JP2012072233A - Polymer, film-forming composition, insulating film, semiconductor device, and method for producing the polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a film-forming composition comprises a polymer which can form an insulating film hard to be damaged even by an etching step, the insulating film, a semiconductor device provided with the insulating film, and a method for producing the polymer.SOLUTION: The film-forming composition comprises a polymer with a dispersion ratio of 1.0 to 2.5 obtained by polymerizing a polymerizable compound containing a compound having a partial structure, in the molecule, including an adamantane type cage structure and a polymerizable reactive group contributing to polymerization reaction.

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.

As such a low dielectric constant insulating film, an inorganic interlayer insulating film mainly composed of silicon such as HSQ (hydrogen-silsesquioxane) and MSQ (methyl-silsesquioxane) has been widely used.
However, such an inorganic interlayer insulating film is easily damaged in an etching process for patterning the same.

  That is, in the etching process of the interlayer insulating film, C atoms are desorbed from the film due to the cleavage of the Si—C bond contained in the film. As a result, an unsaturated bond is generated in the Si atom, and since the Si atom is unstable in this state, for example, a Si—OH bond is formed by reacting with water molecules existing in the atmosphere. To do. Therefore, the dielectric constant of the interlayer insulating film is increased.

  In order to solve such problems, the characteristics of the interlayer insulating film can be recovered by a damage recovery process by the surface treatment of the interlayer insulating film or a damage component removal process on the surface of the interlayer insulating film using irradiation of an electron beam or the like. (For example, refer to Patent Documents 1 and 2). However, in such a method, if the miniaturization of the wiring insulated by the interlayer insulating film further proceeds, the damage received by the interlayer insulating film cannot be sufficiently recovered, or a process for recovering the characteristics of the interlayer insulating film There is a problem of increasing the number.

  In addition, the use of an organic interlayer insulating film in place of the inorganic interlayer insulating film has been studied. However, as in Patent Documents 1 and 2, the number of processes is increased and the dielectric constant is sufficiently reduced. (For example, Example 5 of Patent Document 3).

JP 2007-266099 A JP 2007-317817 A WO2007-123151

  An object of the present invention is to form a film-forming composition containing a polymer, which can form an insulating film that is hardly damaged by an etching process and maintains film characteristics, and the film-forming composition. An object is to provide an insulating film, a semiconductor device including the insulating film, and a method for producing the polymer.

The above object is achieved by the following items (1) to (18).
(1) The dispersion ratio is 1 obtained by polymerizing a polymerizable compound containing a compound C having a partial structure containing an adamantane cage structure and a polymerizable reactive group contributing to the polymerization reaction in the molecule. A polymer of 0 to 2.5.

(2) The polymer according to item (1), wherein the dispersion ratio is 1.3 or more and 2.4 or less.

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

(4) The polymerizable reactive group has an aromatic ring and an ethynyl group or a vinyl group directly bonded to the aromatic ring,
In the compound C, the number of carbons derived from the aromatic ring is 15% or more and 38% or less with respect to the number of carbons of the compound C as a whole. The polymer according to any one of the 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 compound C has a structure represented by the following formula (1) or (2).
[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 (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) Item (14) or Item 14, wherein the change rate of the dielectric constant on the etched surface is 5% or less etched by a reactive ion etching method using a mixed gas of nitrogen and hydrogen or ammonia gas as a processing gas (15) The insulating film according to item.

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

(18) The production of the polymer according to any one of items (1) to (11), wherein suspension polymerization or emulsion polymerization is performed using the compound C and water as essential components. Method.

  According to the present invention, an insulating film formed using the film-forming composition containing the polymer of the present invention is not easily damaged even when subjected to an etching process, leading to a high dielectric constant of the insulating film. The film characteristics are maintained without any problems. 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 containing a compound C having a partial structure containing an adamantane-type cage structure and a polymerizable reactive group contributing to the polymerization reaction in the molecule. It is a polymer having a dispersion ratio (weight average molecular weight / number average molecular weight) of 1.0 or more and 2.5 or less. As a result, the dielectric constant of the film produced by physical and chemical effects is increased with respect to the insulating film formed using the film-forming composition containing such a polymer. Is set in the range of 1.0 to 2.5, the structure of the insulating film formed using the film-forming composition containing such a polymer is composed of uniform particles of uniform size. Therefore, the film has excellent plasma resistance, and can be suppressed or prevented more accurately. Even if an etching process is performed, the film is not easily damaged, and without causing an increase in the dielectric constant of the insulating film. An insulating film with maintained characteristics can be reliably formed.
The polymer of the present invention is obtained by polymerizing a polymerizable compound containing a compound C having a partial structure containing an adamantane cage structure and a polymerizable reactive group contributing to the polymerization reaction in the molecule. However, the present invention also includes a case where the polymerizable compound containing the compound C contains a polymerizable compound other than the compound C within a range that does not affect the characteristics of the present invention. The polymerizable compound other than the compound C may be a compound having a known polymerizable functional group.
The polymerizable compound other than the compound C may be contained in the total polymerizable compound, preferably 30% by mass or less, more preferably 10% by mass or less.

  As described above, in the present invention, the dispersion ratio of the polymer may be 1.0 or more and 2.5 or less, but is preferably 1.3 or more and 2.4 or less. As a result, even when an etching process is performed on an insulating film formed using the film-forming composition containing such a polymer, it is less susceptible to damage and without causing a high dielectric constant of the insulating film. Thus, it is possible to more reliably form an insulating film whose film characteristics are maintained.

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 containing Compound C and the film-forming composition containing the polymer, from which the polymer of the present invention is obtained, will be described in detail.

Hereinafter, Compound C will be described first.
[1] Compound C
Compound C has in its molecule a partial structure containing an adamantane cage structure and a polymerizable reactive group that contributes to the polymerization reaction.
Hereinafter, each of the partial structure and the polymerizable reactive group will be described.

[1.1] Partial Structure The partial structure of Compound C includes an adamantane cage structure. Thereby, the dielectric constant of the film (insulating film) formed using the film-forming composition containing the polymer of the present invention can be made particularly low, and etching for patterning the film into a predetermined shape In the process, it is possible to accurately suppress or prevent the film from having a high dielectric constant.

Examples of the partial structure of Compound C include adamantane, polyadamantane (eg, biadamantane, triadamantane, tetraadamantane, pentaadamantane, hexaadamantane, heptaadamantane, etc.), polyamantane (eg, diamantane, triamantane, tetramantane, Pentavalent, hexamantane, heptamantane, etc.), divalent groups such as compounds in which at least some of the hydrogen atoms constituting these compounds are substituted with alkyl groups or halogen atoms (excluding the two hydrogen atoms constituting the above compounds) Part structure) or those having two or more of these divalent groups (for example, a series of diamantane skeletons such as a bi (diamantane) skeleton, a tri (diamantane) skeleton, a tetra (diamantane) skeleton, etc. (poly (Diamantan One having a skeleton); one in which a plurality of triamantane skeletons such as a bi (triamantane) skeleton, a tri (triamantane) skeleton, and a tetra (triamantane) skeleton are connected (one having a poly (triamantane) skeleton); adamantane A skeleton (or a polyadamantane skeleton) and a polyamantane skeleton, etc.). Hereinafter, some examples of the partial structure are shown by chemical structural formulas, but the partial structure is not limited thereto. However, in the following formulas (A-1) to (A-7), 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 1 represents an integer of 1 or more.

  The partial structure preferably has an adamantane structure. Thereby, the dielectric constant of the film (insulating film) formed using the film-forming composition containing the polymer of the present invention can be made particularly low, and etching for patterning the film into a predetermined shape In the process, it is possible to accurately suppress or prevent the film from having a high dielectric constant.

  The adamantane structure preferably has a methyl group as a substituent. Thereby, the dielectric constant of the film formed using the film-forming composition containing the polymer of the present invention can be made particularly low, and in the etching step for patterning the film into a predetermined shape, the film It is possible to accurately suppress or prevent the increase in the dielectric constant.

  The partial structure may have a diamantane structure. Thereby, the dielectric constant of the film (insulating film) formed using the film-forming composition containing the polymer of the present invention can be made particularly low, and etching for patterning the film into a predetermined shape In the process, it is possible to accurately suppress or prevent the film from having a high dielectric constant.

[1.2] Polymerizable reactive group Compound C has a polymerizable reactive group contributing to the polymerization reaction in addition to the partial structure as described above.
The polymerizable group of the polymerizable reactive group is not particularly limited as long as it is a functional group that is polymerized by heat, an initiator, or the like, but is preferably a polymerizable group having an unsaturated bond, and more preferably a vinyl group or an ethynyl group. More preferred. In addition, vinyl group and ethynyl group are alkyl groups such as methyl group, ethyl group and propyl group other than hydrogen, aryl groups such as phenyl group, tolyl group, naphthyl group and fluorenyl group, cycloalkyl groups such as cyclohexyl group and adamantyl group. It may have a substituent such as. The functional group of the polymerizable reactive group is a polymerizable group when the polymerizable compounds are polymerized with each other and exhibits the same function. A case where the reactive group has an ethynyl group will be described as an example.

  The polymerizable reactive group of the present invention may have a polymerizable group as described above, but has an aromatic ring and a polymerizable group directly bonded to the aromatic ring (hereinafter described as an ethynyl group as an example). In the compound C, the number of carbons derived from the aromatic ring is preferably 15% or more and 38% or less, and is 18% or more and 27% or less with respect to the total number of carbons in the compound C. Is more preferable. By making the number of carbons derived from the aromatic ring in compound C within such a range, the abundance ratio between the partial structure and the polymerizable reactive group becomes suitable, thereby lowering the dielectric constant of the insulating film. Can do. Further, in the etching process for patterning the film into a predetermined shape, it is possible to accurately suppress or prevent the film from increasing in dielectric constant.

The aromatic ring constituting the polymerizable reactive group is not particularly limited. For example, benzene ring, naphthalene ring, anthracene ring, naphthacene ring, phenanthrene ring, chrysene ring, pyrene ring, perylene ring, coronene ring, biphenyl ring, Hydrocarbon ring aromatic rings such as phenyl ring and azulene ring, pyridine ring, furan ring, thiophene ring, pyrrole ring, oxazole ring, indole ring, purine ring, benzofuran ring, benzothiophene ring, carbazole ring, imidazole ring, thiazole And heterocyclic aromatic rings such as a ring, a pyrazole ring, an isoxazole ring, an isothiazole ring, a quinoline ring, and a terthienyl ring. Of these, a benzene ring is preferred as the aromatic ring. As a result, in the etching process for patterning the film into a predetermined shape, it is possible to accurately suppress or prevent the film from increasing in dielectric constant, and to have excellent insulation characteristics and heat resistance. it can.
The aromatic ring constituting the polymerizable reactive group may be bonded to the cage structure constituting the partial structure via at least one other atom, but directly bonded to the cage structure constituting the partial structure It is preferable that Thereby, it can be set as the thing excellent in the insulation characteristic and heat resistance.

The polymerizable reactive group may have one ethynyl group, but has two ethynyl groups, and two ethynyl groups are directly bonded to the aromatic ring as described above. Is preferred. Thus, when the polymerizable reactive group has two ethynyl groups as reaction sites, an initial reaction with respect to the compound C easily occurs. On the other hand, when one of the two ethynyl groups of the polymerizable reactive group reacts (polymerization reaction), the electronic state of the aromatic ring changes, and the reactivity of the other ethynyl group rapidly decreases. To do. For this reason, only one ethynyl group of the two ethynyl groups of the polymerizable reactive group can be selectively reacted under relatively mild conditions. And since the polymerizable compound preferably has two polymerizable reactive groups in the molecule, only one ethynyl group is selected for each of the two polymerizable reactive groups present in the molecule of compound C. In this case, for example, a polymer (chain prepolymer) in which a plurality of polymerizable compounds are one-dimensionally polymerized is obtained by a reaction represented by the following formula (3).
(In formula (3), A represents a partial structure, Ar represents an aromatic ring constituting a polymerizable reactive group, and n represents an integer of 2 or more.)
In the case where the polymerizable reactive group has a vinyl group instead of the ethynyl group, for example, a polymer in which a plurality of polymerizable compounds are polymerized one-dimensionally by a reaction represented by the following formula (3 ′) ( A chain prepolymer) is obtained.
(In (3 ′), A represents a partial structure, Ar represents an aromatic ring constituting a polymerizable reactive group, and n represents an integer of 2 or more.)
When the reaction as described above occurs, the compound C reacts excessively during storage of the film-forming composition, and the film-forming composition becomes extremely viscous (for example, gelates). ) Can be reliably prevented.

On the other hand, when the polymer obtained by the reaction as described above (prepolymer obtained by partial polymerization reaction) has an unreacted ethynyl group, the firing conditions described in detail later Under the heating conditions on the semiconductor substrate, the remaining ethynyl groups can be reliably reacted, and the finally formed film has a three-dimensionally cross-linked structure. As a result, the formed film is particularly excellent in heat resistance and the like.

  As described above, when each polymerizable reactive group constituting the compound C has two ethynyl groups, in the polymerizable reactive group, one ethynyl group is present at the meta position of the other ethynyl group. It is preferable. Thereby, in the state in which one ethynyl group of two polymerizable ethynyl groups has reacted (polymerization reaction), an electronic effect such as an aromatic ring is more remarkably exhibited, and the reaction of the other ethynyl group The reaction site can be reduced more effectively, and the reacted site becomes an appropriate steric hindrance, and the reactivity of the other ethynyl group (unreacted ethynyl group) can be controlled more suitably. As a result, the selectivity for the two ethynyl groups of the polymerizable reactive group (reactivity for the first stage reaction and reactivity for the second stage reaction) should be made higher. In addition, the baking process or heating process described in detail later can be performed under more suitable conditions (conditions that can form a film with excellent productivity while preventing damage to the semiconductor substrate). it can.

  In addition, when the polymerizable reactive group has two ethynyl groups, it is preferable that both of the two ethynyl groups are present at the meta position where the aromatic ring is bonded to the cage structure. Thereby, in the state in which one ethynyl group of two polymerizable ethynyl groups has reacted (polymerization reaction), an electronic effect such as an aromatic ring is more remarkably exhibited, and the reaction of the other ethynyl group The reaction site and the partial structure described above become an appropriate steric hindrance, and the reactivity of the other ethynyl group (unreacted ethynyl group) is more suitable. Can be controlled. As a result, the selectivity for the two ethynyl groups of the polymerizable reactive group (reactivity for the first stage reaction and reactivity for the second stage reaction) should be made higher. In addition, the baking process or heating process described in detail later can be performed under more suitable conditions (conditions that can form a film with excellent productivity while preventing damage to the semiconductor substrate). it can.

As the compound C satisfying the above conditions, that is, a compound having a partial structure and a polymerizable reactive group that are preferable, and a compound C in which the aromatic ring-derived carbon in the compound C is set to a preferable number, And those having a structure represented by the following formula (1) or (2). In the following formulas (1) and (2), n represents an integer of 1 to 5.
By selecting the compound C having such a structure as the compound C, the insulating film formed using the film-forming composition exhibits the above-described effects more remarkably.
In addition, in the compound C which has a structure shown by the said Formula (1) or (2), although what has two two polymerizable reactive groups was illustrated, as other compounds C which have one polymerizable reactive group Examples thereof include those having structures represented by the following formulas (1 ′) and (2 ′). In the following formulas (1 ′) and (2 ′), n represents an integer of 1 or 2.
Compound C may have a partial structure and a partial structure other than the polymerizable reactive group.

In addition, it is thought that the increase in the dielectric constant of the film in the etching process is caused by, for example, physical effects and chemical effects as described below.
The physical effect is that the etching gas accelerated by the plasma collides with the film at a high speed, resulting in unevenness on the film surface. As a result, moisture and the like are adsorbed on the film surface. It is thought that the characteristics change.
In addition, the chemical effect is caused by the fact that the etching gas changes into ions and radicals due to plasma, and when these collide with the film, the chemical bonds in the film are broken and the structure of the film is changed. Therefore, it is considered that the characteristics of the film change.
Forming a film containing such a polymer by setting the high dielectric constant of the film caused by such physical and chemical effects to a dispersion ratio of the polymer within the range of 1.0 to 2.5. The structure of the insulating film formed using the composition for use is composed of uniform particles of uniform size, so that the plasma resistance is excellent, and it can be suppressed or prevented more accurately.
Further, the increase in the dielectric constant of the film can be suppressed or prevented more accurately by setting the number of carbons derived from the aromatic ring in the compound C within the range described above.

The compound C as described above has two polymerizable reactive groups, and when the polymerizable reactive group has two ethynyl groups, for example, it can be synthesized as follows.
That is, a compound A ′ corresponding to a partial structure (a compound in which two hydrogen atoms are bonded to A as a divalent group) is reacted with bromine, and a dibromo form of A ′ (a compound in which two bromo groups are bonded to the partial structure) ), A step of reacting a dibromo form of A ′ with dibromobenzene to obtain a bis (dibromophenyl) form of A ′ (a compound in which two dibromophenyl groups are bonded to a partial structure), and a dibromo form of A ′. Acetylene, phenylacetylene, naphthylacetylene containing a cyclic alkyl group such as acetylene, cyclohexylacetylene, adamantylacetylene, etc. containing an alkyl group such as 1-propyne, 1-butyne, 1-pentyne, 1-hexyne, 1-heptin, etc. Acetylene, trimethylsilylacetylene, triethylsilylamine containing aromatic groups such as fluorenylacetylene Reaction with acetylene containing tri-substituted silyl groups such as triaryl-substituted silyl acetylene such as trialkyl-substituted silyl acetylene, triphenylsilyl acetylene, tolyl silyl acetylene, trinaphthyl silyl acetylene, etc. In the case of A ′, a bis (di (trimethylsilylethynyl) phenyl) form of A ′ (a compound in which two di (trimethylsilylethynyl) phenyl groups are bonded to a partial structure) and a bis (di (trimethylsilylethynyl) phenyl of A ′ The target compound C can be obtained by a method having a step of hydrolyzing (detrimethylsilylating) the product. Further, the hydrolysis step can be omitted for acetylene derivatives that do not require hydrolysis other than acetylene containing a tri-substituted silyl group.

In addition, when a polymerizable reactive group has two vinyl groups instead of two ethynyl groups, the compound C can be synthesized as follows, for example.
That is, after synthesizing the compound C having two ethynyl groups described above, although not particularly limited, Lindlar reduction using hydrogen gas, Brich reduction using sodium and liquid ammonia, diimide reduction using diimide, and the like are performed. Thus, the target compound C can be obtained.
In this case, the vinylation reaction of the ethynyl group may be stopped halfway and the ethynyl group and the vinyl group may coexist.

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 containing a compound C having a partial structure containing an adamantane-type cage structure and a polymerizable reactive group contributing to the polymerization reaction in the molecule. If the dispersion ratio is a polymer of 1.0 or more and 2.5 or less, there is no problem. For example, when solution polymerization is used as a polymerization method, a polymerizable compound containing Compound C is dissolved in a solvent, It can prepare suitably by performing heat processing, a light irradiation process, etc. with respect to the polymeric compound containing the compound C. FIG. 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 containing the compound C 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; Examples include amide solvents such as pyrrolidone, and one or more selected from these may be used in combination.

In the film-forming composition containing the polymer of the present invention, the unreacted polymerizable compound is removed by purification (unreacted polymerizable compound is not contained as much as possible), and the dispersion ratio is 1.0. A polymer of 2.5 or less may be obtained. Thus, by increasing the dielectric constant of the film caused by physical and chemical influences, by setting the dispersion ratio of the polymer of the present invention within the range of 1.0 to 2.5, The structure of the insulating film formed using the film-forming composition containing the film is composed of uniform particles having uniform sizes, so that the plasma resistance is excellent and can be suppressed or prevented more accurately. .

Further, as a preferred polymerization method of the polymer of the present invention, when suspension polymerization is used, a polymerizable compound containing Compound C or a solution obtained by dissolving the polymerizable compound in a solvent and water as essential components are necessary. Accordingly, it can be suitably prepared by mixing the dispersant, vigorously stirring, and subjecting the polymerizable compound containing Compound C to heat treatment in a dispersed state.
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 containing Compound C is dissolved in a solvent and water as essential components, an organic solvent to be used is a polymerizable compound containing Compound C. Although it will not specifically limit if it can be made to melt | dissolve, 1 or more types of organic solvents whose octanol / water partition coefficient is 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 containing Compound C is dissolved in a solvent and water as essential components, the organic layer separated into two layers after the polymerization is extracted. The polymer of the present invention is obtained by performing reprecipitation with a poor solvent and washing, dehydrating and drying the precipitated resin.
In addition, when suspension polymerization is performed with a polymerizable compound containing the compound C of the present invention and water without using a solvent, the aqueous suspension after polymerization is filtered, washed, dehydrated, and dried to obtain the weight of the present invention. Coalescence is obtained.

As another preferred embodiment of the polymerization method, when emulsion polymerization is used, a surfactant containing a polymerizable compound containing Compound C or a solution obtained by dissolving the polymerizable compound in a solvent and water as essential components is necessary. The mixture is mixed with a dispersing agent, and the mixture is vigorously stirred or applied with energy such as ultrasonic treatment with an ultrasonic homogenizer or the like, and is emulsified, that is, the polymerizable compound containing the compound C or the polymerizable compound is used as a solvent. A bimolecular film, vesicles, and micelles in which a surfactant is arranged are formed around the dissolved solution, and the polymerizable compound can be suitably prepared by 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 including Compound C is dissolved in a solvent and water as essential components, the organic compound to be used may be dissolved in the polymerizable compound. Although it will not specifically limit if it can do, The 1 or more types of organic solvent whose octanol / water partition coefficient is 3 or less is 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 ether, fatty acid sorbitan ester, alkyl polyglucoside, fatty acid diethanolamide, alkyl monoglyceryl ether That. 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 Compound C from the viewpoint of stable micelle formation and the properties 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 including the compound C. However, in order to rapidly advance the reaction, the octanol / water partition coefficient is 3 or less. It is preferable to use one or more organic solvents 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.
In addition to the compound C, the polymerizable compound containing the compound C used in the present invention includes thermal polymerization, radical polymerization using a radical initiator, photoradical polymerization using light irradiation, etc., polymerization using the palladium catalyst, A compound having a functional group used for the polymerizable reaction described above, such as polymerization using a transition metal catalyst or polymerization using a transition metal chloride, may be included within a range that does not affect the characteristics of the present invention. .

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 is a polymer containing a compound C having a partial structure including an adamantane cage structure and a polymerizable reactive group contributing to the polymerization reaction in the molecule. Is a polymer having a dispersion ratio of 1.0 or more and 2.5 or less, which is obtained by polymerizing the organic compound, and the content of the polymer of the present invention in the film-forming composition is 1 wt% to 30 wt%. Preferably there is.

[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, a surfactant, and a silane, which include a compound C having a partial structure including an adamantane cage structure and a polymerizable reactive group contributing to the polymerization reaction in the molecule. Examples include coupling agents such as coupling agents; catalysts such as radical initiators and disulfides.
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 dispersion ratio of 1.0 or more and 2.5 or less obtained by polymerizing a polymerizable compound containing the compound C having a polymerizable reactive group that contributes to the Even without this, 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.

<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 2.80 or less, and 2.40 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.

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. Preferably, the insulating film is etched by a reactive ion etching method using a mixed gas of nitrogen and hydrogen or ammonia gas as a processing gas, and the change rate of the dielectric constant on the etched surface is 5% or less. It is possible to more accurately suppress or prevent the interlayer insulating film 3 from having a high dielectric constant, and to reliably maintain the characteristics of this film.
The reactive ion etching conditions in the evaluation of the change rate of the dielectric constant on the etched surface etched by the reactive ion etching method using a mixed gas of nitrogen and hydrogen or ammonia gas as the processing gas are as follows: Using a mixed gas of nitrogen and hydrogen (nitrogen flow rate: 7.5 sccm, hydrogen flow rate: 2.5 sccm) or ammonia gas (ammonia gas flow rate: 10.0 sccm), frequency 13.56 MHz, pressure 12.5 Pa, output 100 W The treatment time is 1 minute.
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. Obtainable.
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 is representatively described, but the position where the insulating film is formed is not limited to this.
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 Compound C (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)
Compound C was obtained in the same manner as in Synthesis Example 1 except that tetramethylbiaadamantane, decamethylpentaadamantane and dodecamethylhexaadamantane were prepared instead of dimethyladamantane.
The structural formula of Compound C 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.
In addition, the external appearance, the mass analysis, and the result of an elemental analysis of the compound C (synthesis example 2) of n = 2 in the said Formula (4) 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
Moreover, the external appearance of the said Formula (4) n = 5 compound C (synthesis example 3), the result of a mass analysis, and an elemental analysis 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 of the said Formula (4) n = 6 compound C (Synthesis example 4), the result of a mass analysis, and an elemental analysis 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. 4,9-diethynyldiamantane, which is Compound C, was synthesized according to the synthesis method described in U.S. Pat.
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 added to 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 (3,5 -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-divinylphenyl as compound C). ) 18.1 g of 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. Compound C 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 except that a product 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 = 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 '',1'''-Tetraadamantane: A product was obtained in the same manner as in Synthesis Example 5 except that 37.1 g (34.9 mmol) 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. The product 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: A product was obtained in the same manner as in Synthesis Example 7 except that 42.6 g (34.9 mmol) was used. It was.
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)
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 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 (6), 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, measured value (/%) C; 91.80, H; 8.11

(Synthesis Example 14)
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. This gave 34.2 g of bis (3,5-divinylphenyl) hexa (diamantane).
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 15)
Macromolecules. , 5262, 5266 (1991), hexaadamantane was used instead of diamantane as a raw material, and a product was obtained.
The appearance of the product, the results of mass spectrometry and elemental analysis are shown below. These data show that the compound obtained above is the compound C represented by n = 6 in the formula (7).
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 16)
Macromolecules. , 5262, 5266 (1991), hexadiamantane was used instead of diamantane as a raw material, and a product 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 the compound C represented by the formula (8).
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] Synthesis of polymer The amount of compound C required for the subsequent synthesis of the polymer and the polymerization required for the evaluation of the insulating film are appropriately determined according to the synthesis examples, examples described later, and comparative examples. Secured.

Example 1
3.13 g (2.73 mmol) of 3,5-dimethyl-1,7-bis (3,5-diethynylphenyl) adamantane, which is the compound C obtained in Synthesis Example 1, and azobisisobutyronitrile 0 .135 g (0.822 mmol), toluene 62.4 g, sodium dodecyl sulfate (HLB value 40) 9.98 g (34.6 mmol), and water 101 g were placed in a 500 mL beaker, and an ultrasonic treatment apparatus (Branson Sonifier 450D, frequency 20 kHz). The emulsion was prepared by sonicating in an ice bath for a total of 1 hour at an output of 50 W. This emulsion was stirred at 80 ° C. for 7 hours to carry out emulsion polymerization. It was confirmed by GPC that the polymer area ratio was 99% or more (monomer area ratio was 1% or less). After adding 3.2 g of sodium chloride to this solution and stirring for 30 minutes, about 700 mL of methanol was poured. The obtained precipitate was separated by filtration, washed with 200 mL of a mixed solvent of ethanol and water (volume ratio 1: 1), and then dried under reduced pressure to obtain 0.91 g (yield 81%) of a polymer solid. It was. The resin obtained by GPC had a weight average molecular weight (Mw) of 19,000, a number average molecular weight (Mn) of 11,800, and a dispersion ratio (Mw / Mn) of 1.6.
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, TSKgel GMHXL (polystyrene conversion exclusion limit 4 × 10 ² (estimated)) × 2 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.

(Examples 2 to 14)
Polymerization was carried out in the same manner as in Example 1 using Compound C obtained in Synthesis Examples 2 to 14, and polymers having the characteristics shown in Table 2 were obtained.

(Comparative Example 1)
Compound C: 5 g synthesized in Synthesis Example 15 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)
The compound C obtained in Synthesis Example 16 was used in Comparative Example 2, and 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)
Compound C: 5 g synthesized in Synthesis Example 11 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.

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

(Preparation Examples 2-14, Comparative Preparation Examples 1-3)
In the same manner as in Preparation Example 1, except that 2g of the polymer of Examples 2 to 14 (corresponding to Preparation Examples 2 to 14, respectively) and Comparative Examples 1 to 3 (corresponding to Comparative Preparation Examples 1 to 3, respectively) were used. A film-forming composition as an insulating film varnish was obtained.

[4] Formation of insulating film (production of substrate with film)
Using the film-forming composition as the organic insulating film varnish obtained in each of the preparation examples and the comparative preparation examples, an insulating film was formed as follows.
First, a film forming composition as a varnish for an organic insulating film was applied on 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 each of the preparation examples and comparative preparation examples, The evaluation was performed by the following evaluation method before and after the reactive ion etching.
The reactive ion etching process is L-201D-L manufactured by Anerva Co., Ltd., frequency 13.56 MHz, pressure 12.5 Pa, output 100 W, flow rate (nitrogen: 7.5 sccm, hydrogen: 2.5 sccm). The treatment time was 1 minute.

(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 was obtained by a calculation formula of ((value after etching) − (value before etching) / (value before etching)) × 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). Note that the change rate of the breakdown voltage was obtained by a calculation formula of ((value before etching) − (value after etching) / (value before etching)) × 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 etching by the value before etching to determine how many times it changed before etching.

(3) Thermal decomposition temperature Using the TG / DTA measuring device (TG / DTA220, manufactured by Seiko Instruments Inc.), the obtained insulating film was heated at a rate of 10 ° C./min. Under a nitrogen gas flow of 200 mL / min. The temperature at which the weight loss reached 5% was determined as the thermal decomposition temperature. The rate of change in heat resistance was determined by the formula ((value before etching) − (value after etching) / (value before etching)) × 100, similarly to the rate of change in breakdown voltage.
The evaluation results are shown in Tables 3 and 4.

As is apparent from Tables 3 and 4, in each adjustment example, the rate of change from before etching to after etching is suppressed low for each evaluation item of dielectric constant, breakdown voltage, leakage current, and thermal decomposition temperature. Such a tendency was particularly noticeable in the dielectric constant, and the rate of change was suppressed to 5% or less.
On the other hand, in each comparative adjustment example, the rate of change from before etching to after etching was large for each of the evaluation items, and this tendency was particularly noticeable particularly in the dielectric constant.

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 dispersion ratio of 1.0 or more obtained by polymerizing a polymerizable compound containing a compound C having a partial structure containing an adamantane-type cage structure and a polymerizable reactive group contributing to the polymerization reaction in the molecule Polymer of 2.5 or less.   The polymer according to claim 1, wherein the dispersion ratio is 1.3 or more and 2.4 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 has an aromatic ring and an ethynyl group or a vinyl group directly bonded to the aromatic ring;
4. The compound C according to claim 1, wherein the number of carbons derived from the aromatic ring in the compound C is 15% or more and 38% or less with respect to the number of carbons in the compound C as a whole. The polymer according to claim 1.   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 the polymer of Claim 5.   7. 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 compound C 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 dielectric constant change rate on the etched surface etched by a reactive ion etching method using a mixed gas of nitrogen and hydrogen or ammonia gas as a processing gas is 5% or less. Insulating film.   A semiconductor device comprising the insulating film according to claim 14.   The method for producing a polymer according to any one of claims 1 to 11, wherein suspension polymerization or emulsion polymerization is performed using the compound C and water as essential components.