JP2011171572A - Insulating film, laminate, semiconductor device, and method of manufacturing semiconductor device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an insulating film which has a low dielectric constant and does not easily cause a problem of insulation failure at the time of application to the manufacture of a semiconductor device. <P>SOLUTION: The insulating film is formed by using a composition including a polymerizable compound having a partial structure comprising a cage structure of the adamantane type and a polymerizable reactive group that contributes to polymerization reaction and/or a polymer in which the polymerizable compound is partially polymerized, in the molecule. The etching rate at the time of etching with fluorine-based gas is 0.75 times or less than that of an SiO film. The polymerizable reactive group has an aromatic ring and an ethynyl group or a vinyl group directly bonded to the aromatic ring. In the polymerizable compound, preferably the number of carbon atoms derived from the aromatic ring is 15-38% relative to the number of carbon atoms of the entire polymerizable compound. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

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

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

  The patterning of the interlayer insulating film as described above in the process of manufacturing a semiconductor device is generally performed as follows (see, for example, Patent Document 1). That is, first, after forming a cap layer made of an inorganic material such as SiO on the surface of the interlayer insulating film, a resist film is formed on the surface of the cap layer, and the resist film is patterned by exposure / development processing. To do. Thereafter, the cap layer is patterned by etching using a fluorine-based gas using the patterned resist film as a mask (first etching step). Thereafter, the resist film is removed, and the interlayer insulating film is patterned by etching using ammonia gas or the like using the patterned cap layer as a mask (second etching step).

  However, conventionally, when the cap layer is patterned in the first etching step, a part of the lower interlayer insulating film (particularly, a part in contact with the cap layer) is also etched (particularly, side etching). There was a thing. When such an inadvertent etching of the interlayer insulating film occurs in the first etching step, a barrier metal layer is formed in a later step, and further, a wiring layer composed of Cu or the like is formed. However, there is a problem that the coverage of the barrier metal layer cannot be sufficiently secured, insulation failure is likely to occur, and the reliability of the manufactured semiconductor device cannot be made sufficiently excellent.

Japanese Patent Laid-Open No. 2002-261082

  An object of the present invention is to provide an insulating film that has a low dielectric constant and is less likely to cause problems such as defective insulation when applied to the manufacture of a semiconductor device, to provide a laminate including the insulating film, and a dielectric constant An object of the present invention is to provide a highly reliable semiconductor device that has a low insulating film and is less likely to cause problems such as insulation failure, and to provide a manufacturing method for reliably manufacturing the semiconductor device.

Such an object is achieved by the present invention described in the following (1) to (14).
(1) A polymerizable compound having a partial structure containing an adamantane cage structure in the molecule and a polymerizable reactive group contributing to the polymerization reaction, and / or a polymer obtained by partially polymerizing the polymerizable compound. An insulating film formed using a composition comprising:
An insulating film having an etching rate of 0.75 times or less that of an SiO film when etched with a fluorine-based gas.

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

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

  (4) The polymerizable reactive group has two ethynyl groups or vinyl groups, and the one ethynyl group or the vinyl group is present at the meta position of the other ethynyl group or the vinyl group. The insulating film according to (2) or (3) above.

  (5) The insulating film according to (4), wherein each of the two ethynyl groups or the vinyl group is present at a meta position of a site where the aromatic ring is bonded to the cage structure.

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

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

［式中、ｎは１〜５の整数を表す。］

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

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

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

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

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

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

  (12) At least one selected from the group consisting of the insulating film according to any one of (1) to (11) above and SiO, SiN, SiC, SiCN, and SiOC provided in contact with the insulating film And a cap layer made of the above material.

  (13) At least one selected from the group consisting of the insulating film according to any one of (1) to (11) and SiO, SiN, SiC, SiCN, and SiOC provided in contact with the insulating film And a cap layer made of the above material.

(14) a semiconductor substrate preparation step of preparing a semiconductor substrate;
Forming a silicon-containing film on the surface of the semiconductor substrate; and
An insulating film forming step of forming the insulating film according to any one of (1) to (11) above on the silicon-containing film;
Forming a cap layer made of at least one material selected from the group consisting of SiO, SiN, SiC, SiCN and SiOC on the surface of the insulating film;
Forming a resist film having a predetermined pattern on the surface of the cap layer; and
A first etching step of etching the cap layer using a fluorine-based gas with the resist film as a mask;
A method of manufacturing a semiconductor device, comprising: a second etching step of etching the interlayer insulating film using the cap layer subjected to the first etching as a mask.

  According to the present invention, it is possible to provide an insulating film that has a low dielectric constant and is less likely to cause problems such as poor insulation when applied to the manufacture of a semiconductor device, to provide a laminate including the insulating film, It is possible to provide a highly reliable semiconductor device that includes an insulating film having a low dielectric constant and hardly causes problems such as insulation failure, and a manufacturing method for reliably manufacturing the semiconductor device.

It is a longitudinal cross-sectional view which shows suitable embodiment of the manufacturing method of a semiconductor device. It is a longitudinal cross-sectional view which shows suitable embodiment of the manufacturing method of a semiconductor device. It is a longitudinal cross-sectional view which shows suitable embodiment of the manufacturing method of a semiconductor device.

Hereinafter, the present invention will be described in detail.
<Insulating film>
The insulating film of the present invention includes a polymerizable compound having a partial structure including an adamantane-type cage structure and a polymerizable reactive group contributing to the polymerization reaction in the molecule and / or the polymerizable compound partially polymerized. It is formed using a composition containing the polymer, and is characterized in that the etching rate when etched with a fluorine-based gas is 0.75 times or less that of the SiO film. That is, in the present invention, the etching rate of the insulating film when etched using a fluorine-based gas is V ₁ [nm / min], and the etching rate when the SiO film is etched under the same conditions is V ₂ [nm / min]. When satisfying the relationship, V ₁ / V ₂ ≦ 0.75 is satisfied. As a result, the dielectric constant of the insulating film is made sufficiently low, and the insulating film is etched when the cap layer is etched (first etching step) in manufacturing a semiconductor device as will be described in detail later. Thus, the finally obtained semiconductor device can be made highly reliable in which occurrence of problems such as defective insulation is reliably prevented.

As described above, in the present invention, the etching rate of the insulating film when etched with a fluorine-based gas may be 0.75 times or less (V ₁ / V ₂ ≦ 0.75) of the SiO film. It is preferably 0.70 times or less (V ₁ / V ₂ ≦ 0.70) of the SiO film, and more preferably 0.65 times or less (V ₁ / V ₂ ≦ 0.65) of the SiO film. preferable. Thereby, the reliability of the semiconductor device manufactured using the insulating film can be made particularly high.

  The dielectric constant of the insulating film of the present invention is preferably 2.80 or less, more preferably 2.40 or less, and even more preferably 2.30 or less. Thereby, it is possible to further increase the speed of the semiconductor device. Note that the dielectric constant of the insulating film can be obtained using, for example, an automatic mercury probe CV measuring device SSM495 manufactured by Nippon SSM Co., Ltd.

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

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

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

[1] Polymerizable compound X
The polymerizable reactive group B of the polymerizable compound X has an aromatic ring and an ethynyl group or a vinyl group directly bonded to the aromatic ring. In the polymerizable compound X, the number of carbons derived from the aromatic ring is The total number of carbon atoms in the polymerizable compound X is preferably 15% or more and 38% or less, more preferably 18% or more and 27% or less. Thereby, the dielectric constant of an insulating film can be made lower. Further, the resistance of the insulating film to the fluorine-based gas can be made particularly excellent, and it is more likely that the insulating film is etched when the cap layer is etched in manufacturing a semiconductor device as described in detail later. This can surely be prevented, and a more reliable semiconductor device can be manufactured.

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

Hereinafter, the partial structure A and the polymerizable reactive group B will be described.
[1.1] Partial structure A
The partial structure A possessed by the polymerizable compound X includes an adamantane cage structure. Thereby, the insulating film formed using the film-forming composition can have a low density, and the dielectric constant of the formed insulating film can be reduced. Further, since the reactivity of the polymerizable compound X having the polymerizable reactive group B as described in detail later can be made appropriate, a film on a member (for example, a semiconductor substrate) on which an insulating film is to be formed. When applying the forming composition, the viscosity of the film forming composition can be surely suitable, and unintentional variations in thickness and characteristics at each site of the insulating film to be formed can be suppressed. In addition, the strength of the finally formed insulating film can be made excellent. Further, the resistance of the insulating film to the fluorine-based gas can be made particularly excellent, and it is more likely that the insulating film is etched when the cap layer is etched in manufacturing a semiconductor device as described in detail later. This can surely be prevented, and a more reliable semiconductor device can be manufactured.

Examples of the partial structure A possessed by the polymerizable compound X include adamantane, polyadamantane (eg, biadamantane, triadamantane, tetraadamantane, pentaadamantane, hexaadamantane, heptaadamantane, etc.), polyamantane (eg, diamantane, triamantane, Tetramantane, pentamantane, hexamantane, heptamantane, etc.), divalent groups such as compounds in which at least a part of hydrogen atoms constituting these compounds are substituted with alkyl groups or halogen atoms (two hydrogen atoms constituting the above compounds) A structure having two or more of these divalent groups (for example, a bi (diamantane) skeleton, a tri (diamantane) skeleton, a tetra (diamantane) skeleton, etc.) Things (Poly (Gia (Having a poly (triamantane) skeleton), such as a bi (triamantane) skeleton, a tri (triamantane) skeleton, and a tetra (triamantane) skeleton. An adamantane skeleton (or a polyadamantane skeleton) and a polyamantane skeleton, etc.) and the like. Hereinafter, a part of the example of the partial structure A is shown by a chemical structural formula, but the partial structure A is not limited to these. However, in the following formulas (A-1) to (A-7), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group, or a halogen group, and l, m, and n are each independently 1 represents an integer of 1 or more.

  The partial structure A preferably has an adamantane structure. Thereby, the dielectric constant of the insulating film formed using the film forming composition can be made particularly low. Further, the resistance of the insulating film to the fluorine-based gas can be made particularly excellent, and it is more likely that the insulating film is etched when the cap layer is etched in manufacturing a semiconductor device as described in detail later. This can surely be prevented, and a more reliable semiconductor device can be manufactured. Further, the reactivity of the polymerizable compound X can be made more suitable, and when the composition for forming a film on a member (for example, a semiconductor substrate) on which an insulating film is to be formed is applied, the film formation is performed. It is possible to make the viscosity of the composition for use more surely suitable, and more effectively suppress unintentional variations in thickness and characteristics in each part of the insulating film to be formed, and finally formed The strength of the insulating film can be made particularly excellent.

  The adamantane structure preferably has a methyl group as a substituent. Thereby, the dielectric constant of the insulating film formed using the film forming composition can be made particularly low. Further, the resistance of the insulating film to the fluorine-based gas can be made particularly excellent, and it is more likely that the insulating film is etched when the cap layer is etched in manufacturing a semiconductor device as described in detail later. This can surely be prevented, and a more reliable semiconductor device can be manufactured. Further, the reactivity of the polymerizable compound X can be made more suitable, and when the composition for forming a film on a member (for example, a semiconductor substrate) on which an insulating film is to be formed is applied, the film formation is performed. It is possible to make the viscosity of the composition for use more surely suitable, and more effectively suppress unintentional variations in thickness and characteristics in each part of the insulating film to be formed, and finally formed The strength of the insulating film can be made particularly excellent.

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

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

  In addition, it is preferable that the partial structure A having such a structure is a structure having symmetry itself. That is, in the above formula (2), n is preferably an even number. Thereby, the reactivity of the polymerizable compound X can be made more appropriate, and when the composition for forming a film on a member (for example, a semiconductor substrate) on which an insulating film is to be formed is applied, the film The viscosity of the forming composition is more surely suitable, and it is possible to more effectively suppress unintentional variations in the thickness and characteristics of each part of the insulating film to be formed, and the final formation. The strength of the insulating film can be made particularly excellent. Further, the resistance of the insulating film to the fluorine-based gas can be made particularly excellent, and it is more likely that the insulating film is etched when the cap layer is etched in manufacturing a semiconductor device as described in detail later. This can surely be prevented, and a more reliable semiconductor device can be manufactured.

  The partial structure A may have a diamantane structure. Thereby, the dielectric constant of the insulating film formed using the film forming composition can be lowered. Further, the reactivity of the polymerizable compound X can be made more suitable, and when the composition for forming a film on a member (for example, a semiconductor substrate) on which an insulating film is to be formed is applied, the film formation is performed. It is possible to make the viscosity of the composition for use more surely suitable, and more effectively suppress unintentional variations in thickness and characteristics in each part of the insulating film to be formed, and finally formed The strength of the insulating film can be made particularly excellent. Further, the resistance of the insulating film to the fluorine-based gas can be made particularly excellent, and it is more likely that the insulating film is etched when the cap layer is etched in manufacturing a semiconductor device as described in detail later. This can surely be prevented, and a more reliable semiconductor device can be manufactured.

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

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

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

  The aromatic ring constituting the polymerizable reactive group B is not particularly limited, and for example, a benzene ring, naphthalene ring, anthracene ring, naphthacene ring, phenanthrene ring, chrysene ring, pyrene ring, perylene ring, coronene ring, biphenyl ring, Hydrocarbon aromatic rings such as terphenyl ring and azulene ring, pyridine ring, furan ring, thiophene ring, pyrrole ring, oxazole ring, indole ring, purine ring, benzofuran ring, benzothiophene ring, carbazole ring, imidazole ring, Examples thereof include heterocyclic aromatic rings such as thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, quinoline ring, and terthienyl ring. Of these, a benzene ring is preferred as the aromatic ring. Thereby, application | coating of the composition for film formation on the member (for example, semiconductor substrate) which should form an insulating film can be performed more easily. Further, the resistance of the insulating film to the fluorine-based gas can be made particularly excellent, and it is more likely that the insulating film is etched when the cap layer is etched in manufacturing a semiconductor device as described in detail later. This can surely be prevented, and a more reliable semiconductor device can be manufactured. In addition, the elastic modulus of the insulating film formed using the film forming composition can be made suitable, and the strength and heat resistance of the formed insulating film and adhesion to the member (semiconductor substrate, etc.) Etc. can be made particularly excellent.

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

  The polymerizable reactive group B may have one ethynyl group, but has two ethynyl groups, and two ethynyl groups are directly bonded to the aromatic ring as described above. Is preferred. As a result, the resistance of the insulating film to the fluorine-based gas can be made particularly excellent, and the insulating film is etched when the cap layer is etched in manufacturing a semiconductor device as will be described in detail later. A semiconductor device that can be prevented more reliably and has higher reliability can be manufactured. Further, since the polymerizable reactive group B has two ethynyl groups as reaction sites, an initial reaction with respect to the polymerizable compound X easily occurs. On the other hand, when one of the two ethynyl groups of the polymerizable reactive group B reacts (polymerization reaction), the electronic state of the aromatic ring changes, and the reactivity of the other ethynyl group rapidly increases. descend. For this reason, only one ethynyl group of the two ethynyl groups of the polymerizable reactive group B can be selectively reacted under relatively mild conditions. And since the polymerizable compound X preferably has two polymerizable reactive groups B in the molecule, one of the two polymerizable reactive groups B present in the molecule of the polymerizable compound X is Only the ethynyl group can be reacted selectively. In this case, for example, a polymer (chain-like prepolymer) in which a plurality of polymerizable compounds X are polymerized one-dimensionally by a reaction shown in the following formula (3). Polymer).

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

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

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

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

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

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

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

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

  In addition, when the polymerizable reactive group B has two ethynyl groups, it is preferable that both of the two ethynyl groups are present at the meta position where the aromatic ring is bonded to the cage structure. Thereby, in the state in which one ethynyl group of the two ethynyl groups of the polymerizable reactive group B has reacted (polymerization reaction), the electronic effect of the aromatic ring or the like is more significantly exhibited, and the other ethynyl group The reactivity can be reduced more effectively, and the reacted site and the partial structure A described above become an appropriate steric hindrance, and the reactivity of the other ethynyl group (unreacted ethynyl group) can be reduced. It can control more suitably. As a result, the reactivity of the two ethynyl groups of the polymerizable reactive group B (reactivity for the first stage reaction and reactivity for the second stage reaction) is made higher. In addition, it is possible to carry out the firing step as described in detail later under more suitable conditions (conditions in which an insulating film can be formed with excellent productivity while preventing damage to the semiconductor substrate). . Further, the resistance of the insulating film to the fluorine-based gas can be made particularly excellent, and it is more likely that the insulating film is etched when the cap layer is etched in manufacturing a semiconductor device as described in detail later. This can surely be prevented, and a more reliable semiconductor device can be manufactured.

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

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

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

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

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

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

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

  That is, after synthesizing the polymerizable compound X having the two ethynyl groups described above, although not particularly limited, Lindlar reduction using hydrogen gas, Brich reduction using sodium and liquid ammonia, diimide reduction using diimide, etc. By carrying out, the target polymeric compound X can be obtained.

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

  This step is, for example, a method by thermal polymerization in which the reaction is carried out without using a catalyst, a method by radical polymerization using a radical initiator such as benzoyl peroxide, t-butyl peroxide, azobisisobutyronitrile, Photoradical polymerization using light irradiation, etc., using palladium catalysts such as dichlorobis (triphenylphosphine) palladium (II), bis (benzonitrile) palladium (II) dichloride and tetrakis (triphenylphosphine) palladium (0) Polymerization method, polymerization method using transition metal catalyst such as copper (II) acetate, polymerization using transition metal chloride such as molybdenum chloride (V), tungsten chloride (VI) and tantalum chloride (V). The method etc. can be mentioned. Among these, since a desired polymer can be easily obtained by controlling the reaction, and impurities need not be removed by remaining a metal catalyst or the like, a method by thermal polymerization or radical polymerization using a radical initiator is desirable.

  When preparing by the thermal polymerization method, the heat treatment conditions are preferably heating temperature: 120 to 190 ° C., heating time: 3 to 11 hours, heating temperature: 140 to 180 ° C., heating time: 3 to 3 hours. More preferably, it is 9 hours. When a radical initiator is used, the heat treatment conditions are preferably heating temperature: 40 to 190 ° C., heating time: 0.5 to 11 hours, heating temperature: 60 to 180 ° C., heating time: 0. More preferably, 5 to 9 hours. Moreover, you may perform the heat processing with respect to the composition (composition containing a polymeric compound) obtained at the said process combining different conditions. For example, in the thermal polymerization, for the composition (composition containing a polymerizable compound) obtained in the above step, the first is performed under the conditions of heating temperature: 150 to 190 ° C. and heating time: 1 to 6 hours. It is also possible to appropriately select the heat treatment and the second heat treatment performed under the conditions of heating temperature: 120 to 160 ° C. and heating time: 2 to 9 hours, or further multi-stage heat treatment. Even in the case of using a radical initiator, for example, a first heat treatment performed under the conditions of heating temperature: 60 to 190 ° C., heating time: 0.5 to 6 hours, heating temperature: 40 to 160 ° C., heating time: A second heat treatment performed under a condition of 0.5 to 9 hours or a multistage heat treatment can be appropriately selected. In addition, it is preferable to perform the above heat processing in the state which melt | dissolved the composition (composition containing a polymeric compound) obtained at the said process in the solvent. In addition, the synthesis of the prepolymer by the heat treatment as described above may be performed in a solvent as a component of the film-forming composition to be prepared, and what is a component of the film-forming composition? You may perform in the solvent of a different composition. That is, after a polymerizable compound is polymerized using a predetermined solvent to obtain a prepolymer, the solvent may be replaced with a solvent as a component of the target film-forming composition. Examples of the solvent (reaction solvent) that can be used for the synthesis of a polymer (prepolymer) in which a polymerizable compound is partially polymerized include alcohol solvents such as methanol, ethanol, isopropanol, 1-butanol, and 2-butanol. ; Ketone solvents such as acetone, acetylacetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, 2-pentanone, 2-heptanone; esters such as ethyl acetate, propyl acetate, butyl acetate, pentyl acetate, propylene glycol monomethyl ether acetate Solvents such as diisopropyl ether, dibutyl ether, diphenyl ether, tetrahydrofuran, anisole, 1,2-dimethoxybenzene, 1,3-dimethoxybenzene, 1,4-dimethoxybenzene, etc. Solvents; aromatic and aliphatic hydrocarbon solvents such as benzene, toluene, mesitylene, ethylbenzene, diethylbenzene, propylbenzene, heptane, hexane, n-octane; chloromethane, dichloroethane, chloroform, dichloroethane, carbon tetrachloride, etc. Halide-based solvents; amide-based solvents such as N-methylpyrrolidone and the like can be mentioned, and one or more selected from these can be used in combination.

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

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

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

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

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

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

  Examples of the solvent include N-methyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylacetamide, dimethyl sulfoxide, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, Propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate, butyl lactate, methyl-1,3-butylene glycol acetate, 1,3-butylene glycol-3-monomethyl ether, methyl pyruvate, ethyl pyruvate, methyl-3-methoxy Propionate, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, tetrahydro Orchids, anisole, mesitylene and the like, can be used singly or in combination of two or more selected from these. Of these, cyclopentanone and cyclohexanone are preferable as the solvent. Examples of the solvent constituting the film forming composition include a solvent (reaction solvent) used for the synthesis of a polymerizable compound and the above-described polymer (a prepolymer obtained by partially polymerizing a polymerizable compound). It may be a thing.

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

[3] Other components The film-forming composition may contain components other than those described above. Examples of such components include surfactants; coupling agents such as silane coupling agents; catalysts such as radical initiators and disulfides.

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

  In the present invention, it is preferable that the film-forming composition does not contain a pore-forming material that foams due to thermal decomposability and forms pores in the formed insulating film. Conventionally, a hole forming material has been used for the purpose of reducing the dielectric constant of the insulating film, but when using such a hole forming material, when etching the cap layer in the manufacture of a semiconductor device, The problem that part of the insulating film is removed together with the cap layer is particularly likely to occur, and when the insulating film is patterned in the manufacture of a semiconductor device, there is a problem that unevenness in the progress of etching at each part is likely to occur. However, in the present invention, there is a problem that the strength of the insulating film to be formed is reduced, the thickness of each part of the insulating film is unintentionally varied in thickness, and the characteristics are varied. Even without using a forming material, the dielectric constant of the formed insulating film can be made sufficiently low. And generation | occurrence | production of the above problems can be prevented reliably by not containing a void | hole formation material.

  The film-forming composition as described above may be used as it is for forming an insulating film, but the polymerizable compound has two polymerizable reactive groups and / or the polymerizable reactive group is In the case of having two ethynyl groups, it may be subjected to a heat treatment prior to application onto a member (for example, a semiconductor substrate) on which an insulating film is to be formed. Thereby, the film-forming composition can include a polymer (prepolymer) in which the polymerizable compound is partially polymerized, and the viscosity of the film-forming composition is more surely suitable and formed. In addition, it is possible to more effectively suppress the unintentional variation in thickness and characteristics of each part of the insulating film, and the strength of the finally formed insulating film can be made particularly excellent. In addition, the insulating film to be formed is compared by subjecting the film forming composition to heat treatment prior to applying the film forming composition onto the member (for example, a semiconductor substrate) on which the insulating film is to be formed. Even if it is thick, it can be suitably formed. In addition, by applying a heat treatment to the film forming composition prior to applying the film forming composition onto a member (for example, a semiconductor substrate) on which an insulating film is to be formed, the amount of heat applied on the member is increased. Since it can reduce, the damage to the said member by the heating can be prevented more reliably. When performing such heat treatment, the heat treatment conditions are preferably heating temperature: 120 to 190 ° C., heating time: 3 to 11 hours, heating temperature: 140 to 180 ° C., heating time: 3 to 9 hours. It is more preferable that Moreover, you may perform the above heat processing combining a different condition. For example, the 1st heat processing performed on the conditions of heating temperature: 150-190 degreeC, heating time: 1-6 hours, and the 2nd heat processing performed on the conditions of heating temperature: 120-160 degreeC and heating time: 2-9 hours And may be given.

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

  By performing the baking treatment as described above, the polymerizable compound or the unreacted polymerizable reactive group of the prepolymer in which the polymerizable compound is partially polymerized undergoes a polymerization reaction, and is composed of a polymer (cured product). An insulating film is obtained. An insulating film composed of a polymer (cured product) having such a chemical structure is excellent in strength, heat resistance, and the like. Further, the insulating film obtained as described above has a low dielectric constant. Further, the insulating film obtained as described above is one in which unintentional variations in film thickness and characteristics at each part are suppressed. For this reason, the insulating film as described above can be suitably used as an insulating film constituting a semiconductor device.

  Examples of the method for applying the film-forming composition onto the member include a spin coating method using a spinner, a spray coating method using a spray coater, dipping, printing, and roll coating.

  Prior to the firing treatment, for example, a treatment (desolvation treatment) for removing the solvent from the film-forming composition applied on the member may be performed. Such solvent removal treatment can be performed, for example, by heat treatment, reduced pressure treatment, or the like.

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

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

  As shown in FIGS. 1 to 3, in the manufacturing method of the present embodiment, a semiconductor substrate preparation step (1 a) for preparing a semiconductor substrate 1 on which elements are formed, and a silicon-containing film 2 is formed on the surface of the semiconductor substrate 1. A silicon-containing film forming step (1b), an insulating film forming step (1c) for forming an interlayer insulating film 3 as an insulating film of the present invention on the surface of the silicon-containing film 2, and a cap layer on the surface of the interlayer insulating film 3 And forming a resist film 8 on the surface of the cap layer 4, and forming a resist film 8 on the surface of the cap layer 4. Step (1e) and exposing / developing the resist film 8 using a photomask to form openings (grooves) at positions corresponding to positions where vias (conductor posts) or wiring grooves are formed in the resist film 8 Resist film paternin A step (1f), a first etching step (1g) for etching the cap layer 4 using the resist film 8 as a mask, and a resist film removal step (1h) for removing the resist film 8 to be carried out if necessary; Using the cap layer 4 as a mask, the interlayer insulating film 3 is etched to form a second etching step (1i) for forming an opening (groove), and a wiring layer 7 to be described later is provided on the surface side on which the interlayer insulating film is provided. A barrier metal layer forming step (1j) for forming a barrier metal layer 6 for preventing the diffusion of the constituent components of the wiring layer, and a wiring layer forming for forming a wiring layer 7 in the groove of the interlayer insulating film 3 covered with the barrier metal layer 6 Step (1k) and a polishing step (1) of removing a portion formed of the wiring material and provided outside the groove portion and a portion formed of the constituent material of the barrier metal layer 6 and provided outside the groove portion by polishing. ) And a.

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

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

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

The first etching step is performed by an etching method (reactive ion etching method) using a fluorine-based gas such as CF ₄ as a processing gas. Since the interlayer insulating film 3 satisfies the above conditions, it is reliably prevented that a part of the interlayer insulating film 3 together with the cap layer 4 is removed by unintentional etching such as side etching. As a result, the semiconductor device 100 finally obtained is highly reliable in which the occurrence of problems such as insulation failure is reliably prevented. In the present invention, the etching rate ratio between the insulating film and the SiO film when etched with a fluorine-based gas is defined. However, the present invention is not limited to the case where the cap layer 4 is made of SiO. Even if it is composed of SiC, SiCN, SiOC, etc., the excellent effects as described above can be obtained. This is because, when etching with a fluorine-based gas, a film composed of SiN, SiC, SiCN, SiOC, etc. shows the same behavior as a film composed of SiO. When the etching rate of the insulating film and the etching rate of the SiO film at the time of etching are greatly different, even if the cap layer 4 is made of a material such as SiCN or SiOC, the first This is because the etching of the interlayer insulating film 3 in the etching process is surely prevented.

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

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

  The barrier metal layer forming step can be performed by a vapor deposition method such as a PVD method or a CVD method. Examples of the constituent material of the barrier metal layer 6 include Ta, Ti, TaN, TiN, and WN.

The wiring layer forming step is preferably performed in combination with a vapor deposition method such as PVD and a wet plating method such as electric field plating. Thereby, the formation efficiency of the wiring layer 7 can be made particularly excellent while the adhesion of the wiring layer 7 to the barrier metal layer 6 is sufficiently excellent. The constituent material of the wiring layer 7 is not particularly limited, but copper (Cu) is preferably used.
The polishing step can be suitably performed by a CMP method (chemical mechanical polishing method).

Through the steps as described above, the semiconductor device 100 can be obtained.
Since the above-described semiconductor device of the present invention uses the above-described interlayer insulating film (insulating film of the present invention), it is highly reliable and does not cause problems such as insulation failure.

  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 silicon-containing film 2 is representatively described, but the position where the insulating film is formed is not limited thereto.

  The insulating film of the present invention is an insulating film formed using a composition containing a polymerizable compound having a partial structure including an adamantane-type cage structure and a polymerizable reactive group contributing to the polymerization reaction. The etching rate when etching with a fluorine-based gas may be 0.75 times or less that of the SiO film, and may not be formed using the composition containing the polymerizable compound X as described above. Good.

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

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

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

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

The crude product was recrystallized from hot ethanol. The obtained recrystallized product was dried under reduced pressure to obtain 37.4 g of a product. IR analysis shows bromo group absorption at 690-515 cm ⁻¹ , and mass analysis molecular weight of 322 indicates that the product is 3,5-dimethyl-1,7-dibromoadamantane. It was.

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

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

  Furthermore, 3,5-dimethyl-1,7-bis (3,5-ditrimethylsilylethynylphenyl) adamantane obtained above: 32.3 g (46.1 mmol) and potassium carbonate: 1.46 g (10.6 mmol) Were stirred in a mixed solvent of tetrahydrofuran: 600 ml and methanol: 300 ml under a nitrogen atmosphere at room temperature for 4 hours. This was poured into 10% aqueous hydrochloric acid solution: 1000 ml, the precipitate was filtered, and the resulting precipitate was washed with water: 1000 ml, further washed with acetone: 1000 ml, and then dried to obtain polymerizable compound X. 3,5-dimethyl-1,7-bis (3,5-diethynylphenyl) adamantane: 15.0 g was obtained.

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

Appearance: White solid MS (FD) (m / z): 413 (M +)
Elemental analysis: Theoretical value (/%) C; 93.16, H; 6.84, Measured value (/%) C; 93.11, H; 6.82

(Synthesis Examples 2 to 5)
A polymerizable compound X was obtained in the same manner as in Synthesis Example 1 except that tetramethylbiadamantane, hexamethyltriadamantane, octamethyltetraadamantane, and decamethylpentaadamantane were prepared instead of dimethyladamantane.

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

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

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

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

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

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

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

  The external appearance of the said compound (1) n = 5 polymeric compound X (Synthesis example 5), the result of mass spectrometry, and an elemental analysis are shown.

Appearance: White solid MS (FD) (m / z): 1062 (M +)
Elemental analysis: theoretical value (/%) C; 90.51, H; 9.49, actual measurement value (/%) C; 90.49, H; 9.47

(Synthesis Example 6)
First, 4,9-dibromodiamantane was synthesized according to the synthesis method described in Journal of Organic Chemistry., 39, 2987-3003 (1974). Absorption of bromo group was observed at 690 to 515 cm ⁻¹ by IR analysis, and the result of molecular weight 346 by mass spectrometry indicated that the product was 4,9-dibromodiamantane.

  Next, in the synthesis of 3,5-dimethyl-1,7-bis (3,5-dibromophenyl) adamantane as a synthesis intermediate in Synthesis Example 1, in the synthesis of 3,5-dimethyl-1,7-dibromoadamantane, Instead, 4,9-bis (3,5-dibromophenyl) was reacted in the same manner as in Synthesis Example 1 except that 3,5.7 g (103.1 mmol) of 4,9-dibromodiamantane was used. ) Diamantane: 56 g was obtained. From the result of the molecular weight of 656 by mass spectrometry, it was shown that the product was 4,9-bis (3,5-dibromophenyl) diamantane.

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

  Further, in the synthesis of 3,5-dimethyl-1,7-bis (3,5-diethynylphenyl) adamantane as the final product in Synthesis Example 1, 3,5-dimethyl-1,7-bis (3, Synthetic Example 1 except that instead of 5-ditrimethylsilylethynylphenyl) adamantane, 38.8 g (53.5 mmol) of 4,9-bis (3,5-ditrimethylsilylethynylphenyl) diamantane obtained above was used. By reacting in the same manner, 14.3 g of 4,9-bis (3,5-diethynylphenyl) diamantane as the polymerizable compound X was obtained.

  The appearance of the product, the results of mass spectrometry and elemental analysis are shown below. These data indicate that the compound obtained above is 4,9-bis (3,5-diethynylphenyl) diamantane.

Appearance: White solid MS (FD) (m / z): 436 (M +)
Elemental analysis: Theoretical value (/%) C; 93.54, H; 6.46, Actual value (/%) C; 93.46, H; 6.38

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

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

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

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

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

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

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

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

(Synthesis Example 10)
First, in a 4-neck 2000 mL flask equipped with a thermometer, a stirrer and a reflux tube, 3,5-dimethyl-1-bromoadamantane: 45.5 g (187.1 mmol) and 1,3-dibromobenzene: 1217 g ( 5161.6 mmol) and stirred, and at 25 ° C. under dry nitrogen, aluminum bromide (III): 24.8 g (93.0 mmol) was added in small portions. This was heated to 60 ° C. and stirred for 8 hours, and then returned to room temperature to obtain a reaction solution.

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

  Next, 3,5, -dimethyl-1- (3,5-dibromophenyl) adamantane obtained above: 47.1 g (118.4 mmol), dichlorobistriphenylphosphine palladium: 6.66 g (9.5 mmol) , Triphenylphosphine: 179.5 g (47.3 mmol), copper (II) iodide: 248.7 g (47.3 mmol), and triethylamine: 750 mL were added to the flask and stirred. After raising the temperature to 75 ° C., 34.9 g (355.2 mmol) of trimethylsilylacetylene was slowly added. This was stirred at 75 ° C. for 7 hours and then heated to 120 ° C. to distill off triethylamine. Then, it returned to room temperature and added dichloromethane: 1000mL to the reaction liquid, and stirred for 20 minutes. The precipitate was removed by filtration, and 5% hydrochloric acid aqueous solution: 1000 mL was added to the filtrate for liquid separation. The organic layer was washed 3 times with 1000 mL of water, and then the solvent of the organic layer was removed under reduced pressure. The obtained compound was dissolved in hexane: 1500 mL. Impurities were removed by filtration, and hexane in the filtrate was removed under reduced pressure. Acetone: 1000 mL was added thereto, and the precipitate was washed with acetone three times to obtain 37 g of 3,5-dimethyl-1- (3,5-ditrimethylsilylethynylphenyl) adamantane. The result of the molecular weight measured by mass spectrometry was 432, indicating that the product was 3,5-dimethyl-1- (3,5-ditrimethylsilylethynylphenyl) adamantane.

  Further, the 3,5-dimethyl-1- (3,5-ditrimethylsilylethynylphenyl) adamantane obtained above (36 g, 83.1 mmol) and potassium carbonate: 2.7 g (19.3 mmol) were mixed with tetrahydrofuran: 600 mL. In a mixed solvent of methanol: 300 mL, the mixture was stirred at room temperature for 4 hours under a nitrogen atmosphere. This was poured into 10% aqueous hydrochloric acid solution: 1000 mL, the precipitate was filtered, and the resulting precipitate was washed with water: 1000 mL, further washed with acetone: 1000 mL, and then dried to obtain 3 as a polymerizable compound. , 5-Dimethyl-1- (3,5-diethynylphenyl) adamantane: 19 g was obtained.

  The appearance of the product, the results of mass spectrometry and elemental analysis are shown below. These data indicate that the compound obtained above is 3,5-dimethyl-1- (3,5-diethynylphenyl) adamantane.

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

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

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

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

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

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

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

  Next, 4- (3,5-dibromophenyl) diamantane obtained above: 50 g (118.4 mmol), dichlorobistriphenylphosphine palladium: 6.66 g (9.5 mmol), triphenylphosphine: 179.5 g ( 47.3 mmol), copper (II) iodide: 248.7 g (47.3 mmol), and triethylamine: 750 mL were added to the flask and stirred. After raising the temperature to 75 ° C., 34.9 g (355.2 mmol) of trimethylsilylacetylene was slowly added. This was stirred at 75 ° C. for 7 hours and then heated to 120 ° C. to distill off triethylamine. Then, it returned to room temperature and added dichloromethane: 1000mL to the reaction liquid, and stirred for 20 minutes. The precipitate was removed by filtration, and 5% hydrochloric acid aqueous solution: 1000 mL was added to the filtrate for liquid separation. The organic layer was washed 3 times with 1000 mL of water, and then the solvent of the organic layer was removed under reduced pressure. The obtained compound was dissolved in hexane: 1500 mL. Impurities were removed by filtration, and hexane in the filtrate was removed under reduced pressure. Acetone: 1000 mL was added thereto, and the precipitate was washed with acetone three times to obtain 41 g of 4- (3,5-ditrimethylsilylethynylphenyl) diamantane. From the result of the molecular weight measured by mass spectrometry being 456, it was shown that the product was 4- (3,5-ditrimethylsilylethynylphenyl) diamantane.

  Furthermore, 4- (3,5-ditrimethylsilylethynylphenyl) diamantane obtained above (40 g, 87.6 mmol) and potassium carbonate: 2.7 g (19.3 mmol) were mixed with tetrahydrofuran: 600 mL and methanol: 300 mL. The mixture was stirred for 4 hours at room temperature in a nitrogen atmosphere. This was poured into 10% aqueous hydrochloric acid solution: 1000 mL, the precipitate was filtered, and the resulting precipitate was washed with water: 1000 mL, further washed with acetone: 1000 mL, and then dried to obtain 4 as a polymerizable compound. -(3,5-diethynylphenyl) diamantane: 23 g was obtained.

  The appearance of the product, the results of mass spectrometry and elemental analysis are shown below. These data indicate that the compound obtained above is 4- (3,5-diethynylphenyl) diamantane.

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

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

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

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

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

(Synthesis Example 14)
In a 5-L eggplant flask, 14.4 g (34.9 mmol) of 3,5-dimethyl-1,7-bis (3,5-diethynylphenyl) adamantane obtained in Synthesis Example 1 and 67.4 g (522 mmol) of quinoline were obtained. 5% palladium-calcium carbonate 0.37 g (0.174 mmol), tetrahydrofuran (1000 mL) and a stirrer were added, and stirring was started at room temperature under a hydrogen stream. When 3.35 L (139 mmol) of hydrogen was consumed, nitrogen was introduced to stop the reaction. After filtering the reaction solution, the filtrate was distilled off under reduced pressure, and the resulting solid was purified by silica gel column chromatography to obtain 3,5-dimethyl-1,7-bis (3,5- Divinylphenyl) adamantane 18.1 g was obtained.

  The appearance of the product, the results of mass spectrometry and elemental analysis are shown below. These data indicate that the compound obtained above is 3,5-dimethyl-1,7-bis (3,5-divinylphenyl) adamantane.

Appearance: White solid MS (FD) (m / z): 420 (M +)
Elemental analysis: Theoretical value (/%) C; 91.37, H; 8.63, Actual value (/%) C; 91.35, H; 8.60

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Appearance: White solid MS (FD) (m / z): 1223 (M +)
Elemental analysis: Theoretical value (/%) C; 90.28, H; 9.72, Actual value (/%) C; 90.26, H; 9.70

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

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

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

(Synthesis Example 24)
According to the synthesis method described in Macromolecules, 5266 (1991), 4,9-diethynyldiamantane was synthesized.

  The appearance of the obtained product, the results of mass spectrometry and elemental analysis are shown. These data indicate that the product obtained is 4,9-diethynyldiamantane.

Appearance: White solid MS (FD) (m / z): 236 (M +)
Elemental analysis: Theoretical value (/%) C; 91.47, H; 8.53, measured value (/%) C; 91.45, H; 8.57

(Synthesis Example 25)
A product was obtained in the same manner as in Synthesis Example 12 except that bromotri (diamantane) was prepared instead of bromodiamantane.

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

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

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

(Preparation Examples 2 to 25)
As the polymerizable compound, except that each synthesized in Synthesis Examples 2 to 25 was used, a polymerization reaction was performed in the same manner as in Preparation Example 1 to obtain a prepolymer, and further using the prepolymer: 2 g, By performing the same treatment as described in Preparation Example 1, a film forming composition as a varnish for an organic insulating film was obtained.

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

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

(Examples 1 to 24)
Insulating films were formed as follows using the film forming compositions as varnishes for organic insulating films obtained in Preparation Examples 1 to 24, 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, Then, a substrate with an insulating film was obtained.

(Comparative Example 1)
A substrate with an insulating film was obtained in the same manner as in the above Example, except that the film-forming composition used was obtained in Preparation Example 25.

[4] Evaluation of Insulating Film (Substrate with Insulating Film) [4.1] Etching Rate Ratio Regarding the insulating film of the substrate with the insulating film of each of the examples and comparative examples prepared in [3] above, fluorine-based materials are used. Etching was performed by reactive ion etching using gas. Then, the rate of change in film thickness before and after etching was determined using n & k Technology, Inc. This was measured using an n & k Analyzer 1500. The measurement point is set to (0,0) for the center coordinates, (0, -38) for the orientation flat part coordinates, and 9 linear coordinates from the coordinates (-38,0) to the coordinates (38,0) at equal intervals. . The numerical value obtained by dividing the rate of change of the 9-point average film thickness before and after etching by the reactive ion etching processing time was taken as the etching rate (V ₁ [nm / min]).

Reactive ion etching is performed using L-201D-L manufactured by Anelva Co., Ltd., with a frequency of 13.56 MHz, a pressure of 20 Pa, an output of 1000 W, a flow rate (CF ₄ : 200 sccm, argon: 400 sccm), and a processing time of 10 seconds. Carried out.

On the other hand, a substrate with an SiO film in which an SiO film (thickness: 100 nm) was formed on a silicon wafer was obtained separately using a plasma CVD method. With respect to the SiO film of the substrate with the SiO film, the etching rate was obtained by performing reactive ion etching under the same conditions as those for the insulating film of the substrate with the insulating film. The etching rate (V ₂ [nm / min]) of the SiO film obtained as a result of the measurement was 240 nm / min.

Then, determined the value obtained by dividing the respective Examples and Comparative Examples of the insulating film etching rate _{(V 1)} a SiO film etching rate _{(V 2)} to _(V 1 / _{V 2)} as an etching rate ratio.

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

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

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

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

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

[4.5] Etch workability Vapor phase film formation as a cap layer on the insulating film of the substrate with an insulating film of each of the examples and comparative examples prepared in [3] so that the film thickness is 50 nm. A SiO film was formed by the method. Next, a resist film was formed on the surface of the cap layer, and the resist film was exposed and developed using a photomask to form an opening (groove) at a position corresponding to the position where the wiring groove of the resist film was to be formed. Next, using the resist film as a mask, the SiO film as the cap layer was etched by a reactive ion etching method using a mixed gas of CF 4 and argon, to form a cap layer opening (groove) of 130 nm. The reactive ion etching was performed using L-201D-L manufactured by Anelva Co., Ltd. at a frequency of 13.56 MHz, a pressure of 20 Pa, an output of 1000 W, and a flow rate (CF4: 200 sccm, argon: 400 sccm). Further, the treatment time was adjusted so that the cap layer was completely opened.

About the board | substrate with the insulating film in which the cap layer produced above was opened, the opening width of the cap layer and the opening width of the insulating film of each of the examples and comparative examples which are lower layers of the cap layer were measured from the SEM observation of the cross section. The presence or absence of a side etching phenomenon in which the opening width of the insulating film is wider than the opening width of the cap layer was evaluated.
These results are shown in Table 2.

  As is apparent from Table 2, excellent results were obtained with the present invention, whereas satisfactory results were not obtained with the comparative example.

DESCRIPTION OF SYMBOLS 1 Semiconductor substrate 2 Silicon-containing film 3 Interlayer insulating film 4 Cap layer 6 Barrier metal layer 7 Wiring layer 8 Resist film 10 Laminate 100 Semiconductor device

Claims (14)

A composition comprising a polymerizable compound having in its molecule a partial structure containing an adamantane cage structure and a polymerizable reactive group contributing to the polymerization reaction, and / or a polymer obtained by partially polymerizing the polymerizable compound. An insulating film formed using
An insulating film having an etching rate of 0.75 times or less that of an SiO film when etched with a fluorine-based gas. The polymerizable reactive group of the polymerizable compound has an aromatic ring and an ethynyl group or a vinyl group directly bonded to the aromatic ring,
2. The insulating film according to claim 1, wherein in the polymerizable compound, the number of carbons derived from the aromatic ring is 15% or more and 38% or less with respect to the number of carbons in the entire polymerizable compound.   The insulating film according to claim 2, wherein the aromatic ring is directly bonded to the cage structure.   3. The polymerizable reactive group has two ethynyl groups or vinyl groups, and one of the ethynyl groups or the vinyl group is present at the meta position of the other ethynyl group or the vinyl group. Or the insulating film of 3.   5. The insulating film according to claim 4, wherein each of the two ethynyl groups or the vinyl group is present at a meta position of a site where the aromatic ring is bonded to the cage structure.   The insulating film according to claim 1, wherein the partial structure has an adamantane structure.   The insulating film according to claim 6, wherein the adamantane structure has a methyl group as a substituent. The insulating film according to claim 7, wherein the polymerizable compound has a structure represented by the following formula (1) or a structure represented by the following formula (5).

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

[Wherein n represents an integer of 1 to 5. ]   6. The insulating film according to claim 1, wherein the partial structure has a diamantane structure.   10. The polymerizable compound according to claim 1, wherein the polymerizable compound has two polymerizable reactive groups, and has a structure in which the polymerizable reactive groups are symmetrically bonded around the partial structure. An insulating film according to the above.   The insulating material according to any one of claims 1 to 10, wherein the insulating film is formed by using the composition that does not include a hole forming material having a function of forming holes in the film by thermal decomposition during film formation. film.   The insulating film according to any one of claims 1 to 11, and at least one material selected from the group consisting of SiO, SiN, SiC, SiCN, and SiOC provided in contact with the insulating film. A laminate comprising a cap layer.   The insulating film according to any one of claims 1 to 11, and at least one material selected from the group consisting of SiO, SiN, SiC, SiCN, and SiOC provided in contact with the insulating film. A semiconductor device comprising a cap layer. A semiconductor substrate preparation step of preparing a semiconductor substrate;
Forming a silicon-containing film on the surface of the semiconductor substrate; and
An insulating film forming step of forming an insulating film according to any one of claims 1 to 11 on the silicon-containing film;
Forming a cap layer made of at least one material selected from the group consisting of SiO, SiN, SiC, SiCN and SiOC on the surface of the insulating film;
Forming a resist film having a predetermined pattern on the surface of the cap layer; and
A first etching step of etching the cap layer using a fluorine-based gas with the resist film as a mask;
A method of manufacturing a semiconductor device, comprising: a second etching step of etching the interlayer insulating film using the cap layer subjected to the first etching as a mask.

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