it is necessary to reduce parasitic resistance and parasitic capacitance. It has been.
As a specific measure for reducing this parasitic capacitance, an attempt has been made to cover the periphery of the wiring with a low dielectric interlayer insulating film.
In addition, the interlayer insulating film is required to have excellent heat resistance that can withstand subsequent steps such as a thin film formation process, chip connection, and pinning during manufacturing of a mounting substrate, and chemical resistance that can withstand a wet process. Furthermore, in recent years, low resistance Cu wiring is being introduced from Al wiring, and along with this, planarization by CMP (Chemical Mechanical Polishing) has become common, and high mechanical strength that can withstand this process is high. It has been demanded.

As such an interlayer insulating film, polyimide and polybenzoxazole are widely known (Patent Document 1). These polymers can be synthesized by dehydration condensation from amine derivatives and phthalic acid derivatives, or dehydration condensation from orthoaminophenol derivatives and carboxylic acid derivatives. However, since these contain a highly polar imide group or oxazole group, they are not sufficiently satisfactory in terms of low dielectric properties, low water absorption, durability, and hydrolysis resistance.
As another interlayer insulating film, thermosetting benzocyclobutene, which is a hydrocarbon polymer, is known (Patent Document 2). This polymer can be synthesized by a cycloaddition reaction of a diene derivative and an ethylene derivative. However, this polymer still has a problem that the heat resistance is not sufficiently high.

JP 2001-279174 A US Pat. No. 4,812,588

  The present invention provides a film-forming coating solution that solves the above problems, an insulating film with good dielectric constant, mechanical strength, and the like, and an electronic device using the same.

It has been found that the above problems are solved by the following <1> to < 5 > configurations.
<1> A coating solution for film formation containing a compound having at least one group obtained by removing one hydrogen atom from a benzyne precursor represented by the following formula (I) .

In formula (I), R ^{1 to} R ¹⁰ each independently represents a hydrogen atom or a substituent.
<2> 1) A step of dissolving, in a solvent, at least a compound having at least one group obtained by removing one hydrogen atom from the benzyne precursor represented by the above formula (I),
2) the step of filtering the solution prepared in 1) with a 0.1 micron filter,
The manufacturing method of the coating liquid for film formation as described in said <1>.
<3> An insulating film obtained by applying the film-forming coating solution according to the above <1> to a substrate and performing a heat treatment.
<4> An electronic device having the insulating film according to <3>.
<5> A method for producing an insulating film by applying the film-forming coating solution according to the above <1> to a substrate and performing a heat treatment.

  Since the coating film formed with the coating liquid for film formation of the present invention is excellent in dielectric constant characteristics and mechanical strength, it can be used as an interlayer insulating film in electronic devices and the like.

Hereinafter, the coating liquid for forming a film of the present invention, an insulating film obtained by using the coating liquid, an electronic device having the same, and a method for manufacturing the insulating film will be described in detail.
The coating solution for film formation of the present invention contains a compound having at least one group obtained by removing one hydrogen atom from the benzyne precursor represented by the formula (I). Other items are also included for reference.
(Benzene precursor)
In the present invention, the benzyne precursor refers to a compound that undergoes a chemical reaction under heating conditions to generate benzyne. Here, the heating condition is a desired heating temperature for film formation as long as benzyne is generated, and is generally 100 to 500 ° C.
The benzyne precursor is not particularly limited. For example, indantrione, phthalic anhydride, o-sulfobenzoic anhydride, 1,2,4-benzotriazine, 1,2,3-benzotriazine, 1H-2,3- Examples thereof include benzoxazin-1-one, 1H-2,4-benzoxazin-1-one, indazolidone, and indazolone-diene adduct.

  In the present invention, a more preferred benzyne precursor is a compound of the following formula (I).

In formula (I), R ^{1 to} R ¹⁰ each independently represents a hydrogen atom or a substituent. The substituent may be any as long as it does not adversely affect various performances required for the insulating film.
Preferable examples of the substituent as R ^{1 to} R ¹⁰ include a halogen atom (fluorine atom, chloro atom, bromine atom, or iodine atom), a linear, branched, cyclic, polyhedral alkyl group having 1 to 20 carbon atoms ( Methyl, t-butyl, cyclohexyl, adamantyl, etc.), C2-C20 alkenyl groups (vinyl, propenyl, etc.), C2-C20 alkynyl groups (ethynyl, phenylethynyl, etc.), C6-C30 aryl Groups (phenyl, 1-naphthyl, 2-naphthyl, etc.), C2-C20 acyl groups (benzoyl, etc.), C6-C30 aryloxy groups (phenoxy, etc.), C6-C30 arylsulfonyl groups (Such as phenylsulfonyl), nitro group, cyano group, silyl group having 1 to 30 carbon atoms (triethoxysilyl, methyldiethoxysilyl, phenyldi) Toxisilyl, etc.), a C1-C30 heterocyclic group (regarding the position of substitution), a C2-C30 alkoxycarbonyl group, a C1-C30 carbamoyl group, a carboxy group or a salt thereof, an oxalyl group, A formyl group, a hydroxy group, an alkoxy group having 1 to 30 carbon atoms (including a group repeatedly containing an ethyleneoxy group or a propyleneoxy group unit), an acyloxy group having 1 to 30 carbon atoms, an amino group, and an acylamino group having 1 to 30 carbon atoms Group, sulfonamide group, ureido group, thioureido group, semicarbazide group, hydrazino group, ammonio group, hydroxyamino group, mercapto group, thio group having 1 to 30 carbon atoms (alkyl, aryl, or heterocyclic), 1 to carbon atoms 30 (alkyl or aryl) sulfonyl groups, sulfo groups or salts thereof Here, the salt means a cation such as alkali metal, alkaline earth metal or heavy metal, or an organic cation such as ammonium ion or phosphonium ion. These substituents may be further substituted with these substituents.

More preferable examples of the substituent as R ^{1 to} R ¹⁰ include a halogen atom (a fluorine atom, a chloro atom, a bromine atom, or an iodine atom), a branched, cyclic, or polyhedral alkyl group having 1 to 20 carbon atoms (t- Butyl, cyclohexyl, adamantyl, etc.), C2-C20 alkenyl groups (vinyl, propenyl, etc.), C2-C20 alkynyl groups (ethynyl, phenylethynyl, etc.), C6-C30 aryl groups (phenyl, 1-naphthyl, 2-naphthyl, etc.), C6-C30 aryloxy groups (phenoxy, etc.), C1-C30 silyl groups (triethoxysilyl, methyldiethoxysilyl, phenyldimethoxysilyl, trivinylsilyl, etc.) ), A C1-C30 heterocyclic group (regarding the position of substitution), a hydroxy group, an alkoxy group (ethylene oxy). It includes groups containing repeating groups or propyleneoxy group units), and the like (alkyl or aryl) sulfonyl group having 1 to 30 carbon atoms.

Particularly preferable examples of the substituent as R ^{1 to} R ¹⁰ include a fluorine atom, a cyclic group having 1 to 20 carbon atoms, a polyhedral alkyl group (cyclohexyl, adamantyl, etc.), and an alkenyl group having 2 to 20 carbon atoms (vinyl, propenyl). Etc.), an alkynyl group having 2 to 20 carbon atoms (such as ethynyl and phenylethynyl), an aryl group having 6 to 30 carbon atoms (such as phenyl, 1-naphthyl and 2-naphthyl), and a silyl group having 1 to 30 carbon atoms (tri) Ethoxysilyl, methyldiethoxysilyl, phenyldimethoxysilyl, trivinylsilyl, etc.), C1-C30 heterocyclic group (regarding the position of substitution), alkoxy group (including ethyleneoxy group or propyleneoxy group unit repeatedly) Group).

In formula (I), R ^{1 to} R ¹⁰ may be bonded to each other to form a 5- to 7-membered unsaturated or saturated hydrocarbon ring or heterocyclic ring. In particular, R ⁵ and R ⁹ are preferably bonded to form a 5- or 6-membered hydrocarbon ring.

In formula (I), at least one of R ^{1 to} R ¹⁰ is a hydrogen atom.

  The molecular weight of the benzyne precursor is preferably 100 to 3000, more preferably 200 to 2000, and particularly preferably 300 to 1000.

  The benzyne precursor can be synthesized by a known method. For example, the compound of the above formula (I) can be synthesized according to the method described in Journal of Chemical Society Chemical Communication, p.

(Compound having benzyne precursor group)
The film forming coating solution contains a compound that generates benzyne under heating conditions as described above, that is, a compound having at least one group (benzine precursor group) obtained by removing one hydrogen atom from a benzyne precursor. . Here, the compound having at least one benzyne precursor group may be the benzyne precursor itself. In addition, in a compound having a benzyne precursor group, the benzyne precursor group is bonded to an arbitrary position in the compound as long as benzyne is generated under heating conditions, regardless of the bond as a monovalent group. , May exist as a polyvalent group.

  The compound having a benzyne precursor group is preferably a cyclic saturated or unsaturated hydrocarbon compound having a benzyne precursor group. A linear, branched or cyclic saturated or unsaturated hetero atom compound containing at least one nitrogen atom, oxygen atom, sulfur atom or silicon atom is also preferred. Furthermore, a compound in which two or more of these are bonded to each other is also a preferred form.

The compound may be a polymer, such as benzene, naphthalene, biphenyl, anthracene, fluorene, benzophenone, diphenyl ether, diphenyl sulfone, poly (arylene ether), poly (arylene ether), poly (arylene ether-ether-ketone). , Poly (ether), polyimide, polyoxazole, polyamic acid, (meth) acrylic polymer, polyamide, polyimide-amide, polyester, polycarbonate, polyquinoxaline, polyoxadiazole, vinylamide polymer, polyalkylene oxide, methyl Silsesquioxane, and a compound in which these combinations have at least one benzyne precursor group.
When the coating liquid for film formation of the present invention is used for forming an insulating film, it is desirable to select a compound that can form a polymer network having a high glass transition temperature (Tg> 300 ° C.). Examples of such a compound include poly (arylene), poly (arylene ether), poly (ether), polyimide, polyoxazole, and polyamide.

A compound having at least two benzyne precursor groups is more preferred.
The benzyne precursor group itself may be a compound formed by bonding a plurality, especially two of them.

  The average molecular weight of the compound having a benzyne precursor group is preferably 150 to 1,000,000, more preferably 300 to 100,000, and particularly preferably 500 to 10,000.

  The compound having a benzyne precursor group of the present invention can be synthesized by a known method.

  Although the specific example of the compound which has the benzyne precursor group of this invention is shown below, it is not limited to these.

(Coating solution)
The coating liquid of the present invention is prepared by dissolving the compound having the benzyne precursor group described above in a solvent.

  Examples of the solvent include mesitylene, pyridine, triethylamine, N-methylpyrrolidinone, cyclopentanone, cyclohexanone, cycloheptanone, dibenzyl ether, diglyme, triglyme, diethylene glycol ethyl ether, diethylene glycol methyl ether, dipropylene glycol methyl ether, dipropylene. Glycol dimethyl ether, propylene glycol phenyl ether, propylene glycol methyl ether, tripropylene glycol methyl ether, polyethylene glycol, anisole, toluene, mesitylene, xylene, propylene glycol monomethyl ether acetate, orthodichlorobenzene, trichlorobenzene, propylene carbonate, diphenyl ether, gamma butyrolac Emissions, dimethylacetamide, dimethylformamide, ethyl lactate, methanol, ethanol, isopropanol, acetone, methyl ethyl ketone, ethyl acetate, butyl acetate, acetonitrile, tetrahydrofuran, acetic acid and mixtures thereof.

More preferred solvents are mesitylene, N-methylpyrrolidinone, cyclohexanone, propylene glycol monomethyl ether, polyethylene glycol, anisole, propylene glycol monomethyl ether acetate, orthodichlorobenzene, gamma butyrolactone, ethyl lactate, isopropanol, acetone, methyl ethyl ketone, butyl acetate, Particularly preferred solvents are mesitylene, cyclohexanone, propylene glycol monomethyl ether, anisole, propylene glycol monomethyl ether acetate, gamma butyrolactone, ethyl lactate, isopropanol and mixtures thereof.

The concentration of the compound having a benzyne precursor group in the coating solution is preferably 1 to 50% by mass, more preferably 2 to 30% by mass, and particularly preferably 3 to 20% by mass.
The concentration of all components other than the solvent containing the benzyne precursor group-containing compound and other components described later in the coating solution of the present invention is preferably 5 to 70% by mass, more preferably 6 to 30% by mass. And particularly preferably 8 to 20% by mass.

In addition to the compound having the benzyne precursor group of the present invention, a compound having a group capable of reacting with benzyne may be added to the coating solution of the present invention. Examples of the group capable of reacting with benzyne include an aromatic hydrocarbon group or a heteroaromatic group. The compound may have a benzyne precursor group.
Examples of the compound include a polymer having an aromatic hydrocarbon group or a heteroaromatic group or a precursor of these polymers, and more specifically, poly (arylene), poly (arylene ether), poly (arylene). Ether-ether-ketone), poly (ether), polyimide, polyoxazole, polyamic acid, (meth) acrylic polymer, polyamide, polyimide-amide, polyester, polycarbonate, polyquinoxaline, polyoxadiazole, vinylamide polymer , Polyalkylene oxide, methyl silsesquioxane and the like. When the compound is added, the mass ratio of the compound and the compound having a benzyne precursor group is preferably 98: 2 to 50:50, and more preferably 95: 5 to 80:20.

  Adhesion promoters such as those based on silane may be added to the coating solution of the present invention.

  Examples of the coating solution of the present invention include surfactants such as nonionic surfactants, anionic surfactants, cationic surfactants, and double-sided surfactants. Furthermore, fluorine-based surfactants, silicon-based surfactants, and the like can be preferably used.

  The coating solution of the present invention contains a pore forming agent (polystyrene, polyethylene glycol, polypropylene glycol, copolymers thereof, polymethyl acrylate, polyacrylamide, etc.) known in the art for the purpose of lowering the dielectric constant. It is preferable to add.

  The coating liquid of the present invention may contain other additives in order to obtain desired physical properties depending on the application. Such additives include metal-containing compounds, such as magnet particles (eg barium ferrite, iron oxide (optionally mixed with cobalt), or other metal-containing materials used in magnetic, optical or other recording media) Particles), conductive particles such as conductive sealants, conductive adhesives, conductive coatings, electromagnetic interference (EMI) / radio frequency interference (RFI) shield coatings, electrostatic dissipation, and metals or carbon for use in electrical contacts And so on.

(Application method)
A method for applying the coating liquid to the base material will be described later according to the base material.
(Coating liquid heating)
The heating timing for generating benzyne from the compound having a benzyne precursor group may be either a process of preparing a coating solution or a baking process after coating on a substrate, but it is more preferably performed after coating on a substrate. preferable.
The conditions for generating benzyne are preferably 100 ° C. to 500 ° C., more preferably 200 ° C. to 480 ° C., particularly preferably 300 ° C. to 450 ° C., preferably 10 seconds to 10 hours, more preferably 1 minute to It is preferably 2 hours, particularly preferably 10 minutes to 1 hour, during which preferably 30% or more, more preferably 50% or more, particularly preferably 80% or more of the benzyne precursor decomposes.

It is well known that the generated benzyne has a property of binding to an aryl group, a heteroaryl group, or reacting with each other.
The generated benzyne causes various reactions with a compound having a benzyne precursor group, a polymer added in addition to the compound having a benzyne precursor group, or a precursor of these polymers, and a polymer network is formed.
In the present invention, an insulating film having high heat resistance and mechanical strength can be formed by utilizing this technique.

  The heating conditions required for solvent removal or curing reaction after the coating solution of the present invention is applied to the substrate are usually 100 ° C. to 475 ° C., preferably 200 ° C. to 450 ° C., particularly preferably 300 ° C. to 450 ° C. Is 10 seconds to 10 hours, more preferably 30 seconds to 2 hours, particularly preferably 1 minute to 1 hour.

(Insulating film)
The insulating film of the present invention can be used as one or more insulating layers or dielectric layers in a single layer or multilayer electrical connection structure for an integrated circuit, a multichip module, or a flat panel display. The insulating film of the present invention can be used as a single dielectric in these applications, or with other organic polymers or inorganic dielectrics such as silicon dioxide, silicon nitride or silicon oxynitride.

The insulating film of the present invention is particularly effective as an insulating material having a low dielectric constant in a connection structure of an integrated circuit, such as one processed with gallium arsenide or silicon. Integrated circuits typically have many layers of metal conductors separated by one or more insulating materials. The insulating film of the present invention can be used as an insulator between separate metal conductors in the same layer and / or between conductors of a connection structure. It can also be used with other materials such as SiO ₂ or Si ₃ N ₄ in composite connection structures. For example, the coating solution for film formation of the present invention is taught in US Pat. Nos. 5,550,405, 5,591,677, Hayashi et al., 1996 Symposium on VLSI Technology Digest of Technical Papers, p.88-89. The present invention can be used in a method for manufacturing an integrated circuit device.

  An insulating film of the present invention is an insulating film (dielectric material) in a method used for processing an integrated circuit including an electrical connection structure including a patterned metal line and an active substrate including a transistor, at least partially separated by the insulating film. ).

  The insulating film of the present invention is also effective for planarization of materials such as silicon wafers used in semiconductors to enable the manufacture of smaller (high density) circuits. In order to achieve the desired planarization, the coating solution of the present invention is applied from the solution, for example by spin coating or spray coating, to make the roughness on the surface of the substrate uniform. This method is described in documents such as Jenekhe, SA., Polymer Processing to Thin Films for Microelectronic Applications in Polymers for High Technology, Bowden et al., American Chemical Society 1987, p.261-269.

The film-forming coating solution of the present invention can be applied on a substrate by dip coating, spray coating, extrusion coating, or preferably spin coating. In all cases, the environment surrounding the substrate and coating prior to curing needs to be properly controlled for temperature and humidity.

  The insulating film of the present invention can be used in "damascene" metalworking or subtractive metal patterning methods for processing integrated circuit connection structures. Damascoline and bias processing methods are well known in the art. See, for example, US Pat. Nos. 5,262,354 and 5,093,279.

Material patterning uses oxygen, argon, helium, carbon dioxide, fluorine-containing compounds, or mixtures of these with other gases, and photoresist “soft masks” such as epoxy novolacs, or inorganic “hard masks” such as SiO 2 _2. Reactive ion etching may be performed using a photoresist combined with Si ₃ N ₄ or metal.

  Insulating films of the present invention include Al, Al alloy, Cu, Cu alloy, gold, silver, W, and other common metal conductive materials deposited by physical vapor deposition, chemical vapor deposition, evaporation, electrodeposition, and other deposition methods. Can be used with materials (for conductive lines and plugs). Fill the base metal conductor with other metal layers, such as tantalum, titanium, tungsten, chromium, cobalt, alloys thereof, or nitrides to enhance adhesion, provide a barrier, or provide metal reflectivity It may be improved.

  Depending on the processing method, the dielectric material or metal of the present invention may be removed or planarized using a chemical-mechanical polishing method. A multichip module may be constructed with a polymer of the present invention as a dielectric material on an active or immobile substrate such as silicon, silicate glass, silicon carbide, aluminum, aluminum nitride, or FR-4.

  Flat panel displays on active or immobile substrates such as silicon, silicate glass, silicon carbide, aluminum, aluminum nitride, or FR-4 may be constructed with the polymers of the present invention as dielectric materials.

The film-forming coating solution of the present invention may be used as a protective coating on an integrated circuit chip for protection against alpha particles. Semiconductor devices are susceptible to soft errors when alpha particles emitted from small amounts of radioactive impurities in the package strike the active surface. Usually, the integrated circuit chip is placed on a substrate and fixed with a suitable adhesive. The coating of the coating solution for film formation of the present invention provides an alpha particle protective layer on the active surface of the chip. If desired, further protection may be provided, for example, by an encapsulant made of epoxy or silicone.

The layer formed by the insulating film of the present invention is Polymers for Electronic Applications, Lai,
Patterned by wet etching, plasma etching, reactive ion etching (RIE), dry etching, or optical laser ablation as described in CRCPress (1989) p.42-47. Patterning is performed by a multi-level method in which a pattern is formed by lithographic printing in a resist layer coated on the polymeric dielectric layer and then etched into the bottom layer. A particularly effective method is to mask the oligomer or polymer portion that should not be removed, remove the unmasked portion of the oligomer or polymer, and then cure the remaining oligomer or polymer, for example by heat. Including.

  Furthermore, the coating liquid for film formation of the present invention can also be used for the production of molded products, films, fibers and foams.

  The coating solution for film formation of the present invention is solution adhesion, liquid phase epitaxy, screen printing, melt spin, dip coating, spinning, brushing (such as varnish), spray coating, powder coating, plasma deposition, dispersion spray, solution Casting, slurry spray, dry powder spray, fluidized bed method, weld ring, explosion method (including Wire Explosion Spraying Method and explosion bonding), heat-applied press bonding, plasma polymerization, dispersion in dispersion medium, then dispersion Media removal, pressure bonding, pressurized heat bonding, gas environment vulcanization, extrusion melt polymer, hot gas welding, baking, coating and thin It can be applied to various substrates by a number of methods, such as a ring. A single layer and multilayer film can also be attached to the substrate at the air-water interface or other interfaces using the Langmuir Blodget process.

  The base material to be coated with the coating liquid for film formation of the present invention may be any material as long as it has sufficient integrity to be coated. Examples of substrates are wood, metal, ceramics, glass, other polymers, paper, cardboard, woven fabric, nonwoven mat, synthetic fiber, Kevlar ™, carbon fiber, gallium arsenide, silicon and other inorganic substrates And these oxides. The substrate used is selected based on the desired application. Examples include glass fibers (woven fabrics, non-woven fabrics or strands), ceramics, metals such as aluminum, magnesium, titanium, copper, chromium, gold, silver, tungsten, stainless steel, Hastalloy (TM), carbon steel, other metals Alloys and their oxides as well as thermosetting and thermoplastic polymers such as epoxy resins, polyimides, perfluorocyclobutane polymers, benzocyclobutane polymers, polystyrene, polyamides, polycarbonates, polyarylene ethers and polyesters. These substrates may be cured polymers of the present invention.

  The substrate can have any shape, and this shape depends on the end use. For example, the substrate can be a disk, plate, wire, tube, plate, sphere, rod, pipe, cylinder, lump, fiber, woven or non-woven fabric, yarn (including mixed yarn), ordered polymer, and woven or non-woven mat. The shape may be In each case, the substrate may be hollow or solid. In the case of being hollow, the polymer layer may be provided on either or both of the inside and the outside of the substrate. The substrate may include porous layers such as graphite mats or fabrics, glass mats or fabrics, scrims, and particulate materials.

Insulating films of the present invention can be made of many materials, such as compatible polymers, polymers with common solvents, metals, especially surface textured metals, silicon, silicon dioxide, especially etched silicon and silicon dioxide, glass, silicon nitride, nitriding Adheres directly to aluminum, alumina, gallium arsenide, quartz, and ceramics.
However, if high adhesion is desired, the material to be bonded may be pretreated with an adhesion promoter in order to improve the adhesion in advance.

Such adhesion promoters include, for example, silanes, preferably organosilanes such as trimethoxyvinylsilane, triethoxyvinylsilane, hexamethyldisilazane [(CH ₃ ) ₃ —Si—NH—Si (CH ₃ ) ₃ ], or aminosilane coupling agent, for example, γ- aminopropyltriethoxysilane, or chelates such as aluminum monoethylacetoacetate diisopropylate [(iso _{C 3 H 7 O) 2 Al} (OCOC 2 H 5 CHCOCH 3)] be exemplified Can do.
This adhesion promoter is applied in a 0.01% to 5% by weight solution, excess solution is removed, and then a film-forming coating solution is applied.

Also spread a chelate toluene solution on the substrate, then baked the coated substrate in oxygen at 350 ° C. for 30 minutes to form a very thin (eg 5 nanometer) adhesion promoting layer of aluminum oxide on the surface. It is also possible to mix a chelate of aluminum monoethyl acetoacetate diisopropylate on the substrate. Other means of depositing aluminum oxide are equally suitable.

  The insulating films of the present invention are environmentally protective (ie, manufactured, stored) such as metals, semiconductors, capacitors, inductors, conductors, solar cells, glass, glass fibers, quartz, and coatings that immobilize surfaces on quartz fibers. And protection against at least one substance in the environment including use conditions).

  The following examples illustrate the invention and are not intended to limit its scope. In this example, parts and percentages are by weight unless otherwise indicated.

<Example 1>
1.0 g of the compound (B-1) and 10.0 g of (P-1) described below were dissolved in a mixed solution of 50 ml of cyclohexanone and 20 ml of N-methylpyrrolidinone. This solution was filtered through a 0.1 micron tetrafluoroethylene filter and then spin-coated on a silicon wafer to form a coating film having a thickness of 1 micron. This coating film was heated on a hot plate at 150 ° C. for 60 seconds under a nitrogen stream, and further heated on a hot plate at 250 ° C. for 90 seconds. Further, this silicon wafer was put in an oven purged with nitrogen and heated at 420 ° C. for 1 hour to prepare a cured coating film. The obtained insulating film had excellent dielectric properties, such as a relative dielectric constant of 2.6 and a Young's modulus of 5.5 GPa.

<Example 2>
1.0 g of the compound (B-9) described below was dissolved in 7 ml of cyclohexanone. This solution was filtered through a 0.1 micron tetrafluoroethylene filter and then spin-coated on a silicon wafer to form a coating film having a thickness of 1 micron. This coating film was heated on a hot plate at 150 ° C. for 60 seconds under a nitrogen stream, and further heated on a hot plate at 250 ° C. for 90 seconds. Further, this silicon wafer was placed in an oven purged with nitrogen and heated at 430 ° C. for 1 hour to prepare a cured coating film. The insulating film thus obtained had excellent dielectric properties, such as a relative dielectric constant of 2.6 and a Young's modulus of 5.8 GPa.

<Comparative Example 1>
In Example 1, an insulating film was formed by the same method except that the compound (B-1) was not added. The obtained dielectric film had a relative dielectric constant of 2.6 and a Young's modulus of 2.0 GPa, and the mechanical strength was lower than that of the insulating film of the present invention.

(Evaluation methods)
<Dielectric constant>
It calculated from the capacity | capacitance value in 1 MHz using the HP4285A LCR meter made from the mercury prober made from For Dimension, and Yokogawa Hewlett-Packard Co., Ltd. <Young's modulus>
Measurement was performed using a nanoindenter SA2 manufactured by MTS.

Claims (5)

A film-forming coating solution containing a compound having at least one group obtained by removing one hydrogen atom from a benzyne precursor represented by the following formula (I) .

In formula (I), R ^{1 to} R ¹⁰ each independently represents a hydrogen atom or a substituent.   1) A step of dissolving in a solvent at least a compound having at least one group obtained by removing one hydrogen atom from a benzyne precursor represented by the following formula (I):
  2) Filtering the solution prepared in 1) with a 0.1 micron filter,
The manufacturing method of the coating liquid for film formation of Claim 1 consisting of these.

In formula (I), R ¹ ~ R ^Ten Each independently represents a hydrogen atom or a substituent. The insulating film obtained by apply | coating the coating liquid for film formation of Claim 1 to a board | substrate, and heat-processing. Electronic device having absolute Enmaku of claim 3. A method for producing an insulating film by applying the film-forming coating solution according to claim 1 to a substrate and performing a heat treatment.