JP2010215819A - Composition for film forming, insulator film and semiconductor device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an insulator film having a low dielectric constant, excellent strength and in which undesirable variations in film thickness can be avoided, and to provide a composition for film forming, which is suitably used for forming the insulator film, and also a semiconductor device equipped with the insulator film. <P>SOLUTION: The composition for film making contains a polymer in which a polymerizable compound having a polymerizable functional group and/or the polymerizable compound is partly polymerized. The polymerizable compound contains a partial structure A including adamantane-like cage structure, and two polymerizable reactive group contributing to a polymerization reaction. The polymerizable reactive group has two ethynyl groups directly bonded to the aromatic ring. The polymerizable compound has a structure of symmetrical bonding of the polymerizable reactive groups centering the partial structure A. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a film forming composition, an insulating film, and a semiconductor device.

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

  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.

JP 2005-243903 A

  An object of the present invention is to provide an insulating film having a low dielectric constant, excellent strength, and suppressed unintentional variation in film thickness, and for film formation that can be suitably used for forming the insulating film It is to provide a composition and to provide a semiconductor device provided with the insulating film.

Such an object is achieved by the present invention described in the following (1) to (13).
(1) A film-forming composition comprising a polymerizable compound having a polymerizable functional group and / or a polymer obtained by partially polymerizing the polymerizable compound,
The polymerizable compound has in its molecule a partial structure A including an adamantane-type cage structure and two polymerizable reactive groups contributing to the polymerization reaction,
The polymerizable reactive group has an aromatic ring and two ethynyl groups directly bonded to the aromatic ring;
The composition for film formation, wherein the polymerizable compound has a structure in which the polymerizable reactive groups are symmetrically bonded around the partial structure A.

  (2) The film forming composition according to (1), wherein the aromatic ring is directly bonded to the cage structure.

  (3) The film-forming composition as described in (1) or (2) above, wherein one of the ethynyl groups in the polymerizable reactive group is present at the meta position of the other ethynyl group.

  (4) The film forming composition according to (2), wherein each of the two ethynyl groups is present at a meta position of a site where the aromatic ring is bonded to the cage structure.

  (5) The film-forming composition according to any one of (1) to (4), wherein the partial structure A is a structure having symmetry itself.

  (6) The film forming composition according to any one of (1) to (5), wherein the partial structure A has a biadamantan structure.

  (7) The film-forming composition according to (6), wherein the biadamantane structure has a methyl group as a substituent.

  (8) The film forming composition according to any one of (1) to (7), wherein the partial structure A has a diamantane structure.

(9) The film forming composition according to any one of (1) to (8), wherein the polymerizable compound has a structure represented by the following formula (1).

  (10) The film-forming composition as described in any one of (1) to (9) above, which does not contain a pore-forming material having a function of forming pores in the film by thermal decomposition during film formation.

  (11) An insulating film formed by using the film forming composition according to any one of (1) to (10).

  (12) The insulating film according to (11), wherein the insulating film is in contact with a member made of SiOC, SiCN, or SiO.

  (13) A semiconductor device comprising the insulating film according to (11) or (12).

  According to the present invention, it is possible to provide an insulating film having a low dielectric constant, excellent strength, and suppressed unintentional variation in film thickness. Moreover, the film formation composition which can be used suitably for formation of the said insulating film can be provided. In addition, a semiconductor device including the insulating film can be provided.

It is sectional drawing which shows typically an example of the semiconductor device of this invention.

Hereinafter, the present invention will be described in detail.
<Film forming composition>
First, the film forming composition of the present invention will be described.

  The film-forming composition of the present invention comprises a polymerizable compound X having a polymerizable functional group and / or a polymer (prepolymer) in which the polymerizable compound X is partially polymerized. The polymerizable compound X has in its molecule a partial structure A including an adamantane cage structure and two polymerizable reactive groups B that contribute to the polymerization reaction. , Having an aromatic ring and two ethynyl groups directly bonded to the aromatic ring, and the polymerizable compound X has a structure in which the polymerizable reactive group B is symmetrically bonded around the partial structure A. Is.

  The film-forming composition contains a polymerizable compound X having such a structure and / or a polymer (prepolymer) in which the polymerizable compound X is partially polymerized, so that it has a low dielectric constant and strength. It is possible to suitably form a film that is excellent in the thickness and suppresses unintentional thickness variations.

Hereinafter, the polymerizable compound X will be described.
[1] Polymerizable compound X
The polymerizable compound X has a partial structure A including an adamantane-type cage structure and two polymerizable reactive groups B that contribute to the polymerization reaction in the molecule.

[1.1] Partial structure A
The partial structure A possessed by the polymerizable compound X includes an adamantane cage structure. Thereby, the film formed using the film-forming composition can have a low density, and the dielectric constant of the formed film can be reduced. In addition, since the reactivity of the polymerizable compound X having the polymerizable reactive group B as described later in detail can be made appropriate, film formation on a member (for example, a semiconductor substrate) on which a film is to be formed When applying the composition for the film, the viscosity of the film-forming composition is surely suitable, and unintentional variations in thickness and characteristics at each part of the formed film can be suppressed, The strength of the finally formed film can be made excellent.

Examples of the partial structure A of the polymerizable compound X include adamantane, polyadamantane (eg, biadamantane, triadamantane, tetraadamantane, heptaadamantane, hexaadamantane, etc.), polyamantane (eg, diamantane, triamantane, tetramantane, Pentavalent, hexamantane, heptamantane, etc.), divalent groups such as compounds in which at least some of the hydrogen atoms constituting these compounds are substituted with alkyl groups or halogen atoms (excluding the two hydrogen atoms constituting the above compounds) Part structure) or those having two or more of these divalent groups (for example, a series of diamantane skeletons such as a bi (diamantane) skeleton, a tri (diamantane) skeleton, a tetra (diamantane) skeleton, etc. (poly (Diamantane) has a skeleton One); a combination of a plurality of triamantane skeletons such as a bi (triamantane) skeleton, a tri (triamantane) skeleton, a tetra (triamantane) skeleton (having a poly (triamantane) skeleton); an adamantane skeleton (or And a polyadamantane skeleton) and a polyamantane skeleton). 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.

  Further, the partial structure A is preferably a structure having symmetry itself. 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 a film is to be formed is applied, the film formation is performed. The viscosity of the composition for use is more surely suitable, and it is possible to more effectively suppress unintentional variations in thickness and characteristics at each part of the formed film, and the film finally formed Can be made particularly excellent in strength.

  Moreover, it is preferable that the partial structure A has a biadamantan structure. Thereby, the dielectric constant of the film | membrane formed using the composition for film | membrane formation can be made especially low. Further, the reactivity of the polymerizable compound X can be made more suitable, and when the composition for film formation on a member (for example, a semiconductor substrate) on which a film is to be formed is applied, The viscosity of the composition is more surely suitable, and it is possible to more effectively suppress unintentional variations in thickness and characteristics at each part of the formed film, and the film formed finally The strength can be made particularly excellent.

  The biadamantane structure preferably has a methyl group as a substituent. Thereby, the dielectric constant of the film | membrane formed using the composition for film | membrane formation can be made especially low. Further, the reactivity of the polymerizable compound X can be made more suitable, and when the composition for film formation on a member (for example, a semiconductor substrate) on which a film is to be formed is applied, The viscosity of the composition is more surely suitable, and it is possible to more effectively suppress unintentional variations in thickness and characteristics at each part of the formed film, and the film formed finally The strength can be made particularly excellent.

  In particular, the partial structure A preferably has a structure represented by the following formula (2).

  Thereby, the dielectric constant of the film | membrane formed using the composition for film | membrane formation can be made especially low. Further, the reactivity of the polymerizable compound X can be made more suitable, and when the composition for film formation on a member (for example, a semiconductor substrate) on which a film is to be formed is applied, The viscosity of the composition is more surely suitable, and it is possible to more effectively suppress unintentional variations in thickness and characteristics at each part of the formed film, and the film formed finally The strength can be made particularly excellent.

  The partial structure A may have a diamantane structure. Thereby, the dielectric constant of the film | membrane formed using the composition for film | membrane formation can be made especially low. Further, the reactivity of the polymerizable compound X can be made more suitable, and when the composition for film formation on a member (for example, a semiconductor substrate) on which a film is to be formed is applied, The viscosity of the composition is more surely suitable, and it is possible to more effectively suppress unintentional variations in thickness and characteristics at each part of the formed film, and the film formed finally The strength 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 two polymerizable reactive groups B that contribute to the polymerization reaction.

  Each of the two polymerizable reactive groups B has an aromatic ring and two ethynyl groups directly bonded to the aromatic ring, and these polymerizable reactive groups B have a partial structure in the polymerizable compound X. They are coupled symmetrically around A. When the polymerizable compound X has such a polymerizable reactive group B, the reactivity of the polymerizable compound X can be made appropriate, and onto a member (for example, a semiconductor substrate) on which a film is to be formed. When applying the film-forming composition, the viscosity of the film-forming composition is surely suitable, and unintentional variations in thickness and characteristics at each part of the formed film can be suppressed. In addition, the strength of the finally formed film can be made excellent.

  As described above, in the present invention, the polymerizable compound X has the two polymerizable reactive groups B together with the partial structure A, and furthermore, these have a specific arrangement, whereby an excellent effect is obtained. On the other hand, when any one of the above conditions is lacking, such an excellent effect cannot be obtained.

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

  The aromatic ring constituting the polymerizable reactive group B may be bonded to the cage structure constituting the partial structure A through another atom, but directly bonded to the cage structure constituting the partial structure A. It is preferable that As a result, the reactivity of the polymerizable compound X can be made more suitable, and the film formation can be performed when a film forming composition is applied onto a member (for example, a semiconductor substrate) on which a film is to be formed. The viscosity of the composition for use is more surely suitable, and it is possible to more effectively suppress unintentional variations in thickness and characteristics at each part of the formed film, and the film finally formed Can be made particularly excellent in strength.

  The polymerizable reactive group B is obtained by directly bonding two ethynyl groups to the aromatic ring as described above. Thus, when the polymerizable reactive group B has two ethynyl groups as reaction sites, an initial reaction with respect to the polymerizable compound X is likely to occur. 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. The polymerizable compound X has two polymerizable reactive groups B in the molecule. For this reason, each of the two polymerizable reactive groups B present in the molecule of the polymerizable compound X can selectively react with only one ethynyl group, for example, as shown in the following formula (3) By the reaction, a polymer (chain prepolymer) in which a plurality of polymerizable compounds X are polymerized one-dimensionally 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 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). Can be reliably prevented, and the viscosity of the film-forming composition is surely suitable for applying the film-forming composition onto a member (for example, a semiconductor substrate) on which a film is to be formed. Can be. As a result, it is possible to reliably suppress the occurrence of unintentional variations in thickness and characteristics at each site of the formed 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 reacted with certainty, and the film finally formed has a three-dimensionally cross-linked structure. As a result, the formed film has excellent heat resistance and the like.

  As described above, each polymerizable reactive group B constituting the polymerizable compound X has two ethynyl groups. In each polymerizable reactive group B, one ethynyl group is the other ethynyl group. It is preferably present at the meta position of the group. 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 perform a baking step as will be described in detail later under more suitable conditions (conditions capable of forming a film with excellent productivity while preventing damage to the semiconductor substrate).

  The two ethynyl groups of the polymerizable reactive group B are preferably both present at the meta position of the site where the aromatic ring is bonded to the cage structure. Thereby, in the state in which one ethynyl group 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 perform a baking step as will be described in detail later under more suitable conditions (conditions capable of forming a film with excellent productivity while preventing damage to the semiconductor substrate).

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

  When the polymerizable compound X has such a structure, the dielectric constant of the film formed using the film forming composition can be made particularly low. In addition, the productivity of the film can be made particularly excellent, and it is possible to more effectively suppress unintentional variations in thickness and characteristics at each part of the film to be formed. The strength of the film formed can be made particularly excellent.

  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 can be synthesized, for example, as follows. 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.

  The film-forming composition may contain the polymerizable compound X as described above, or a polymer obtained by partially polymerizing the polymerizable compound X (for example, two ethynyls possessed by the polymerizable reactive group B) A prepolymer obtained by polymerization reaction of only one ethynyl group among the groups may be included. 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 part of the film to be formed In addition, it is possible to more effectively suppress unintentional variations in thickness and characteristics of the film, and it is possible to make the strength of the finally formed film particularly excellent. In addition, the film forming composition is subjected to heat treatment prior to applying the film forming composition onto the member (for example, a semiconductor substrate) on which the film is to be formed, so that the film to be formed is relatively thick. Even if it is a thing, it can form suitably. In addition, when the film-forming composition contains a prepolymer of the polymerizable compound X, when a film is formed on a member (for example, a semiconductor substrate), the amount of heat applied on the member can be reduced. Damage to the member due to heating can be prevented more reliably. Such a film-forming composition containing a prepolymer of the polymerizable compound X can be suitably used as an insulating film varnish.

  A film-forming composition containing a polymer (prepolymer) in which the polymerizable compound X is partially polymerized can be suitably prepared by subjecting the polymerizable compound X to a heat treatment, for example. In this case, 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. preferable. Moreover, you may perform the heat processing with respect to the polymeric compound X combining different conditions. For example, for the polymerizable compound X, the first heat treatment performed under the conditions of heating temperature: 150 to 190 ° C., heating time: 1 to 6 hours, heating temperature: 120 to 160 ° C., heating time: 2 to 9 You may perform the 2nd heat processing performed on condition of time. In addition, it is preferable to perform the above heat processing in the state which melt | dissolved the polymeric compound X in the solvent. The synthesis of the prepolymer by the heat treatment as described above may be performed in a solvent as a constituent of the film-forming composition as described later, May be carried out in a solvent having a different composition. That is, after polymerizing the polymerizable compound X using a predetermined solvent to obtain a prepolymer, the solvent may be replaced with a solvent as a constituent of the target film-forming composition. Examples of the solvent (reaction solvent) that can be used for the synthesis of the polymer (prepolymer) in which the polymerizable compound X is partially polymerized include alcohols such as methanol, ethanol, isopropanol, 1-butanol, and 2-butanol. Solvent: Ketone solvents such as acetone, acetylacetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, 2-pentanone, 2-heptanone; ethyl acetate, propyl acetate, butyl acetate, pentyl acetate, propylene glycol monomethyl ether acetate, etc. Ester solvents; ether solvents such as diisopropyl ether, dibutyl ether, diphenyl ether, tetrahydrofuran, anisole, 1,3-dimethoxybenzene, dioxane, 1,3-dimethoxybenzene; Aromatic and aliphatic hydrocarbon solvents such as zen, toluene, mesitylene, ethylbenzene, diethylbenzene, propylbenzene, heptane, hexane, n-octane; halide solvents such as chloromethane, dichloroethane, chloroform, dichloroethane, carbon tetrachloride Amide type solvents such as N-methylpyrrolidone and the like can be mentioned, and one or more selected from these can be used in combination.

  Further, 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 substantially contained). Is preferred. Thereby, various characteristics, such as the intensity | strength of the film | membrane formed using the film forming composition, can be made more reliably excellent.

  The content of the polymerizable compound X in the film-forming composition and a polymer obtained by partially polymerizing the polymerizable compound X (for example, only one ethynyl group of the two ethynyl groups of the polymerizable reactive group B has The sum of the content of the prepolymer subjected to the polymerization reaction is preferably 1.0 to 30 wt%, and more preferably 2.0 to 18 wt%.

[2] Solvent The film-forming composition is a polymer obtained by partially polymerizing the polymerizable compound X and / or the polymerizable compound X as described above (for example, among the two ethynyl groups of the polymerizable reactive group B). Any one containing only a prepolymer obtained by polymerization reaction of only one ethynyl group may be used, but usually contains a solvent that dissolves the polymerizable compound X and / or the polymer (prepolymer).

  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 the polymerizable compound X and the above-described polymer (a prepolymer obtained by partially polymerizing the polymerizable compound X). May be included.

  Although the content rate of the solvent in the composition for film formation is not specifically limited, It is preferable that it is 70-98 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.

  The film-forming composition may contain a naphthoquinonediazide 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, the film-forming composition preferably does not contain a pore-forming material that foams due to thermal decomposability and forms pores in the formed film. Conventionally, a pore forming material has been used for the purpose of reducing the dielectric constant of the film. However, when such a pore forming material is used, the strength of the formed film is reduced, or at each part of the film. However, in the present invention, by containing the polymerizable compound X and / or the prepolymer of the polymerizable compound X as described above, Even without using a hole forming material, the dielectric constant of the formed film can be made sufficiently low. And generation | occurrence | production of the above problems can be prevented reliably by not containing a void | hole formation material.

  The film forming composition as described above may be used for forming a film as it is, but before being applied on a member (for example, a semiconductor substrate) on which a film is to be formed, it is subjected to a heat treatment. It may be done. Thus, the film-forming composition can include a polymer (prepolymer) in which the polymerizable compound X 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 unintentional variations in thickness and characteristics of each portion of the film to be formed, and to make the finally formed film particularly excellent in strength. In addition, the film forming composition is subjected to heat treatment prior to applying the film forming composition onto the member (for example, a semiconductor substrate) on which the film is to be formed, so that the film to be formed is relatively thick. Even if it is a thing, it can form suitably. In addition, by applying a heat treatment to the film-forming composition prior to applying the film-forming composition onto a member (for example, a semiconductor substrate) on which a film is to be formed, the amount of heat applied on the member is reduced. Therefore, damage to the member due to heating can be prevented more reliably. When performing such heat treatment, the heat treatment conditions are preferably heating temperature: 120 to 190 ° C., heating time: 3 to 11 hours, heating temperature: 140 to 180 ° C., heating time: 3 to 9 hours. It is more preferable that Moreover, you may perform the above heat processing combining a different condition. For example, the 1st heat processing performed on the conditions of heating temperature: 150-190 degreeC, heating time: 1-6 hours, and the 2nd heat processing performed on the conditions of heating temperature: 120-160 degreeC and heating time: 2-9 hours And may be given.

<Insulating film>
The insulating film of the present invention is formed using the film forming composition as described above.

  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.

  When applied on the member, the film-forming composition preferably contains a polymer (prepolymer) in which the polymerizable compound X is partially polymerized. As a result, the viscosity of the film-forming composition applied on the member is more surely suitable, and it is possible to more effectively suppress unintentional variations in thickness and characteristics at each site of the formed film. In addition, the strength of the finally formed film can be made particularly excellent. Moreover, even if the film | membrane which should be formed is a comparatively thick thing, it can form suitably.

  By carrying out the baking treatment as described above, the unreacted ethynyl group of the polymerizable compound X or the prepolymer partially polymerized by the polymerizable compound X undergoes a polymerization reaction and has a structure in which a three-dimensional crosslinking reaction occurs. A film (insulating film) composed of a polymer (cured product) is obtained. A film (insulating film) composed of a polymer (cured product) having such a chemical structure is excellent in strength, heat resistance, and the like. Further, the film obtained as described above has a low dielectric constant. Further, the film obtained as described above is one in which unintentional variations in film thickness and characteristics at each part are suppressed. For these reasons, the above film can be suitably used as an insulating film constituting a semiconductor device.

  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: 300 to 450 degrees and a processing time of 15 to 60 minutes, and is performed under conditions of a processing temperature: 330 to 420 degrees and a processing time: 20 to 50 minutes. More preferred. In the baking step, heat treatments with different conditions may be combined.

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

  The thickness of the insulating film is not particularly limited, but when the insulating film is used as an interlayer insulating film for a semiconductor, it is preferably 0.01 to 20 μm, more preferably 0.05 to 10 μm, More preferably, it is 0.1-0.7 micrometer.

  In the case where the insulating film is used as a protective film for a semiconductor, the thickness of the insulating film is preferably 0.01 to 70 μm, and more preferably 0.05 to 50 μm.

<Semiconductor device>
Next, the semiconductor device of the present invention will be described based on a preferred embodiment.

FIG. 1 is a cross-sectional view schematically showing an example of a semiconductor device of the present invention.
As shown in FIG. 1, a semiconductor device 100 is provided on a semiconductor substrate 1 on which elements are formed, a SiN film 2 provided on the upper side (upper side in FIG. 1), and a SiN film 2. A copper wiring layer 7 covered with an interlayer insulating film 3 and a barrier layer 6 is provided. The semiconductor device 100 of this embodiment includes an interlayer insulating film 3 as an insulating film of the present invention.

  A recess corresponding to the pattern to be wired is formed in the interlayer insulating film 3, and a copper wiring layer 7 is provided in the recess.

In addition, a modified treatment layer 5 is provided between the interlayer insulating film 3 and the copper wiring layer 7.
A hard mask layer 4 is formed on the upper side of the interlayer insulating film 3 (on the side surface opposite to the SiN film 2).

The semiconductor device 100 as described above can be manufactured, for example, as follows.
First, a semiconductor substrate 1 in which a device such as a transistor is provided on a silicon wafer is prepared, and an interlayer insulating film 3 and a hard mask layer 4 are formed thereon.

  Further, a photoresist layer is formed thereon, and a wiring groove penetrating into a predetermined position of the insulating layer composed of the interlayer insulating film and the hard mask layer is processed by dry etching.

  Next, a modified treatment layer 5 is formed on the inner surface of the wiring groove by plasma treatment or the like, and further a barrier composed of Ta, Ti, TaN, TiN, WN or the like by a method such as PVD method or CVD method. Layer 6 is formed.

  Further, a copper wiring layer 7 to be a wiring layer is formed by an electrolytic plating method or the like, and then the copper wiring layer and the barrier metal layer other than the wiring portion are polished and removed and planarized by a CMP method. Obtainable.

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

  Since the semiconductor device of the present invention described above uses the interlayer insulating film (insulating film of the present invention) as described above, it has excellent dimensional accuracy and can sufficiently exhibit insulation, thereby providing excellent connection reliability. Yes.

  In addition, since the interlayer insulating film (the insulating film of the present invention) as described above has excellent adhesion to the wiring layer, the connection reliability of the semiconductor device can be further improved.

  In addition, since the interlayer insulating film (the insulating film of the present invention) as described above has an excellent elastic modulus, it can be suitably adapted to a process for forming a wiring of a semiconductor device (for example, a baking process).

  In addition, 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 SiN film 2 is representatively described. However, the position where the insulating film is formed is not limited to this.

  In the above-described embodiments, the insulating film provided with the interlayer insulating film is representatively described. However, the insulating film of the present invention may be applied to other than the interlayer insulating film. .

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

[1] Synthesis of polymerizable compound (Synthesis Example 1)
First, in a 4-neck 2000 mL flask equipped with a thermometer, a stirrer, and a reflux tube, 28 g (1.2 mol) of metallic sodium and 1200 ml of n-octane were put, and the internal temperature was cooled to 0 ° C.

  Next, while vigorously stirring the contents of the four-necked flask, a solution obtained by dissolving 1-bromo-3,5-dimethyladamantane: 145.9 g (0.6 mol) in n-octane: 600 ml was gradually added dropwise. . During the dropping, the internal temperature was kept at 0 to 5 ° C. After the completion of dropping, the reaction was continued for another hour after the temperature did not rise.

Then, it poured into about 3000 mL of cold water, the crude product was separated by filtration, washed with pure water, and dried.
The crude product was recrystallized from hot hexane. The obtained recrystallized product was dried under reduced pressure to obtain 65.2 g of product. From the result that the absorption of Br group (around 690 to 515 cm ⁻¹ ) disappeared by infrared spectroscopy (IR) analysis and the molecular weight by mass spectrometry was 326, the product was 3,3 ′, 5,5′-tetramethyl. It was shown to be −1,1′-biadamantane.

Next, carbon tetrachloride: 700 mL and bromine: 35 g (0.22 mol) were placed in a four-necked 2000 mL flask equipped with a thermometer, a stirrer, and a reflux tube. ', 5,5'-Tetramethyl-1,1'-biadamantane: 54.1 g (0.2 mol) was added in small portions. 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 58.0 g of a product. From the result that the absorption of bromo group is observed at 690 to 515 cm ⁻¹ by IR analysis and the molecular weight by mass spectrometry is 484, the product is 3,3 ′, 5,5′-tetramethyl-7,7′- Dibromo-1,1′-biadamantane was shown.

  Next, in the flask, 3,3 ′, 5,5′-tetramethyl-7,7′-dibromo-1,1′-biadamantane obtained above: 50 g (103.2 mmol) and 1,3- Dibromobenzene: 1217 g (5161.6 mmol) was stirred, and aluminum bromide (III): 24.8 g (93.0 mmol) was added in small portions 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. 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 three times with 1000 ml of acetone: 3,3 ′, 5,5′-tetramethyl-7,7′-bis (3,5-dibromophenyl) -1,1′- Biadamantane: 70 g was obtained. From the result that the molecular weight by mass spectrometry is 794, the product is 3,3 ′, 5,5′-tetramethyl-7,7′-bis (3,5-dibromophenyl) -1,1′-biadamantane. It was shown that there is.

  Next, 3,3 ′, 5,5′-tetramethyl-7,7′-bis (3,5-dibromophenyl) -1,1′-biadamantane obtained above: 50 g (62.9 mmol) , Dichlorobistriphenylphosphine palladium: 3.53 g (5.0 mmol), triphenylphosphine: 6.60 g (25.2 mmol), copper (II) iodide: 4.79 g (25.2 mmol), triethylamine: 750 ml 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 3,3 ′, 5,5′-tetramethyl-7,7′-bis (3,5-ditrimethylsilylethynylphenyl). 43 g of -1,1'-biadamantane was obtained. From the result that the molecular weight by mass spectrometry is 863, the product is 3,3 ′, 5,5′-tetramethyl-7,7′-bis (3,5-ditrimethylsilylethynylphenyl) -1,1′-bi- It was shown to be adamantane.

  Furthermore, 3,3 ′, 5,5′-tetramethyl-7,7′-bis (3,5-ditrimethylsilylethynylphenyl) -1,1′-biadamantane obtained above: 39.8 g (46 .1 mmol) and 1.46 g (10.6 mmol) of potassium carbonate 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. 3,3 ′, 5,5′-tetramethyl-7,7′-bis (3,5-diethynylphenyl) -1,1′-biadamantane: 21.2 g was obtained.

  The appearance of the product, the results of mass spectrometry and elemental analysis are shown below. These data show that the compound obtained above is 3,3 ′, 5,5′-tetramethyl-7,7′-bis (3,5-diethynylphenyl) -1,1′-biadamantane. It is shown that.

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

  The structural formula of 3,3 ′, 5,5′-tetramethyl-7,7′-bis (3,5-diethynylphenyl) -1,1′-biadamantane obtained in this synthesis example is represented by the following formula ( Shown in 4).

(Synthesis Example 2)
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, synthesis of 3,3 ′, 5,5′-tetramethyl-7,7′-bis (3,5-dibromophenyl) -1,1′-biadamantane as a synthesis intermediate in Synthesis Example 1 In this, 3,9 ′, 5,5′-tetramethyl-7,7′-dibromo-1,1′-biadamantane was replaced with 3,9-dibromodiamantane: 35.7 g (103.1 mmol). The reaction was conducted in the same manner as in Synthesis Example 1 to obtain 56 g of 4,9-bis (3,5-dibromophenyl) diamantane. 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, 3,3 ′, 5,5′-tetramethyl-7,7′-bis (3,5-ditrimethylsilylethynylphenyl) -1,1′-biadamantane as a synthesis intermediate in Synthesis Example 1 In the synthesis of 3,4 ′ obtained above instead of 3,3 ′, 5,5′-tetramethyl-7,7′-bis (3,5-dibromophenyl) -1,1′-biadamantane 9-bis (3,5-dibromophenyl) diamantane: By reacting in the same reaction as in Synthesis Example 1 except that 41.2 g (62.8 mmol) was used, 4,9-bis (3,5-di Trimethylsilylethynylphenyl) diamantane: 35.5 g 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.

  Furthermore, in the synthesis of 3,3 ′, 5,5′-tetramethyl-7,7′-bis (3,5-diethynylphenyl) -1,1′-biadamantane as the final product in Synthesis Example 1. 3,3 ′, 5,5′-tetramethyl-7,7′-bis (3,5-ditrimethylsilylethynylphenyl) -1,1′-biadamantane By reacting in the same reaction as in Synthesis Example 1 except that 38.8 g (53.5 mmol) of bis (3,5-ditrimethylsilylethynylphenyl) diamantane was used, 4,9-bis as the polymerizable compound X was obtained. (3,5-diethynylphenyl) diamantane: 14.3 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 4,9-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

  The structural formula of 4,9-bis (3,5-diethynylphenyl) diamantane obtained in this synthesis example is shown in the following formula (5).

(Synthesis Example 3)
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

  The structural formula of 4- (3,5-diethynylphenyl) diamantane obtained in this synthesis example is shown in the following formula (6).

(Synthesis Example 4)
First, 3,3 ′, 5,5′-tetramethyl-7,7′-dibromo-1,1′-biadamantane: 25 g (51.6 mmol) and phenol: 354 g, which are synthesis intermediates in Synthesis Example 1. (3.8 mol) was placed in a flask equipped with a thermometer, a stirrer and a reflux tube, heated to 60 ° C. and stirred for 30 minutes, then heated to 160 ° C. and stirred for 30 minutes. After the internal temperature was adjusted to 50 ° C., 2500 mL of water was added, and immediately after the addition, the internal temperature was raised to 75 ° C. and stirred for 30 minutes. The precipitate was filtered while hot, and the resulting precipitate was washed with 7000 mL of water and dried to give 3,3 ′, 5,5′-tetramethyl-7,7′-bis (4-hydroxyphenyl). ) -1,1′-biadamantane: 24 g was obtained. From the result that the molecular weight by mass spectrometry is 510, the product is 3,3 ′, 5,5′-tetramethyl-7,7′-bis (4-hydroxyphenyl) -1,1′-biadamantane. It has been shown.

  Next, 3,3 ′, 5,5′-tetramethyl-7,7′-bis (4-hydroxyphenyl) -1,1′-biadamantane obtained by repeating the above: 50 g (97.9 mmol) , And 220 g of pyridine were placed in a flask and dissolved by stirring at room temperature. Dry ice / methanol was used, and the internal temperature was cooled to −5 ° C. or lower. Thereafter, 74.5 g (264.3 mmol) of trifluoromethanesulfonic anhydride was added dropwise little by little while keeping the internal temperature at 5 ° C. or lower. After completion of the dropwise addition, the internal temperature was stirred at 5 to 10 ° C. for 30 minutes, and the temperature was returned to room temperature and stirred for 4 hours. Next, 1000 mL of 1% hydrochloric acid aqueous solution was put into a 2000 mL beaker, cooled to 0 to 10 ° C., and the reaction solution was added dropwise, followed by stirring for 30 minutes. The precipitate was filtered off, recrystallized from methanol (400 mL), and then dried to give 3,3 ′, 5,5′-tetramethyl-7,7′-bis (4-trifluoromethylsulfonylphenyl)- 1,1'-biadamantane: 68 g was obtained. From the result that the molecular weight by mass spectrometry is 774, the product is 3,3 ′, 5,5′-tetramethyl-7,7′-bis (4-trifluoromethylsulfonylphenyl) -1,1′-biadamantane. It was shown that.

  Further, 3,3 ′, 5,5′-tetramethyl-7,7′-bis (4-trifluoromethylsulfonylphenyl) -1,1′-biadamantane obtained above: 50 g (64.5 mmol), Dichlorobistriphenylphosphine palladium: 4.56 g (6.6 mmol), triphenylphosphine: 6.80 g (25.8 mmol), copper (II) iodide 4.91 g (25.8 mmol), triethylamine: 760 ml were added to the flask. And stirred. After raising the temperature to 75 ° C., 38.1 g (387.2 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. Thereafter, the temperature was returned to room temperature, and 1200 mL of dichloromethane was added to the reaction solution, followed by stirring 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. 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 three times with acetone, whereby 3,3 ′, 5,5′-tetramethyl-7,7′-bis (4-trimethylsilylethynylphenyl) -1, 1'-biadamantane: 36 g was obtained. From the result that the molecular weight by mass spectrometry is 671, the product is 3,3 ′, 5,5′-tetramethyl-7,7′-bis (4-trimethylsilylethynylphenyl) -1,1′-biadamantane. It was shown that.

  Furthermore, 3,3 ′, 5,5′-tetramethyl-7,7′-bis (4-trimethylsilylethynylphenyl) -1,1′-biadamantane obtained as described above: 35 g (52.1 mmol) and potassium carbonate : 1.58 g (11.5 mmol) was stirred in a mixed solvent of tetrahydrofuran: 700 mL and methanol: 350 mL under a nitrogen atmosphere at room temperature for 4 hours. This was poured into 10% aqueous hydrochloric acid solution: 1100 mL, the precipitate was filtered, and the resulting precipitate was washed with water: 1100 mL, further washed with acetone: 1100 mL, and then dried to obtain 3 as a polymerizable compound. , 3 ′, 5,5′-tetramethyl-7,7′-bis (4-ethynylphenyl) -1,1′-biadamantane: 24.2 g.

  The appearance of the product, the results of mass spectrometry and elemental analysis are shown below. These data indicate that the compound obtained above is 3,3 ′, 5,5′-tetramethyl-7,7′-bis (4-ethynylphenyl) -1,1′-biadamantane. ing.

Appearance: White solid MS (FD) (m / z): 526 (M +)
Elemental analysis: Theoretical value (/%) C; 91.20, H; 8.80, Actual value (/%) C; 91.02, H; 8.73

  The structural formula of 3,3 ′, 5,5′-tetramethyl-7,7′-bis (4-ethynylphenyl) -1,1′-biadamantane obtained in this synthesis example is represented by the following formula (7). Show.

(Synthesis Example 5)
First, 3,3 ′, 5,5′-tetramethyl-7,7′-dibromo-1,1′-biadamantane, which is a synthetic intermediate in Synthesis Example 1, 50 g (90.8 mmol), 1,3 -Dibromobenzene: 21.4 g (90.8 mmol) and chloroform: 1000 mL were stirred in a flask, and aluminum bromide (III): 24.8 g (93.0 mmol) was added in small portions at 25 ° C under dry nitrogen. did. The mixture was heated to 50 ° C. and stirred for 18 hours, and then returned to room temperature to obtain a reaction solution. 5% aqueous hydrochloric acid solution: The reaction solution was added to 700 mL and stirred. The aqueous layer was removed, and the organic layer was poured into 2000 mL of acetone. The precipitate was filtered and washed with acetone: 1000 mL three times to obtain a solid content. The solid content was stirred with a mixed solution of chloroform: 600 mL and dichloroethane: 400 mL for 30 minutes, and insolubles were removed by filtration to obtain a filtrate part. Chloroform and dichloroethane in the filtrate were removed under reduced pressure, and washed with acetone: 1000 mL twice to obtain 3,3 ′, 5,5′-tetramethyl-7-bromo-7 ′-(3,5-dibromophenyl. ) -1,1′-biadamantane: 5.8 g was obtained. From the result that the molecular weight by mass spectrometry was 639, the product was 3,3 ′, 5,5′-tetramethyl-7-bromo-7 ′-(3,5-dibromophenyl) -1,1′-biadamantane. It was shown that.

  Next, 3,3 ′, 5,5′-tetramethyl-7-bromo-7 ′-(3,5-dibromophenyl) -1,1′-biadamantane 20 g (31) obtained by repeating the above operation was obtained. .3 mmol) and 107 g (1.1 mol) of phenol were put into a flask equipped with a thermometer, a stirrer and a reflux tube, heated to 60 ° C. and stirred for 30 minutes, and then heated to 160 ° C. Stir for 30 minutes. The internal temperature was adjusted to 50 ° C., and then added to 2000 mL of water. Immediately after the addition, the internal temperature was raised to 75 ° C. and stirred for 30 minutes. After the precipitate was filtered while hot, the resulting precipitate was washed with 6500 mL of water and dried to give 3,3 ′, 5,5′-tetramethyl-7- (4-hydroxyphenyl) -7 ′. -(3,5-dibromophenyl) -1,1'-biadamantane: 18.2 g was obtained. From the result that the molecular weight by mass spectrometry is 652, the product is 3,3 ′, 5,5′-tetramethyl-7- (4-hydroxyphenyl) -7 ′-(3,5-dibromophenyl) -1, It was shown to be 1'-biadamantane.

  Next, 3,3 ′, 5,5′-tetramethyl-7- (4-hydroxyphenyl) -7 ′-(3,5-dibromophenyl) -1,1′- obtained by repeating the above operation. Biadamantane: 50 g (76.6 mmol) and pyridine: 170 g were placed in a flask and stirred at room temperature to dissolve. Dry ice / methanol was used, and the internal temperature was cooled to −5 ° C. or lower. Thereafter, 29.2 g (103.4 mmol) of trifluorochlorosulfonic anhydride was added dropwise little by little while keeping the internal temperature at 5 ° C. or lower. After completion of the dropwise addition, the internal temperature was stirred at 5 to 10 ° C. for 30 minutes, and the temperature was returned to room temperature and stirred for 4 hours. Next, 1000 mL of 1% hydrochloric acid aqueous solution was put into a 2000 mL beaker, cooled to 0 to 10 ° C., and the reaction solution was added dropwise, followed by stirring for 30 minutes. The precipitate was separated by filtration, recrystallized from 500 mL of methanol, and then dried to give 3,3 ′, 5,5′-tetramethyl-7- (4-trifluoromethylsulfonylphenyl) -7 ′-( 3,5-Dibromophenyl) -1,1′-biadamantane: 54 g was obtained. From the result that the molecular weight by mass spectrometry is 784, the product is 3,3 ′, 5,5′-tetramethyl-7- (4-trifluoromethylsulfonylphenyl) -7 ′-(3,5-dibromophenyl). It was shown to be −1,1′-biadamantane.

  Furthermore, 3,3 ′, 5,5′-tetramethyl-7- (4-trifluoromethylsulfonylphenyl) -7 ′-(3,5-dibromophenyl) -1,1′-biadamantane obtained above : 50 g (63.7 mmol), dichlorobistriphenylphosphine palladium: 4.50 g (6.4 mmol), triphenylphosphine: 6.73 g (25.5 mmol), copper (II) iodide: 4.85 g (25.5 mmol) ), Triethylamine: 700 ml was added to the flask and stirred. After raising the temperature to 75 ° C., 37.6 g (382.4 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, 1100 mL of dichloromethane was added to the reaction liquid, and it 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. 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 three times with acetone, whereby 3,3 ′, 5,5′-tetramethyl-7- (4-trimethylsilylethynylphenyl) -7 ′-(3, 5-Ditrimethylsilylethynylphenyl) -1,1′-biadamantane: 42 g was obtained. From the result that the molecular weight by mass spectrometry is 767, the product is 3,3 ′, 5,5′-tetramethyl-7- (4-trimethylsilylethynylphenyl) -7 ′-(3,5-ditrimethylsilylethynylphenyl). It was shown to be −1,1′-biadamantane.

  Furthermore, 3,3 ′, 5,5′-tetramethyl-7- (4-trimethylsilylethynylphenyl) -7 ′-(3,5-ditrimethylsilylethynylphenyl) -1,1′-biadamantane obtained above : 40 g (52.1 mmol) and potassium carbonate: 1.58 g (11.5 mmol) were stirred in a mixed solvent of tetrahydrofuran: 700 mL and methanol: 350 mL under a nitrogen atmosphere at room temperature for 4 hours. This was poured into 10% aqueous hydrochloric acid solution: 1100 mL, the precipitate was filtered, and the resulting precipitate was washed with water: 1100 mL, further washed with acetone: 1100 mL, and then dried to obtain 3 as a polymerizable compound. , 3 ′, 5,5′-tetramethyl-7- (4-ethynylphenyl) -7 ′-(3,5-diethynylphenyl) -1,1′-biadamantane: 24.7 g.

  The appearance of the product, the results of mass spectrometry and elemental analysis are shown below. These data indicate that the compound obtained above is 3,3 ′, 5,5′-tetramethyl-7- (4-ethynylphenyl) -7 ′-(3,5-diethynylphenyl) -1,1. '-Indicates that it is Biadamantan.

Appearance: White solid MS (FD) (m / z): 550 (M +)
Elemental analysis: Theoretical value (/%) C; 91.58, H; 8.42, Actual value (/%) C; 91.42, H; 8.31

  Of the 3,3 ′, 5,5′-tetramethyl-7- (4-ethynylphenyl) -7 ′-(3,5-diethynylphenyl) -1,1′-biadamantane obtained in this synthesis example The structural formula is shown in the following formula (8).

[2] Preparation of film-forming composition (Example 1)
3,3 ′, 5,5′-tetramethyl-7,7′-bis (3,5-diethynylphenyl) -1,1′-biadamantane as the polymerizable compound synthesized in Synthesis Example 1 above: 5 g was dissolved in 1,3-dimethoxybenzene: 45 g, reacted at 170 ° C. for 3 hours under dry 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 42,000. The reaction solution was heated again and reacted at 150 ° C. for 6 hours. The reaction solution was added dropwise to a mixed solvent of 10 times volume of methanol / tetrahydrofuran = 3/1, and the precipitate was collected and dried. A prepolymer was obtained (yield: 54%). 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.

(Example 2)
Except for using 4,9-bis (3,5-diethynylphenyl) diamantane synthesized in Synthesis Example 2 as the polymerizable compound, a polymerization reaction was performed in the same manner as in Example 1 to obtain a prepolymer, Further, a film forming composition as a varnish for an organic insulating film was obtained by performing the same treatment as described in Example 1 using 2 g of the prepolymer. In this example, the prepolymer synthesized using 5 g of the polymerizable compound (4,9-bis (3,5-diethynylphenyl) diamantane) was 2.4 g (yield: 48). %).

(Comparative Example 1)
As the polymerizable compound, except that 4- (3,5-diethynylphenyl) diamantane synthesized in Synthesis Example 3 was used, a polymerization reaction was performed in the same manner as in Example 1 to obtain a prepolymer. Using the prepolymer: 2 g, the same treatment as described in Example 1 was performed to obtain a film-forming composition as a varnish for an organic insulating film. In this comparative example, the prepolymer synthesized using 5 g of the polymerizable compound (4- (3,5-diethynylphenyl) diamantane) was 3.8 g (yield: 76%).

(Comparative Example 2)
Except for using 3,3 ′, 5,5′-tetramethyl-7,7′-bis (4-ethynylphenyl) -1,1′-biadamantane synthesized in Synthesis Example 4 as the polymerizable compound, A polymerization reaction is carried out in the same manner as in Example 1 to obtain a prepolymer. Further, by using the prepolymer: 2 g, the same treatment as described in Example 1 is performed, whereby a varnish for an organic insulating film is obtained. A film-forming composition was obtained. In this comparative example, 5 g of a polymerizable compound (3,3 ′, 5,5′-tetramethyl-7,7′-bis (4-ethynylphenyl) -1,1′-biadamantane) was used. The synthesized prepolymer was 3.4 g (yield: 68%).

(Comparative Example 3)
As a polymerizable compound, 3,3 ′, 5,5′-tetramethyl-7- (4-ethynylphenyl) -7 ′-(3,5-diethynylphenyl) -1,1 ′ synthesized in Synthesis Example 5 -A polymerization reaction was carried out in the same manner as in Example 1 except that biadamantane was used to obtain a prepolymer, and the same treatment as described in Example 1 was performed using 2 g of the prepolymer. To give a film forming composition as a varnish for an organic insulating film. In this comparative example, 5 g of a polymerizable compound (3,3 ′, 5,5′-tetramethyl-7- (4-ethynylphenyl) -7 ′-(3,5-diethynylphenyl) -1, The prepolymer synthesized using 1′-biadamantane was 2.3 g (yield: 46%).

(Comparative Example 4)
In the same manner as prepared in Comparative Example 3, 3,3 ′, 5,5′-tetramethyl-7- (4-ethynylphenyl) -7 ′-(3,5-diethynylphenyl) -1, After obtaining a prepolymer of 1′-biadamantane, 2 g of the obtained prepolymer and a polypropylene glycol diol type as a pore forming material (manufactured by Wako Pure Chemical Industries, Ltd., Polypropylene Glycol, Diol Type, 400) ): 0.7 g was dissolved in 18 g of cyclopentanone, and further filtered through a filter to obtain a film-forming composition as a varnish for an organic insulating film. That is, in this comparative example, a film forming composition as a varnish for an organic insulating film was obtained in the same manner as in the comparative example 3 except that the pore forming material was included.

[3] Formation of insulating film (production of substrate with film)
Using the film forming composition as the organic insulating film varnish obtained in each of the above Examples and Comparative Examples, an insulating film was formed as follows.

  First, a film forming composition as a varnish for an organic insulating film was applied on a silicon wafer by a spin coater. At this time, the rotation speed and time of the spin coater were set so that the thickness of the insulating film after the heat treatment was 100 nm.

  Next, the silicon wafer provided with the coating film as described above was placed on a hot plate at 200 ° C. for 1 minute to remove the solvent (cyclopentanone) contained in the coating film.

  Thereafter, the silicon wafer provided with the dried coating film is subjected to a heat treatment (baking treatment) for 30 minutes in a nitrogen atmosphere in an oven at 400 ° C., thereby curing the prepolymer constituting the coating film, Thus, a substrate with a film (substrate with an insulating film) was obtained.

[4] Evaluation of insulating film (substrate with film) With respect to the insulating film (substrate with film) according to each of the examples and comparative examples, dielectric constant, breakdown voltage, leakage current, glass transition temperature, elastic modulus, heat resistance Each of the properties of adhesion and adhesion was evaluated by the following evaluation methods.

[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] Breakdown voltage and leakage current The breakdown voltage and leakage current were evaluated using an automatic mercury probe CV measuring device SSM495 manufactured by Nippon SSM Co., Ltd., in the same manner as the dielectric constant.

The breakdown voltage is a voltage applied when a current of 1 × 10 ⁻² A flows, and a breakdown voltage, and the electric field strength (voltage (MV) applied when a current of 1 × 10 ⁻² A flows) is expressed as a film thickness (cm The value divided by), expressed in units of MV / cm).

The leakage current is defined as a leakage current that flows when the electric field intensity is 1 MV / cm, and the current density (A) that flows when the electric field intensity is 1 MV / cm is the mercury electrode area of the automatic mercury probe CV measuring device ( the value obtained by dividing the cm ²⁾ unit:. shown in A / cm ^2).

[4.3] Glass transition temperature (Tg)
Tg was evaluated by a differential scanning calorimeter DSC-Q1000 apparatus manufactured by TA Instruments Co., Ltd. using the insulating film on the silicon wafer obtained above as a measurement sample. The measurement temperature range was 250 to 450 ° C., and the temperature increase rate was 2 ° C./min. The glass transition temperature was evaluated by analyzing whether there is an inflection point in the reverse heat flow in the temperature range of 250 to 450 ° C.

[4.4] Elastic Modulus The elastic modulus is a region in which a signal with an indentation depth of up to one-tenth of the film thickness is stabilized by using a thin film measuring program with a thin film mechanical property measuring device Nano Indenter manufactured by MTS. It was evaluated with.

[4.5] Heat resistance Heat resistance was evaluated based on the thermal decomposition temperature. The obtained insulating film was measured using a TG / DTA measuring device (Seiko Instruments Co., Ltd., TG / DTA220) under a nitrogen gas flow of 200 mL / min. Under a temperature rising rate of 10 ° C./min. The temperature at which the weight loss reached 5% was defined as the thermal decomposition temperature.

[4.6] Adhesiveness JIS K 5600-5-6 Adhesiveness (cross) for the film-coated substrates (silicon wafer / organic insulating film laminate) according to each Example and each Comparative Example prepared in [3] above. 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.

  Further, in the same manner as described above, a SiOC film, an organic insulating film (for film formation of each of the above examples and comparative examples) is formed on a silicon wafer using the film forming composition of each of the above examples and comparative examples. An insulating film formed using a composition) is laminated in this order on a substrate with a film, a silicon wafer, a SiCN film, an organic insulating film (using the film forming compositions of the above-mentioned examples and comparative examples) The insulating film formed in this order was formed on the substrate with the film and the silicon wafer, and the SiCN film and the organic insulating film were formed using the film forming compositions of the respective examples and comparative examples. Insulating film) and a substrate with a film in which an SiO film was laminated in this order were prepared, and the adhesion with these film-attached substrates was also evaluated by the same method (tape test) as described above. In the production of the substrate with these films, the SiOC film is formed by the plasma CVD method so as to have a thickness of 100 nm, and the SiCN film is formed by the plasma CVD method so that the thickness becomes 60 nm. The film was formed by a plasma CVD method so as to have a thickness of 30 nm. In addition, the conditions for forming each film were the same in each Example and each Comparative Example.

[4.7] In-plane uniformity In accordance with the formation of the insulating film described in [3] above, an insulating film is formed on a silicon wafer having a diameter of 300 mm. The film thickness was measured using an n & k Analyzer 1500 manufactured by the manufacturer. The measurement point is set to (0,0) for the center coordinates, (0, -150) for the notch coordinates, and 25 points for the linear coordinates from the coordinates (-150,0) to the coordinates (150,0) at equal intervals. . The value obtained by multiplying the standard deviation (σ) of 25 points by 3 and dividing by the average value was used as a measure of in-plane uniformity.

These results are shown in Tables 1 and 2. Moreover, the weight average molecular weight (Mw), the number average molecular weight (Mn), and the dispersion ratio (Mw / Mn) of the prepolymer constituting the organic insulating film varnish (film forming composition) of each example and each comparative example It is shown in Table 3. In addition, about the weight average molecular weight (Mw) of a prepolymer, a number average molecular weight (Mn), and a dispersion ratio (Mw / Mn), a gel permeation chromatograph (GPC) apparatus (the Tosoh Corporation make, HLC-8220GPC) is used. In addition, as a column, TSKgel GMHXL (polystyrene conversion exclusion limit 4 × 10 ² (estimated)) × 2 and TSKgel G2000HXL (polystyrene conversion exclusion limit 1 × 10 ⁴ ) × 2 are connected in series as a detector. Measurement was performed using a refractometer (RI) or an ultraviolet / visible detector (UV (254 nm)), and the results obtained by RI or UV were analyzed. The measurement conditions were mobile phase: tetrahydrofuran, temperature: 40 ° C., flow rate: 1.00 mL / min, sample concentration: 0.1 wt% tetrahydrofuran solution. In the table, the silicon wafer is indicated by “Si”, the organic insulating film (insulating film formed by using the film forming compositions of the respective examples and comparative examples) is indicated by “Org”, and the SiOC film Is indicated by “SiOC”, the SiCN film is indicated by “SiCN”, and the SiO film is indicated by “SiO”.

As is clear from Tables 1 and 2, the present invention shows excellent electrical characteristics as an insulating film because of its low dielectric constant, high breakdown voltage, and low leakage current. Further, the glass transition temperature is high, the heat resistance is excellent, the elastic modulus is high, and the mechanical strength is excellent. Moreover, in this invention, it was excellent in the adhesiveness of the insulating film to the semiconductor substrate etc. In particular, since the adhesion between the upper layer portion and the lower layer portion is excellent, it can be seen that the compatibility in the manufacturing process of the semiconductor device is excellent. Further, in the present invention, the unintentional thickness variation in each part of the formed film was sufficiently prevented (excellent film thickness uniformity). From this, it can be said that in the present invention, unintentional variation in characteristics at each part of the film is prevented. Further, as apparent from Table 3, in the present invention, the dispersion ratio of the prepolymer constituting the film forming composition was small. From this, it can be seen that in the present invention, an excellent effect is exhibited by controlling the structure of the prepolymer.
On the other hand, satisfactory results were not obtained in each comparative example.

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

Claims (13)

A film-forming composition comprising a polymerizable compound having a polymerizable functional group and / or a polymer obtained by partially polymerizing the polymerizable compound,
The polymerizable compound has in its molecule a partial structure A including an adamantane-type cage structure and two polymerizable reactive groups contributing to the polymerization reaction,
The polymerizable reactive group has an aromatic ring and two ethynyl groups directly bonded to the aromatic ring;
The composition for film formation, wherein the polymerizable compound has a structure in which the polymerizable reactive groups are symmetrically bonded around the partial structure A.   The film-forming composition according to claim 1, wherein the aromatic ring is directly bonded to the cage structure.   3. The film-forming composition according to claim 1, wherein one of the ethynyl groups in the polymerizable reactive group is present at the meta position of the other ethynyl group.   The film forming composition according to claim 2, wherein each of the two ethynyl groups is present at a meta position of a site where the aromatic ring is bonded to the cage structure.   The film-forming composition according to claim 1, wherein the partial structure A is a structure having symmetry itself.   6. The film forming composition according to claim 1, wherein the partial structure A has a biadamantan structure.   The film forming composition according to claim 6, wherein the biadamantane structure has a methyl group as a substituent.   The film-forming composition according to any one of claims 1 to 7, wherein the partial structure A has a diamantane structure. The film-forming composition according to claim 1, wherein the polymerizable compound has a structure represented by the following formula (1).

  The film-forming composition according to any one of claims 1 to 9, which does not contain a pore-forming material having a function of forming pores in the film by thermal decomposition during film formation.   An insulating film formed using the film forming composition according to claim 1.   The insulating film according to claim 11, wherein the insulating film is in contact with a member made of SiOC, SiCN, or SiO.   A semiconductor device comprising the insulating film according to claim 11.

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