JP2012077176A - Insulation film, laminated body, and semiconductor device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an insulation film having a low dielectric constant, high adhesion with a substrate (a member on which the insulating film is formed), high reliability, and high yield during manufacturing.SOLUTION: This insulation film is formed using a composition containing a polymerizable compound having a partial structure including an adamantane type basket structure in a molecule and a polymerizable reactive group contributing to polymerizable reaction and/or polymer where the polymerizable compound is polymerized partially. The linear expansion coefficient of the insulation film in the surface direction is 9×10Kor higher and 25×10Kor lower. The polymerizable reactive group of the polymerizable compound contains an aromatic ring, and an ethynyl group or vinyl group directly bonded to the aromatic ring. In the polymerizable compound, preferably, the number of carbons originating in the aromatic ring is 15% or more and 38% or less of the number of carbons in the whole polymerizable compound.

Description

  The present invention relates to an insulating film, a stacked body, and a semiconductor device.

  In the field of electronic materials, as semiconductor devices become more highly integrated, faster and have higher performance, delay time due to increased resistance between wires and increased capacitance of semiconductor integrated circuits has become a major problem. In order to reduce the delay time and increase the speed of the semiconductor device, it is necessary to use an interlayer insulating film having a low dielectric constant for the circuit.

  Conventionally, in order to reduce the dielectric constant of an insulating film, a composition containing a thermally decomposable component (hole forming material) is used, and the thermally decomposable component is decomposed in a heating and firing step when forming the insulating film. A method of forming holes has been used (see, for example, Patent Document 1). However, when such a method is used, the formed insulating film has low strength. In addition, there is a problem that an undesired variation in film thickness tends to occur in the formed insulating film, resulting in a large difference in characteristics at each part. In addition, the insulating properties of the formed insulating film are not stable, and an insulating film having a relatively low resistance value may be formed.

  In addition, there is an attempt to prevent the above problems from occurring while using a polymer having a specific chemical structure while reducing the dielectric constant (see, for example, Patent Document 2). However, such an insulating film has insufficient adhesion to a bonded substrate (particularly, adhesion when a temperature change occurs), and the reliability of a semiconductor device or the like provided with the insulating film is low. There was a problem of becoming. Further, in such an insulating film, the insulating film to be formed is unintentional from the substrate (the member on which the insulating film is formed) at the time of manufacturing the semiconductor device accompanied by the baking process (heat treatment) (at the time of forming the insulating film). There is a problem that peeling occurs and the yield of the semiconductor device decreases.

JP 2005-243903 A JP 2006-526672 A

  An object of the present invention is to provide an insulating film having a low dielectric constant, excellent adhesion to a substrate (a member on which an insulating film is formed), high reliability, and excellent yield in manufacturing. Providing a highly reliable laminate with an insulating film that is low and has excellent adhesion to the substrate (and cap layer), and also has low dielectric constant and excellent adhesion to the substrate (and cap layer) Another object of the present invention is to provide a semiconductor device that has an insulating film with high reliability and excellent yield in manufacturing.

Such an object is achieved by the present invention described in the following (1) to (15).
(1) A polymerizable compound having a partial structure containing an adamantane cage structure in the molecule and a polymerizable reactive group contributing to the polymerization reaction, and / or a polymer obtained by partially polymerizing the polymerizable compound. An insulating film formed using a composition comprising:
An insulating film having a linear expansion coefficient in a plane direction of 9 × 10 ⁻⁶ K ⁻¹ or more and 25 × 10 ⁻⁶ K ⁻¹ or less.

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

  (3) The insulating film according to (2), wherein the aromatic ring is directly bonded to the cage structure.

  (4) 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 insulating film according to (2) or (3) above.

  (5) The insulating film according to (4), 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.

  (6) The insulating film according to any one of (1) to (5), wherein the partial structure has an adamantane structure.

  (7) The insulating film according to (6), wherein the adamantane structure has a methyl group as a substituent.

［式中、ｎは１〜５の整数を表す。］

［式中、ｎは１〜５の整数を表す。］ (8) The insulating film according to (7), wherein the polymerizable compound has a structure represented by the following formula (1) or a structure represented by the following formula (5).

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

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

  (9) The insulating film according to any one of (1) to (5), wherein the partial structure has a diamantane structure.

  (10) The above (1), wherein the polymerizable compound has two polymerizable reactive groups and has a structure in which the polymerizable reactive groups are symmetrically bonded around the partial structure. Or the insulating film according to any one of (9).

  (11) The above-described (1) to (10), which is formed using the composition not containing a pore-forming material having a function of forming pores in the film by thermal decomposition during film formation The insulating film according to any one of the above.

  (12) The insulating film according to any one of (1) to (11), wherein the insulating film is formed using a composition containing the polymer having a weight average molecular weight of 90000 to 110,000.

  (13) The insulating film according to any one of (1) to (12), wherein the dielectric constant is 1.80 or more and 2.30 or less.

  (14) At least one selected from the group consisting of the insulating film according to any one of (1) to (13) and SiO, SiN, SiC, SiCN, and SiOC provided in contact with the insulating film And a cap layer made of the above material.

  (15) At least one selected from the group consisting of the insulating film according to any one of (1) to (13) and SiO, SiN, SiC, SiCN, and SiOC provided in contact with the insulating film And a cap layer made of the above material.

  According to the present invention, it is possible to provide an insulating film having a low dielectric constant, excellent adhesion to a substrate (a member on which an insulating film is formed), high reliability, and excellent manufacturing yield. Provides a highly reliable laminate with an insulating film that has low adhesion and excellent adhesion to the substrate (and cap layer), and has low dielectric constant and excellent adhesion to the substrate (cap layer) In addition, a semiconductor device that includes the insulating film and has high reliability and excellent manufacturing yield can be provided.

It is a longitudinal cross-sectional view which shows suitable embodiment of the manufacturing method of a semiconductor device. It is a longitudinal cross-sectional view which shows suitable embodiment of the manufacturing method of a semiconductor device. It is a longitudinal cross-sectional view which shows suitable embodiment of the manufacturing method of a semiconductor device. It is a figure for demonstrating how to obtain | require the linear expansion coefficient in the surface direction of an insulating film.

Hereinafter, the present invention will be described in detail.
<Insulating film>
The insulating film of the present invention includes a polymerizable compound having a partial structure including an adamantane-type cage structure and a polymerizable reactive group contributing to the polymerization reaction in the molecule and / or the polymerizable compound partially polymerized. The linear expansion coefficient in the surface direction is 9 × 10 ⁻⁶ K ⁻¹ or more and 25 × 10 ⁻⁶ K ⁻¹ or less. . As a result, an insulating film having a low dielectric constant, excellent adhesion to the substrate (a member on which the insulating film is formed), high reliability, and excellent manufacturing yield can be provided.

  As described above, according to the present invention, as a result of earnest research, the insulating film is formed using a compound having a predetermined chemical structure, and the linear expansion coefficient in the surface direction of the insulating film is in a predetermined range. It has the characteristic in the point which discovered that the above outstanding effects were acquired by being inside. Therefore, when the insulating film is simply formed using a compound having a predetermined chemical structure (when the linear expansion coefficient in the surface direction of the insulating film is not included in the predetermined range), or simply the insulating film When the linear expansion coefficient in the plane direction is within a predetermined range (when the insulating film is not formed using a compound having a predetermined chemical structure), and further, the line in the thickness direction of the insulating film Even if the expansion coefficient is within a predetermined range, the above-described excellent effect cannot be obtained if the linear expansion coefficient in the surface direction of the insulating film is not within the predetermined range.

  The composition used for forming the insulating film is a polymer in which a “polymerizable compound having a partial structure including an adamantane-type cage structure and a polymerizable reactive group contributing to the polymerization reaction” is partially polymerized. The polymer contains a polymerizable compound other than “a polymerizable compound having a partial structure including an adamantane-type cage structure and a polymerizable reactive group contributing to the polymerization reaction” (hereinafter referred to as “other compounds”). It may contain a "polymerizable compound"). When the polymer contains other polymerizable compound, the content of the other polymerizable compound in the polymer (value calculated by converting the weight of the polymerizable compound used for polymer synthesis) is: It is preferably 30 wt% or less, more preferably 20 wt% or less, and even more preferably 10 wt% or less.

As described above, in the present invention, the linear expansion coefficient in the plane direction of the insulating film may be 9 × 10 ⁻⁶ K ⁻¹ or more and 25 × 10 ⁻⁶ K ⁻¹ or less, but 10 × 10 ^−6. It is preferably K ⁻¹ or more and 24 × 10 ⁻⁶ K ⁻¹ or less. Thereby, the effects as described above can be exhibited more remarkably.

  The dielectric constant of the insulating film of the present invention is preferably 1.80 or more and 2.30 or less, and more preferably 2.00 or more and 2.25 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.

  The thickness of the insulating film is not particularly limited, but is preferably 0.01 μm or more and 20 μm or less, more preferably 0.02 to 10 μm, and further preferably 0.03 μm or more and 0.7 μm or less. .

  As described above, the insulating film of the present invention includes a polymerizable compound having a partial structure including an adamantane cage structure and a polymerizable reactive group contributing to a polymerization reaction in the molecule, and / or the polymerizable compound. Is formed using a composition (film-forming composition) containing a partially polymerized polymer. Hereinafter, the film forming composition used for forming the insulating film will be described in detail.

(Film forming composition)
The composition used for forming the insulating film as described above (film forming composition) includes a partial structure A including an adamantane cage structure in the molecule, and a polymerizable reactive group B that contributes to the polymerization reaction. As long as it includes a polymerizable compound having a polymer and / or a polymer in which the polymerizable compound is partially polymerized, the polymerizable compound X and / or the polymerizable compound X as described below is partially It preferably contains a polymerized polymer.

[1] Polymerizable compound X
The polymerizable reactive group B of the polymerizable compound X has an aromatic ring and an ethynyl group or a vinyl group directly bonded to the aromatic ring. In the polymerizable compound X, the number of carbons derived from the aromatic ring is The total number of carbon atoms in the polymerizable compound X is preferably 15% or more and 38% or less, more preferably 18% or more and 27% or less. Thereby, the dielectric constant of an insulating film can be made lower. In addition, the linear expansion coefficient in the surface direction of the insulating film can be made more suitable, and the adhesion with the member on which the insulating film is formed can be made particularly excellent. As a result, the reliability of the stacked body including the insulating film and the semiconductor device can be made particularly high. In addition, the yield of an insulating film or a semiconductor device including the insulating film can be made particularly excellent.

  In addition, since the ethynyl group or vinyl group which the polymerizable reactive group B has is a polymerizable group when the polymerizable compounds are polymerized and exhibits the same function, the polymerizable reactive group will be described below. The case where B has an ethynyl group will be described representatively.

Hereinafter, the partial structure A and the polymerizable reactive group B will be described.
[1.1] Partial structure A
The partial structure A possessed by the polymerizable compound X includes an adamantane cage structure. Thereby, the insulating film formed using the film-forming composition can have a low density, and the dielectric constant of the formed insulating film can be reduced. In addition, the linear expansion coefficient in the surface direction of the insulating film can be made more suitable, and the adhesion with the member on which the insulating film is formed can be made particularly excellent. As a result, the reliability of the stacked body including the insulating film and the semiconductor device can be made particularly high. In addition, the yield of an insulating film or a semiconductor device including the insulating film can be made particularly excellent. Further, since the reactivity of the polymerizable compound X having the polymerizable reactive group B as described in detail later can be made appropriate, a film on a member (for example, a semiconductor substrate) on which an insulating film is to be formed. When applying the forming composition, the viscosity of the film forming composition can be surely suitable, and unintentional variations in thickness and characteristics at each site of the insulating film to be formed can be suppressed. In addition, the strength of the finally formed insulating film can be made excellent.

Examples of the partial structure A possessed by the polymerizable compound X include adamantane, polyadamantane (eg, biadamantane, triadamantane, tetraadamantane, pentaadamantane, hexaadamantane, heptaadamantane, etc.), polyamantane (eg, diamantane, triamantane, Tetramantane, pentamantane, hexamantane, heptamantane, etc.), divalent groups such as compounds in which at least a part of hydrogen atoms constituting these compounds are substituted with alkyl groups or halogen atoms (two hydrogen atoms constituting the above compounds) A structure having two or more of these divalent groups (for example, a bi (diamantane) skeleton, a tri (diamantane) skeleton, a tetra (diamantane) skeleton, etc.) Things (Poly (Gia (Having a poly (triamantane) skeleton), such as a bi (triamantane) skeleton, a tri (triamantane) skeleton, and a tetra (triamantane) skeleton. An adamantane skeleton (or a polyadamantane skeleton) and a polyamantane skeleton, etc.) and the like. Hereinafter, a part of the example of the partial structure A is shown by a chemical structural formula, but the partial structure A is not limited to these. However, in the following formulas (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 A preferably has an adamantane structure. Thereby, the dielectric constant of the insulating film formed using the film forming composition can be made particularly low. In addition, the linear expansion coefficient in the surface direction of the insulating film can be made more suitable, and the adhesion with the member on which the insulating film is formed can be made particularly excellent. As a result, the reliability of the stacked body including the insulating film and the semiconductor device can be made particularly high. In addition, the yield of an insulating film or a semiconductor device including the insulating film can be made particularly excellent. Further, the reactivity of the polymerizable compound X can be made more suitable, and when the composition for forming a film on a member (for example, a semiconductor substrate) on which an insulating film is to be formed is applied, the film formation is performed. It is possible to make the viscosity of the composition for use more surely suitable, and more effectively suppress unintentional variations in thickness and characteristics in each part of the insulating film to be formed, and finally formed The strength of the insulating film can be made particularly excellent.

  The adamantane structure preferably has a methyl group as a substituent. Thereby, the dielectric constant of the insulating film formed using the film forming composition can be made particularly low. In addition, the linear expansion coefficient in the surface direction of the insulating film can be made more suitable, and the adhesion with the member on which the insulating film is formed can be made particularly excellent. As a result, the reliability of the stacked body including the insulating film and the semiconductor device can be made particularly high. In addition, the yield of an insulating film or a semiconductor device including the insulating film can be made particularly excellent. Further, the reactivity of the polymerizable compound X can be made more suitable, and when the composition for forming a film on a member (for example, a semiconductor substrate) on which an insulating film is to be formed is applied, the film formation is performed. It is possible to make the viscosity of the composition for use more surely suitable, and more effectively suppress unintentional variations in thickness and characteristics in each part of the insulating film to be formed, and finally formed The strength of the insulating film can be made particularly excellent.

  From the above, as the partial structure A, one having a structure represented by the following formula (2) is particularly suitable. In the following formula (2), n represents an integer of 1 or more.

  By selecting a structure having such a structure as the partial structure A, the insulating film formed using the film-forming composition exhibits the above-described effects more remarkably.

  In addition, it is preferable that the partial structure A having such a structure is a structure having symmetry itself. That is, in the above formula (2), n is preferably an even number. Thereby, the reactivity of the polymerizable compound X can be made more appropriate, and when the composition for forming a film on a member (for example, a semiconductor substrate) on which an insulating film is to be formed is applied, the film The viscosity of the 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 insulating film to be formed, and the final formation. The strength of the insulating film can be made particularly excellent.

  The partial structure A may have a diamantane structure. Thereby, the dielectric constant of the insulating film formed using the film forming composition can be lowered. Further, the reactivity of the polymerizable compound X can be made more suitable, and when the composition for forming a film on a member (for example, a semiconductor substrate) on which an insulating film is to be formed is applied, the film formation is performed. It is possible to make the viscosity of the composition for use more surely suitable, and more effectively suppress unintentional variations in thickness and characteristics in each part of the insulating film to be formed, and finally formed The strength of the insulating film can be made particularly excellent. In addition, the linear expansion coefficient in the surface direction of the insulating film can be made more suitable, and the adhesion with the member on which the insulating film is formed can be made particularly excellent. As a result, the reliability of the stacked body including the insulating film and the semiconductor device can be made particularly high. In addition, the yield of an insulating film or a semiconductor device including the insulating film can be made particularly excellent.

[1.2] Polymerizable reactive group B
In addition to the partial structure A as described above, the polymerizable compound X has a polymerizable reactive group B that contributes to the polymerization reaction.

  As a preferred embodiment of the polymerizable compound X, the polymerizable reactive group B has an aromatic ring and an ethynyl group directly bonded to the aromatic ring. The polymerizable compound X may have one polymerizable reactive group B, but has two, and these have a structure in which they are symmetrically bonded around the partial structure A. preferable. Thereby, the reactivity of the polymerizable compound X can be made appropriate, and when the composition for forming a film on a member (for example, a semiconductor substrate) on which an insulating film is to be formed is applied, the film formation is performed. The viscosity of the composition for use is surely suitable, and it is possible to suppress unintentional variations in the thickness and characteristics of each part of the insulating film to be formed, and to reduce the strength of the insulating film to be finally formed. It can be excellent.

  As described above, the polymerizable compound X has two polymerizable reactive groups B together with the partial structure A, and furthermore, these have a specific arrangement, so that particularly excellent effects are exhibited.

  The aromatic ring constituting the polymerizable reactive group B is not particularly limited, and for example, a benzene ring, naphthalene ring, anthracene ring, naphthacene ring, phenanthrene ring, chrysene ring, pyrene ring, perylene ring, coronene ring, biphenyl ring, Hydrocarbon aromatic rings such as terphenyl 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, Examples thereof include heterocyclic aromatic rings such as thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, quinoline ring, and terthienyl ring. Of these, a benzene ring is preferred as the aromatic ring. Thereby, application | coating of the composition for film formation on the member (for example, semiconductor substrate) which should form an insulating film can be performed more easily. In addition, the linear expansion coefficient in the surface direction of the insulating film can be made more suitable, and the adhesion with the member on which the insulating film is formed can be made particularly excellent. As a result, the reliability of the stacked body including the insulating film and the semiconductor device can be made particularly high. In addition, the yield of an insulating film or a semiconductor device including the insulating film can be made particularly excellent. In addition, the elastic modulus of the insulating film formed using the film forming composition can be made suitable, and the strength and heat resistance of the formed insulating film can be made particularly excellent.

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

  The polymerizable reactive group B 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. Thereby, the linear expansion coefficient in the surface direction of an insulating film can be made more suitable, and the adhesiveness with the member in which an insulating film is formed can be made especially excellent. As a result, the reliability of the stacked body including the insulating film and the semiconductor device can be made particularly high. Further, since the polymerizable reactive group B has two ethynyl groups as reaction sites, an initial reaction with respect to the polymerizable compound X easily occurs. On the other hand, when one of the two ethynyl groups of the polymerizable reactive group B reacts (polymerization reaction), the electronic state of the aromatic ring changes, and the reactivity of the other ethynyl group rapidly increases. descend. For this reason, only one ethynyl group of the two ethynyl groups of the polymerizable reactive group B can be selectively reacted under relatively mild conditions. And since the polymerizable compound X preferably has two polymerizable reactive groups B in the molecule, one of the two polymerizable reactive groups B present in the molecule of the polymerizable compound X is Only the ethynyl group can be reacted selectively. In this case, for example, a polymer (chain-like prepolymer) in which a plurality of polymerizable compounds X are polymerized one-dimensionally by a reaction shown in the following formula (3). Polymer).

（式（３）中、Ａは部分構造Ａを示し、Ａｒは重合性反応基Ｂを構成する芳香環を示す。また、ｎは、２以上の整数を表す。）

(In formula (3), A represents the partial structure A, Ar represents an aromatic ring constituting the polymerizable reactive group B, and n represents an integer of 2 or more.)

  In the case where the polymerizable reactive group B has a vinyl group instead of an ethynyl group, a polymer in which a plurality of polymerizable compounds X are polymerized one-dimensionally by a reaction shown in the following formula (3 ′) ( A chain prepolymer) is obtained.

（式（３’）中、Ａは部分構造Ａを示し、Ａｒは重合性反応基Ｂを構成する芳香環を示す。また、ｎは、２以上の整数を表す。）

(In the formula (3 ′), A represents the partial structure A, Ar represents an aromatic ring constituting the polymerizable reactive group B, and n represents an integer of 2 or more.)

  When the reaction as described above occurs, the polymerizable compound X reacts excessively during storage of the film-forming composition, and the film-forming composition becomes extremely viscous (for example, gelation). When the composition for film formation on the member (for example, a semiconductor substrate) on which the insulating film is to be formed is applied, the viscosity of the film formation composition is surely ensured. It can be made suitable. As a result, it is possible to reliably suppress the occurrence of unintentional variations in thickness and characteristics at each portion of the formed insulating film.

  On the other hand, since 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 insulating film has a three-dimensionally cross-linked structure. As a result, the formed insulating film is particularly excellent in heat resistance and the like.

  As described above, when each polymerizable reactive group B constituting the polymerizable compound X has two ethynyl groups, in the polymerizable reactive group B, one ethynyl group is a meta of the other ethynyl group. It is preferable that it exists in a position. Thereby, in the state in which one ethynyl group of the two ethynyl groups of the polymerizable reactive group B has reacted (polymerization reaction), the electronic effect of the aromatic ring or the like is more significantly exhibited, and the other ethynyl group The reactivity can be reduced more effectively, the reacted site becomes an appropriate steric hindrance, and the reactivity of the other ethynyl group (unreacted ethynyl group) can be more suitably controlled. . As a result, the reactivity of the two ethynyl groups of the polymerizable reactive group B (reactivity for the first stage reaction and reactivity for the second stage reaction) is made higher. In addition, it is possible to carry out the firing step as described in detail later under more suitable conditions (conditions in which an insulating film can be formed with excellent productivity while preventing damage to the semiconductor substrate). .

  In addition, when the polymerizable reactive group B 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 the two ethynyl groups of the polymerizable reactive group B has reacted (polymerization reaction), the electronic effect of the aromatic ring or the like is more significantly exhibited, and the other ethynyl group The reactivity can be reduced more effectively, and the reacted site and the partial structure A described above become an appropriate steric hindrance, and the reactivity of the other ethynyl group (unreacted ethynyl group) can be reduced. It can control more suitably. As a result, the reactivity of the two ethynyl groups of the polymerizable reactive group B (reactivity for the first stage reaction and reactivity for the second stage reaction) is made higher. In addition, it is possible to carry out the firing step as described in detail later under more suitable conditions (conditions in which an insulating film can be formed with excellent productivity while preventing damage to the semiconductor substrate). . In addition, the linear expansion coefficient in the surface direction of the insulating film can be made more suitable, and the adhesion with the member on which the insulating film is formed can be made particularly excellent. As a result, the reliability of the stacked body including the insulating film and the semiconductor device can be made particularly high. In addition, the yield of an insulating film or a semiconductor device including the insulating film can be made particularly excellent.

  A polymerizable compound X that satisfies the above conditions, that is, a preferable one as the partial structure A and the polymerizable reactive group B is selected, and an aromatic ring-derived carbon in the polymerizable compound X is set to an appropriate number. Examples of the polymerizable compound X include those having a structure represented by the following formula (1) and structures represented by the following formula (5). In the following formula (1), in the following formula (5), n represents an integer of 1 to 5.

  By selecting the compound having such a structure as the polymerizable compound X, the insulating film formed using the film-forming composition exhibits the above-described effects more remarkably.

  In addition, in the polymerizable compound X having the structure represented by the above formula (1), those having two polymerizable reactive groups B are exemplified, but other polymerizable compounds having one polymerizable reactive group B are exemplified. Examples of X include those having a structure represented by the following formula (1 ′). In the following formula (1 ′), n represents an integer of 1 or 2.

  The polymerizable compound X may have a partial structure other than the partial structure A and the polymerizable reactive group B.

  The polymerizable compound X as described above has two polymerizable reactive groups B, and when the polymerizable reactive group B has two ethynyl groups, for example, it can be synthesized as follows. it can.

  That is, a compound A ′ corresponding to partial structure A (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 ′ (two bromo groups are bonded to partial structure A) A compound obtained by 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 partial structure A), and A Reacting a dibromophenyl form of 'with trimethylsilylacetylene to obtain a bis (di (trimethylsilylethynyl) phenyl) form of A' (a compound in which two di (trimethylsilylethynyl) phenyl groups are bonded to partial structure A); And a step of hydrolyzing (detrimethylsilylating) the bis (di (trimethylsilylethynyl) phenyl) form of It can be obtained that the polymerizable compound X.

  In the case where the polymerizable reactive group B has two vinyl groups instead of two ethynyl groups, the polymerizable compound X can be synthesized, for example, as follows.

  That is, after synthesizing the polymerizable compound X having the 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, etc. By carrying out, the target polymeric compound X can be obtained.

  Further, the case where the ethynyl group and the vinyl group coexist is also preferable in the present invention. For example, when the ethynyl group is reduced to a vinyl group, by controlling conditions such as stopping the reduction reaction halfway. The ethynyl group and the vinyl group can coexist.

  The film-forming composition may contain the polymerizable compound X alone as described above. For example, the polymerizable compound X has two polymerizable reactive groups B and / or polymerizes. When the polymerizable reactive group B has two ethynyl groups, a polymer in which the polymerizable compound X is partially polymerized (a prepolymer in which only one polymerizable reactive group B of the two polymerizable reactive groups B is polymerized or reacted) And a prepolymer obtained by polymerization reaction of only one ethynyl group of the two ethynyl groups of the polymerizable reactive group B. The polymer may further contain other polymerizable compound (polymerizable compound other than the polymerizable compound X). When the film-forming composition contains a polymer (prepolymer) in which the polymerizable compound X is partially polymerized, the viscosity of the film-forming composition is more surely suitable, and each of the insulating films to be formed Unintentional variations in thickness and characteristics at the site can be more effectively suppressed, and the strength of the finally formed insulating film can be made particularly excellent. Further, even if the insulating film to be formed is relatively thick, it can be suitably formed. In addition, when the film-forming composition contains the prepolymer of the polymerizable compound X, when an insulating film is formed on a member (for example, a semiconductor substrate), the amount of heat applied on the member can be reduced. The damage to the member due to heating can be more reliably prevented. Such a film-forming composition containing a prepolymer of the polymerizable compound X can be suitably used as an insulating film varnish.

  This step is, for example, a method by thermal polymerization in which the reaction is carried out without using a catalyst, a method by radical polymerization using a radical initiator such as benzoyl peroxide, t-butyl peroxide, azobisisobutyronitrile, Photoradical polymerization using light irradiation, etc., using palladium catalysts such as dichlorobis (triphenylphosphine) palladium (II), bis (benzonitrile) palladium (II) dichloride and tetrakis (triphenylphosphine) palladium (0) Polymerization method, polymerization method using transition metal catalyst such as copper (II) acetate, polymerization using transition metal chloride such as molybdenum chloride (V), tungsten chloride (VI) and tantalum chloride (V). The method etc. can be mentioned. 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. Moreover, you may perform the heat processing with respect to the composition (composition containing a polymeric compound) obtained at the said process combining different conditions. For example, in the thermal polymerization, for the composition (composition containing a polymerizable compound) obtained in the above step, the first is performed under the conditions of heating temperature: 150 to 190 ° C. and heating time: 1 to 6 hours. It is also possible to appropriately select the heat treatment and the second heat treatment performed under the conditions of heating temperature: 120 to 160 ° C. and heating time: 2 to 9 hours, or further multi-stage heat treatment. 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 composition (composition containing a polymeric compound) obtained at the said process in the solvent. In addition, the synthesis of the prepolymer by the heat treatment as described above may be performed in a solvent as a component of the film-forming composition to be prepared, and what is a component of the film-forming composition? You may perform in the solvent of a different composition. That is, after a polymerizable compound is polymerized using a predetermined solvent to obtain a prepolymer, the solvent may be replaced with a solvent as a component of the target film-forming composition. Examples of the solvent (reaction solvent) that can be used for the synthesis of a polymer (prepolymer) in which a polymerizable compound is partially polymerized include alcohol solvents such as methanol, ethanol, isopropanol, 1-butanol, and 2-butanol. ; Ketone solvents such as acetone, acetylacetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, 2-pentanone, 2-heptanone; esters such as ethyl acetate, propyl acetate, butyl acetate, pentyl acetate, propylene glycol monomethyl ether acetate Solvents such as diisopropyl ether, dibutyl ether, diphenyl ether, tetrahydrofuran, anisole, 1,2-dimethoxybenzene, 1,3-dimethoxybenzene, 1,4-dimethoxybenzene, etc. Solvents; aromatic and aliphatic hydrocarbon solvents such as benzene, toluene, mesitylene, ethylbenzene, diethylbenzene, propylbenzene, heptane, hexane, n-octane; chloromethane, dichloroethane, chloroform, dichloroethane, carbon tetrachloride, etc. Halide-based solvents; amide-based solvents such as N-methylpyrrolidone and the like can be mentioned, and one or more selected from these can be used in combination.

  In addition, when the film-forming composition contains a prepolymer of the polymerizable compound X, the unreacted polymerizable compound X is removed by purification (the unreacted polymerizable compound X is not included as much as possible). Is preferred. Thereby, various characteristics such as strength of the insulating film formed using the film forming composition can be more reliably improved.

  The content of the polymerizable compound X in the film-forming composition and a polymer in which the polymerizable compound X is partially polymerized (for example, only one polymerizable reactive group B out of two polymerizable reactive groups B undergoes a polymerization reaction). The sum of the prepolymer and the content of the prepolymer obtained by polymerization reaction of only one ethynyl group of the two ethynyl groups of the polymerizable reactive group B is preferably 1.0 to 30 wt%.

  In the above description, a case where a polymerizable compound having a polymerizable reactive group having an aromatic ring and an ethynyl group or a vinyl group directly bonded to the aromatic ring (polymerizable compound X) is representatively described. However, in the present invention, the polymerizable compound only needs to have a partial structure including an adamantane cage structure and a polymerizable reactive group that contributes to the polymerization reaction. Other than the polymerizable compound X as described above It may be. For example, in the present invention, the polymerizable compound may not have an aromatic ring. Further, in the present invention, the polymerizable compound has a polymerizable reactive group as a functional group other than an ethynyl group and a vinyl group (for example, a group in which a hydrogen atom of an ethynyl group is substituted with another atom or an atomic group, a vinyl group, In which at least one of the hydrogen atoms constituting is substituted with another atom or atomic group).

  In addition, when the ethynyl group has a substituent, the trimethylsilylacetylene is substituted with an alkyl group-substituted acetylene such as propyne, butyne, pentine, or the like, or an aryl group such as phenylacetylene acetylene, naphthylacetylene, fluorenylacetylene, or the like. A polymerizable compound having a corresponding substituted ethynyl group can be obtained by performing the above steps other than detrimethylsilylation by replacing with substituted acetylene, and further with a cycloalkyl group-substituted acetylene such as cyclohexylacetylene, adamantylacetylene and the like.

  Further, when the polymerizable compound has a substituted vinyl group, the corresponding substituted vinyl group can be synthesized by performing the same reduction reaction on the substituted ethynyl group.

[2] Solvent The film-forming composition may contain a polymerizable compound and / or a polymer obtained by partially polymerizing the polymerizable compound as described above, but usually contains a solvent that dissolves them. It is a waste.

  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 and the like, can be used singly or in combination of two or more selected from these. Of these, cyclopentanone and cyclohexanone are preferable as the solvent. Examples of the solvent constituting the film forming composition include a solvent (reaction solvent) used for the synthesis of a polymerizable compound and the above-described polymer (a prepolymer obtained by partially polymerizing a polymerizable compound). It may be a thing.

  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 surfactants; coupling agents such as silane coupling agents; catalysts such as radical initiators and disulfides; “partial structures including an adamantane-type cage structure and contribution to the polymerization reaction” Polymerizable compounds (other polymerizable compounds) other than the “polymerizable compound having a polymerizable reactive group”, polymers obtained by polymerizing the “other polymerizable compounds” (other polymers), and the like.

  The film-forming composition may contain a naphthoquinone diazide compound as a photosensitizer. Thereby, the composition for film formation can be used suitably for formation of the surface protection film which has photosensitivity.

  In the present invention, it is preferable that the film-forming composition does not contain a pore-forming material that foams due to thermal decomposability and forms pores in the formed insulating film. Conventionally, a hole forming material has been used for the purpose of reducing the dielectric constant of the insulating film. However, when such a hole forming material is used, the strength of the formed insulating film decreases, Although there were problems such as undesired thickness variations and characteristic variations in each part, the present invention has a sufficient dielectric constant of the insulating film to be formed without using a hole forming material. Can be 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 forming an insulating film, but the polymerizable compound has two polymerizable reactive groups and / or the polymerizable reactive group is In the case of having two ethynyl groups, it may be subjected to a heat treatment prior to application onto a member (for example, a semiconductor substrate) on which an insulating film is to be formed. Thereby, the film-forming composition can include a polymer (prepolymer) in which the polymerizable compound is partially polymerized, and the viscosity of the film-forming composition is more surely suitable and formed. In addition, it is possible to more effectively suppress the unintentional variation in thickness and characteristics of each part of the insulating film, and the strength of the finally formed insulating film can be made particularly excellent. In addition, the insulating film to be formed is compared by subjecting the film forming composition to heat treatment prior to applying the film forming composition onto the member (for example, a semiconductor substrate) on which the insulating film is to be formed. Even if it is thick, it can be suitably formed. 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 an insulating film is to be formed, the amount of heat applied on the member is increased. Since it can reduce, the damage to the said member by the 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.

  In the insulating film of the present invention, for example, the film-forming composition as described above is applied onto a member such as a semiconductor substrate, and subjected to a treatment (baking treatment) such as heating or irradiation with active energy rays. Is formed.

  By performing the baking treatment as described above, the polymerizable compound or the unreacted polymerizable reactive group of the prepolymer in which the polymerizable compound is partially polymerized undergoes a polymerization reaction, and is composed of a polymer (cured product). An insulating film is obtained. An insulating film composed of a polymer (cured product) having such a chemical structure is excellent in strength, heat resistance, and the like. Further, the insulating film obtained as described above has a low dielectric constant. Further, the insulating film obtained as described above is one in which unintentional variations in film thickness and characteristics at each part are suppressed. For this reason, the insulating film as described above can be suitably used as an insulating film constituting a semiconductor device. In addition, as described above, the insulating film of the present invention has excellent adhesion to the member on which the insulating film is formed, and is formed even when the above baking treatment (heat treatment) is performed. The insulating film thus formed is preferably prevented from unintentionally peeling from the member to which the film forming composition is applied (the member on which the insulating film is formed). As a result, the yield of an insulating film or a semiconductor device including the insulating film can be improved.

  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.

  The baking treatment is preferably performed under conditions of, for example, a processing temperature: 200 to 450 ° C. and a processing time of 1 to 60 minutes, and a processing temperature of 250 to 400 ° C. and a processing time of 5 to 30 minutes. More preferred. In the baking step, heat treatments with different conditions may be combined.

<Manufacturing method of semiconductor device, laminated body, semiconductor device>
1 to 3 are longitudinal sectional views showing a preferred embodiment of a method for manufacturing a semiconductor device. In the following description, the upper side in FIGS. 1 to 3 is referred to as “upper” and the lower side is referred to as “lower”.

  As shown in FIGS. 1 to 3, in the manufacturing method of the present embodiment, a semiconductor substrate preparation process for preparing a semiconductor substrate 1 on which elements are formed, and a barrier film 2 such as a SiCN film is formed on the surface of the semiconductor substrate 1. A barrier film forming step (1b), an insulating film forming step (1c) for forming an interlayer insulating film 3 as an insulating film of the present invention on the surface of the barrier film 2, and a cap layer 4 on the surface of the interlayer insulating film 3 A cap layer forming step (1d) for forming a laminated body 10 having a laminated structure of the interlayer insulating film 3 and the cap layer 4 and a resist film forming step for forming a resist film 7 on the surface of the cap layer 4 (see FIG. 1e) and a resist that exposes and develops the resist film 7 using a photomask to form an opening (groove) at a position corresponding to a position where a via (conductor post) or a wiring groove is formed in the resist film 7 Film patterning process 1f), a first etching step (1g) for etching the cap layer 4 using the resist film 7 as a mask, a resist film removing step (1h) for removing the resist film 7, and an interlayer using the cap layer 4 as a mask A second etching step (1i) for etching the insulating film 3 to form an opening (groove), and a barrier for preventing diffusion of constituent components of the wiring layer 6 to be described later on the surface provided with the interlayer insulating film A barrier metal forming step (1j) for forming the metal 5, a wiring layer forming step (1k) for forming the wiring layer 6 in the groove portion of the interlayer insulating film 3 covered with the barrier metal 5, and a groove portion made of a wiring material And a polishing step (1l) for removing the portion formed of the constituent material of the barrier metal 5 and provided outside the groove by polishing.

The barrier film forming step can be suitably performed using a vapor phase film forming method.
The insulating film forming step can be suitably performed by applying the film forming composition to the surface of the barrier film 2 by the method as described above. The interlayer insulating film 3 can also be formed by laminating a resin film (insulating film) separately prepared as a dry film in advance on the barrier film 2. More specifically, using a film forming composition, a resin film (insulating film) is formed on a member and dried in advance to obtain a dry film. The dry film is peeled from the member, The interlayer insulating film 3 may be formed by laminating the barrier film 2 and irradiating it with heat and / or radiation. The barrier film 2 may be made of a material known to those skilled in the art as a barrier film and an etch stopper film, but SiCN or SiC is preferably used.

  The cap layer forming step can be suitably performed using a vapor phase film forming method. The cap layer 4 is usually made of SiO, but may be made of SiN, SiC, SiCN, SiOC or the like, for example.

  The resist film forming step can be performed using, for example, various coating methods, and among them, methods such as spin coating using a spinner, spray coating using a spray coater, dipping, printing, roll coating, etc. are preferably applied. can do.

The first etching step is performed by an etching method (reactive ion etching method) using a fluorine-based gas such as CF ₄ as a processing gas. Since the interlayer insulating film 3 satisfies the above conditions, it is reliably prevented that a part of the interlayer insulating film 3 together with the cap layer 4 is removed by unintentional etching. As a result, the semiconductor device 100 finally obtained is highly reliable in which the occurrence of problems such as insulation failure is reliably prevented.

  The second etching step can be performed by an etching method (reactive ion etching method) using a mixed gas of nitrogen and hydrogen, ammonia gas, or the like as a processing gas.

  Note that a resist film removing step by ashing can be appropriately performed before and after the second etching step.

  The barrier metal formation step can be performed by a vapor deposition method such as a PVD method. Examples of the constituent material of the barrier metal 5 include Ta, Ti, TaN, TiN, and WN.

The wiring layer forming step is preferably performed in combination with a vapor deposition method such as PVD and a wet plating method such as electric field plating. Thereby, the formation efficiency of the wiring layer 6 can be made particularly excellent while the adhesion of the wiring layer 6 to the barrier metal 5 is sufficiently excellent. The constituent material of the wiring layer 6 is not particularly limited, but copper (Cu) is preferably used.
The polishing step can be suitably performed by a CMP method (chemical mechanical polishing method).

The above is an example of a preferable manufacturing process of the single-layer wiring of the semiconductor device, but this process is repeated in the case of multilayer wiring.
Through the steps as described above, the semiconductor device 100 can be obtained.

  The semiconductor device of the present invention has another film adjacent to the insulating film in the stacked structure of the semiconductor device, for example, a SiCN film, a SiC film, a SiO film, a SiN film, a SiOC film used as a barrier film or a cap layer. Therefore, it is highly reliable that an adhesion failure is reliably prevented from occurring due to a thermal history during manufacture.

  In addition, since the interlayer insulating film (the insulating film of the present invention) as described above is excellent in dielectric characteristics, signal loss of the semiconductor device can be reduced.

  In addition, the interlayer insulating film (the insulating film of the present invention) as described above is excellent in dielectric characteristics, so that the wiring delay can be reduced.

  As mentioned above, although this invention was demonstrated based on suitable embodiment, this invention is not limited to these.

  For example, in the above description, the example in which the interlayer insulating film 3 as the insulating film of the present invention is formed on the barrier film 2 has been representatively described, but the position where the insulating film is formed is not limited thereto.

The insulating film of the present invention is an insulating film formed using a composition containing a polymerizable compound having a partial structure including an adamantane-type cage structure and a polymerizable reactive group contributing to the polymerization reaction. The linear expansion coefficient in the plane direction may be 9 × 10 ⁻⁶ K ⁻¹ or more and 25 × 10 ⁻⁶ K ⁻¹ or less, and is formed using the composition containing the polymerizable compound X as described above. It does not have to be. In the above-described embodiments, the insulating film provided with the interlayer insulating film is representatively described. However, the insulating film of the present invention may be applied to other than the interlayer insulating film. .

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

[1] Synthesis of polymerizable compound (Synthesis Example 1)
First, 1,3-dimethyladamantane was prepared, and carbon tetrachloride: 700 mL and bromine: 35 g (0.22 mol) were placed in a 4-neck 2000 mL flask equipped with a thermometer, a stirrer, and a reflux tube, and stirred. However, the prepared 1,3-dimethyladamantane: 32.9 g (0.2 mol) was added little by little. During the addition, the internal temperature was kept at 20-30 ° C.

After the addition was completed, the reaction was continued for another hour after the temperature did not rise.
Then, it poured into about 2000 mL of cold water, and the crude product was separated by filtration, washed with pure water, and dried.

The crude product was recrystallized from hot ethanol. The obtained recrystallized product was dried under reduced pressure to obtain 37.4 g of a product. IR analysis shows bromo group absorption at 690-515 cm ⁻¹ , and mass analysis molecular weight of 322 indicates 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 obtain polymerizable compound X. 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 5)
A polymerizable compound X was obtained in the same manner as in Synthesis Example 1 except that tetramethylbiadamantane, hexamethyltriadamantane, octamethyltetraadamantane, and decamethylpentaadamantane were prepared instead of dimethyladamantane.

  The structural formula of the polymerizable compound X obtained in Synthesis Examples 1 to 5 is shown in the following formula (1). In the following formula (1), n represents an integer of 1 to 5, and the number of n corresponds to the number of each synthesis example.

  In addition, the external appearance of n = 2 polymerizable compound X (Synthesis example 2) in the said Formula (1), the result of a mass analysis, and an elemental analysis are shown.

Appearance: White solid MS (FD) (m / z): 574 (M +)
Elemental analysis: Theoretical value (/%) C; 91.93, H; 8.07, Actual value (/%) C; 91.87, H; 8.00

  Moreover, the external appearance of the said compound (1) n = 3 polymeric compound X (synthesis example 3), the result of a mass analysis, and an elemental analysis are shown.

Appearance: White solid MS (FD) (m / z): 737 (M +)
Elemental analysis: Theoretical value (/%) C; 91.25, H; 8.75, Actual value (/%) C; 91.21, H; 8.77

  The external appearance of the said compound (1) n = 4 polymeric compound X (synthesis example 4), the result of a mass analysis, and an elemental analysis are shown.

Appearance: White solid MS (FD) (m / z): 899 (M +)
Elemental analysis: Theoretical value (/%) C; 90.81, H; 9.19, Measured value (/%) C; 90.75, H; 9.16

  The external appearance of the said compound (1) n = 5 polymeric compound X (Synthesis example 5), the result of mass spectrometry, 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

(Synthesis Example 6)
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 reacting in the same manner, 14.3 g of 4,9-bis (3,5-diethynylphenyl) diamantane as the polymerizable compound X 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

(Synthesis Examples 7-9)
A polymerizable compound X was obtained in the same manner as in Synthesis Example 6 except that dibromodi (diamantane), dibromotri (diamantane), and dibromotetra (diamantane) were prepared instead of dibromodiamantane.

  The structural formula of the polymerizable compound X obtained in Synthesis Examples 6 to 9 is shown in the following formula (4). In following formula (4), n represents the integer of 1-4 and the number of n respond | corresponds to (number-5 of each synthesis example).

  In addition, the external appearance of the said Formula (4) n = 2 polymerizable compound X (Synthesis example 7), the result of a mass analysis, and an elemental analysis are shown.

Appearance: White solid MS (FD) (m / z): 622 (M +)
Elemental analysis: Theoretical value (/%) C; 92.56, H; 7.44, Measured value (/%) C; 92.53, H; 7.41

  Moreover, the external appearance of the said compound (4) n = 3 polymeric compound X (synthesis example 8), the result of a mass analysis, and an elemental analysis are shown.

Appearance: White solid MS (FD) (m / z): 809 (M +)
Elemental analysis: Theoretical value (/%) C; 92.03, H; 7.97, Actual value (/%) C; 92.01, H; 7.94

  The external appearance of the said compound (4) n = 4 polymeric compound X (Synthesis example 9), the result of mass spectrometry, and an elemental analysis are shown.

Appearance: White solid MS (FD) (m / z): 995 (M +)
Elemental analysis: theoretical value (/%) C; 91.70, H; 8.30, actual value (/%) C; 91.67, H; 8.28

(Synthesis Example 10)
First, in a 4-neck 2000 mL flask equipped with a thermometer, a stirrer and a reflux tube, 3,5-dimethyl-1-bromoadamantane: 45.5 g (187.1 mmol) and 1,3-dibromobenzene: 1217 g ( 5161.6 mmol) and stirred, and at 25 ° C. under dry nitrogen, aluminum bromide (III): 24.8 g (93.0 mmol) 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.

  Next, the reaction solution was added to 700 mL of 5% hydrochloric acid aqueous solution and stirred. The aqueous layer was removed, and the organic layer was poured into 2000 mL of acetone. The precipitate was filtered and washed 3 times with acetone: 1000 mL to obtain 3,5,5-dimethyl-1- (3,5-dibromophenyl) adamantane: 51.4 g. From the result of the molecular weight of 398 by mass spectrometry, it was shown that the product was 3,5, -dimethyl-1- (3,5-dibromophenyl) adamantane.

  Next, 3,5, -dimethyl-1- (3,5-dibromophenyl) adamantane obtained above: 47.1 g (118.4 mmol), dichlorobistriphenylphosphine palladium: 6.66 g (9.5 mmol) , Triphenylphosphine: 179.5 g (47.3 mmol), copper (II) iodide: 248.7 g (47.3 mmol), and triethylamine: 750 mL were added to the flask and stirred. After raising the temperature to 75 ° C., 34.9 g (355.2 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% hydrochloric acid aqueous solution: 1000 mL was added to the filtrate for liquid separation. The organic layer was washed 3 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 hexane: 1500 mL. Impurities were 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 37 g of 3,5-dimethyl-1- (3,5-ditrimethylsilylethynylphenyl) adamantane. The result of the molecular weight measured by mass spectrometry was 432, indicating that the product was 3,5-dimethyl-1- (3,5-ditrimethylsilylethynylphenyl) adamantane.

  Further, the 3,5-dimethyl-1- (3,5-ditrimethylsilylethynylphenyl) adamantane obtained above (36 g, 83.1 mmol) and potassium carbonate: 2.7 g (19.3 mmol) were mixed with tetrahydrofuran: 600 mL. In a mixed solvent of methanol: 300 mL, the mixture was stirred at room temperature for 4 hours under a nitrogen atmosphere. 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 obtain 3 as a polymerizable compound. , 5-Dimethyl-1- (3,5-diethynylphenyl) adamantane: 19 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- (3,5-diethynylphenyl) adamantane.

Appearance: White solid MS (FD) (m / z): 288 (M +)
Elemental analysis: Theoretical value (/%) C; 91.61, H; 8.39, Actual value (/%) C; 91.59, H; 8.37

(Synthesis Example 11)
A polymerizable compound X was obtained in the same manner as in Synthesis Example 10 except that tetramethylbromobiadamantane was prepared instead of dimethylbromoadamantane.

  The structural formula of the polymerizable compound X obtained in Synthesis Examples 10 and 11 is shown in the following formula (1 ′). In the following formula (1 '), n represents an integer of 1 to 2, and the number of n corresponds to (Number-9 in each synthesis example).

  The appearance, mass analysis, and elemental analysis results of the polymerizable compound X (Synthesis Example 11) having the formula (1 ′) n = 2 are shown.

Appearance: White solid MS (FD) (m / z): 450 (M +)
Elemental analysis: theoretical value (/%) C; 90.61, H; 9.39, actual value (/%) C; 90.59, H; 9.36

(Synthesis Example 12)
First, 4-bromodiamantane: 50 g (187.1 mmol) and 1,3-dibromobenzene: 1217 g (5161.6 mmol) were placed in a 4-neck 2000 mL flask equipped with a thermometer, a stirrer and a reflux tube. Then, 24.8 g (93.0 mmol) of aluminum bromide (III) was added little by little at 25 ° C. under dry nitrogen. This was heated to 60 ° C. and stirred for 8 hours, and then returned to room temperature to obtain a reaction solution.

  Next, the reaction solution was added to 700 mL of 5% hydrochloric acid aqueous solution and stirred. The aqueous layer was removed, and the organic layer was poured into 2000 mL of acetone. The precipitate was filtered and washed 3 times with acetone: 1000 mL to obtain 56 g of 4- (3,5-dibromophenyl) diamantane. The result of the molecular weight of 422 by mass spectrometry showed that the product was 4- (3,5-dibromophenyl) diamantane.

  Next, 4- (3,5-dibromophenyl) diamantane obtained above: 50 g (118.4 mmol), dichlorobistriphenylphosphine palladium: 6.66 g (9.5 mmol), triphenylphosphine: 179.5 g ( 47.3 mmol), copper (II) iodide: 248.7 g (47.3 mmol), and triethylamine: 750 mL were added to the flask and stirred. After raising the temperature to 75 ° C., 34.9 g (355.2 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% hydrochloric acid aqueous solution: 1000 mL was added to the filtrate for liquid separation. The organic layer was washed 3 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 hexane: 1500 mL. Impurities were 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 41 g of 4- (3,5-ditrimethylsilylethynylphenyl) diamantane. From the result of the molecular weight measured by mass spectrometry being 456, it was shown that the product was 4- (3,5-ditrimethylsilylethynylphenyl) diamantane.

  Furthermore, 4- (3,5-ditrimethylsilylethynylphenyl) diamantane obtained above (40 g, 87.6 mmol) and potassium carbonate: 2.7 g (19.3 mmol) were mixed with tetrahydrofuran: 600 mL and methanol: 300 mL. The mixture was stirred for 4 hours at room temperature in a nitrogen atmosphere. 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 obtain 4 as a polymerizable compound. -(3,5-diethynylphenyl) diamantane: 23 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 4- (3,5-diethynylphenyl) diamantane.

Appearance: White solid MS (FD) (m / z): 312 (M +)
Elemental analysis: Theoretical value (/%) C; 92.26, H; 7.74, Actual value (/%) C; 92.12, H; 7.70

(Synthesis Example 13)
A polymerizable compound X was obtained in the same manner as in Synthesis Example 12 except that bromobi (diamantane) was prepared instead of bromodiamantane.

  The structural formula of the polymerizable compound X obtained in Synthesis Examples 12 and 13 is represented by the following formula (4 ′). In the following formula (4 '), n represents an integer of 1 to 2, and the number of n corresponds to (No. 11 of each synthesis example).

  The appearance, mass analysis, and elemental analysis results of the polymerizable compound X (Synthesis Example 13) having the formula (4 ′) n = 2 are shown.

Appearance: White solid MS (FD) (m / z): 498 (M +)
Elemental analysis: Theoretical value (/%) C; 91.51, H; 8.94, Actual value (/%) C; 91.49, H; 8.46

(Synthesis Example 14)
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) adamantane 18.1 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-divinylphenyl) adamantane.

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 Examples 15-22)
The same as Synthesis Example 14 except that the polymerizable compound obtained in Synthesis Examples 2 to 9 was prepared instead of 3,5-dimethyl-1,7-bis (3,5-diethynylphenyl) adamantane. Thus, a polymerizable compound X was obtained.

  The structural formula of the polymerizable compound X obtained in Synthesis Examples 14 to 18 is shown in the above formula (5), and the structural formula of the polymerizable compound X obtained in Synthesis Examples 19 to 22 is shown in the following formula (6). . Moreover, in Formula (5), n represents the integer of 1-5, the number of n respond | corresponds to (number-13 of each synthesis example), and in Formula (6), n represents the integer of 1-4. , N corresponds to (number -18 in each synthesis example).

  In addition, the external appearance of the said Formula (5) n = 2 polymerizable compound X (Synthesis example 15), the result of a mass analysis, and an elemental analysis are shown.

Appearance: White solid MS (FD) (m / z): 582 (M +)
Elemental analysis: theoretical value (/%) C; 90.66, H; 9.34, actual measurement value (/%) C; 90.63, H; 9.31

  Moreover, the external appearance of the said compound (5) n = 3 polymeric compound X (synthesis example 16), the result of a mass analysis, and an elemental analysis are shown.

Appearance: White solid MS (FD) (m / z): 745 (M +)
Elemental analysis: theoretical value (/%) C; 90.26, H; 9.74, actual measurement value (/%) C; 90.24, H; 9.70

  The external appearance of the said compound (5) n = 4 polymeric compound X (Synthesis example 17), the result of a mass analysis, and an elemental analysis are shown.

Appearance: White solid MS (FD) (m / z): 907 (M +)
Elemental analysis: Theoretical value (/%) C; 90.00, H; 10.00, Actual value (/%) C; 89.96, H; 9.97

  The external appearance of the said compound (5) n = 5 polymeric compound X (Synthesis example 18), the result of a mass analysis, and an elemental analysis are shown.

Appearance: White solid MS (FD) (m / z): 1069 (M +)
Elemental analysis: Theoretical value (/%) C; 89.82, H; 10.18, Actual value (/%) C; 89.80, H; 10.14

  The external appearance of the said compound (6) n = 1 polymeric compound X (Synthesis example 19), the result of mass spectrometry, and an elemental analysis are shown.

Appearance: White solid MS (FD) (m / z): 444 (M +)
Elemental analysis: Theoretical value (/%) C; 91.84, H; 8.16, measured value (/%) C; 91.81, H; 8.13

  The external appearance of the said compound (6) n = 2 polymerizable compound X (synthesis example 20), the result of a mass analysis, and an elemental analysis are shown.

Appearance: White solid MS (FD) (m / z): 630 (M +)
Elemental analysis: Theoretical value (/%) C; 91.37, H; 8.63, Actual value (/%) C; 91.32, H; 8.61

  The external appearance of the said Formula (6) n = 3 polymeric compound X (Synthesis example 21), the result of a mass analysis, and an elemental analysis are shown.

Appearance: White solid MS (FD) (m / z): 817 (M +)
Elemental analysis: Theoretical value (/%) C; 91.12, H; 8.88, measured value (/%) C; 91.10, H; 8.84

  The external appearance of the said Formula (6) n = 4 polymeric compound X (Synthesis example 22), the result of a mass analysis, and an elemental analysis are shown.

Appearance: White solid MS (FD) (m / z): 1003 (M +)
Elemental analysis: Theoretical value (/%) C; 90.96, H; 9.04, measured value (/%) C; 90.93, H; 9.01

(Synthesis Example 23)
First, a reaction was carried out in the same manner as in Synthesis Example 1 except that dodecamethyl hexaadamantane was prepared instead of dimethyladamantane to obtain a product.
The appearance of the obtained product, the results of mass spectrometry and 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

  These data indicate that the obtained product is a compound represented by n = 6 in the formula (1).

Next, a polymerizable compound X was obtained by carrying out the same reaction as in Synthesis Example 14.
The appearance of the product, the results of mass spectrometry and elemental analysis are shown below. These data show that the compound (polymerizable compound X) obtained above is a compound represented by n = 6 in the formula (5).

Appearance: White solid MS (FD) (m / z): 1231 (M +)
Elemental analysis: theoretical value (/%) C; 89.69, H; 10.31, actual value (/%) C; 89.66, H; 10.29

(Synthesis Example 24)
A product was obtained in the same manner as in Synthesis Example 12 except that bromotri (diamantane) was prepared instead of bromodiamantane.

  The appearance of the obtained product, the results of mass spectrometry and elemental analysis are shown. These data indicate that the obtained product is a compound represented by n = 3 in the formula (4 ').

Appearance: White solid MS (FD) (m / z): 684 (M +)
Elemental analysis: Theoretical value (/%) C; 91.17, H; 8.83, Actual value (/%) C; 91.14, H; 8.86

(Synthesis Example 25)
Using diamantane as a raw material, Macromolecules. 4,9-diethynyldiamantane 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

Next, 10 g of 4,9-diethynyldiamantane, 50 ml of 1,3,5-triisopropylbenzene and 120 mg of Pd (PPh ₃ ) ₄ were stirred at an internal temperature of 190 ° C. for 12 hours under a nitrogen stream. After the reaction solution was brought to room temperature, 300 ml of isopropyl alcohol was added. The precipitated solid was filtered and washed with methanol to obtain a compound represented by the following formula (7). The obtained compound had a mass average molecular weight of 20000.

[2] Preparation of film-forming composition (Preparation Example 1)
3,5-dimethyl-1,7-bis (3,5-diethynylphenyl) adamantane: 5 g as a polymerizable compound synthesized in Synthesis Example 1 was dissolved in 45 g of 1,3-dimethoxybenzene and dried. The reaction was carried out at 170 ° C. for 3 hours under nitrogen, and the reaction solution was once cooled to room temperature. When the molecular weight was measured by GPC, the number average molecular weight was 46,000. The reaction solution was heated again and reacted at 150 ° C. for 6 hours. The reaction solution was added dropwise to a 10-fold volume of a mixed solvent of methanol / tetrahydrofuran = 3/1, and the precipitate was collected and dried. A prepolymer was obtained (yield: 56%). 2 g of the obtained prepolymer was dissolved in 18 g of cyclopentanone and filtered through a filter to obtain a film forming composition as a varnish for an organic insulating film.

(Preparation Examples 2 to 24)
As the polymerizable compound, except that each synthesized in Synthesis Examples 2 to 24 was used, a polymerization reaction was performed in the same manner as in Preparation Example 1 to obtain a prepolymer, and further, using the prepolymer: 2 g, By performing the same treatment as described in Preparation Example 1, a film forming composition as a varnish for an organic insulating film was obtained.

(Preparation Example 25)
As a polymerizable compound, 2.0 g of the compound synthesized in Synthesis Example 25 was dissolved in 20 g of cyclohexanone and filtered through a filter to obtain a film-forming composition as a varnish for an organic insulating film.

  In addition, about the polymerizable compound used for preparation of the film-forming composition in each preparation example, the number of carbons derived from the aromatic ring, the number of carbons derived from the polymerizable reactive group, the number of carbons derived from the partial structure, and the aromatic ring-derived, respectively. The ratio of carbon is shown in Table 1.

[3] Formation of insulating film (production of substrate with insulating film)
In the following manner, a plurality of substrates with insulating films were prepared for each of the examples and comparative examples.

(Examples 1 to 23)
Insulating films were formed as follows using the film forming compositions as varnishes for organic insulating films obtained in Preparation Examples 1 to 23, respectively.

  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 150 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) in a 400 ° C. oven in a nitrogen atmosphere for 10 minutes to cure the prepolymer constituting the coating film, and to form an insulating film. Then, a substrate with an insulating film was obtained.

(Comparative Example 1)
A substrate with an insulating film was obtained in the same manner as in the above example, except that the composition for film formation was the same as that obtained in Preparation Example 24.

(Comparative Example 2)
As the film forming composition, the film forming composition as the organic insulating film varnish obtained in Preparation Example 25 was used, and 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 150 nm.

  Next, the silicon wafer provided with the coating film as described above was placed on a hot plate at 110 ° C. for 1 minute and 30 seconds under a nitrogen stream, and then placed on a hot plate at 250 ° C. for 1 minute under a nitrogen stream, The solvent (cyclohexanone) contained in the coating film was removed.

Thereafter, for the silicon wafer provided with the dried coating film, electron beam irradiation (Ar atmosphere, pressure 20 kPa, substrate temperature 350 ° C., electron acceleration voltage 20 kV: electron beam dose 1 μC cm ⁻² : Mini-EB manufactured by USHIO INC.) Then, a substrate with an insulating film was obtained.

[4] Evaluation of Insulating Film (Substrate with Insulating Film) [4.1] Dielectric Constant The dielectric constant was evaluated using an automatic mercury probe CV measuring device SSM495 manufactured by Nippon SSM Co., Ltd.

[4.2] Linear expansion coefficient in plane direction In accordance with the method for forming an insulating film described in [3] above, an insulating film is formed (production of a substrate with an insulating film) for each example and each comparative example The linear expansion coefficient in the surface direction of each insulating film was determined. That is, each of the film forming compositions obtained in each of the above preparation examples was applied on a silicon wafer having a diameter of 300 mm, placed on a hot plate at 200 ° C. for 1 minute, and the solvent (cyclopenta Non) was removed.

  For Comparative Example 2, after being placed on a hot plate at 110 ° C. for 1 minute and 30 seconds under a nitrogen stream, it was placed on a hot plate at 250 ° C. under a nitrogen stream for 1 minute to remove the solvent (cyclohexanone) contained in the coating film. did.

  The amount of warpage of the silicon wafer after removal of the solvent was measured with a surface roughness measuring instrument (Surfcoder SE3500 manufactured by Kosaka Laboratory Ltd.). Subsequently, the same silicon wafer was subjected to heat treatment (baking treatment) in a 400 ° C. oven in a nitrogen atmosphere for 10 minutes, and then the warpage amount was measured again with a surface roughness meter. For Comparative Example 2, the amount of warpage was measured with a surface roughness meter after electron beam irradiation.

From each warpage amount, the stress σ was determined using the following formula (A) and formula (B).
σ = D ² E _Si / (6Rt (1-ν)) (A)
R (curvature radius) = (a ² + 4X ² ) / 8X (B)

From the respective stress values, the linear expansion coefficient α _k in the plane direction of the insulating film was determined using the following formula (C) and formula (D).

Δσ = (σ _{400 ° C.−} σ _{200 ° C.} ) × (400−200) (C)
σ = Δσ / ΔT = (E _Si (α _k −α _Si )) / (1-ν) (D)

In the above formula, σ is stress, Δσ is internal stress change with respect to temperature change, σ _{400 ° C.} is internal stress after heat treatment at 400 ° C., σ _{200 ° C.} is internal stress after heat treatment at 200 ° C., D is silicon wafer thickness, E _Si Is the elastic modulus of the silicon wafer, ν is the Poisson's ratio, R is the radius of curvature, a is the length, X is the amount of warpage, α _Si is the linear expansion coefficient of the silicon wafer, and α _k is the linear expansion coefficient of the insulating film. FIG. 4 shows a method for obtaining the linear expansion coefficient in the surface direction of the insulating film.

[4.3] Yield of Laminated Wafer A silicon substrate having a diameter of 300 mm is prepared, a SiCN film having a thickness of 30 nm is formed on the silicon substrate by a CVD method, and then each example is performed according to the method described in [3] above. And the insulating film of 150 nm was formed using the film-forming composition obtained for each of the comparative examples. A 30 nm thick SiO ₂ film was formed on this insulating film by CVD. Next, as a barrier metal, a TaN film and a Ta film were formed in a thickness of 20 nm by PVD method. Furthermore, after depositing a copper seed film by the PVD method, a copper film was formed by the electrolytic plating method. Removal and planarization were performed by CMP until the copper thickness reached 100 nm. After the completion of CMP, a SiCN film having a thickness of 30 nm was formed by a CVD method to form the first layer of the laminated wafer. Further, according to the method described in [3] above, the steps from the formation of the 150 nm insulating film to the formation of the 30 nm thick SiCN film by the CVD method were repeated five times to produce a laminated wafer for yield evaluation. For the evaluation of the yield of the laminated wafer, the center coordinate of the silicon substrate is (0, 0), the notch portion is (0, -150), and a square of 3 cm × 3 cm square from the coordinate (0, 0) is a virtual one-chip area. (Square with a missing outer peripheral part is also regarded as one chip), each chip was checked for peeling after lamination. The value of (number of chips with peeling) / (number of chips without peeling) was evaluated as the yield of the laminated wafer. It can be said that the larger the value, the lower the yield of the laminated wafer.

[4.4] Tape Test JIS K 5600-5-6 Adhesiveness (Cross) for the substrate with film (laminated body of silicon wafer / organic insulating film) according to each Example and each Comparative Example prepared in [3] According to the cutting method), adhesion was evaluated by a tape test. That is, 100 square squares of 1 mm square were formed on the insulating film with a cutter knife, and cello tape (registered trademark) was stretched thereon. After 1 minute, the substrate was held down and the tape was peeled off, and the number of resin films peeled off from the substrate was counted. The thickness of the insulating film was 100 nm.

  These results are shown in Table 2. Table 2 also shows the linear expansion coefficient in the thickness direction obtained by the temperature variable X-ray reflectivity method for each insulating film.

As is clear from Table 2, the insulating film of the present invention having a linear expansion coefficient in the plane direction of 9 × 10 ⁻⁶ K ⁻¹ or more and 25 × 10 ⁻⁶ K ⁻¹ or less has excellent adhesion and reliability. However, in the comparative example, a satisfactory result was not obtained, whereas a high result was obtained with a high yield during production.

DESCRIPTION OF SYMBOLS 1 Semiconductor substrate 2 Barrier film 3 Interlayer insulating film 4 Cap layer 5 Barrier metal 6 Wiring layer 7 Resist film 10 Laminated body 100 Semiconductor device

Claims (15)

A composition comprising a polymerizable compound having in its molecule a partial structure containing an adamantane-type cage structure and a polymerizable reactive group contributing to the polymerization reaction, and / or a polymer obtained by partially polymerizing the polymerizable compound. An insulating film formed using
An insulating film having a linear expansion coefficient in a plane direction of 9 × 10 ⁻⁶ K ⁻¹ or more and 25 × 10 ⁻⁶ K ⁻¹ or less. The polymerizable reactive group of the polymerizable compound has an aromatic ring and an ethynyl group or a vinyl group directly bonded to the aromatic ring,
2. The insulating film according to claim 1, wherein in the polymerizable compound, the number of carbons derived from the aromatic ring is 15% or more and 38% or less with respect to the number of carbons in the entire polymerizable compound.   The insulating film according to claim 2, wherein the aromatic ring is directly bonded to the cage structure.   3. The polymerizable reactive group has two ethynyl groups or vinyl groups, and one of the ethynyl groups or the vinyl group is present at the meta position of the other ethynyl group or the vinyl group. Or the insulating film of 3.   5. The insulating film according to claim 4, 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 insulating film according to claim 1, wherein the partial structure has an adamantane structure.   The insulating film according to claim 6, wherein the adamantane structure has a methyl group as a substituent. The insulating film according to claim 7, wherein the polymerizable compound has a structure represented by the following formula (1) or a structure represented by the following formula (5).

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

[Wherein n represents an integer of 1 to 5. ]   6. The insulating film according to claim 1, wherein the partial structure has a diamantane structure.   10. The polymerizable compound according to claim 1, wherein the polymerizable compound has two polymerizable reactive groups, and has a structure in which the polymerizable reactive groups are symmetrically bonded around the partial structure. An insulating film according to the above.   The insulating material according to any one of claims 1 to 10, wherein the insulating film is formed by using the composition that does not include a hole forming material having a function of forming holes in the film by thermal decomposition during film formation. film.   The insulating film according to any one of claims 1 to 11, wherein the insulating film is formed using a composition containing the polymer having a weight average molecular weight of 90000 or more and 110,000 or less.   The insulating film according to claim 1, which has a dielectric constant of 1.80 or more and 2.30 or less.   An insulating film according to any one of claims 1 to 13, and at least one material selected from the group consisting of SiO, SiN, SiC, SiCN, and SiOC provided in contact with the insulating film. A laminate comprising a cap layer.   An insulating film according to any one of claims 1 to 13, and at least one material selected from the group consisting of SiO, SiN, SiC, SiCN, and SiOC provided in contact with the insulating film. A semiconductor device comprising a cap layer.

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