JP2013147537A - Polymer, film-forming composition, insulating film, semiconductor device and method for producing polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymer and a composition which are useful to form an insulating film having a combination of low dielectric constant, high glass transition temperature and high elastic modulus, and to provide an insulating film obtained therefrom, and an electronic device having the film.SOLUTION: A polymer is obtained by polymerizing a polymerizable compound having a partial structure including an adamantane-type polyhedral structure and a polymerizable reactive group contributing to polymerization reaction in a molecule. The polymer has a molecular form parameter α value, which is the power of molecular weight determined using the Mark-Houwink-Sakurada equation, of 0.1 or more and 0.5 or less. A film-forming composition including the polymer, and an insulating film formed using the film-forming composition are also provided.

Description

  The present invention relates to a polymer, a film-forming composition, an insulating film, a semiconductor device, and a method for producing the polymer.

  In recent years, in the field of electronic materials, as the integration, speed, and performance of semiconductor devices increase, the delay time due to the increase in inter-wire resistance and the increase in electric capacity of semiconductor integrated circuits has become a big problem. Yes. In order to reduce the delay time and increase the speed of the semiconductor device, it is necessary to use an insulating film having a low dielectric constant for the circuit.

  In order to reduce the dielectric constant of the insulating film, methods such as reducing the polarity of the material or reducing the density of the insulating film are mainly studied. For example, in order to reduce the polarity, it is known to use a material that does not contain a highly polar element such as nitrogen (see, for example, Patent Document 1). In order to reduce the density, it is known to introduce a bulky structure having a space in a molecule such as adamantane (see, for example, Patent Document 2). In addition, it is known that a compound having a three-dimensional structure and a compound having a two-dimensional structure are polymerized to form molecular-level pores (see, for example, Patent Document 3). Furthermore, it is known to make a film porous by using a pore forming agent (for example, see Patent Document 1). It is also known to form a porous film by forming a film using a composition containing fine particles (see, for example, Patent Document 4).

  However, the material formed by making the film porous with a pore-forming agent shows a value of 2.2 or less as the dielectric constant of the single film, but has low mechanical strength, In particular, metal and various chemicals are likely to permeate, which is a serious problem in the reliability of semiconductor devices. In addition, a material having a structure such as adamantane in order to reduce the density without using a pore forming agent, or a material that does not contain an element such as nitrogen having a high polarity has a dielectric constant of 2.3. However, the dielectric constant of 2.3 or less required in the semiconductor field has not been realized. As another example, a material in which two (or more) compounds described above are polymerized to form molecular-level vacancies has a dielectric constant of 2.3 or less. Since the polymerization reaction is based on an acid-base reaction or the like, the storage stability of the resulting material is poor, and the degree of progress and uniformity of the reaction vary depending on the reaction conditions (film formation conditions). There is a problem that it is difficult to develop stable film characteristics. Furthermore, the one that forms a composition containing particles of several nanometers to form a porous low dielectric constant film is the same as that made porous with a pore-forming agent in terms of nanostructure. Furthermore, since the composition (coating solution) is a dispersion of fine particles, solids are likely to precipitate due to aggregation of the fine particles, and the storage stability is poor.

JP 2006-265513 A JP-A-11-214382 JP 2001-332543 A JP 2007-77289 A

  Under such circumstances, the present invention provides a polymer and a composition useful for forming an insulating film having a low dielectric constant, a high glass transition temperature and a high elastic modulus, and an insulating film obtained therefrom and the same. It is an object of the present invention to provide an electronic device.

Such an object is achieved by the present invention described in the following items (1) to (18).
(1) A polymer obtained by polymerizing a polymerizable compound having in its molecule a partial structure containing an adamantane-type cage structure and a polymerizable reactive group that contributes to the polymerization reaction, and the Mark-Houwink A polymer having a molecular form parameter α value of 0.1 or more and 0.5 or less, which is a power of a molecular weight determined using the Sakurada formula.

(2) The polymer according to item (1), wherein a molecular form parameter α value which is a power number of the polymer is 0.1 or more and 0.4 or less.

(3) The polymer according to (1) or (2), wherein the polymer has a weight average molecular weight of 15,000 or more and 200,000 or less.

(4) The polymerizable reactive group of the polymerizable compound has an aromatic ring and an ethynyl group or a vinyl group directly bonded to the aromatic ring,
In the polymerizable compound, the number of carbons derived from the aromatic ring is 15% or more and 38% or less with respect to the number of carbons in the entire polymerizable compound. (3) The polymer according to any one of items.

(5) The polymer according to item (4), wherein the aromatic ring is directly bonded to the cage structure.

(6) The polymerizable reactive group has two ethynyl groups or vinyl groups, and the one ethynyl group or the vinyl group is present at the meta position of the other ethynyl group or the vinyl group. The polymer according to item (4) or (5).

(7) The polymer according to item (6), wherein each of the two ethynyl groups or the vinyl group is present at a meta position of a site where the aromatic ring is bonded to the cage structure.

(8) The polymer according to any one of (1) to (7), wherein the partial structure has an adamantane structure.

(9) The polymer according to item (8), wherein the adamantane structure has a methyl group as a substituent.

(10) The polymer according to item (9), wherein the polymerizable compound has a structure represented by the following formula (1) or (2).

［式中、ｎは１〜５の整数を表す。］

[Wherein n represents an integer of 1 to 5. ]

(11) The polymer according to any one of (1) to (7), wherein the partial structure has a diamantane structure.

(12) A film-forming composition comprising the polymer described in any one of (1) to (11).

(13) The film-forming composition according to item (12), which does not contain a pore-forming material having a function of forming pores in the film by thermal decomposition during film formation.

(14) An insulating film formed using the film forming composition described in item (12) or (13).

(15) The insulating film according to item (14), wherein the dielectric constant is 1.80 or more and 2.30 or less.

(16) The insulating film according to (14) or (15), wherein the dielectric constant has a rate of change of 3% or less after heat treatment at 400 ° C. for 1 hour in a nitrogen atmosphere.

(17) A semiconductor device comprising the insulating film according to any one of items (14) to (16).

(18) Suspension polymerization or emulsion polymerization using a polymerizable compound having a partial structure including an adamantane cage structure and a polymerizable reactive group contributing to the polymerization reaction and water as essential components in the molecule. The method for producing a polymer according to any one of items (1) to (11), wherein:

  According to the present invention, an insulating film having a low dielectric constant, a high glass transition temperature, and a high elastic modulus can be formed. In addition, a highly reliable semiconductor device including the insulating film can be provided.

It is a longitudinal cross-sectional view which shows an example of the method of forming the interlayer insulation film patterned by the predetermined shape. It is a longitudinal cross-sectional view which shows typically an example of the semiconductor device of this invention.

  Hereinafter, the present invention will be described in detail.

<Polymer>
The polymer of the present invention is obtained by polymerizing a polymerizable compound having a partial structure containing an adamantane-type cage structure and a polymerizable reactive group contributing to the polymerization reaction in the molecule. Mark-Houwink- It is characterized by having a molecular form parameter α value of 0.1 or more and 0.5 or less, which is a power of the molecular weight determined using the Sakurada equation. As a result, the polymer of the present invention has a more nearly spherical molecular form in the solution from the value of the molecular form parameter α, and thus is formed using the film-forming composition containing the polymer of the present invention. The insulating film has a film structure in which a polymer structure having a molecular shape close to a spherical shape is arranged, and uniform voids are generated between the molecules, and has a low dielectric constant, a high glass transition temperature, and a high elastic modulus. These characteristics have a low rate of change even when heat treatment is repeated.

  In the present invention, the polymer has a molecular form parameter α value that is a power of the molecular weight determined using the Mark-Houwink-Sakurada equation, and is 0.1 or more and 0.5 or less. .4 or less is preferable.

Here, in the following Mark-Houwink-Sakurada formula, the power α of the molecular weight is a power of the absolute molecular weight M between the intrinsic viscosity [η] of the polymer solution and the absolute molecular weight M.
[η] = KM ^α
K and α in the above formula are constants determined by the type of polymer, the type of solvent, and the temperature. If the molecular form of the polymer chain in the solution is close to a sphere, α will be close to 0 and close to a rod shape. For example, α is a value larger than 1.

  As an example of a method for measuring the molecular shape parameter α value, first, a 0.1% by mass solution of the polymer is prepared using tetrahydrofuran (THF) as a solvent. Next, for the polymer solution, the absolute molecular weight and intrinsic viscosity of the polymer are measured using high-performance liquid chromatography and a low-angle light scattering detector at a temperature (column hot bath) of 40 ° C. From the absolute molecular weight and intrinsic viscosity obtained here, the value of the slope obtained by plotting the relationship between the absolute molecular weight and the logarithm of intrinsic viscosity can be calculated as the α value.

  The polymer of the present invention preferably has a polystyrene-reduced weight average molecular weight of 15,000 or more and 200,000 or less as measured by gel permeation chromatography (GPC). Although it can be used outside the above range, the polymer is highly soluble in an organic solvent, has a good appearance, and has excellent heat resistance.

  Hereinafter, the polymerizable compound and the film-forming composition containing the polymer from which the polymer of the present invention can be obtained will be described in detail.

Hereinafter, the polymerizable compound will be described first.
[1] Polymerizable compound As the polymerizable compound having a partial structure A including an adamantane-type cage structure and a polymerizable reactive group B contributing to the polymerization reaction in the molecule, the following partial structure is used. Examples thereof include those having A and a polymerizable reactive group B. The polymerizable compound preferably has an aromatic ring in which the polymerizable reactive group B is directly bonded to the partial structure A and an ethynyl group or a vinyl group directly bonded to the aromatic ring. Those having a structure in which the number is 15% or more and 38% or less with respect to the total number of carbon atoms of the compound having the cage structure are more preferable.

[1.1] Partial structure A
The partial structure A possessed by the compound having a cage structure includes an adamantane cage structure. Thereby, the film formed using the film-forming composition containing the polymer obtained by the present invention can have a low density, and the dielectric constant of the formed film can be reduced. it can. Moreover, since the reactivity of a polymeric compound provided with the polymeric reactive group B which is explained in full detail later can be made appropriate, film | membrane formation on the member (for example, semiconductor substrate) which should form a film | membrane When the composition for application is applied, the viscosity of the film-forming composition is surely suitable, and the strength of the finally formed film can be made excellent.

Here, as the partial structure A, for example, adamantane, polyadamantane (eg, biadamantane, triadamantane, tetraadamantane, heptaadamantane, hexaadamantane, etc.), polyamantane (eg, diamantane, triamantane, tetramantane, pentamantane, hexaxane) A divalent group (part excluding two hydrogen atoms constituting the partial structure) such as a partial structure obtained by substituting at least a part of hydrogen atoms constituting these partial structures with an alkyl group or a halogen atom. Structure having two or more of these divalent groups (for example, a structure in which a plurality of diamantane skeletons such as a bi (diamantane) skeleton, a tri (diamantane) skeleton, and a tetra (diamantane) skeleton are linked (poly ( (Diamantane) having a skeleton); A structure in which a plurality of triamantane skeletons such as a (triamantane) skeleton, a tri (triamantane) skeleton, and a tetra (triamantane) skeleton are connected (having a poly (triamantane) skeleton); an adamantane skeleton (or a polyadamantane skeleton) And a polyamantane skeleton, etc.). Hereinafter, a part of the example of the partial structure A is shown by a chemical structural formula, but the partial structure A is not limited to these. However, in the following formulas (C-1) to (C-7), the substituents R ¹ and R ² each independently represent a hydrogen atom, an alkyl group, or a halogen group, and l, m, and n are each Independently represents an integer of 1 or more.

  The adamantane structure preferably has a methyl group as a substituent. Thereby, the solubility to an organic solvent can be improved.

  In particular, the partial structure A preferably has a structure represented by the following formula (1).

［式中、ｎは１〜５の整数を表す。］

[Wherein n represents an integer of 1 to 5. ]

  The partial structure A may have a diamantane structure. By using these partial structures A, the dielectric constant of the film formed using the film forming composition can be made particularly low. Moreover, when the reactivity of a polymeric compound can be made more suitable and it provides the film forming composition on the member (for example, semiconductor substrate) which should form a film | membrane, the said film forming composition The viscosity of the product can be made more suitable and the strength of the finally formed film can be made particularly excellent.

[1.1] Polymerizable reactive group B
The compound having a cage structure used in the present invention has a polymerizable reactive group B that contributes to the polymerization reaction in addition to the partial structure A as described above. The polymerizable reactive group B is not limited as long as it has a polymerizable functional group as a reactive group. For example, the polymerizable reactive group B has a carbon-carbon double bond or a carbon-carbon triple bond. Examples include groups having a carbon-carbon unsaturated bond polymerizable functional group such as a group, maleimide group, nadiimide group, biphenylene group, cyanato group, and cyclopentadienyl group, and have high reactivity and higher heat resistance. In view of the above, a group having a carbon-carbon unsaturated bond, such as a group having a carbon-carbon double bond, a group having a carbon-carbon triple bond, a group having both a carbon-carbon double bond and a carbon-carbon triple bond, preferable.

  The group having a carbon-carbon double bond is preferably a group having a vinyl group, and may be an alkenyl group other than a vinyl group. Specific examples of such alkenyl groups include linear aliphatic substitution such as unsubstituted alkenyl groups such as 1,3-butadienyl group, 1-propenyl group, 1-butenyl group, 1-hexenyl group and 1-decenyl group. Cycloaliphatic substituted alkenyl groups such as alkenyl groups, 2-cyclohexylvinyl groups and 2- (bicyclo [2,2,1] heptyl) vinyl groups and styryl groups, 2-tolylvinyl groups, 2-xylylvinyl groups, 2-naphthylvinyls. Groups, aromatic substituted alkenyl groups such as 2-anthracenyl vinyl group, and the like, but are not limited thereto. The group having a carbon-carbon triple bond is preferably an ethynyl group, and may be an alkynyl group other than an ethynyl group. Specific examples of such alkynyl groups include chain aliphatic substitution such as unsubstituted alkenyl groups such as 1,3-butadiynyl group, 1-propynyl group, 1-butynyl group, 1-hexynyl group and 1-decynyl group. Cycloaliphatic substituted alkynyl groups and aromatic substituted alkynyl groups such as alkynyl group, 2-cyclohexylethynyl group and 2- (bicyclo [2,2,1] heptyl) ethynyl group, 2-tolylethynyl group, 2-xylylethynyl Groups, aromatic substituted alkynyl groups such as 2-naphthylethynyl group and 2-anthracenylethynyl group, but are not limited thereto.

  When the polymerizable compound has such a polymerizable reactive group B, the reactivity of the polymerizable compound can be made appropriate, and a film on a member (for example, a semiconductor substrate) on which a film is to be formed. When the forming composition is applied, the viscosity of the film forming composition is surely suitable and the strength of the finally formed film can be made excellent.

  As the polymerizable reactive group B, one having an aromatic ring in the polymerizable reactive group can be used, and examples of such an aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, a naphthacene ring, a phenanthrene ring, Hydrocarbon aromatic rings such as chrysene ring, pyrene ring, perylene ring, coronene ring, biphenyl ring, terphenyl ring and azulene ring, pyridine ring, furan ring, thiophene ring, pyrrole ring, oxazole ring, indole ring, purine And heterocyclic aromatic rings such as a ring, benzofuran ring, benzothiophene ring, carbazole ring, imidazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, quinoline ring, and terthienyl ring. Of these, a benzene ring is preferred as the aromatic ring. Thereby, application | coating of the composition for film formation on the member (for example, semiconductor substrate) which should form a film | membrane can be performed more easily. Also, the elastic modulus of the film formed using the film forming composition can be made suitable, and the strength of the formed film, the adhesion to the member (semiconductor substrate, etc.), etc. are particularly excellent. Can be.

  Moreover, in a polymeric compound, what has a structure whose carbon number derived from the said aromatic ring is 15% or more and 38% or less with respect to the carbon number of the whole compound which has the said cage structure is preferable. Thereby, the reactivity of the compound having a cage structure can be made more suitable, and when the film forming composition is applied onto a member (for example, a semiconductor substrate) on which the film is to be formed, the film The viscosity of the composition for forming can be made more suitable and the strength of the finally formed film can be made particularly excellent.

  The aromatic ring constituting the polymerizable reactive group B may be bonded to the cage structure constituting the partial structure A via at least one other atom, but the cage structure constituting the partial structure A It is preferable that it is directly bonded to. Thereby, the reactivity of the compound having a cage structure can be made more suitable, and when the film forming composition is applied onto a member (for example, a semiconductor substrate) on which the film is to be formed, the film The viscosity of the composition for forming can be made more suitable and the strength of the finally formed film can be made particularly excellent.

  As described above, the polymerizable reactive group B constituting the polymerizable compound preferably has an ethynyl group or a vinyl group directly bonded to the aromatic ring. In the polymerizable reactive group B, the vinyl group on the aromatic ring is More preferably, it has two ethynyl groups or vinyl groups, and the one ethynyl group or the vinyl group is present at the meta position of the other ethynyl group or the vinyl group. Thereby, in the state in which one ethynyl group or vinyl group of the two ethynyl groups or vinyl groups of the polymerizable reactive group B has reacted (polymerization reaction), the electronic effect of the aromatic ring or the like is more prominently exhibited. , The reactivity of the other ethynyl group or vinyl group can be reduced more effectively, and the reacted site becomes an appropriate steric hindrance, and the other ethynyl group or vinyl group (unreacted ethynyl group or The reactivity of the vinyl group can be controlled more suitably. As a result, the selectivity of the reactivity with respect to the two ethynyl groups or vinyl groups of the polymerizable reactive group B can be increased, and the firing step for forming the film can be performed under more suitable conditions ( The film can be formed under conditions capable of forming a film with excellent productivity while preventing damage to the semiconductor substrate.

  Moreover, it is preferable that the two ethynyl groups or vinyl groups that the polymerizable reactive group B may have are both present at the meta position of the site where the aromatic ring is bonded to the cage structure. Thereby, in the state in which one ethynyl group or vinyl group of two ethynyl groups or vinyl groups that the polymerizable reactive group B may have reacted (polymerization reaction), an electronic effect such as an aromatic ring is obtained. It is exhibited more remarkably, and the reactivity of the other vinyl group can be reduced more effectively, and the reacted site and the partial structure A described above become an appropriate steric hindrance, and the other ethynyl group Alternatively, the reactivity of the vinyl group (unreacted ethynyl group or vinyl group) can be controlled more suitably. As a result, the selectivity of the reactivity with respect to the two ethynyl groups or vinyl groups of the polymerizable reactive group B can be increased, and the baking step for forming the film can be performed under more suitable conditions (semiconductor substrate). Under the condition that a film can be formed with excellent productivity while preventing damage to the substrate.

  Examples of the compound having a cage structure that satisfies the above conditions include those having a structure represented by the following formula (1) or (2).

［式中、ｎは１〜５の整数を表す。］

[Wherein n represents an integer of 1 to 5. ]

［式中、ｎは１〜５の整数を表す。］

[Wherein n represents an integer of 1 to 5. ]

Next, the method for producing the polymer of the present invention will be described.
The polymer of the present invention is obtained by polymerizing a polymerizable compound having a partial structure including an adamantane-type cage structure and a polymerizable reactive group contributing to the polymerization reaction in the molecule, Mark-Houwink- It has a molecular form parameter α value of 0.1 to 0.5, which is the power of the molecular weight determined using the Sakurada equation. For example, radical polymerization, thermal polymerization, suspension polymerization, emulsion polymerization, etc. as polymerization methods Among these, emulsion polymerization is preferable.

Hereinafter, specific examples of the polymerization method will be described.
In the case of using the solution polymerization, it can be suitably prepared by subjecting the polymerizable compound to a heat treatment, a light irradiation treatment or the like in a state where the polymerizable compound is dissolved in a solvent. In this case, as the treatment conditions, for example, a method of thermal polymerization in which the reaction is performed without using a catalyst, a radical initiator such as benzoyl peroxide, t-butyl peroxide, azobisisobutyronitrile, or the like is used. Radical polymerization method, photo radical polymerization method using light irradiation, etc., dichlorobis (triphenylphosphine) palladium (II), bis (benzonitrile) palladium (II) dichloride and tetrakis (triphenylphosphine) palladium (0 ), A method using polymerization using a palladium catalyst, a method using polymerization using a transition metal catalyst such as copper (II) acetate, transition metals such as molybdenum chloride (V), tungsten chloride (VI) and tantalum chloride (V) Examples thereof include a method by polymerization using a chloride. Among these, since a desired polymer can be easily obtained by controlling the reaction, and impurities need not be removed by remaining a metal catalyst or the like, a method by thermal polymerization or radical polymerization using a radical initiator is desirable.

  When preparing by the thermal polymerization method, the heat treatment conditions are preferably heating temperature: 120 to 190 ° C., heating time: 3 to 11 hours, heating temperature: 140 to 180 ° C., heating time: 3 to 3 hours. More preferably, it is 9 hours. When a radical initiator is used, the heat treatment conditions are preferably heating temperature: 40 to 190 ° C., heating time: 0.5 to 11 hours, heating temperature: 60 to 180 ° C., heating time: 0. More preferably, 5 to 9 hours. The heat treatment may be performed by combining different conditions. For example, in thermal polymerization, the first heat treatment performed under the conditions of heating temperature: 150 to 190 ° C., heating time: 1 to 6 hours, and heating temperature: 120 to 160 ° C., heating time: 2 to 9 hours. A second heat treatment to be performed or a multistage heat treatment can be appropriately selected. Even in the case of using a radical initiator, for example, a first heat treatment performed under the conditions of heating temperature: 60 to 190 ° C., heating time: 0.5 to 6 hours, heating temperature: 40 to 160 ° C., heating time: A second heat treatment performed under a condition of 0.5 to 9 hours or a multistage heat treatment can be appropriately selected. In addition, it is preferable to perform the above heat processing in the state which melt | dissolved the polymeric compound in the solvent. Further, the synthesis of the polymer by the heat treatment as described above may be performed in a solvent as a constituent of the film-forming composition to be prepared, and what is a constituent of the film-forming composition? You may perform in the solvent of a different composition. That is, after a polymerizable compound containing compound C is polymerized using a predetermined solvent to obtain a polymer, the solvent may be replaced with a solvent as a constituent of the target film-forming composition.

  Examples of the solvent (reaction solvent) that can be used for the synthesis of the polymer of the present invention include alcohol solvents such as methanol, ethanol, isopropanol, 1-butanol, and 2-butanol; acetone, acetylacetone, methyl ethyl ketone, and methyl isobutyl ketone. Ketone solvents such as cyclohexanone, cyclopentanone, 2-pentanone and 2-heptanone; ester solvents such as ethyl acetate, propyl acetate, butyl acetate, pentyl acetate and propylene glycol monomethyl ether acetate; diisopropyl ether, dibutyl ether, diphenyl ether Ether solvents such as tetrahydrofuran, anisole, 1,2-dimethoxybenzene, 1,3-dimethoxybenzene, 1,4-dimethoxybenzene; benzene, toluene, mesithi Aromatic and aliphatic hydrocarbon solvents such as ethylene, ethylbenzene, diethylbenzene, propylbenzene, heptane, hexane and n-octane; halide solvents such as chloromethane, dichloromethane, chloroform, dichloroethane and carbon tetrachloride; N-methyl Examples include amide solvents such as pyrrolidone, and one or more selected from these may be used in combination.

  In addition, about the film formation composition containing the polymer of this invention, the unreacted polymerizable compound is removed by refinement | purification (an unreacted polymerizable compound is not contained as much as possible), and the molecular form parameter alpha value is A polymer of 0.1 or more and 0.5 or less may be obtained. This increases the dielectric constant of the film caused by physical and chemical influences by setting the molecular shape parameter α value of the polymer of the present invention within the range of 0.1 to 0.5. The structure of the insulating film formed by using the film-forming composition containing the polymer becomes a film structure in which polymer structures having molecular shapes having a nearly spherical shape are arranged, and uniform voids are generated between the molecules. It has a low dielectric constant, a high glass transition temperature, and a high elastic modulus, and these characteristics do not change even when heat treatment is repeated.

Further, as a preferred polymerization method of the polymer of the present invention, when suspension polymerization is used, a polymerizable compound or a solution obtained by dissolving the polymerizable compound in a solvent and water are essential components, and if necessary, a dispersant. Can be suitably prepared by subjecting the polymerizable compound to a heat treatment in a state of being mixed, vigorously stirred and dispersed.
In this case, as the heat treatment conditions, for example, conditions generally used by those skilled in the art such as the conditions in the radical polymerization may be adopted. As initiators, benzoyl peroxide, t-butyl peroxide, azobisiso Examples thereof include a method by radical polymerization using an oil-soluble radical initiator such as butyronitrile.

  In the case of preparing by the suspension polymerization method, the conditions for the heat treatment can be the same conditions as in the case of using the radical initiator for the polymerization by the solution polymerization method. In the polymerization reaction, when suspension polymerization is performed using a solution in which a polymerizable compound is dissolved in a solvent and water as essential components, the organic solvent to be used is one that can dissolve the polymerizable compound. Although not particularly limited, one or more organic solvents having an octanol / water partition coefficient of 3 or less are preferable. For example, examples of the organic solvent having an octanol / water partition coefficient of 3 or less include toluene, methylene chloride, chloroform, and the like. Among these, toluene can be more preferably used.

As described above, when suspension polymerization is performed using a solution in which a polymerizable compound is dissolved in a solvent and water as essential components, the organic layer separated into two layers after the polymerization is extracted, and the poor solvent is used. The polymer of the present invention is obtained by performing reprecipitation and washing, dehydrating and drying the precipitated resin.
In addition, when suspension polymerization is performed with a polymerizable compound and water without using a solvent, the polymer of the present invention can be obtained by filtering, washing, dehydrating and drying the aqueous suspension after polymerization.

  As another preferred method of polymerization, when emulsion polymerization is used, a polymerizable compound or a solution obtained by dissolving the polymerizable compound in a solvent and water as essential components, a surfactant, and optionally dispersed. Mixing with the agent, applying energy such as sonication by vigorous stirring or ultrasonic homogenizer, etc., in an emulsified state, that is, around the polymerizable compound or a solution in which the polymerizable compound is dissolved in a solvent, It can be suitably prepared by forming a bilayer film, vesicles, and micelles in which surfactants are arranged, and subjecting the polymerizable compound to heat treatment.

In addition, the heating / stirring step may be performed while applying energy such as vigorous stirring or sonication. If the step of applying energy for forming micelles is performed in the manufacturing process, The order is not particularly limited.
In this case, as the conditions for the heat treatment, for example, conditions generally used by those skilled in the art such as the conditions in the radical polymerization may be adopted, and water-soluble initiators such as potassium persulfate and hydrogen peroxide are used as initiators. Examples thereof include a method by radical polymerization using an agent and a method by radical polymerization using an oil-soluble radical initiator such as benzoyl peroxide, t-butyl peroxide, azobisisobutyronitrile, and the like.

In the polymerization reaction, when emulsion polymerization is performed using a solution in which a polymerizable compound is dissolved in a solvent and water as essential components, the organic solvent to be used is one that can dissolve the polymerizable compound. Although not particularly limited, one or more organic solvents having an octanol / water partition coefficient of 3 or less are preferable.
On the other hand, if the octanol / water partition coefficient exceeds 3, the hydrophobicity increases, and it is difficult to form a reaction field suitable for emulsion polymerization.
For example, examples of the organic solvent having an octanol / water partition coefficient of 3 or less include toluene, methylene chloride, chloroform, and the like. Among these, toluene can be more preferably used.

  The surfactant used in the present invention has a hydrophobic site and a hydrophilic site. When the surfactant is added to the reaction system under desired conditions, the surfactant has a bimolecular film due to the properties of the surfactant. , Vesicles and micelles can be formed. Among these, in order to further improve the polymerization yield, those that form micelles are preferred. Examples of micelles include micelles centered on hydrophobic sites and reverse micelles centered on hydrophilic sites. In this embodiment, a micelle structure centered on a hydrophobic site is more preferable.

  Examples of such surfactants include anionic surfactants, cationic surfactants, amphoteric surfactants, and nonionic surfactants. More specifically, examples of the anionic surfactant include alkyl aryl sulfonates, alkyl sulfates, fatty acid alkali salts, alkyl phosphates, and alkyl phosphonates. Among these, alkyl aryl sulfonates having 8 to 18 carbon atoms in the alkyl group, alkyl sulfates having 8 to 18 carbon atoms in the alkyl group, and fatty acid alkali salts having 8 to 18 carbon atoms in the alkyl group are preferable, In particular, sodium dodecyl sulfate can be preferably used. In addition, surfactants having an HLB value of 18 or more and 42 or less are preferable from the viewpoints of dispersion stabilization and micelle formation. For example, even if the surfactant is allowed to stand for 1 hour after dispersion, it remains suspended or emulsified. This is preferable from the viewpoint of manufacturing convenience. Such surfactant may be used independently and may be used in combination of 2 or more type. The cationic surfactant is not particularly limited as long as it becomes a cation when dissociated in water, and examples thereof include alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkylbenzyldimethylammonium salts, and the like. The activator is not particularly limited as long as it has both an anionic site and a cationic site in the molecule. Examples thereof include alkyldimethylamine oxide and alkylcarboxybetaine. Nonionic surfactants have a hydrophilic portion. Any non-electrolytes, that is, those having a non-ionized hydrophilic portion may be used. Examples include polyoxyethylene alkyl ethers, fatty acid sorbitan esters, alkyl polyglucosides, fatty acid diethanolamides, and alkyl monoglyceryl ethers. The Among these, an anionic surfactant is preferable, and specifically, sodium dodecyl sulfate is particularly preferable.

  The amount of the surfactant used in the present invention is preferably 4 times mol or more and 15 times mol or less with respect to the polymerizable compound from the viewpoint of stable micelle formation and the characteristics of the resin obtained by polymerization. Although the amount of the surfactant can be used even outside the above range, by setting it within this range, more stable micelles can be formed, and the yield of the polymer can be increased.

  The amount of water added is preferably 5 times by mass or more and 15 times by mass or less with respect to the surfactant from the viewpoint of stable micelle formation and the properties of the obtained resin. A water addition amount outside the above range can also be used, but by setting it within this range, stable micelles can be formed and the yield of the polymer can be increased.

  Further, as described above, the organic solvent is not particularly limited as long as it can dissolve the polymerizable compound. However, one or more kinds having an octanol / water partition coefficient of 3 or less are used for promptly proceeding the reaction. The organic solvent is preferably used at a ratio of 20 wt% to 80 wt% with respect to water. Although it can be used outside this range, by making it within this range, the reaction is further promoted and the yield is improved.

As the ultrasonic processing apparatus used in the preferred example of the present invention, any ultrasonic processing apparatus can be used as long as it can apply ultrasonic waves. For example, a known ultrasonic processing apparatus can be used. For example, any appropriate ultrasonic homogenizer, ultrasonic wave Examples include a washing machine.
Examples of ultrasonic treatment conditions include frequency and amplitude. Although there is no restriction | limiting in particular as a frequency, From a dispersibility viewpoint, Preferably it is 30 kHz or less, It can use more suitably in the range of 10 kHz or more and 30 kHz or less especially. Since the cavitation pressure also increases as the amplitude increases, it is preferable to use the amplitude within a general amplitude range of 20 μm or more and 60 μm or less.

  The polymerization reaction in the method for producing a polymer of the present invention preferably includes a step of mixing by ultrasonic treatment in emulsion polymerization using a surfactant, whereby uniform and stable micelles can be formed. As a reaction field, the polymerization proceeds and the monomers react efficiently, so that the reaction rate of the monomers is increased and the yield is improved.

  The reaction solution obtained by the method for producing a polymer of the present invention is, for example, added with sodium chloride and stirred, and then poured into a solvent such as methanol to precipitate the reaction product, and the resulting precipitate is filtered off. It can be purified by washing with a mixed solvent of ethanol and water (volume ratio 1: 1) and then drying under reduced pressure.

Hereinafter, the film forming composition containing the polymer of the present invention will be described in detail.
[1] Polymer As described above, the polymer of the present invention polymerizes a polymerizable compound having a partial structure including an adamantane cage structure in the molecule and a polymerizable reactive group contributing to the polymerization reaction. Is a polymer having a molecular form parameter α value of 0.1 or more and 0.5 or less, which is a power of the molecular weight obtained using the Mark-Houwink-Sakurada formula. The content of the polymer of the present invention in is preferably 1 wt% to 30 wt%.

[2] Solvent The film-forming composition may contain the polymer of the present invention, but usually contains a solvent that dissolves them.
Examples of the solvent include N-methyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylacetamide, dimethyl sulfoxide, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, Propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate, butyl lactate, methyl-1,3-butylene glycol acetate, 1,3-butylene glycol-3-monomethyl ether, methyl pyruvate, ethyl pyruvate, methyl-3-methoxy Propionate, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, tetrahydro Orchids, anisole, mesitylene, toluene. Can be used singly or in combination of two or more selected from these. Of these, cyclopentanone and cyclohexanone are preferable as the solvent. As a solvent which comprises the composition for film formation, the solvent (reaction solvent) etc. which were used for the synthesis | combination of a polymeric compound, the synthesis | combination of the polymer mentioned above, etc. may be included, for example.

  Although the content rate of the solvent in the composition for film formation is not specifically limited, It is preferable that it is 70 to 99 wt%.

[3] Other components The film-forming composition may contain components other than those described above. Examples of such components include a polymerizable compound having a partial structure containing an adamantane-type cage structure in the molecule and a polymerizable reactive group contributing to the polymerization reaction, a surfactant; a silane coupling agent, and the like. Coupling agents; radical initiators, catalysts such as disulfides, and the like.
The film-forming composition may contain a naphthoquinone diazide compound as a photosensitizer. Thereby, the composition for film formation can be used suitably for formation of the surface protection film which has photosensitivity.

  In the present invention, it is preferable that the film-forming composition does not contain a pore-forming material that foams due to thermal decomposability and forms pores in the formed film. Conventionally, a pore forming material has been used for the purpose of reducing the dielectric constant of the film. However, when such a pore forming material is used, the strength of the formed film is reduced, or at each part of the film. However, the film-forming composition of the present invention has a partial structure containing an adamantane cage structure in the molecule and a polymerization reaction. Since it contains a polymer having a molecular form parameter α value of 0.1 or more and 0.5 or less obtained by polymerizing a polymerizable compound having a polymerizable reactive group contributing to the In addition, the dielectric constant of the formed film can be made sufficiently low. And generation | occurrence | production of the above problems can be prevented reliably by not containing a void | hole formation material.

  The film-forming composition as described above may be used as it is for film formation, but if necessary, prior to application onto a member (for example, a semiconductor substrate) on which a film is to be formed. It may be subjected to heat treatment. As a result, the viscosity of the film-forming composition is more surely suitable, and it is possible to more effectively suppress unintentional variations in the thickness and characteristics of each part of the film to be formed. The strength of the film formed can be made particularly excellent. In addition, the film forming composition is subjected to heat treatment prior to applying the film forming composition onto the member (for example, a semiconductor substrate) on which the film is to be formed, so that the film to be formed is relatively thick. Even if it is a thing, it can form suitably. In addition, by applying a heat treatment to the film-forming composition prior to applying the film-forming composition onto a member (for example, a semiconductor substrate) on which a film is to be formed, the amount of heat applied on the member is reduced. Therefore, damage to the member due to heating can be prevented more reliably. When performing such heat treatment, the heat treatment conditions are preferably heating temperature: 120 to 190 ° C., heating time: 3 to 11 hours, heating temperature: 140 to 180 ° C., heating time: 3 to 9 hours. It is more preferable that Moreover, you may perform the above heat processing combining a different condition. For example, the 1st heat processing performed on the conditions of heating temperature: 150-190 degreeC, heating time: 1-6 hours, and the 2nd heat processing performed on the conditions of heating temperature: 120-160 degreeC and heating time: 2-9 hours And may be given. Here, a method for preventing damage due to heat treatment of the film-forming composition has been described, but the film-forming resin composition using the polymer of the present invention has a dielectric constant, even if these heat treatments are repeated. It is not easily damaged by film properties such as glass transition temperature and elastic modulus.

<Insulating film>
The insulating film of the present invention is formed using the film forming composition as described above, and the dielectric constant of the insulating film is preferably 2.40 or less, and 2.35 or less. Is more preferably 2.30 or less, and most preferably 1.80 or more and 2.30 or less. Thereby, it is possible to further increase the speed of the semiconductor device. Note that the dielectric constant of the insulating film can be obtained using, for example, an automatic mercury probe CV measuring device SSM495 manufactured by Nippon SSM Co., Ltd.

  Although the thickness of an insulating film is not specifically limited, It is preferable that it is 0.01-20 micrometers, It is more preferable that it is 0.02-10 micrometers, It is further more preferable that it is 0.03-0.7 micrometers.

  Furthermore, with respect to the method for producing an insulating film of the present invention, a specific example in the case of using the film-forming composition varnish will be described. First, the film-forming composition varnish is used as an appropriate support, such as a polyester film. An organic base material, a metal plate such as copper foil, and a base material such as a semiconductor substrate such as a silicon wafer or a ceramic substrate are applied to form a coating film. Examples of the coating method include spin coating using a spinner, spray coating using a spray coater, dipping, printing, roll coating, and the like. After that, the coating film is dried, subjected to treatment such as heating, followed by solvent removal, followed by curing by a method using heating, a method of irradiating active energy rays, a method using both of these methods, etc. An excellent organic film can be obtained. The term “curing” as used herein means that a cross-linked structure or the like is formed by the reaction of unreacted reactive groups in the polymerization reaction, or agglomeration between the polymers. It is a general term for phenomena such as an increase in action.

  FIG. 1 is a longitudinal sectional view showing an example of a method for forming an interlayer insulating film patterned in a predetermined shape. In the following description, the upper side in FIG. 1 is referred to as “upper” and the lower side is referred to as “lower”.

The insulating film of the present invention is provided, for example, with a film forming composition as described above on a member such as a semiconductor substrate, and on the other hand, a treatment such as heating or irradiation with active energy rays (firing treatment) if necessary. It is formed by applying.
By performing such a baking treatment, the remaining polymerizable group can be surely reacted, the three-dimensional crosslinking reaction is sufficient, and the formed film has sufficient heat resistance.

Examples of the method for applying the film-forming composition onto the member include a spin coating method using a spinner, a spray coating method using a spray coater, dipping, printing, and roll coating.
Prior to the firing treatment, for example, a treatment (desolvation treatment) for removing the solvent from the film-forming composition applied on the member may be performed. Such solvent removal treatment can be performed, for example, by heat treatment, reduced pressure treatment, or the like.
For example, the baking treatment is preferably performed under the conditions of treatment temperature: 200 to 450 degrees, treatment time: 1 to 60 minutes, and treatment temperature: 250 to 400 degrees, treatment time: 5 to 30 minutes. More preferred. In the baking step, heat treatments with different conditions may be combined.

  Further, when such an insulating film is applied to, for example, an interlayer insulating film that insulates wiring layers formed on a semiconductor substrate, vias (conductor posts) that electrically connect the wiring layers included in the semiconductor substrate are provided between the layers. It is formed so as to penetrate in the thickness direction of the insulating film. Therefore, the interlayer insulating film needs to have a predetermined shape patterned corresponding to the shape of the via (conductor post).

The interlayer insulating film having a predetermined shape as described above can be formed as follows, for example.
First, a semiconductor substrate 1 on which a barrier film 2 is formed is prepared, and an interlayer insulating film 3, a hard mask layer 4, and a photoresist layer 8 are formed in this order on the barrier film 2 (see FIG. 1A). .)
The interlayer insulating film 3 is formed by the above-described method using the film forming composition of the present invention.
Next, the photoresist layer 8 is exposed and developed using a photomask to obtain a photoresist layer 8 patterned into a shape having an opening at a position where a via (conductor post) or a wiring groove is to be formed (see FIG. (See 1 (b).)
Next, the hard mask layer 4 is formed using the photoresist layer 8 as a mask by a reactive ion etching method using a gas generally used for patterning a hard mask material such as a fluorine-based gas such as CF ₄ as a processing gas. By etching, a hard mask layer 4 having a predetermined shape is formed (see FIG. 1C).
Next, an interlayer insulating film using the hard mask layer 4 as a mask by a reactive ion etching method using a mixed gas of nitrogen and hydrogen generally used for etching of an organic film or the like as a processing gas, or ammonia gas, etc. 3 is etched to form an interlayer insulating film 3 having a predetermined shape (see FIG. 1D).

  The interlayer insulating film 3 having a predetermined shape is obtained as described above. In the present invention, the interlayer insulating film 3 is an insulating film formed using the film forming composition of the present invention as described above. For example, even if a heat treatment is performed at 400 ° C. for 1 hour, since the dielectric film has a change rate of the dielectric constant of 5% or less, the interlayer dielectric film 3 can be more appropriately suppressed or prevented from having a high dielectric constant. And the characteristics of the film can be reliably maintained.

  Furthermore, the insulating film is preferably in contact with a member (for example, a semiconductor substrate, an intermediate film, etc.) made of SiOC, SiCN, SiO, or the like. Thereby, the adhesiveness etc. of the insulating film with respect to the member can be made particularly excellent.

The thickness of the insulating film is not particularly limited, but when the insulating film is used as an interlayer insulating film for a semiconductor, it is preferably 0.01 to 20 μm, more preferably 0.02 to 10 μm, More preferably, it is 0.05-0.7 micrometer.
In the case where the insulating film is used as a protective film for a semiconductor, the thickness of the insulating film is preferably 0.01 to 70 μm, and more preferably 0.05 to 50 μm.

<Semiconductor device>
Next, the semiconductor device of the present invention will be illustrated and described based on preferred embodiments.
FIG. 2 is a longitudinal sectional view schematically showing an example of the semiconductor device of the present invention.
As shown in FIG. 2, the semiconductor device 100 is provided on the semiconductor substrate 1 on which elements are formed, the barrier film 2 provided on the upper side (upper side in FIG. 2) of the semiconductor substrate 1, and the barrier film 2. A copper wiring layer 7 covered with an interlayer insulating film 3 and a barrier metal layer 6 is provided. The semiconductor device 100 of this embodiment includes an interlayer insulating film 3 as an insulating film of the present invention.
A recess corresponding to the pattern to be wired is formed in the interlayer insulating film 3, and a copper wiring layer 7 is provided in the recess.
In addition, a modified treatment layer 5 is provided between the interlayer insulating film 3 and the copper wiring layer 7.
A hard mask layer 4 is formed on the upper side of the interlayer insulating film 3 (on the side surface opposite to the barrier film 2).
The semiconductor device 100 as described above can be manufactured, for example, as follows.
First, by using the method described in the above insulating film, an insulating film having a predetermined shape in which a penetrating wiring groove is formed at a predetermined position of the insulating film composed of the interlayer insulating film 3 and the hard mask layer 4 is formed. Form.
Next, a modified treatment layer 5 is formed on the inner surface of the wiring groove by plasma treatment or the like, and further a barrier composed of Ta, Ti, TaN, TiN, WN or the like by a method such as PVD method or CVD method. A metal layer 6 is formed.
Further, a copper wiring layer 7 to be a wiring layer is formed by an electrolytic plating method or the like, and then the copper wiring layer and the barrier metal layer other than the wiring portion are polished and removed and planarized by a CMP method. Can be obtained.

  The interlayer insulating film 3 can be formed by the method described in the description of the insulating film of the present invention. However, a resin film dry film is prepared in advance, and this is used as a barrier of the semiconductor substrate 1. It can also be formed so as to be laminated on the film 2. More specifically, a resin film is formed on a member in advance using a film-forming composition and dried to obtain a dry film. The dry film is peeled off from the member, and the semiconductor substrate is separated from the semiconductor substrate. The interlayer insulating film 3 may be formed by laminating on one barrier film 2 and irradiating with heat and / or radiation.

Since the semiconductor device of the present invention described above uses the interlayer insulating film (insulating film of the present invention) as described above, it has excellent dimensional accuracy and can sufficiently exhibit insulation, thereby providing excellent connection reliability. Yes.
In addition, since the interlayer insulating film (the insulating film of the present invention) as described above has excellent adhesion to the wiring layer, the connection reliability of the semiconductor device can be further improved.
In addition, since the interlayer insulating film (the insulating film of the present invention) as described above has an excellent elastic modulus, it can be suitably adapted to a process for forming a wiring of a semiconductor device (for example, a baking process).
In addition, as described above, the interlayer insulating film (the insulating film of the present invention) can suppress or prevent etching damage during wiring processing, thereby suppressing or preventing changes in the characteristics of the insulating film during semiconductor device fabrication. be able to.
In addition, since the interlayer insulating film (the insulating film of the present invention) as described above is excellent in dielectric characteristics, signal loss of the semiconductor device can be reduced.
In addition, the interlayer insulating film (the insulating film of the present invention) as described above is excellent in dielectric characteristics, so that the wiring delay can be reduced.

As mentioned above, although this invention was demonstrated based on suitable embodiment, this invention is not limited to these.
For example, in the above description, the example in which the interlayer insulating film 3 as the insulating film of the present invention is formed on the barrier film 2 has been representatively described, but the position where the insulating film is formed is not limited thereto.
In the above-described embodiments, the insulating film provided with the interlayer insulating film is representatively described. However, the insulating film of the present invention may be applied to other than the interlayer insulating film. .

  EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example and a comparative example, this invention is not limited to this.

[1] Synthesis of polymerizable compound (Synthesis Example 1)
First, 1,3-dimethyladamantane was prepared, and carbon tetrachloride: 700 mL and bromine: 35 g (0.22 mol) were placed in a 4-neck 2000 mL flask equipped with a thermometer, a stirrer, and a reflux tube, and stirred. However, the prepared 1,3-dimethyladamantane: 32.9 g (0.2 mol) was added little by little. During the addition, the internal temperature was kept at 20-30 ° C. After the addition was completed, the reaction was continued for another hour after the temperature did not rise. Then, it poured into about 2000 mL of cold water, and the crude product was separated by filtration, washed with pure water, and dried.
The crude product was recrystallized from hot ethanol. The obtained recrystallized product was dried under reduced pressure to obtain 37.4 g of a product. IR analysis shows absorption of bromo group at 690-515 cm ⁻¹ and results of mass analysis 322 molecular weight indicate that the product is 3,5-dimethyl-1,7-dibromoadamantane. It was.
Next, 3,5-dimethyl-1,7-dibromoadamantane: 33.2 g (103.2 mmol) and 1,3-dibromobenzene: 1217 g (5161.6 mmol) obtained above were stirred in the flask, At 25 ° C. under dry nitrogen, 24.8 g (93.0 mmol) of aluminum (III) bromide was added in small portions. This was heated to 60 ° C. and stirred for 8 hours, and then returned to room temperature to obtain a reaction solution. The reaction solution was added to 700 ml of 5% aqueous hydrochloric acid solution and stirred. The aqueous layer was removed, and the organic layer was put into 2000 ml of acetone. The precipitate was filtered and washed with acetone: 1000 ml three times to obtain 57 g of 3,5-dimethyl-1,7-bis (3,5-dibromophenyl) adamantane. From the result of the molecular weight by mass spectrometry being 632, it was shown that the product was 3,5-dimethyl-1,7-bis (3,5-dibromophenyl) adamantane.

  Next, 3,5,5-dimethyl-1,7-bis (3,5-dibromophenyl) adamantane obtained above: 39.8 g (62.9 mmol), dichlorobistriphenylphosphine palladium: 3.53 g (5 0.0 mmol), triphenylphosphine: 6.60 g (25.2 mmol), copper (II) iodide: 4.79 g (25.2 mmol), and triethylamine: 750 ml were added to the flask and stirred. After raising the temperature to 75 ° C., 37.1 g (377.7 mmol) of trimethylsilylacetylene was slowly added. This was stirred at 75 ° C. for 7 hours and then heated to 120 ° C. to distill off triethylamine. Then, it returned to room temperature and added dichloromethane: 1000ml to the reaction liquid, and stirred for 20 minutes. The precipitate was removed by filtration, and 5% aqueous hydrochloric acid solution (1000 ml) was added to the filtrate for liquid separation. The organic layer was washed three times with 1000 ml of water, and then the solvent of the organic layer was removed under reduced pressure. The obtained compound was dissolved in 1500 ml of hexane. Insoluble matter was removed by filtration, and hexane in the filtrate was removed under reduced pressure. Acetone: 1000 ml was added thereto, and the precipitate was washed with acetone three times to obtain 3,5-dimethyl-1,7-bis (3,5-ditrimethylsilylethynylphenyl) adamantane: 36.1 g. . From the result of the molecular weight of 701 by mass spectrometry, it was shown that the product was 3,5-dimethyl-1,7-bis (3,5-ditrimethylsilylethynylphenyl) adamantane.

Furthermore, 3,5-dimethyl-1,7-bis (3,5-ditrimethylsilylethynylphenyl) adamantane obtained above: 32.3 g (46.1 mmol) and potassium carbonate: 1.46 g (10.6 mmol) Were stirred in a mixed solvent of tetrahydrofuran: 600 ml and methanol: 300 ml under a nitrogen atmosphere at room temperature for 4 hours. This was poured into 10% aqueous hydrochloric acid solution: 1000 ml, the precipitate was filtered, and the resulting precipitate was washed with water: 1000 ml, further washed with acetone: 1000 ml, and then dried to give 3, 5-Dimethyl-1,7-bis (3,5-diethynylphenyl) adamantane: 15.0 g was obtained.
The appearance of the product, the results of mass spectrometry and elemental analysis are shown below. These data indicate that the compound obtained above is 3,5-dimethyl-1,7-bis (3,5-diethynylphenyl) adamantane.
Appearance: White solid MS (FD) (m / z): 413 (M +)
Elemental analysis: Theoretical value (/%) C; 93.16, H; 6.84, Measured value (/%) C; 93.11, H; 6.82

(Synthesis Examples 2 to 4)
A polymerizable compound was obtained in the same manner as in Synthesis Example 1 except that tetramethylbiadamantane, decamethylpentaadamantane, and dodecamethylhexaadamantane were prepared instead of dimethyladamantane.
The structural formula of the polymerizable compounds obtained in Synthesis Examples 1 to 4 is shown in the following formula (4). In the following formula (4), n represents an integer of 1, 2, 5, or 6.

The appearance of n = 2 polymerizable compound (Synthesis Example 2) in the above formula (4), the results of mass spectrometry, and elemental analysis are shown.
Appearance: White solid MS (FD) (m / z): 574 (M +)
Elemental analysis: Theoretical value (/%) C; 91.93, H; 8.07, Actual value (/%) C; 91.87, H; 8.00

In addition, the appearance, mass analysis, and elemental analysis results of the polymerizable compound of Formula (4) n = 5 (Synthesis Example 3) are shown.
Appearance: White solid MS (FD) (m / z): 1062 (M +)
Elemental analysis: theoretical value (/%) C; 90.51, H; 9.49, actual measurement value (/%) C; 90.49, H; 9.47

Furthermore, the external appearance, mass analysis, and elemental analysis results of the polymerizable compound of Formula (4) n = 6 (Synthesis Example 4) are shown.
Appearance: White solid MS (FD) (m / z): 1223 (M +)
Elemental analysis: Theoretical value (/%) C; 90.28, H; 9.72, Actual value (/%) C; 90.26, H; 9.70

(Synthesis Example 5)
Using diamantane as a raw material, Macromolecules. , 5262, 5266 (1991), 4,9-diethynyldiamantane, which is a polymerizable compound, was synthesized.
The appearance of the obtained product, the results of mass spectrometry and elemental analysis are shown. These data indicate that the product obtained is 4,9-diethynyldiamantane.
Appearance: White solid MS (FD) (m / z): 236 (M +)
Elemental analysis: Theoretical value (/%) C; 91.47, H; 8.53, measured value (/%) C; 91.45, H; 8.57

(Synthesis Example 6)
First, 3,5-dimethyl-1,7-bis (3,5-dibromophenyl) adamantane was synthesized in the same manner as in Synthesis Example 1. Next, 3,5, -dimethyl-1 obtained above was synthesized. , 7-bis (3,5-dibromophenyl) adamantane: 39.8 g (62.9 mmol), dichlorobistriphenylphosphine palladium: 3.53 g (5.0 mmol), triphenylphosphine: 6.60 g (25.2 mmol) , Copper (II) iodide: 4.79 g (25.2 mmol), triethylamine: 750 ml, ethynylbenzene: 38.5 g (377.7 mmol) were added to the flask and stirred at 95 ° C. for 6 hours. The reaction solution was poured into 1 L of acetone, and the precipitated solid was washed with 1 L of 2 mol / L hydrochloric acid aqueous solution and 1 L of acetone, and then dried under reduced pressure, whereby 3,5-dimethyl-1,7-bis (3,3) as a polymerizable compound was obtained. 5-bis (phenylethynyl) phenyl) adamantane: 37.4 g was obtained.
The appearance of the product, the results of mass spectrometry and elemental analysis are shown below. These data indicate that the compound obtained above is 3,5-dimethyl-1,7-bis (3,5-bis (phenylethynyl) phenyl) adamantane.
Appearance: White solid MS (FD) (m / z): 717 (M +)
Elemental analysis: Theoretical value (/%) C; 93.81, H; 6.19, Measured value (/%) C; 93.75, H; 6.15

(Synthesis Example 7)
In a 5-L eggplant flask, 14.4 g (34.9 mmol) of 3,5-dimethyl-1,7-bis (3,5-diethynylphenyl) adamantane obtained in Synthesis Example 1 and 67.4 g (522 mmol) of quinoline were obtained. 5% palladium-calcium carbonate 0.37 g (0.174 mmol), tetrahydrofuran (1000 mL) and a stirrer were added, and stirring was started at room temperature under a hydrogen stream. When 3.35 L (139 mmol) of hydrogen was consumed, nitrogen was introduced to stop the reaction. After filtering the reaction solution, the filtrate was distilled off under reduced pressure, and the resulting solid was purified by silica gel column chromatography to obtain 3,5-dimethyl-1,7-bis (3,5-divinyl as a polymerizable compound. 18.1 g of phenyl) adamantane was obtained.
The appearance of the product, the results of mass spectrometry and elemental analysis are shown below. These data indicate that the compound obtained above is 3,5-dimethyl-1,7-bis (3,5-divinylphenyl) adamantane (n = 1 in formula (5)).
Appearance: White solid MS (FD) (m / z): 420 (M +)
Elemental analysis: Theoretical value (/%) C; 91.37, H; 8.63, Actual value (/%) C; 91.35, H; 8.60

(Synthesis Example 8)
Instead of 3,5-dimethyl-1,7-bis (3,5-diethynylphenyl) adamantane, 3,3 ′, 5,5′-tetramethyl-7,7 ′ obtained in Synthesis Example 2 was used. A polymerizable compound was obtained in the same manner as in Synthesis Example 7 except that -bis (3,5-diethynylphenyl) -1,1'-biadamantane was prepared.
The appearance of the product, the results of mass spectrometry and elemental analysis are shown below. These data indicate that the compound obtained above is 3,3 ′, 5,5′-tetramethyl-7,7′-bis (3,5-divinylphenyl) -1,1′-biadamantane (formula ( It is shown that n = 2) in 5).
Appearance: White solid MS (FD) (m / z): 583 (M +)
Elemental analysis: Theoretical value (/%) C; 90.66, H; 9.34, Measured value (/%) C; 90.61, H; 9.29

(Synthesis Example 9)
In Synthesis Example 1, in the same manner as in Synthesis Example 1 except that hexamethyltriadamantane: 97.8 g (0.2 mol) was used instead of 1,3-dimethyladamantane: 32.9 g (0.2 mol). 3,3 ′, 3 ″, 5,5 ′, 5 ″ -hexamethyl-7,7 ″ -bis (3,5-diethynylphenyl) -1,1 ′: 7 ′, 1 ″ -tri Adamantane: 39.1 g was obtained.
In Synthesis Example 7, in place of 14.4 g (34.9 mmol) of 3,5-dimethyl-1,7-bis (3,5-diethynylphenyl) adamantane, 3,3 ′, 3 ′ obtained above ', 5,5', 5 "-Hexamethyl-7,7" -bis (3,5-diethynylphenyl) -1,1 ': 7', 1 "-triadamantane: 25.7 g (34 0.9 mmol) was used in the same manner as in Synthesis Example 7 to obtain a product (polymer compound).
In addition, about the product obtained here, the result of an external appearance, mass spectrometry, and elemental analysis is as follows, In the compound which has a cage structure represented by Formula (5), it is a structure of n = 3. It shows that there is.
Appearance: White solid MS (FD) (m / z): 745 (M ⁺ )
Elemental analysis: theoretical value (/%): C, 90.26; H, 9.74, actual measurement value (/%): C, 90.25; H, 9.71

(Synthesis Example 10)
In Synthesis Example 1, in the same manner as in Synthesis Example 1 except that octamethyltetraadamantane: 130.2 g (0.2 mol) was used instead of 1,3-dimethyladamantane: 32.9 g (0.2 mol). 3,3 ′, 3 ″, 3 ′ ″, 5,5 ′, 5 ″, 5 ′ ″-octamethyl-7,7 ′ ″-bis (3,5-diethynylphenyl) -1, 1 ′: 7 ′, 1 ″: 7 ″, 1 ′ ″-tetraadamantane: 49.5 g was obtained.
In Synthesis Example 7, 3,3 ′, 3 ″, 3 ″ was substituted for 14.4 g (34.9 mmol) of 3,5-dimethyl-1,7-bis (3,5-diethynylphenyl) adamantane. ', 5,5', 5 '', 5 '''-octamethyl-7,7'''-bis (3,5-diethynylphenyl) -1,1 ': 7', 1 '': 7 ' A product (polymer compound) was obtained in the same manner as in Synthesis Example 5 except that 37.1 g (34.9 mmol) of ', 1'''-tetraadamantane was used.
In addition, about the product obtained here, the result of an external appearance, mass spectrometry, and elemental analysis is as follows, In the compound which has a cage structure represented by Formula (5), it is a structure of n = 4. It shows that there is.
Appearance: White solid MS (FD) (m / z): 907 (M +)
Elemental analysis: Theoretical value (/%): C, 90.00; H, 10.00, Actual value (/%): C, 89.87; H, 9.99

(Synthesis Example 11)
In Synthesis Example 7, 3,4-dimethyl-1,7-bis (3,5-diethynylphenyl) adamantane was replaced with 14.4 g (34.9 mmol) of 3,5 3 ′, 3 ″, 3 ′ ″, 3 ″ ″, 5, 5 ′, 5 ″, 5 ′ ″, 5 ″ ″-decamethyl-7, 7 ″ ″-bis ( 3,5-diethynylphenyl) -1,1 ′: 7 ′, 1 ″: 7 ″, 1 ′ ″: 7 ′ ″, 1 ″ ″-pentaadamantane: 37.1 g (34. A product (polymer compound) was obtained in the same manner as in Synthesis Example 7 except that 9 mmol) was used.
In addition, about the product obtained here, the result of an external appearance, a mass spectrometry, and an elemental analysis is as follows, and in the compound which has a cage structure represented by Formula (5), it is a structure of n = 5. It shows that there is.
Appearance: White solid MS (FD) (m / z): 1069 (M +)
Elemental analysis: theoretical value (/%): C, 89.82; H, 10.18, actual measurement value (/%): C, 89.67; H, 10.16

(Synthesis Example 12)
In Synthesis Example 7, 3,4-dimethyl-1,7-bis (3,5-diethynylphenyl) adamantane was replaced with 14.4 g (34.9 mmol). 3 ′, 3 ″, 3 ′ ″, 3 ″ ″, 3 ′ ″ ″, 5, 5 ′, 5 ″, 5 ′ ″, 5 ″ ″, 5 ″ ″ '-Dodecamethyl-7,7'''''-bis (3,5-diethynylphenyl) -1,1 ': 7', 1 '': 7 '', 1 ''':7''', 1 ″ ″: 7 ″ ″, 1 ′ ″ ″-hexaadamantane: The product (heavy product) was obtained in the same manner as in Synthesis Example 7 except that 42.6 g (34.9 mmol) was used. Combined compound) was obtained.
In addition, about the product obtained here, the result of an external appearance, mass spectrometry, and elemental analysis is as follows, In the compound which has a cage structure represented by Formula (5), it is a structure of n = 6. It shows that there is.
Appearance: White solid MS (FD) (m / z): 1231 (M +)
Elemental analysis: Theoretical value (/%): C, 89.69; H, 10.31, Measured value (/%): C, 89.67; H, 10.28

(Synthesis Example 13)
In the same manner as in Synthesis Example 7, when 1.68 L (79.5 mmol) of hydrogen was consumed, nitrogen was introduced to stop the reaction. After filtering the reaction solution, the filtrate was distilled off under reduced pressure, and the resulting solid was purified by silica gel column chromatography to obtain 3,5-dimethyl-1,7-bis (3-vinylphenyl-) as a polymerizable compound. 18.1 g of 5-ethynylphenyl) adamantane was obtained.
The appearance of the product, the results of mass spectrometry and elemental analysis are shown below. These data indicate that the compound obtained above is 3,5-dimethyl-1,7-bis (3-vinylphenyl-5-ethynylphenyl) adamantane (n = 1 in formula (6)). ing.
Appearance: White solid MS (FD) (m / z): 416 (M +)
Elemental analysis: Theoretical value (/%) C; 92.26, H; 7.74, Actual value (/%) C; 92.27, H; 7.72

(Synthesis Example 14)
First, 4,9-dibromodiamantane was synthesized according to the synthesis method described in Journal of Organic Chemistry., 39, 2987-3003 (1974). Absorption of bromo group was observed at 690 to 515 cm ⁻¹ by IR analysis, and the result of molecular weight 346 by mass spectrometry indicated that the product was 4,9-dibromodiamantane.
Next, in the synthesis of 3,5-dimethyl-1,7-bis (3,5-dibromophenyl) adamantane as a synthesis intermediate in Synthesis Example 1, in the synthesis of 3,5-dimethyl-1,7-dibromoadamantane, Instead, 4,9-bis (3,5-dibromophenyl) was reacted in the same manner as in Synthesis Example 1 except that 3,5.7 g (103.1 mmol) of 4,9-dibromodiamantane was used. ) Diamantane: 56 g was obtained. From the result of the molecular weight of 656 by mass spectrometry, it was shown that the product was 4,9-bis (3,5-dibromophenyl) diamantane.

  Next, in the synthesis of 3,5-dimethyl-1,7-bis (3,5-ditrimethylsilylethynylphenyl) adamantane as a synthesis intermediate in Synthesis Example 1, 3,5, -dimethyl-1,7- Synthesis Example 1 except that 41.2 g (62.8 mmol) of 4,9-bis (3,5-dibromophenyl) diamantane obtained above was used instead of bis (3,5-dibromophenyl) adamantane By reacting in the same manner as above, 3,5.5 g of 4,9-bis (3,5-ditrimethylsilylethynylphenyl) diamantane was obtained. From the result of the molecular weight measured by mass spectrometry of 725, it was shown that the product was 4,9-bis (3,5-ditrimethylsilylethynylphenyl) diamantane.

Further, in the synthesis of 3,5-dimethyl-1,7-bis (3,5-diethynylphenyl) adamantane as the final product in Synthesis Example 1, 3,5-dimethyl-1,7-bis (3, Synthetic Example 1 except that instead of 5-ditrimethylsilylethynylphenyl) adamantane, 38.8 g (53.5 mmol) of 4,9-bis (3,5-ditrimethylsilylethynylphenyl) diamantane obtained above was used. By making it react by the same reaction, 4,9-bis (3,5-diethynylphenyl) diamantane: 14.3g was obtained.
The appearance of the product, the results of mass spectrometry and elemental analysis are shown below. These data indicate that the compound obtained above is 4,9-bis (3,5-diethynylphenyl) diamantane.
Appearance: White solid MS (FD) (m / z): 436 (M +)
Elemental analysis: Theoretical value (/%) C; 93.54, H; 6.46, Actual value (/%) C; 93.46, H; 6.38

In Synthesis Example 7, in place of 14.4 g (34.9 mmol) of 3,5-dimethyl-1,7-bis (3,5-diethynylphenyl) adamantane, the 4,9-bis (3,5-di- A product (polymer compound) was obtained in the same manner as in Synthesis Example 7 except that 15.2 g (34.9 mmol) of ethynylphenyl) diamantane was used.
In addition, about the product obtained here, the result of an external appearance, mass spectrometry, and elemental analysis is as follows, and in the compound which has a cage structure represented by Formula (7), it is a structure of n = 1. It shows that there is.
Appearance: White solid MS (FD) (m / z): 444 (M +)
Elemental analysis: Theoretical value (/%) C; 91.84, H; 8.16, Actual value (/%) C; 91.80, H; 8.11

(Synthesis Example 15)
Dibromohexa (diamantane) was obtained in the same manner as in Synthesis Example 13 except that hexa (diamantane) was prepared instead of diamantane. Absorption of bromo group was observed at 690 to 515 cm ⁻¹ by IR analysis and the molecular weight by mass spectrometry was 1278, indicating that the product was dibromohexa (diamantane).
Next, in the synthesis of 3,5-dimethyl-1,7-bis (3,5-dibromophenyl) adamantane as a synthetic intermediate in Synthesis Example 1, in place of 3,5-dimethyl-1,7-dibromoadamantane Bis (3,5-dibromophenyl) hexa (diamantane): 134 g by reacting in the same manner as in Synthesis Example 1 except that 131.7 g (103.1 mmol) was used. Got. The result of the molecular weight by mass spectrometry being 1587 showed that the product was bis (3,5-dibromophenyl) hexa (diamantane).

  Next, in the synthesis of 3,5-dimethyl-1,7-bis (3,5-ditrimethylsilylethynylphenyl) adamantane as a synthesis intermediate in Synthesis Example 1, 3,5, -dimethyl-1,7- Synthetic Example 1 except that bis (3,5-dibromophenyl) hexa (diamantane): 99.7 g (62.8 mmol) obtained above was used instead of bis (3,5-dibromophenyl) adamantane By reacting in the same manner, 76 g of bis (3,5-ditrimethylsilylethynylphenyl) hexa (diamantane) was obtained. From the result of the molecular weight by mass spectrometry being 1656, it was shown that the product was bis (3,5-ditrimethylsilylethynylphenyl) hexa (diamantane).

  Further, in the synthesis of 3,5-dimethyl-1,7-bis (3,5-diethynylphenyl) adamantane in Synthesis Example 1, 3,5-dimethyl-1,7-bis (3,5-ditrimethylsilylethynyl) The reaction is conducted in the same manner as in Synthesis Example 1 except that 88.6 g (53.5 mmol) of bis (3,5-ditrimethylsilylethynylphenyl) hexa (diamantane) obtained above is used instead of (phenyl) adamantane. This gave 44 g of bis (3,5-diethynylphenyl) hexa (diamantane).

Next, in the synthesis of 3,5-dimethyl-1,7-bis (3,5-divinylphenyl) adamantane in Synthesis Example 7, 3,5-dimethyl-1,7-bis (3,5-diethynyl) Instead of (phenyl) adamantane, the reaction is carried out in the same manner as in Synthesis Example 7, except that 47.7 g (34.9 mmol) of bis (3,5-diethynylphenyl) hexa (diamantane) obtained above is used. As a result, 34.2 g of bis (3,5-divinylphenyl) hexa (diamantane) was obtained as a polymer compound.
The appearance of the product, the results of mass spectrometry and elemental analysis are shown below. These data indicate that the compound obtained above is bis (3,5-divinylphenyl) hexa (diamantane) (n = 6 in formula (6)).
Appearance: White solid MS (FD) (m / z): 1378 (M +)
Elemental analysis: Theoretical value (/%) C; 90.77, H; 9.23, Measured value (/%) C; 90.71, H; 9.14

(Synthesis Example 16)
Macromolecules. , 5262, 5266 (1991), hexaadamantane was used instead of diamantane as a raw material to obtain a product (polymer compound).
The appearance of the product, the results of mass spectrometry and elemental analysis are shown below. These data indicate that the compound obtained above is compound C represented by n = 6 in formula (8).
Appearance: White solid MS (FD) (m / z): 1023 (M +)
Elemental analysis: Theoretical value (/%) C; 89.17, H; 10.83, Actual value (/%) C; 89.11, H; 10.78

(Synthesis Example 17)
Macromolecules. , 5262, 5266 (1991), hexadiamantane was used instead of diamantane as a raw material to obtain a product (polymer compound).
The appearance of the product, the results of mass spectrometry and elemental analysis are shown below. These data indicate that the compound obtained above is a compound represented by the formula (9).
Appearance: White solid MS (FD) (m / z): 1167 (M +)
Elemental analysis: theoretical value (/%) C; 90.51, H; 9.49, actual measurement value (/%) C; 90.49, H; 9.47

  Table 1 shows the characteristics of the compounds obtained in the synthesis example.

[2] Polymer synthesis Polymerization required in the subsequent evaluation of the insulating film was appropriately secured in accordance with the synthesis examples, examples described later, and comparative examples.

Example 1
3,5-dimethyl-1,7-bis (3,5-diethynylphenyl) adamantane 5.00 g (12.1 mmol), toluene 276 g, sodium dodecyl sulfate, which are the polymer compounds obtained in Synthesis Example 1 (HLB value 40) 44.2 g (153 mmol) and 447 g of water were placed in a 1000 mL beaker and circulated for 1 hour at a pressure of 60 bar using a high pressure homogenizer (NIDO SOAVI PANDA2K type) to prepare an emulsion. . Emulsion polymerization was performed by adding 0.600 g (3.64 mmol) of azobisisobutyronitrile to this emulsion and stirring at 85 ° C. for 8 hours. It was confirmed by GPC that the polymer area ratio was 99% or more (monomer area ratio was 1% or less). After adding 111 g of salt to this solution and stirring for 30 minutes, 3000 mL of methanol was poured. The obtained precipitate was separated by filtration, washed with 500 mL of a mixed solvent of ethanol and water (volume ratio 1: 1), and then dried under reduced pressure to obtain 4.6 g of a polymer solid (yield 92%). It was. The weight average molecular weight (Mw) of the resin obtained by GPC was 28,000, and the number average molecular weight (Mn) was 14,700.
Moreover, when the absolute molecular weight and the intrinsic viscosity were measured, and the molecular morphology parameter α, which was a slope value obtained by plotting the logarithm of the absolute molecular weight and the intrinsic viscosity, was calculated, α = 0.15.

In addition, about the weight average molecular weight (Mw), number average molecular weight (Mn), and dispersion ratio (Mw / Mn) of the polymer in this example and other examples and comparative examples described later, gel permeation chromatograph ( GPC) apparatus (manufactured by Tosoh Corporation, HLC-8220GPC), and as columns, two TSKgel GMHXL (polystyrene conversion exclusion limit 4 × 10 ² (estimated)) and TSKgel G2000HXL (polystyrene conversion exclusion limit 1 × 10) ⁴ ) Connect x2 in series, measure using refractometer (RI) or ultraviolet / visible detector (UV (254nm)) as detector, and analyze results obtained by RI or UV Was determined by The measurement conditions were mobile phase: tetrahydrofuran, temperature: 40 ° C., flow rate: 1.00 mL / min, sample concentration: 0.1 wt% tetrahydrofuran solution.

  Further, the absolute molecular weight and intrinsic viscosity necessary for determining the molecular form parameter α were measured using an HLC-8220GPC manufactured by Tosoh Corporation as a measurement model and TriSEC302TD manufactured by Viscotec as a detector, and a mobile phase: tetrahydrofuran, temperature. : 40 ° C., light scattering angle: 7 °, sample concentration 0.1 wt% tetrahydrofuran solution.

(Examples 2 to 15)
Polymerization was carried out in the same manner as in Example 1 using the polymerizable compounds obtained in Synthesis Examples 2 to 15, and polymers having the characteristics shown in Table 2 were obtained.

(Comparative Example 1)
The polymerizable compound synthesized in Synthesis Example 16: 5 g was dissolved in 1,3-dimethoxybenzene: 45 g and reacted at 170 ° C. for 3 hours under dry nitrogen. Thereafter, the mixture was reacted at 150 ° C. for 6 hours. The reaction solution was dropped into a mixed solvent of 10 times volume of methanol / tetrahydrofuran = 3/1, and the precipitate was collected and dried to obtain 2.8 g of a polymer. .
The properties of the polymer obtained by the above procedure are shown in Table 2.

(Comparative Example 2)
Using the compound obtained in Synthesis Example 17 in Comparative Example 2, polymerization was performed in the same manner as in Comparative Example 1 to obtain a polymer having the characteristics shown in Table 2.

(Comparative Example 3)
The polymerizable compound synthesized in Synthesis Example 11: 5 g and azobisisobutyronitrile: 0.12 g were dissolved in toluene: 250 g and reacted at 80 ° C. for 3 hours under dry nitrogen. Thereafter, the reaction solution was dropped into a 10-fold volume of a mixed solvent of methanol / tetrahydrofuran = 3/1, and the precipitate was collected and dried to obtain 2.5 g of a polymer having the characteristics shown in Table 2.

[3] Preparation of film-forming composition (Example 16)
2 g of the polymer obtained in Example 1 was dissolved in 18 g of cyclopentanone and filtered through a filter to obtain a film-forming composition as a film-forming varnish.

(Examples 17-30, Comparative Examples 4-6)
Film formation in the same manner as in Example 16 except that the polymer 2g of Examples 2 to 15 (corresponding to Examples 17 to 30 respectively) and Comparative Examples 1 to 3 (corresponding to Comparative Examples 4 to 6 respectively) is used. A film-forming composition as a varnish was obtained.

[4] Formation of insulating film (production of substrate with film)
Using the film forming compositions as the film forming varnishes obtained in Examples 16 to 30 and Comparative Examples 4 to 6, insulating films were formed as follows.
First, a film forming composition as a film forming varnish was applied onto a silicon wafer by a spin coater. At this time, the rotation speed and time of the spin coater were set so that the thickness of the insulating film after the heat treatment was 1000 nm.
Next, the silicon wafer provided with the coating film as described above was placed on a hot plate at 200 ° C. for 1 minute to remove the solvent (cyclopentanone) contained in the coating film.
Thereafter, the silicon wafer provided with the dried coating film is subjected to a heat treatment (baking treatment) for 30 minutes in a nitrogen atmosphere in an oven at 400 ° C., thereby curing the prepolymer constituting the coating film, Thus, a substrate with a film (substrate with an insulating film) was obtained.

[5] Evaluation of Insulating Film (Substrate with Film) Each characteristic of dielectric constant, breakdown voltage, leakage current, and thermal decomposition temperature of the insulating film (substrate with film) according to the examples and comparative examples is evaluated as follows. The method was evaluated.

(1) Dielectric constant The dielectric constant was evaluated using an automatic mercury probe CV measuring device SSM495 manufactured by Nippon SSM Co., Ltd. Note that the change rate of the dielectric constant by heat treatment at 400 ° C. for 1 hour was obtained by a calculation formula of ((value after heat treatment) − (value before heat treatment) / (value before heat treatment)) × 100.

(2) Breakdown voltage and leakage current The breakdown voltage and leakage current were evaluated using an automatic mercury probe CV measuring device SSM495 manufactured by Nippon SSM Co., Ltd., as with the dielectric constant.
The breakdown voltage is a voltage applied when a current of 1 × 10 ⁻² A flows, and a breakdown voltage, and the electric field strength (voltage (MV) applied when a current of 1 × 10 ⁻² A flows) is expressed as a film thickness (cm The value divided by), expressed in units of MV / cm). The change rate of the breakdown voltage is ((value after heat treatment) − (value before heat treatment) / (value before heat treatment)) × 100 or ((before heat treatment) so that the value becomes a positive value. Value) − (value after heat treatment) / (value before heat treatment)) × 100.
The leakage current is defined as a leakage current that flows when the electric field intensity is 1 MV / cm, and the current density (A) that flows when the electric field intensity is 1 MV / cm is the mercury electrode area of the automatic mercury probe CV measuring device ( the value obtained by dividing the cm ²⁾ unit:. shown in A / cm ^2). The change in leakage current was determined by dividing the value after heat treatment by the value before heat treatment to determine how many times it changed before heat treatment.

(3) Glass transition temperature The above-obtained insulating film on the silicon wafer before and after the heat treatment at 400 ° C. for 1 hour was scraped off, and this was used as a measurement sample, respectively, as a differential scanning calorimeter DSC- manufactured by TA Instruments Inc. Evaluation was performed with a Q1000 apparatus. The measurement temperature range was 250 to 450 ° C., and the temperature increase rate was 2 ° C./min. The glass transition temperature was evaluated by analyzing from the inflection point in reverse heat flow in the temperature range of 250 to 450 ° C.
The change rate of the glass transition temperature was determined by a calculation formula of ((value after heat treatment) − (value before heat treatment) / (value before heat treatment)) × 100, similarly to the change rate of breakdown voltage.

(4) Modulus of elasticity Modulus of elasticity is evaluated in a region where the signal with an indentation depth of up to one-tenth of the film thickness is stable by using a thin film measuring program with a thin film mechanical property measuring device Nanoindenter manufactured by MTS. did.
The change rate of the elastic modulus was obtained by the calculation formula of ((value after heat treatment) − (value before heat treatment) / (value before heat treatment)) × 100, similarly to the change rate of the breakdown voltage.
The evaluation results are shown in Tables 3, 4, and 5.

As is apparent from Tables 3, 4, and 5, in each example, each evaluation item of dielectric constant, breakdown voltage, leakage current, glass transition temperature, and elastic modulus was evaluated from before heat treatment at 400 ° C. for 1 hour to after heat treatment. The rate of change was suppressed to a low level. Such a tendency was particularly noticeable in the dielectric constant, and the rate of change was suppressed to 5% or less even before and after heating.
On the other hand, in each comparative example, the rate of change from before heat treatment to after heat treatment was large for each of the evaluation items, and such a tendency was particularly noticeable in the dielectric constant. Moreover, the change of the characteristic value was large before and after heating.

DESCRIPTION OF SYMBOLS 1 Semiconductor substrate 2 Barrier film 3 Interlayer insulation film 4 Hard mask layer 5 Modification process layer 6 Barrier metal layer 7 Copper wiring layer 8 Photoresist layer 100 Semiconductor device

Claims (18)

A polymer obtained by polymerizing a polymerizable compound having a partial structure including an adamantane-type cage structure in the molecule and a polymerizable reactive group that contributes to the polymerization reaction, the Mark-Houwink-Sakurada formula A polymer having a molecular form parameter α value of 0.1 or more and 0.5 or less, which is a power of a molecular weight obtained using 2. The polymer according to claim 1, wherein a molecular form parameter α value which is a power of the polymer is 0.1 or more and 0.4 or less. The polymer according to claim 1 or 2, wherein the polymer has a weight average molecular weight of 15,000 or more and 200,000 or less. The polymerizable reactive group of the polymerizable compound has an aromatic ring and an ethynyl group or a vinyl group directly bonded to the aromatic ring,
The number of carbons derived from the aromatic ring in the polymerizable compound is 15% or more and 38% or less with respect to the number of carbons in the entire polymerizable compound. The polymer of any one of these. The polymer according to claim 4, wherein the aromatic ring is directly bonded to the cage structure. 5. The polymerizable reactive group has two ethynyl groups or vinyl groups, and the one ethynyl group or vinyl group is present at the meta position of the other ethynyl group or vinyl group. Or 5. The polymer according to 5. The polymer according to claim 6, wherein each of the two ethynyl groups or the vinyl group is present at a meta position of a site where the aromatic ring is bonded to the cage structure. The polymer according to any one of claims 1 to 7, wherein the partial structure has an adamantane structure. The polymer according to claim 8, wherein the adamantane structure has a methyl group as a substituent. The polymer according to claim 9, wherein the polymerizable compound has a structure represented by the following formula (1) or (2).

[Wherein n represents an integer of 1 to 5. ] The polymer according to any one of claims 1 to 7, wherein the partial structure has a diamantane structure. The composition for film formation containing the polymer of any one of Claim 1 thru | or 11. The film-forming composition according to claim 12, which does not contain a pore-forming material having a function of forming pores in the film by thermal decomposition during film formation. An insulating film formed using the film-forming composition according to claim 12. The insulating film according to claim 14, wherein the dielectric constant is 1.80 or more and 2.30 or less. The insulating film according to (14) or (15), wherein the rate of change in dielectric constant is 3% or less after a heat treatment at 400 ° C. for 1 hour in a nitrogen atmosphere. A semiconductor device comprising the insulating film according to claim 14. Suspension polymerization or emulsion polymerization using a polymerizable compound having a partial structure including an adamantane cage structure in the molecule and a polymerizable reactive group contributing to the polymerization reaction and water as essential components The method for producing a polymer according to any one of claims 1 to 11, wherein:

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