JP5407851B2 - Film forming composition, insulating film, and semiconductor device - Google Patents

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.

  Further, conventionally, there has been a problem that the insulating film formed is not stable and an insulating film having a relatively low resistance value may be formed.

JP 2005-243903 A

  An object of the present invention is to provide an insulating film having a low dielectric constant, exhibiting stable insulation, excellent strength, and suppressing unintentional variations in film thickness and characteristics, and formation of the insulating film. An object of the present invention is to provide a film forming composition that can be suitably used, 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 ( 14 ).
(1) Formation of a film containing a polymerizable compound having a partial structure a1 including an adamantane-type cage structure and a polymerizable functional group in the molecule and / or a polymer obtained by partially polymerizing the polymerizable compound A composition for
A polyvalent reactive olefin having a plurality of polymerizable reactive groups in the molecule and having at least one polymerizable double bond as the polymerizable reactive group is included as the polymerizable compound.
A hydrogenated product in which at least a part of the polymerizable reactive group of the polyvalent reactive olefin product is substituted with a hydrogen atom;
The polyvalent reactive olefin has a structure in which the polymerizable reactive group is directly bonded to an aromatic ring, and has a structure in which two polymerizable reactive groups are directly bonded to one aromatic ring, A tetravalent reactive olefin body having four polymerizable reactive groups,
When the polymerizable compound is not polymerized, the hydride has a mole fraction of 0.01 to 10 mol% with respect to the total number of moles of the polyvalent reactive olefin and hydride. A composition for forming a film, characterized by comprising:

  (2) The film-forming composition according to the above (1), wherein the polyvalent reactive olefinic body has no halogen atom in the molecule.

  (3) The film-forming composition according to (1) or (2), wherein all of the polymerizable reactive groups of the polyvalent reactive olefin are polymerizable double bonds.

  (4) The film according to (1) or (2), wherein the polyvalent reactive olefin body further includes an acetylene-based reactive group in addition to the polymerizable double bond as the polymerizable reactive group. Forming composition.

( 5 ) The film-forming composition according to any one of ( 1 ) to (4), wherein the aromatic ring is directly bonded to the cage structure.

( 6 ) In the polyvalent reactive olefin body, one of the polymerizable reactive groups is present in the meta position of the other polymerizable reactive group, according to any one of ( 1 ) to (5) above. A film forming composition.

( 7 ) The two polymerizable reactive groups according to any one of ( 1 ) to (6) , wherein each of the two polymerizable reactive groups is present at a meta position of a site where the aromatic ring is bonded to the cage structure. Film forming composition.

( 8 ) The film forming composition according to any one of (1) to ( 7 ), wherein the partial structure a1 has a biadamantan structure.

( 9 ) The film-forming composition according to ( 8 ), wherein the biadamantane structure has a methyl group as a substituent.

( 10 ) The film-forming composition according to any one of (1) to ( 9 ), wherein the partial structure a1 has a diamantane structure.

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

( 12 ) An insulating film formed by using the film forming composition as described in any of (1) to ( 11 ) above.

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

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

  According to the present invention, it is possible to provide an insulating film that has a low dielectric constant, exhibits stable insulating properties, is excellent in strength, and suppresses unintentional variations in film thickness and characteristics. 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 a longitudinal cross-sectional view which shows an example of the method of forming the interlayer insulation film patterned by the predetermined shape. It is a longitudinal cross-sectional view which shows typically an example of the semiconductor device of this invention.

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

  A film containing, in the molecule, a polymerizable compound having a partial structure a1 including an adamantane cage structure and a polymerizable functional group and / or a polymer (prepolymer) in which the polymerizable compound is partially polymerized It is a composition for formation. And a polyvalent reactive olefin having a plurality of polymerizable reactive groups in the molecule and having at least one polymerizable double bond (carbon-carbon double bond) as the polymerizable reactive group. It contains as a polymerizable compound and contains a predetermined amount of a hydride having a structure in which at least a part of the polymerizable reactive group of the polyvalent reactive olefin is substituted with a hydrogen atom.

  The film-forming composition has such a structure, and thus has a low dielectric constant, stable insulation, excellent strength, excellent adhesion to the adherend, and poor film thickness and characteristics. A film in which the intentional variation is suppressed can be suitably formed. As the polymerizable group (olefin-based reactive group) containing a polymerizable double bond (carbon-carbon double bond), one of the terminal hydrogen atoms of the vinyl group is an alkyl group, a cyclic alkyl group or an aromatic group. Although the thing substituted by the group group is mentioned, A vinyl group is preferable.

[1] Polyvalent reactive olefin body The polyvalent reactive olefin body includes a partial structure a1 including an adamantane cage structure and a plurality of polymerizable reactive groups in the molecule, It has at least one polymerizable double bond.

  The partial structure a1 possessed by the polyvalent reactive olefin body includes an adamantane cage structure. Thereby, the film formed using the film forming composition of the present invention can have a low density, and the dielectric constant of the formed film can be reduced.

Examples of the partial structure a1 possessed by the polyvalent reactive olefin include, for example, adamantane, polyadamantane (eg, biadamantane, triadamantane, tetraadamantane, heptaadamantane, hexaadamantane, etc.), polyamantane (eg, diamantane, triamantane, tetraamantane). Divalent groups such as mantan, pentamantane, hexamantane, heptamantane, etc., and compounds in which at least some of the hydrogen atoms constituting these compounds are substituted with alkyl groups (excluding the two hydrogen atoms constituting the above compounds) Structure having two or more of these divalent groups (for example, a structure in which a plurality of diamantane skeletons such as a bi (diamantane) skeleton, a tri (diamantane) skeleton, and a tetra (diamantane) skeleton are linked (poly ( (Diamantane) having skeleton) A structure in which a plurality of triamantane skeletons such as a bi (triamantane) skeleton, a tri (triamantane) skeleton, and a tetra (triamantane) skeleton are connected (having a poly (triamantane) skeleton); an adamantane skeleton (or a polyadamantane skeleton) ) And a polyamantane skeleton, etc.). Hereinafter, a part of the example of the partial structure a1 is shown by a chemical structural formula, but the partial structure a1 is not limited thereto. However, in the following formulas (C-1) to (C-7), R ¹ and R ² each independently represent a hydrogen atom or an alkyl group, and l, m, and n each independently represent 1 or more. Represents an integer.

  Moreover, it is preferable that the partial structure a1 is a structure which itself has symmetry. As a result, the reactivity of the polymerizable compound and / or the polymer (prepolymer) obtained by partially polymerizing the polymerizable compound contained in the film-forming composition can be made more appropriate. When applying the film-forming composition on the member to be formed (for example, a semiconductor substrate), the viscosity of the film-forming composition is more surely suitable, and the thickness of each part of the film to be formed It is possible to more effectively suppress the unintentional variation in the sheath characteristics, and to make the finally formed film particularly excellent in strength.

  Moreover, it is preferable that the partial structure a1 has a biadamantan structure. Thereby, the dielectric constant of the film formed using the film forming composition of the present invention can be made particularly low. In addition, the reactivity of the polymerizable compound and / or the polymer (prepolymer) obtained by partially polymerizing the polymerizable compound contained in the film-forming composition can be further improved to form a film. When applying the film-forming composition on the member to be formed (for example, a semiconductor substrate), the viscosity of the film-forming composition is more surely suitable, and the thickness at each part of the film to be formed Unintentional variations in characteristics can be suppressed more effectively, and the strength of the finally formed film can be made particularly excellent.

  The biadamantane structure preferably has a methyl group as a substituent. Thereby, the dielectric constant of the film formed using the film forming composition of the present invention can be made particularly low. In addition, the reactivity of the polymerizable compound and / or the polymer (prepolymer) obtained by partially polymerizing the polymerizable compound contained in the film-forming composition can be further improved to form a film. When applying the film-forming composition on the member to be formed (for example, a semiconductor substrate), the viscosity of the film-forming composition is more surely suitable, and the thickness at each part of the film to be formed Unintentional variations in characteristics can be suppressed more effectively, and the strength of the finally formed film can be made particularly excellent.

  In particular, the partial structure a1 preferably has a structure represented by the following formula (2).

  Thereby, the dielectric constant of the film formed using the film forming composition of the present invention can be made particularly low. In addition, the reactivity of the polymerizable compound and / or the polymer (prepolymer) obtained by partially polymerizing the polymerizable compound contained in the film-forming composition can be further improved to form a film. When applying the film-forming composition on the member to be formed (for example, a semiconductor substrate), the viscosity of the film-forming composition is more surely suitable, and the thickness at each part of the film to be formed Unintentional variations in characteristics can be suppressed more effectively, and the strength of the finally formed film can be made particularly excellent.

  The partial structure a1 may have a diamantane structure. Thereby, the dielectric constant of the film formed using the film forming composition of the present invention can be made particularly low. In addition, the reactivity of the polymerizable compound and / or the polymer (prepolymer) obtained by partially polymerizing the polymerizable compound contained in the film-forming composition can be further improved to form a film. When applying the film-forming composition on the member to be formed (for example, a semiconductor substrate), the viscosity of the film-forming composition is more surely suitable, and the thickness at each part of the film to be formed Unintentional variations in characteristics can be suppressed more effectively, and the strength of the finally formed film can be made particularly excellent.

  As described above, the polyvalent reactive olefin has a plurality of polymerizable reactive groups in the molecule. Examples of the polymerizable reactive group include an acetylene-based reactive group and a polymerizable double bond, and the polyvalent reactive olefin body has at least one polymerizable double group as the polymerizable reactive group in the molecule. Has a bond. Thus, by providing a polymerizable double bond as the polymerizable reactive group, when forming a film using the film-forming composition, the polymerization reaction can be suitably advanced, and the formed film However, while having sufficient hardness, it is prevented that a film | membrane becomes hard too much and it becomes the thing excellent in the adhesiveness with respect to a to-be-adhered body.

  Moreover, the polyvalent reactive olefin body may have an acetylene type reactive group in addition to the polymerizable double bond as a polymerizable reactive group. Thereby, when forming a film | membrane using the composition for film | membrane formation, a polymerization reaction can be advanced more suitably and the film | membrane formed can be made higher in hardness.

  In addition, when the polymerizable reactive groups of the polyvalent reactive olefin are all polymerizable double bonds, the film formed using the film-forming composition should be more flexible. And the adhesion of the film to the adherend can be made particularly excellent.

  As described above, the polyvalent reactive olefin body includes a partial structure a1 including an adamantane cage structure, a plurality of polymerizable reactive groups (including at least one polymerizable double bond) in the molecule. However, those having a structure in which a polymerizable reactive group is directly bonded to an aromatic ring are preferable. As a result, the reactivity of the polymerizable compound and / or the polymer (prepolymer) obtained by partially polymerizing the polymerizable compound contained in the film-forming composition can be further improved. When applying the film-forming composition on the member to be formed (for example, a semiconductor substrate), the viscosity of the film-forming composition is more surely suitable, and the thickness of each part of the film to be formed It is possible to more effectively suppress the unintentional variation in the sheath characteristics, and to further improve the strength of the finally formed film.

  Further, in the polyvalent reactive olefin, when the polymerizable reactive group has a structure directly bonded to the aromatic ring, the aromatic ring is preferably directly bonded to the cage structure. As a result, the reactivity of the polymerizable compound and / or the polymer (prepolymer) obtained by partially polymerizing the polymerizable compound contained in the film-forming composition can be further improved. When applying the film-forming composition on the member to be formed (for example, a semiconductor substrate), the viscosity of the film-forming composition is more surely suitable, and the thickness of each part of the film to be formed It is possible to more effectively suppress the unintentional variation in the sheath characteristics, and to further improve the strength of the finally formed film.

  Moreover, it is preferable that a polyvalent reactive olefin body has a structure in which two polymerizable reactive groups are directly bonded to one aromatic ring. As a result, the reactivity of the polymerizable compound and / or the polymer (prepolymer) obtained by partially polymerizing the polymerizable compound contained in the film-forming composition can be further improved. When applying the film-forming composition on the member to be formed (for example, a semiconductor substrate), the viscosity of the film-forming composition is more surely suitable, and the thickness of each part of the film to be formed It is possible to more effectively suppress the unintentional variation in the sheath characteristics, and to further improve the strength of the finally formed film.

  When the polyvalent reactive olefin has a structure in which two polymerizable reactive groups are directly bonded to one aromatic ring, one polymerizable reactive group is present at the meta position of the other polymerizable reactive group. It is preferable that Thereby, in the state in which one polymerizable reactive group of two polymerizable reactive groups bonded to the aromatic ring of the polyvalent reactive olefin body has reacted (polymerization reaction), the electronic effect of the aromatic ring or the like is more enhanced. Remarkably exerted, the reactivity of the other polymerizable reactive group can be reduced more effectively, and the reacted site becomes an appropriate steric hindrance, and the other polymerizable reactive group (unreacted polymerization group) The reactivity of the reactive group) can be more suitably controlled. As a result, the selectivity (reactivity for the first-stage reaction and reactivity for the second-stage reaction) of the two polymerizable reactive groups bonded to the aromatic ring 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).

  In the case of having a structure in which two polymerizable reactive groups are directly bonded to one aromatic ring, both of the two polymerizable reactive groups are present at the meta position of the site where the aromatic ring is bonded to the cage structure. It is preferable. Thereby, in the state in which one polymerizable reactive group of two polymerizable reactive groups bonded to the aromatic ring of the polyvalent reactive olefin body has reacted (polymerization reaction), the electronic effect of the aromatic ring or the like is more enhanced. Remarkably exerted, the reactivity of the other polymerizable reactive group can be reduced more effectively, and the reacted site and the partial structure a1 described above become an appropriate steric hindrance, and the other polymerization The reactivity of the reactive reactive group (unreacted polymerizable reactive group) can be more suitably controlled. As a result, the selectivity (reactivity for the first-stage reaction and reactivity for the second-stage reaction) of the two polymerizable reactive groups bonded to the aromatic ring 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 polyvalent reactive olefin may be any one having at least two polymerizable reactive groups in the molecule, but preferably has three or more polymerizable reactive groups. It is more preferable that it has 4 or more and 6 or less, and even more preferable that it has 4 polymerizable reactive groups (tetravalent reactive olefin). Thereby, the intensity | strength etc. of the film | membrane formed using the film forming composition of this invention can be made especially excellent.

  Moreover, it is preferable that the polyvalent reactive olefin body (the hydrogenated body mentioned later is also the same) which does not have a halogen atom in a molecule | numerator. Since a halogen atom (a halogen atom that does not contribute to the polymerization reaction) generally has a relatively large steric hindrance, if a halogen atom is present in a polyvalent reactive olefin (also a hydrogenated product described later), It becomes difficult to favorably proceed the polymerization reaction during film formation. On the other hand, if the polyvalent reactive olefin body (the same applies to the hydrogenated body described later) does not have a halogen atom in the molecule, the polymerization reaction can be suitably advanced during film formation. In addition, a three-dimensionally cross-linked network can be formed, and the strength of the formed film can be improved. In addition, if a compound having a halogen atom is included in the film-forming composition, problems such as a decrease in insulation of the formed film are likely to occur, and the reliability of the formed film becomes low. However, the occurrence of such a problem can be effectively prevented when the polyvalent reactive olefin (as well as the hydrogenated product described later) does not have a halogen atom in the molecule. In addition, a polyvalent reactive olefin body (also the hydrogenated body described later) has no halogen atom in the molecule, and the film formed by using the film forming composition of the present invention. The insulation stability can be made particularly excellent.

  Examples of the polyvalent reactive olefin that satisfies the above conditions include those having a structure represented by the following formula (1 ′), and among them, those having a structure represented by the following formula (1) Is preferred.

However, in formula (1 ′) and formula (1), Ad represents a partial structure including an adamantane cage structure, and R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ are respectively Independently, it represents a hydrogen atom or an alkyl group. The same applies to formulas (3) to (7) described later. In the formula (1 ′), R ′ represents a hydrogen atom, an alkyl group, a cyclic alkyl group, or an aromatic group.

  When the polyvalent reactive olefin has such a structure, the dielectric constant of the film formed using the film-forming composition of the present invention 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. In addition, the insulating stability of the film formed using the film forming composition of the present invention can be made particularly excellent.

  In the following description, the case where the polyvalent reactive olefin body has a structure represented by the above formula (1) will be mainly described.

  In addition, the film forming composition of the present invention may include a plurality of types of polyvalent reactive olefins.

[2] Hydrogenated substance The hydrogenated substance has a structure in which at least a part of the polymerizable reactive group of the polyvalent reactive olefin is substituted with a hydrogen atom.

  By including such a hydride in a predetermined ratio together with the polyvalent reactive olefin, the polymerization reaction proceeds sufficiently to form a film while the polymerization reaction proceeds to form a film. It is possible to reliably prevent the reaction from proceeding excessively and the formed film from being inferior in flexibility or the like. In addition, the hydrogenated product has the same structure as the polyvalent reactive olefin compound except that at least a part of the polymerizable reactive group is substituted with a hydrogen atom. In a film formed by using a film-forming composition, the region is mainly composed of a material derived from a polyvalent reactive olefin body and mainly composed of a hydride or a material derived from a hydride. Occurrence of a problem such as phase separation from the remaining region can be reliably prevented. For this reason, it is possible to achieve both excellent film strength and excellent adhesion to an adherend (a member on which a film is to be formed). Further, by containing a hydride, the ratio of polymerizable reactive groups (relatively bulky polymerizable reactive groups) in the compound having an adamantane cage structure constituting the film-forming composition is reduced. Therefore, the applicability of the film-forming composition is improved, and unintentional variations in film thickness can be effectively suppressed for the formed film. The hydride may be contained as long as it has a structure as described above in a state where the polymerizable compound is not polymerized. In the film-forming composition, an independent compound (as a polymerizable compound) is used. A compound having a structure in which at least a part of the polymerizable reactive group of the polyvalent reactive olefin is substituted with a hydrogen atom), or is incorporated into the prepolymer by polymerization. It may be a thing.

  The hydride is contained in the film forming composition part at a predetermined ratio as a component of an independent compound or prepolymer. That is, when the polymerizable compound is not polymerized, the mole fraction of the hydride (relative content of the hydride) relative to the total number of moles of the polyvalent reactive olefin and hydride is: 0.01 to 10 mol%. By including a hydride in such a range, the effects as described above can be obtained. On the other hand, when the content of the hydride is less than the lower limit, when the film is formed by advancing the polymerization reaction, the polymerization reaction proceeds excessively, and the formed film is inferior in flexibility or the like. As a result, defects such as cracks are likely to occur, and excellent adhesion to the adherend (member on which the film is to be formed) and the reliability of the formed film cannot be sufficiently improved. Moreover, the applicability | paintability of the composition for film formation improves, and it becomes easy to produce the unintentional dispersion | variation in film thickness about the film | membrane formed. On the other hand, when the content of the hydride content exceeds the upper limit, the strength of the film formed using the film-forming composition is significantly reduced. In addition, the tendency of the dielectric constant of the film to be formed becomes significant.

  As described above, the mole fraction of hydride (relative content of hydride) with respect to the total number of moles of polyvalent reactive olefin and hydride when the polymerizable compound is not polymerized. ) Is from 0.01 to 10 mol%, preferably from 0.01 to 5 mol%, more preferably from 0.01 to 3 mol%. Thereby, the effects as described above are more remarkably exhibited.

  In addition, the content (relative content) of the hydride may be obtained by any method, but when the content (relative content) of the hydride cannot be obtained directly, For example, you may obtain | require indirectly from the quantity of the unreacted component about a raw material and an intermediate product. In such a case, if the theoretically calculated value (calculated value) has a predetermined width, the minimum value and the maximum value of the calculated value are values included in the above range. Is preferred. Thereby, the effects as described above are surely exhibited.

  In the case where the polyvalent reactive olefin body is one having the structure represented by the above formula (1) (tetravalent reactive olefin body), examples of the hydride include the following formulas (3) to (7). Examples are shown.

  The halogen content (in terms of the mass of halogen atoms) relative to the solid content in the film-forming composition is preferably 30 ppm or less, and more preferably 10 ppm or less. As a result, problems such as a decrease in the insulating properties of the film formed using the film forming composition can be reliably prevented, and the reliability of the formed film can be made particularly high.

  In the film-forming composition, the content of the polyvalent reactive olefin as the polymerizable compound, the content of the hydride, and the content of the polymer (prepolymer) in which the polymerizable compound is partially polymerized Is preferably 0.5 to 30 wt%, and more preferably 1.0 to 18 wt%.

[3] Solvent The film-forming composition contains a polyvalent reactive olefin and a hydrogenated compound as a polymerizable compound as independent compounds and / or as a constituent of a polymer (prepolymer). Usually, a solvent for dissolving them is included.

  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 those used for the synthesis of polyreactive olefins and hydrides and the above-mentioned polymers (prepolymers) (reaction solvents). There may be.

  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%.

[4] 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 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, 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, the dielectric constant of the film to be formed is sufficiently low even without using a hole forming material. can do. 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. 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 unintentional variations in the thickness and characteristics of each part 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 such heat treatment is performed, 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, it is 5 to 9 hours. Moreover, you may perform the above heat processing combining a different condition. For example, the first heat treatment performed under the conditions of heating temperature: 80 to 190 ° C., heating time: 0.5 to 6 hours, and heating temperature: 60 to 160 ° C., heating time: 0.5 to 9 hours A second heat treatment may be performed.

<Method for producing film-forming composition>
Next, a preferred embodiment of the method for producing the film forming composition of the present invention as described above will be described.

  The manufacturing method of the film forming composition of the present embodiment is a compound A preparation step in which a compound A having a partial structure a1 including an adamantane cage structure and a halogen atom bonded to a carbon atom is prepared in the molecule. And reacting compound A with an acetylene derivative, replacing the halogen atom with an acetylene derivative, allowing acetylene derivative to be introduced, allowing Mg or Li to act, and further allowing a hydrogen source to act so that no reaction occurs in the acetylene derivative introduction step. A hydrogenation step (dehalogenation step) in which the carbon-halogen bond is replaced with a carbon-hydrogen bond; a reduction step in which the acetylene-based reactive group is reduced to form a polymerizable double bond; And a partial polymerization step for polymerizing. When the acetylene derivative is a tri-substituted silyl acetylene group, a de-tri-substituted silylation step in which the tri-substituted silyl group is eliminated by hydrolysis at an appropriate step such as between the hydrogenation step (dehalogenation step) and the reduction step. You may have.

  By using such a method, an insulating film having a low dielectric constant, stable insulation, excellent strength, excellent adhesion to an adherend, and suppression of unintentional variation in film thickness. A film-forming composition that can be suitably used for forming the film can be suitably produced.

[Compound A preparation step]
First, a compound A having a partial structure a1 including an adamantane cage structure and a halogen atom bonded to a carbon atom is prepared in the molecule. Compound A has the same structure as the polyvalent reactive olefin body described above except that the polymerizable reactive group is replaced with a halogen atom. That is, for example, when the film-forming composition to be produced includes a polyvalent reactive olefin having a structure represented by the above formula (1), the compound A is represented by the following formula (8). The one having a structure is used.

In the formula (8), Ad represents a partial structure including an adamantane cage structure, X ¹ , X ² , X ³ , and X ⁴ each independently represent a halogen atom, and R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or an alkyl group. The same applies to formulas (9) to (22) and formulas (9 ′) to (17 ′) described later.

  The halogen atom that the compound A has is preferably a bromine atom. Thereby, the reactivity in the acetylene derivative introduction | transduction process and hydrogenation process (dehalogenation process) which are explained in full detail later can be made higher, and the compound containing an unreacted halogen atom is contained in the film-forming composition. Inclusion can be more effectively prevented. As a result, the reliability of the film formed using the film forming composition can be made higher.

  The compound A having the structure as described above allows the reactivity in the hydrogenation step (dehalogenation step) described in detail later to be higher, and the compound contains an unreacted halogen atom. Can be more effectively prevented from being contained in the film-forming composition. As a result, the reliability of the film formed using the film forming composition can be made higher.

[Acetylene derivative introduction process]
Next, compound A is reacted with an acetylene derivative to obtain an acetylene derivative-introduced body (ethynyl body) in which a halogen atom is substituted with an acetylene derivative.

  In particular, when compound A has a structure represented by the above formula (8), a compound represented by the following formula (9 ') is obtained as a main product by this step. In formula (9 ′), R ″ represents an alkyl group, a cyclic alkyl group, an aromatic group, or a tri-substituted silyl group. The same applies to formulas (10 ') to (17') described later. In this step, when obtaining an acetylene derivative-introduced product in which R ″ in formula (9 ′) is an alkyl group, examples of the acetylene derivative include 1-propyne, 1-butyne, 1-pentyne, 1-hexyne, 1-heptin or the like can be used, and in this step, when an acetylene derivative-introduced body in which R ″ in formula (9 ′) is a cyclic alkyl group is obtained, examples of the acetylene derivative include cyclohexylacetylene, Adamantyl acetylene or the like can be used, and in this step, when an acetylene derivative-introduced product in which R ″ in the formula (9 ′) is an aromatic group is obtained, examples of the acetylene derivative include phenylacetylene, naphthyl, and the like. Acetylene, fluorenylacetylene and the like can be used, and in this step, R ″ in the formula (9 ′) is When obtaining an acetylene derivative-introduced body that is a resubstituted silyl group, examples of the acetylene derivative include trialkyl-substituted silylacetylenes such as trimethylsilylacetylene, triethylsilylacetylene, triisopropylsilylacetylene, and triaryl-substituted acetylenes such as triphenylsilylacetylene However, it is not limited to these.

  In the present invention, trisubstituted silylacetylene is preferably used as the acetylene derivative, and trimethylsilylacetylene is more preferably used. Thereby, the reaction rate of the above reaction can be made particularly high, and the yield of the acetylene derivative-introduced product (tri-substituted silylethynyl product) can be made higher. Also in the detrisubstituted silylation step, the reaction rate can be made particularly high, and the yield of the detrisubstituted silyl compound can be made higher.

When tri-substituted silylacetylene is used as the acetylene derivative, a compound represented by the following formula (9) is obtained by this step. In formula (9), R ⁷ , R ⁸ and R ⁹ each independently represents a hydrocarbon group such as an alkyl group or an aryl group. The same applies to formulas (10) to (17) described later.

In this step, it is preferable to use triphenylphosphine ((Ph) ₃ P). Thereby, the reaction rate of the reaction as described above can be made particularly high, and the productivity of the film forming composition can be made more excellent. In addition, undesired impurities remain in the composition (a composition containing an acetylene derivative-introduced body (ethynyl form)) used in the hydrogenation process (dehalogenation process), and the hydrogenation process (dehalogenation process). It is possible to reliably prevent adverse effects. Further, it is possible to effectively prevent impurities from remaining in the finally obtained film forming composition.

  In this step, it is preferable to use copper (I) iodide. Thereby, the reaction rate of the reaction as described above can be made particularly high, and the productivity of the film forming composition can be made more excellent. In addition, undesired impurities remain in the composition (a composition containing an acetylene derivative-introduced body (ethynyl form)) used in the hydrogenation process (dehalogenation process), and the hydrogenation process (dehalogenation process). It is possible to reliably prevent adverse effects. Further, it is possible to effectively prevent impurities from remaining in the finally obtained film forming composition.

In this step, it is preferable to use dichlorobistriphenylphosphine palladium (Pd ((Ph) ₃ P) ₂ Cl ₂ ). Thereby, the reaction rate of the reaction as described above can be made particularly high, and the productivity of the film forming composition can be made more excellent. In addition, undesired impurities remain in the composition (a composition containing an acetylene derivative-introduced body (ethynyl form)) used in the hydrogenation process (dehalogenation process), and the hydrogenation process (dehalogenation process). It is possible to reliably prevent adverse effects. Further, it is possible to effectively prevent impurities from remaining in the finally obtained film forming composition.

  In this step, it is preferable to use triethylamine as the amine. Thereby, the reaction rate of the reaction as described above can be made particularly high, and the productivity of the film forming composition can be made more excellent. In addition, undesired impurities remain in the composition (a composition containing an acetylene derivative-introduced body (ethynyl form)) used in the hydrogenation process (dehalogenation process), and the hydrogenation process (dehalogenation process). It is possible to reliably prevent adverse effects. Further, it is possible to effectively prevent impurities from remaining in the finally obtained film forming composition.

[Hydrogenation process (dehalogenation process)]
As described above, in the acetylene derivative introduction step, an acetylene derivative-introduced body (ethynyl body) in which the halogen atom of compound A is substituted with an acetylene derivative is formed.

  However, the reaction in such an acetylene derivative introduction step is difficult to achieve a reaction rate of 100%, and usually a compound in which a halogen atom not substituted with an acetylene derivative remains is contained in the reaction product. It will be. Such a compound in which an unreacted halogen atom remains (particularly included in a reaction product when an acetylene derivative introduction step is performed using compound A having a plurality of halogen atoms in the molecule as a raw material) The compound in which unreacted halogen atoms remain) is difficult to completely remove by various purification methods, and this has a great adverse effect on the insulation properties of the finally obtained film-forming composition. As a result of intensive studies by the present inventors, it has become clear. Therefore, in the production method of the present embodiment, in the acetylene derivative introduction step, the halogen atom that has not been substituted with the acetylene derivative is replaced with hydrogen to obtain a precursor of the hydride. As a result, not only can the adverse effects due to the inclusion of the compound in which unreacted halogen atoms remain as described above be eliminated, but the hydride can be prepared without separately preparing raw materials for producing the hydride. It can be synthesized in the same system as the polyvalent reactive olefin compound, can make the productivity of the film forming composition as described above particularly excellent, and further eliminates waste of raw materials. From the viewpoint of resource saving.

  In particular, in the present embodiment, the reaction product obtained in the acetylene derivative introduction step is allowed to act on Mg or Li, and further, by acting a hydrogen source, the carbon- which has not been reacted in the acetylene derivative introduction step. A reaction for substituting the halogen bond with a carbon-hydrogen bond (reaction for substituting the remaining unreacted halogen atom with hydrogen) is performed. Since such a reaction generally proceeds at a very high reaction rate, a compound having an unreacted halogen atom can be prevented from being substantially contained in the composition.

  In the case where the compound A prepared in the compound A preparing step is represented by the above formula (8), as a compound in which an unreacted halogen atom that may be contained in the composition provided in this step remains In addition to the unreacted compound A, examples include those represented by the following formulas (10 ′) to (13 ′).

  The compounds represented by the above formulas (10 ') to (13') become compounds represented by the following formulas (14 ') to (17'), respectively, by this step.

  In particular, when tri-substituted silylacetylene is used as the acetylene derivative in the above step, the compounds corresponding to the above formulas (10 ′) to (13 ′) are represented by the following formulas (10) to (13), These compounds become compounds represented by the following formulas (14) to (17) by this step, respectively.

  Moreover, the unreacted compound A becomes a compound (hydrogenated product) as shown in the above formula (7) by this step.

[Detrimethylsilylation step]
When tri-substituted silylacetylene is used as the acetylene derivative in the acetylene derivative introduction step, the tri-substituted silyl group is then eliminated from the compound into which the tri-substituted silylethynyl group has been introduced by hydrolysis, and the polymerizable compound is used as a polymerizable compound. An ethynyl form (detrisubstituted silyl form) is obtained.

  This step can be carried out, for example, by allowing potassium carbonate to act in a mixed solvent of an ether solvent such as tetrahydrofuran and an alcohol solvent such as methanol.

  When the composition used in this step contains a compound represented by the above formula (9), the compound is a compound represented by the following formula (18).

  Moreover, when the composition used for this process contains the compound shown by said Formula (14)-Formula (17), these compounds are respectively shown to following formula (19)-Formula (22). It becomes such a compound.

[Reduction process]
Next, the acetylene type reactive group which the compound contained in the composition obtained at the said process has is reduce | restored to make a polymerizable double bond, and the olefin body which has a polymerizable double bond is obtained as a polymerizable compound.

  This step may be carried out so as to reduce all the acetylene-based reactive groups of the compound contained in the composition obtained in the step to polymerizable double bonds, or obtained in the step You may carry out so that only a part of acetylene type reactive group which the compound contained in a composition may have may be reduce | restored to a polymerizable double bond.

  This step can be suitably performed by, for example, Lindlar reduction using hydrogen gas, Brich reduction using sodium and liquid ammonia, diimide reduction using diimide, and the like.

[Partial polymerization process]
The film-forming composition may contain a polymerizable compound (a polyvalent reactive olefin and / or hydrogenated product) as described above, but a polymer obtained by partially polymerizing the polymerizable compound. It may contain a coalescence (prepolymer). When the film-forming composition contains a polymer (prepolymer) obtained by partially polymerizing the polymerizable compound, the viscosity of the film-forming composition is more surely suitable, and each of the formed films Unintentional variations in thickness and characteristics at the site can be more effectively suppressed, and the strength of the finally formed film can be made particularly excellent. In addition, a film to be formed is relatively thick by performing a heat treatment on the film forming composition prior to applying the film forming composition onto a member (for example, a semiconductor substrate) on which the film is to be formed. However, it can be suitably formed. In addition, when the film-forming composition contains a prepolymer of the polymerizable compound, when forming a film 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 can be suitably used as an insulating film varnish.

  Therefore, in the present embodiment, a partial polymerization step of partially polymerizing the polymerizable compound is provided after the step.

  This step can be suitably performed, for example, by subjecting the composition (composition containing a polymerizable compound) obtained in the above step to heat treatment.

  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., 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 by 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.

  In this case, 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: 1 to 9 hours. Is more preferable. Moreover, you may perform the heat processing with respect to the composition (composition containing a polymeric compound) obtained by the heavy said process combining different conditions. For example, for the composition (composition containing a polymerizable compound) obtained in the above step, the first heat treatment performed under the conditions of heating temperature: 80 to 190 ° C. and heating time: 0.5 to 6 hours; The second heat treatment performed under the conditions of heating temperature: 60 to 160 ° C. and heating time: 1 to 9 hours may be performed. 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: ether solvents such as diisopropyl ether, dibutyl ether, diphenyl ether, tetrahydrofuran, anisole, 1,3-dimethoxybenzene; benzene, toluene, mesitylene, ethylbenze Aromatic and aliphatic hydrocarbon solvents such as diethylbenzene, propylbenzene, heptane, hexane and n-octane; halide solvents such as chloromethane, dichloroethane, chloroform, dichloroethane and carbon tetrachloride; N-methylpyrrolidone and the like Examples thereof include amide solvents, and one or two or more selected from these can be used in combination.

  Moreover, when the film-forming composition to be prepared contains a prepolymer of a polymerizable compound, the unpolymerized polymerizable compound is removed by purification (substantially free of the unpolymerized polymerizable compound). 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.

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

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

  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 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, a polymerizable compound or a polymer having a structure in which a polymerizable reactive group of a prepolymer obtained by partially polymerizing the polymerizable compound reacts and reacts three-dimensionally (cured) A film (insulating film) composed of a material 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, for example, under the conditions of treatment temperature: 200 to 450 degrees, treatment time: 1 to 60 minutes, and treatment temperature: 250 to 400 degrees, treatment time: 1 to 30 minutes. More preferred. In the baking step, heat treatments with different conditions may be combined.

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

  The interlayer insulating film having a predetermined shape as described above can be formed as follows, for example.

  First, the semiconductor substrate 1 on which the SiN film 2 is formed is prepared, and the interlayer insulating film 3, the hard mask layer 4 and the photoresist layer 8 are formed in this order on the SiN film 2 (see FIG. 1A). .)

  The interlayer insulating film 3 is formed by the above-described method using the film forming composition of the present invention.

  Next, the photoresist layer 8 is exposed and developed using a photomask to obtain a photoresist layer 8 patterned into a shape having an opening at a position where a via (conductor post), a wiring groove or the like is formed ( (Refer FIG.1 (b).).

Next, the hard mask layer 4 is formed using the photoresist layer 8 as a mask by a reactive ion etching method using a gas generally used for patterning a hard mask material such as a fluorine-based gas such as CF ₄ as a processing gas. By etching, a hard mask layer 4 having a predetermined shape is formed (see FIG. 1C).

  Next, the photoresist layer 8 and the hard mask layer 4 patterned by a reactive ion etching method using a mixed gas of nitrogen and hydrogen generally used for etching an organic film or the like as a processing gas, or ammonia gas or the like. As a mask, the interlayer insulating film 3 is etched to form the interlayer insulating film 3 having a predetermined shape (see FIG. 1D).

  The interlayer insulating film 3 having a predetermined shape is obtained as described above. In the present invention, since the interlayer insulating film 3 is formed using the film forming composition of the present invention as described above, the interlayer insulating film 3 is formed. It is possible to more accurately suppress or prevent the film 3 from having a high dielectric constant, and to maintain the characteristics of the film with certainty.

  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 0.02 to 10 μm, More preferably, it is 0.05-0.7 micrometer.

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

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

FIG. 2 is a longitudinal sectional view schematically showing an example of the semiconductor device of the present invention.
As shown in FIG. 2, the semiconductor device 100 is provided on the semiconductor substrate 1 on which elements are formed, the SiN film 2 provided on the upper side of the semiconductor substrate 1 (upper side in FIG. 2), and the 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, by using the method described in the above insulating film, an insulating film having a predetermined shape in which a penetrating wiring groove is formed at a predetermined position of the insulating film composed of the interlayer insulating film 3 and the hard mask layer 4 is formed. Form.

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

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

  The interlayer insulating film 3 can be formed by the method described in the 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).

  Further, as described above, the interlayer insulating film (the insulating film of the present invention) can suppress / prevent the change in the characteristics of the insulating film when the semiconductor device is manufactured.

  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. .

  In the above-described embodiment, the compound A preparation step, the acetylene derivative introduction step, the hydrogenation step, the detrisubstituted silylation step, and the reduction step have been described as having a partial polymerization step. The tri-substituted silylation step may not be performed.

  In addition, the film-forming composition of the present invention includes a polymerizable compound having a partial structure a1 containing an adamantane-type cage structure and a polymerizable functional group in the molecule and / or the polymerizable compound is partially contained. A film-forming composition comprising a polymer polymerized in a polyvalent reaction comprising a plurality of polymerizable reactive groups in the molecule and at least one polymerizable double bond as the polymerizable reactive group And a hydrogenated product having a structure in which at least a part of the polymerizable reactive group of the polyvalent reactive olefin product is substituted with a hydrogen atom at a predetermined ratio. It may be sufficient, and may be manufactured by a method other than the method described above. The film-forming composition of the present invention may be prepared, for example, by mixing separately synthesized polyvalent reactive olefins and hydrides.

  Moreover, in the manufacturing method as described above, the order of the steps may be changed. For example, in the above-described embodiment, the detrimethylsilylation process is performed after the hydrogenation process. However, the detrimethylsilylation process may be performed before the hydrogenation process. In the above-described embodiment, the reduction process is performed after the detrimethylsilylation process. However, the reduction process may be performed before the detrimethylsilylation process.

  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] Production of film-forming composition (Example 1)
First, a film forming composition as a first sample was produced as follows.

[1.1] Compound A Preparation Step First, 1,3-dimethyladamantane is prepared, and carbon tetrachloride: 700 mL, bromine: 35 g (in a four-necked 2000 mL flask equipped with a thermometer, a stirrer, and a reflux tube ( The prepared 1,3-dimethyladamantane: 32.9 g (0.2 mol) was added little by little while stirring. During the addition, the internal temperature was kept at 20-30 ° C.
After the addition was completed, the reaction was continued for another hour after the temperature did not rise.

Then, it poured into about 2000 mL of cold water, and the crude product was separated by filtration, washed with pure water, and dried.
The crude product was recrystallized from hot ethanol. The obtained recrystallized product was dried under reduced pressure to obtain 37.4 g of a product. IR analysis shows absorption of bromo group at 690-515 cm ⁻¹ and results of mass analysis 322 molecular weight indicate that the product is 3,5-dimethyl-1,7-dibromoadamantane. It was.

  Next, 3,5-dimethyl-1,7-dibromoadamantane: 33.2 g (103.2 mmol) and 1,3-dibromobenzene: 1217 g (5161.6 mmol) obtained above were stirred in the flask, At 25 ° C. under dry nitrogen, 24.8 g (93.0 mmol) of aluminum (III) bromide was added in small portions. This was heated to 60 ° C. and stirred for 8 hours, and then returned to room temperature to obtain a reaction solution. The reaction solution was added to 700 ml of 5% aqueous hydrochloric acid solution and stirred. The aqueous layer was removed, and the organic layer was put into 2000 ml of acetone. The precipitate was filtered and washed with acetone: 1000 ml three times to obtain 57 g of 3,5-dimethyl-1,7-bis (3,5-dibromophenyl) adamantane. From the result of the molecular weight by mass spectrometry being 632, it was shown that the product was 3,5-dimethyl-1,7-bis (3,5-dibromophenyl) adamantane as Compound A.

[1.2] Acetylene derivative introduction step (trimethylsilylethynylation step)
Next, 3,5,5-dimethyl-1,7-bis (3,5-dibromophenyl) adamantane as compound A obtained above: 39.8 g (62.9 mmol), dichlorobistriphenylphosphine palladium: 3 0.53 g (5.0 mmol), triphenylphosphine: 6.60 g (25.2 mmol), copper (I) 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 three times with acetone to obtain a product. From the results of mass spectrometry and the like, it was shown that the product was mainly composed of 3,5-dimethyl-1,7-bis (3,5-ditrimethylsilylethynylphenyl) adamantane.

Further, as a result of quantitative analysis of bromine (Br) by a flask combustion method and an ion chromatography method for the product in this step concerning the first sample, bromine (Br) in the product was 3100 ppm. In addition, the quantitative analysis of bromine (Br) by the flask combustion method and the ion chromatography method was performed according to the following procedures. That is, first, an absorbing solution was placed in a flask, a sample of 50 mg and a filter paper for a conducting wire were placed in a platinum basket, and the flask was filled with oxygen. Thereafter, the filter paper was lit, the flask was sealed, and the sample was completely burned. Next, gas components generated by combustion are absorbed in an absorption liquid (H ₂ O ₂ : 100 μL, 2N KOH aqueous solution: 100 μL, H ₂ O: 5 mL mixed liquid), and after standing to cool and constant volume, ion chromatography is performed. The amount of bromine was determined from the measurement results.

Further, as a result of ¹³ C-NMR for the product, a signal was confirmed in the range of 120 to 124 ppm, so that a part of the bromine atom contained in the compound A constitutes the product in the product. It seems that it remains in the compound.

[1.3] Hydrogenation process (dehalogenation process)
Next, 1.5 g of magnesium ribbon and 300 mL of dehydrated tetrahydrofuran were placed in a 4-neck 2000 mL flask equipped with a thermometer, a stirrer, and a reflux tube. This was stirred at 25 ° C. under dry nitrogen for 8 hours. Subsequently, 36.0 g of a product mainly composed of 3,5-dimethyl-1,7-bis (3,5-ditrimethylsilylethynylphenyl) adamantane obtained in the trimethylsilylethynylation step was added to 700 mL of dehydrated tetrahydrofuran. The solution dissolved in was added in small portions. After completion of the addition, the temperature was raised to 60 ° C. and stirred for 3 hours. The flask was cooled to room temperature and the dry nitrogen was changed to hydrogen. The temperature was raised again to 60 ° C., and the mixture was stirred for 3 hours under a hydrogen stream. Then, it returned to room temperature and stirred for 30 minutes after adding methanol: 100mL. After completion of the stirring, the magnesium ribbon was removed by filtration, and tetrahydrofuran and methanol in the filtrate were removed under reduced pressure. Pure water: 600 mL and acetone: 100 mL were added thereto, and after stirring for 30 minutes, the solid was separated by filtration. The product was obtained by washing the solid three times with 700 mL of acetone: As a result of the same quantitative analysis of halogen as described above for the product in this step concerning this first sample, bromine (Br) in the product was 8 ppm. As a result of ¹³ C-NMR, it was confirmed that the signal in the range of 120 to 124 ppm confirmed for the product in the trimethylsilylethynylation step disappeared after this step.

[1.4] Detrisubstituted silylation step (Detrimethylsilylation step)
The product obtained by the hydrogenation step (dehalogenation step): 32.3 g and potassium carbonate: 1.46 g (10.6 mmol) were mixed with nitrogen in a mixed solvent of tetrahydrofuran: 600 ml and methanol: 300 ml. The mixture was stirred at room temperature for 4 hours under an atmosphere. This was poured into 10% hydrochloric acid aqueous solution: 1000 ml, the precipitate was filtered, and the obtained precipitate was washed with water: 1000 ml, further washed with acetone: 1000 ml, and then dried. This gave 15.0 g of product. As a result of mass spectrometry, elemental analysis and the like showed that the product was mainly composed of 3,5-dimethyl-1,7-bis (3,5-diethynylphenyl) adamantane.

[1.5] Reduction Step Next, in a 5 L eggplant flask, the product obtained in the above step: 14.4 g, quinoline: 67.4 g (522 mmol), 5% palladium-calcium carbonate: 0.37 g (0. 174 mmol), tetrahydrofuran (1000 mL), and a stirring bar 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 18.1 g of a product containing a polyvalent reactive olefin.

[1.6] Partial polymerization step Next, 5 g of the product obtained in the above step was dissolved in 120 g of anisole, 0.1 g of azobisisobutyronitrile was added, and the reaction was performed at 70 ° C. for 1 hour under dry nitrogen. The reaction solution was once cooled to room temperature. When the molecular weight was measured by GPC, the number average molecular weight was 33,200. The reaction solution was heated again and reacted at 60 ° C. for 2 hours. Then, the reaction solution was concentrated and added dropwise to a 10-fold volume mixed solution of methanol / tetrahydrofuran = 1/1. Obtained 1 g of prepolymer. The number average molecular weight of the obtained prepolymer was 42,000 (yield 42%). 2 g of the obtained prepolymer was dissolved in 18 g of cyclopentanone and filtered through a filter to obtain a film-forming composition (first sample) as a varnish for an organic insulating film.

  Furthermore, using the same method as described above, a total of 10 samples (first sample to 10th sample) film-forming compositions were obtained.

(Examples 2 to 5)
A total of 10 samples (first sample to 10th sample) varnish for organic insulating film, respectively, in the same manner as in Example 1 except that the raw materials used for the synthesis of Compound A were changed to those shown in Table 1. A film-forming composition was obtained.

(Example 6)
Except that the hydrogenation step (dehalogenation step) was performed as follows, a total of 10 samples (first sample to tenth sample) as varnishes for organic insulating films were obtained in the same manner as in Example 1. A film forming composition was obtained.

  First, a product containing a trimethylsilylethynyl compound was obtained by performing the same steps as the compound A preparation step and the trimethylsilylethynylation step of Example 1.

Next, 1.5 g of lithium wire (manufactured by Kanto Chemical Co., Inc.) and 300 mL of diethyl ether dry-distilled with calcium hydride: 300 mL were placed in a 4-neck 2000 mL flask equipped with a thermometer, a stirrer, and a reflux tube. This was stirred at −10 ° C. under dry nitrogen for 8 hours. Subsequently, a product obtained by dissolving the product obtained in the trimethylsilylethynylation step (product containing a trimethylsilylethynyl compound): 36.0 g in diethyl ether obtained by dry distillation with calcium hydride: 700 mL was added little by little. Then, methanol: 100mL was added and it stirred for 30 minutes. After completion of the stirring, the lithium wire was removed by filtration, and diethyl ether and methanol in the filtrate were removed under reduced pressure. Pure water: 600 mL and acetone: 100 mL were added thereto, and after stirring for 30 minutes, the solid was separated by filtration. The product was obtained by washing the solid three times with 700 mL of acetone: As a result of the same quantitative analysis of halogen as described above for the product in this step concerning the first sample, bromine (Br) in the product was 9 ppm. Further, as a result of ¹³ C-NMR, it was confirmed that the signal in the range of 120 to 124 ppm confirmed for the product containing the trimethylsilylethynyl compound disappeared after this step.

(Examples 7 to 10)
Except that the hydrogenation step (dehalogenation step) was carried out by the same method as shown in Example 6, respectively, a total of 10 samples (first sample) were respectively obtained in the same manner as in Examples 2-5. To 10th sample) were obtained as a film forming composition as a varnish for an organic insulating film.

  In the film forming compositions of the above Examples (Examples 1 to 10), all of the polymerizable reactive groups possessed by the polyvalent reactive olefin contained in the film forming composition are all polymerizable double. It was a bond.

(Example 11)
Except that the polyvalent reactive olefin was obtained as a polymerizable reactive group in addition to the polymerizable double bond and further provided with an acetylenic reactive group by changing the conditions in the reduction step, Similarly, the film formation composition as a varnish for organic insulation films of a total of 10 samples (1st sample-10th sample) was obtained, respectively.

In this example, the reduction process was performed under the following conditions.
That is, in a 5 L eggplant flask, the product obtained in the step [1.4]: 14.4 g, quinoline: 67.4 g (522 mmol), 5% palladium-calcium carbonate: 0.37 g (0.174 mmol), tetrahydrofuran (1000 mL) and a stirring bar were added, and stirring was started at room temperature under a hydrogen stream. When 1.68 L (70 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 17.8 g of a product containing a polyvalent reactive olefin.

(Examples 12 to 15)
A total of 10 samples (first sample to 10th sample) of organic materials were respectively obtained in the same manner as in Examples 2 to 5 except that the reduction step was performed in the same manner as described in Example 11. A film-forming composition as an insulating film varnish was obtained.

(Comparative Examples 1-5)
Except for omitting the hydrogenation step (dehalogenation step), respectively, in the same manner as in Examples 1 to 5, respectively, a total of 10 samples (first sample to 10th sample) as varnishes for organic insulating films, respectively. A film forming composition was obtained.

  Table 1 summarizes the production conditions of the above Examples and Comparative Examples. In Table 1, 3,5-dimethyl-1,7-bis (3,5-dibromophenyl) adamantane is referred to as “A1”, 3,3 ′, 5,5′-tetramethyl-7,7′-bis. (3,5-dibromophenyl) -1,1′-biadamantane is designated as “A2”, 3,3 ′, 5,5′-tetramethyl-7,7′-dibromo-1,1′-biadamantane as “ "A3", 4,9-bis (3,5-dibromophenyl) diamantane is indicated by "A4", and 4,9-dibromodiamantane is indicated by "A5". Table 1 also shows the total moles of the polyvalent reactive olefin and hydride when the polymerizable compound is not polymerized in the film forming compositions of the examples and comparative examples. The molar fraction (relative content) of the hydride with respect to the number is also shown. In addition, as the content (relative content) of the hydride, bromine (Br) content in the product obtained by the acetylene derivative introduction step, bromine (Br) in the product obtained by the hydrogenation step Maximum value theoretically determined from the quantitative results of the content (calculated values assuming that all bromine removed in the hydrogenation process is derived from a compound in which only one atom of bromine remains in the molecule) And the minimum value (calculated value obtained on the assumption that all bromine removed in the hydrogenation step was derived from unreacted compound A).

[2] Formation of insulating film (production of substrate with film)
About each said Example and each comparative example, the insulating film was formed as follows using the composition for film formation of 10 samples, 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 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.

[3] Evaluation of Insulating Film (Substrate with Film) For each of the above Examples and Comparative Examples, the dielectric constant and breakdown voltage of the insulating film (substrate with film) manufactured using 10 samples of the film-forming composition, respectively. Each of the characteristics of leakage current, glass transition temperature, elastic modulus, heat resistance and adhesion was evaluated by the following evaluation methods.

[3.1] Dielectric Constant The dielectric constant was evaluated using an automatic mercury probe CV measuring device SSM495 manufactured by Nippon SSM Co., Ltd.

[3.2] 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).

[3.3] Glass transition temperature (Tg)
The glass transition temperature was evaluated by a differential scanning calorimeter DSC-Q1000 apparatus manufactured by TA Instruments, 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 from the inflection point in reverse heat flow in the temperature range of 250 to 450 ° C.

[3.4] Elastic modulus The elastic modulus is a region where 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.

[3.5] 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.

[3.6] Adhesiveness JIS K 5600-5-6 Adhesiveness (Cross) for the substrate with a film (laminated body of silicon wafer / organic insulating film) according to each of Examples and Comparative Examples prepared in [2] 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, for each of the above examples and comparative examples, 10 samples of the film forming composition were used, and a SiOC film, an organic insulating film (the above examples and each comparative example) were formed on the silicon wafer. An insulating film formed using the film forming composition of the example) in this order, a substrate with a film, a silicon wafer, a SiCN film, an organic insulating film (for film formation of each of the above examples and comparative examples) An insulating film formed using the composition) in this order and a film-coated substrate, and a silicon wafer, a SiCN film, an organic insulating film (the film forming composition of each of the examples and comparative examples). Insulating films formed by using the film), and substrates with films in which SiO films were laminated in this order were produced, and the adhesion of these substrates with films was 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. About the sample which peeled, the average value of the number which 10 samples peeled was described in the table | surface.

[3.7] In-plane uniformity In accordance with the formation of the insulating film described in [2] above, an insulating film was formed on a silicon wafer having a diameter of 300 mm, and n & k Technology, Inc. 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 Table 2, Table 3, and Table 4. In addition, regarding the dielectric constant, breakdown voltage, leakage current, elastic modulus, heat resistance, and in-plane uniformity, the amount of variation (difference between the maximum value and the minimum value) among 10 samples for each of the above evaluation items is also shown. . The minimum value was shown for the glass transition temperature. 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 Table 5 shows. 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. The weight average molecular weight (Mw), number average molecular weight (Mn), and dispersion ratio (Mw / Mn) of the prepolymer are (sample value) ((maximum value−minimum value) / average value) × 100) among 10 samples. Since it was small, the average value was described. 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 apparent from Tables 2, 3, and 4, in the present invention, since the dielectric constant is low, the breakdown voltage is high, and the leakage current is small, an insulating film exhibiting excellent electrical characteristics as an insulating film is stably formed. We were able to. Further, the glass transition temperature was high, the heat resistance was excellent, the elastic modulus was high, and the mechanical strength was excellent. Moreover, in this invention, it was excellent in the adhesiveness of the insulating film to the semiconductor substrate etc. Since there is little variation between samples, it can be seen that the semiconductor device has excellent compatibility in the manufacturing process. Further, in the present invention, the unintentional thickness variation in each part of the formed film was sufficiently prevented (the film thickness uniformity between samples was excellent). Thus, in the present invention, it can be said that unintentional variation in characteristics at each part of the film and unintentional variation in characteristics between samples are prevented.
On the other hand, satisfactory results were not obtained in each comparative example.

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

Claims (14)

A film-forming composition comprising a polymerizable compound having a partial structure a1 containing an adamantane-type cage structure and a polymerizable functional group in the molecule and / or a polymer obtained by partially polymerizing the polymerizable compound Because
A polyvalent reactive olefin having a plurality of polymerizable reactive groups in the molecule and having at least one polymerizable double bond as the polymerizable reactive group is included as the polymerizable compound.
A hydrogenated product in which at least a part of the polymerizable reactive group of the polyvalent reactive olefin product is substituted with a hydrogen atom;
The polyvalent reactive olefin has a structure in which the polymerizable reactive group is directly bonded to an aromatic ring, and has a structure in which two polymerizable reactive groups are directly bonded to one aromatic ring, A tetravalent reactive olefin body having four polymerizable reactive groups,
When the polymerizable compound is not polymerized, the hydride has a mole fraction of 0.01 to 10 mol% with respect to the total number of moles of the polyvalent reactive olefin and hydride. A composition for forming a film, characterized by comprising:   The film-forming composition according to claim 1, wherein the polyvalent reactive olefin compound has no halogen atom in the molecule.   The film-forming composition according to claim 1 or 2, wherein all of the polymerizable reactive groups of the polyvalent reactive olefin are polymerizable double bonds.   The composition for film formation according to claim 1, wherein the polyvalent reactive olefin body further includes an acetylene-based reactive group in addition to the polymerizable double bond as the polymerizable reactive group. The film-forming composition according to any one of claims 1 to 4, wherein the aromatic ring is directly bonded to the cage structure. 6. The film-forming composition according to claim 1, wherein one of the polymerizable reactive groups is present at the meta position of the other polymerizable reactive group in the polyvalent reactive olefin. . The film-forming composition according to any one of claims 1 to 6 , wherein each of the two polymerizable reactive groups is present at a meta position of a site where the aromatic ring is bonded to the cage structure. The partial structure a1, the film forming composition according to any one of claims 1 and has a biadamantane structure 7. The film forming composition according to claim 8 , wherein the biadamantane structure has a methyl group as a substituent. The partial structure a1, the film forming composition according to any one of claims 1 and has a diamantane structure 9. The film-forming composition according to any one of claims 1 to 10 , which does not contain a pore-forming material having a function of forming pores in the film by thermal decomposition during film formation. It claims 1 to insulating film, which is formed by using the film forming composition according to any one of 11. The insulating film according to claim 12 , 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 12 or 13.

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