JP2009256631A - Resin composition, resin film and semiconductor device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition capable of forming a resin film having a low dielectric constant and being excellent in mechanical strengths, a resin film having a low dielectric constant and excellent in heat resistance and mechanical strengths, and a semiconductor device having the resin film. <P>SOLUTION: The resin composition comprises a polymer of a cage structure compound having a polymerizable unsaturated bond and a cage structure with an adamantan structure as a minimum unit, wherein the polymer has 0-5% ratio of peak area Al of the peak L detected by elution time less than that corresponding to 9,000 polystyrene-converted weight average molecular weight to the total area of (Ap+Am) in molecular weight peaks measured by gel permeation chromatography, wherein Ap represents the peak area of the peak P for detecting the polymer and Am represents the peak area of the peak M for detecting the residual monomer. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a resin composition, a resin film, and a semiconductor device.

  In recent years, in the field of electronic materials, as semiconductor devices become more highly integrated, faster, and more powerful, signal delays caused by increased wiring resistance and increased capacitance between wires in semiconductor integrated circuits have occurred. It has become a big problem. In order to solve this signal delay problem and to increase the operation speed of the semiconductor device, it is necessary to use a low dielectric constant material for the insulating film in the multilayer wiring structure. In addition to the low dielectric constant characteristics, the material must have high mechanical strength and high heat resistance that can withstand the multilayer wiring structure formation process.

  As a low dielectric constant material, a porous material has been studied for the purpose of reducing the dielectric constant. As a method for making the porous layer, there is a method in which a thermally decomposable component (porogen) is introduced by mixing or bonding, and the porogen is decomposed in a heating and firing step in forming the insulating film to form pores in the insulating film. is there. However, in the porous formation by such a method, the pores existing in the film have a size of several nanometers to several tens of nanometers, and these pores exist not connected independently but connected. Therefore, the strength of the material inevitably decreases, and various problems due to vacancies have been pointed out in the semiconductor process. As a method for solving the problem, studies such as introduction of a process such as pore sealing have been conducted, but there is a concern that the number of manufacturing steps increases and costs increase.

On the other hand, a material having a large number of vacancies at the molecular level inside the resin structure has been reported (for example, see Patent Document 1). This is because the first cross-linking component and the second cross-linking component are combined to form a molecular level hole, and the dielectric constant is reduced. However, such a material cannot have a low dielectric constant with a single component, and is easy to gel when synthesizing the resin, the solubility of the polymer in the synthesis, and the storage stability as a varnish. It was very difficult to handle due to bad things.
As a report of improving gelation and polymer solubility during synthesis, a report has been made that the dielectric constant is reduced with a material composed of a compound having a —C≡CH group in the molecule as a cage structure compound (for example, (See Patent Document 2). However, in order to realize a dielectric constant of 2.35 or less, a pore forming agent (porogen, pore generator) had to be used in combination.

JP 2001-332543 A (paragraph numbers 0015 to 0019) JP 2007-70597 A

The objective of this invention is providing the resin composition which can form the resin film excellent in the low dielectric constant, high mechanical strength, and high heat resistance for solving the said problem.
Another object of the present invention is to provide a resin film having a low dielectric constant, high mechanical strength, and high heat resistance, and a semiconductor device having the resin film.

  Such an object is achieved by the present invention described in the following (1) to (20).

(1) A resin composition comprising a polymer containing a polymerizable unsaturated bond and a polymer of a cage structure compound having a cage structure having an adamantane structure as a minimum unit, and used for forming a resin film,
In the molecular weight peak measured by gel permeation chromatography, the polymer has a peak total area (Ap + Am) obtained by adding the peak area Ap of the peak P for detecting the polymer and the peak area Am of the peak M for detecting the residual monomer. On the other hand, the ratio of the peak area Al of the peak L in the region detected in the elution time slower than the elution time corresponding to the weight average molecular weight in terms of polystyrene of 9000 among the molecular weight peaks is 0 to 5% or less. A resin composition characterized by the above.
(2) The resin composition according to item (1), wherein the ratio of peak area Al of peak L is 0 to 3% or less.
(3) The resin composition according to (1) or (2), wherein the polymer is a prepolymer of the cage structure compound.
(4) The group containing a polymerizable unsaturated bond and the cage structure compound having a cage structure having an adamantane structure as a minimum unit are compounds represented by the following formula (1), item (1) -The resin composition of any one of the (3) term.

（式（１）中、Ｘ_１及びＹ_１は、それぞれ、同一又は異なる重合性不飽和結合を含む１又は２以上の基を示す。Ｒ_１は、アダマンタン構造又はポリアマンタン構造を有する基を示すが、ｍが２以上である場合、それぞれ同一であっても、異なっていても良い。ｍは１又は２以上の整数である。）

(In Formula (1), X ₁ and Y ₁ each represent one or two or more groups containing the same or different polymerizable unsaturated bond. R ₁ represents a group having an adamantane structure or a polyamantane structure. When m is 2 or more, they may be the same or different, and m is 1 or an integer of 2 or more.)

(5) The group containing a polymerizable unsaturated bond and the cage structure compound having a cage structure having an adamantane structure as a minimum unit is a compound represented by the following formula (2), item (1) -The resin composition of any one of the (4) term.

（式（２）中、Ｘ_２及びＹ_２は、それぞれ、同一又は異なる重合性不飽和結合を含む１又は２以上の基を示す。Ｒ_２及びＲ_３は、それぞれ、水素又は有機基を示すが、ｎ^１が２以上である場合、繰り返し単位毎に、同一であっても異なっていても良い。ｎ^１は１又は２以上の整数である。）

(In formula (2), X ₂ and Y ₂ each represent one or more groups containing the same or different polymerizable unsaturated bonds. R ₂ and R ₃ each represent hydrogen or an organic group. However, when n ¹ is 2 or more, it may be the same or different for each repeating unit. N ¹ is 1 or an integer of 2 or more.)

(6) The resin composition according to any one of items (1) to (5), wherein the cage structure having the adamantane structure as a minimum unit is an adamantane structure, a polyamantane structure, or a polyadamantane structure. .
(7) The resin composition according to any one of (1) to (6), wherein the group containing a polymerizable unsaturated bond is a group containing a carbon-carbon triple bond.
(8) The peak P for detecting the polymer measured by gel permeation chromatography has a polystyrene-equivalent number average molecular weight of 9,000 to 500,000, items (1) to (7) The resin composition according to any one of the above.
(9) The peak P for detecting the polymer measured by gel permeation chromatography has a polystyrene-equivalent number average molecular weight of 15,000 or more and 200,000 or less of items (1) to (8). The resin composition according to any one of the above.
(10) The peak P for detecting the polymer measured by gel permeation chromatography has a polydispersity (Mw / Mn) of 20 or less, which is the ratio of the weight average molecular weight in terms of polystyrene to the number average molecular weight. The resin composition according to any one of items (1) to (9).
(11) The peak P for detecting the polymer measured by gel permeation chromatography has a polydispersity (Mw / Mn) which is a ratio of the weight average molecular weight in terms of polystyrene and the number average molecular weight of 10 or less. The resin composition according to any one of (1) to (10).
(12) The peak top of the peak M for detecting the residual monomer measured by gel permeation chromatography is detected at an elution time later than the elution time corresponding to a polystyrene-equivalent weight average molecular weight of 1500. Item 11. The resin composition according to any one of Items (11) to (11).
(13) In the resin film formed using the resin composition, a first peak top having a pore size corresponding to a positron annihilation lifetime obtained by measurement by a positron annihilation lifetime measurement method is 1 nm or more. The resin composition according to any one of items (1) to (12), which is in the region.
(14) The resin composition according to item (13), wherein the resin film further has a pore size second peak top in a region of less than 1 nm.
(15) The resin composition according to item (14), wherein the intensity of the first peak top is stronger than the intensity of the second peak top.
(16) The resin composition according to any one of (13) to (15), wherein a pore size in the first peak top is 1 nm or more and 3 nm or less.
(17) The resin composition according to any one of (1) to (16), wherein the density of the resin film is 0.7 or more and 1.0 or less.
(18) The resin composition according to any one of (1) to (17), wherein the resin composition does not substantially contain a pore forming agent.
(19) A coating formed by applying the resin composition according to any one of items (1) to (18), heating, active energy rays, or heating and active energy rays A resin film obtained by crosslinking reaction by irradiation.
(20) A semiconductor device comprising the resin film according to item (19).

ADVANTAGE OF THE INVENTION According to this invention, the resin composition which can form the resin film excellent in the low dielectric constant, high mechanical strength, and high heat resistance can be obtained.
In addition, according to the present invention, it is possible to obtain a resin film having a low dielectric constant, a high mechanical strength, and a high heat resistance, and a semiconductor device having the resin film.

It is a figure which shows the definition of the molecular weight peak of polystyrene conversion measured by gel permeation chromatography. It is a figure which shows an example of the positron annihilation lifetime spectrum obtained by the positron annihilation lifetime measurement method. It is sectional drawing which showed the semiconductor device typically.

Hereinafter, the resin composition, the resin film, and the semiconductor device of the present invention will be described.
The resin composition of the present invention includes a polymer of a cage structure compound having a group containing a polymerizable unsaturated bond and a cage structure having an adamantane structure as a minimum unit, and is used for forming a resin film In the molecular weight peak measured by gel permeation chromatography, the polymer has a total peak area obtained by adding the peak area Ap of the peak P for detecting the polymer and the peak area Am of the peak M for detecting the residual monomer. The ratio of the peak area Al of the peak L in the region detected with an elution time slower than the elution time corresponding to 9000 corresponding to a polystyrene-reduced weight average molecular weight in the molecular weight peak with respect to (Ap + Am) is 0 to It is characterized by being 5% or less.

In addition, the resin film of the present invention is obtained by subjecting a coating film formed by coating using the above resin composition to a crosslinking reaction by heating, active energy rays, or heating and active energy ray irradiation. To do.
A semiconductor device according to the present invention includes the resin film described above.

First, the resin composition and the resin film will be described.
The resin composition of the present invention is used for forming a resin film. Examples of the resin film include insulating films, interlayer insulating films and surface protective films for semiconductor devices, interlayer insulating films for multilayer circuits, etching protective films, solder resist films, cover coats for flexible copper-clad plates, liquid crystal alignment films, and the like. It is done. Among these, at least one film selected from an interlayer insulating film for semiconductor devices, a surface protective film, and an etching protective film is preferable. Thereby, the electrical capacitance of the semiconductor element can be reduced.

The resin composition of the present invention comprises a polymer of a cage structure compound having a group containing a polymerizable unsaturated bond and a cage structure having an adamantane structure as a minimum unit.
Crosslinking of the polymerizable unsaturated bond improves heat resistance and mechanical strength, and the cage structure having the adamantane structure as a minimum unit can reduce the dielectric constant of the skeleton itself.
By having the characteristics of the molecular weight peak of the polymer, in the resin film obtained using the resin composition, in addition to the voids of less than 1 nm derived from the skeleton constituting the cage compound, a new 1 nm or more A film having voids can be obtained without using a pore forming agent, the dielectric constant of the film can be further reduced, and the mechanical strength is also good.
Although there may be a plurality of peaks P for detecting the polymer, in the present invention, all of the plurality of peaks are targeted for the peak P, and the area value Ap of the peak P is also indicated by the sum of the areas of the plurality of peaks.

  In the present invention, by setting the molecular weight in the above range, many voids of about 1 to 3 nm are obtained for the voids in the resin film measured by the positron annihilation lifetime measurement method. Results in a low dielectric constant of 2.3 or less.

The analysis conditions for gel permeation chromatography may be any conditions as long as the peak P for detecting the polymer and the peak M for detecting the residual monomer can be separated and detected. Specifically, it can be achieved by using a separation column that has an exclusion limit molecular weight of 600,000 (polystyrene equivalent weight average molecular weight) or more and linearity is obtained in a calibration curve in the range of standard polystyrene molecular weight of 50 to 500,000. As one specific example, two columns of polystyrene conversion exclusion limit molecular weight ⁴ × 10 ⁸ (estimated) (TSKgel GMH _XL manufactured by Tosoh Corporation) and polystyrene conversion exclusion limit molecular weight 1 × 10 ⁴ (TSKgel G2000H _XL manufactured by Tosoh Corporation) An analytical column that combines two columns in series is used. The eluent is tetrahydrofuran, and the measurement temperature is 40 ° C. ± 5 ° C.
In the detection method, when X ₁ and Y ₁ in the formula (1) are all aliphatic unsaturated hydrocarbons and R ₁ is a saturated hydrocarbon or an alicyclic hydrocarbon, the differential refractive index method is used. Uses an ultraviolet absorption method with a wavelength of 200 to 300 nm.

  First, a group having a polymerizable unsaturated bond and a cage structure compound having a cage structure having an adamantane structure as a minimum unit will be described.

  Examples of the group containing a polymerizable unsaturated bond include a group containing a carbon-carbon triple bond, a group containing a carbon-nitrogen triple bond, a group containing a carbon-carbon double bond, and the like. A group containing a bond is more preferable from the viewpoint of ease of synthesis of the polymer and heat resistance, and an ethynyl group is particularly preferable. These groups may have a substituent such as a phenyl group. Examples of the group containing a polymerizable unsaturated bond include those bonded to a group such as a phenyl group and a naphthyl group.

  Specific examples of the group containing a polymerizable unsaturated bond include those represented by the following formulas (3) to (5), typically an ethynyl group, as the group containing a carbon-carbon triple bond. As a group containing a carbon-nitrogen triple bond, a nitrile group can be cited as a representative group, and a maleimide group, a nadiimide group, a biphenylene group, a cyclopentadienyl group, and the like can also be exemplified. Examples of the group containing a carbon-carbon double bond include those represented by the following formulas (6) to (8), typically a vinyl group.

但し、式（３）中、Ｚは単結合または芳香族基を示し、Ｒ_４は脂肪族基を示し、Ｒ_５は水素原子または有機基を示す。Ｚが単結合の時、ｎ２は１であり、Ｚが芳香族基の時、ｎ２は１または２である。

In formula (3), Z represents a single bond or an aromatic group, R ₄ represents an aliphatic group, and R ₅ represents a hydrogen atom or an organic group. When Z is a single bond, n2 is 1, and when Z is an aromatic group, n2 is 1 or 2.

但し、式（４）中、Ｒ_６は水素又は有機基を示す。

However, in formula (4), R ₆ represents hydrogen or an organic group.

但し、式（５）中、Ｒ_７は水素又は有機基を示す。ｎ３は１〜５の整数であり、好ましくは１〜３である。

However, in formula (5), R ₇ represents hydrogen or an organic group. n3 is an integer of 1 to 5, preferably 1 to 3.

但し、式（６）中、Ｚは単結合または芳香族基を示し、Ｒ_８は脂肪族基を示し、Ｒ_９〜Ｒ_１１は水素又は有機基を示し、互いに独立しており、それぞれが同一又は異なる。Ｚが単結合の時、ｎ４は１であり、Ｚが芳香族基の時、ｎ４は１または２である。

However, in formula (6), Z represents a single bond or an aromatic group, R ₈ represents an aliphatic group, R _{9 to} R ₁₁ represent hydrogen or an organic group, are independent of each other, and are the same Or different. When Z is a single bond, n4 is 1, and when Z is an aromatic group, n4 is 1 or 2.

但し、式（７）中、Ｒ_１２〜Ｒ_１４は水素又は有機基を示し、互いに独立しており、それぞれが同一又は異なる。

However, in Formula (7), R < ₁₂ > -R < ₁₄ > shows hydrogen or an organic group, is mutually independent, and each is the same or different.

但し、式（８）中、Ｒ_１５〜Ｒ_１７は水素又は有機基を示し、互いに独立しており、それぞれが同一又は異なる。ｎ５は１〜５の整数であり、好ましくは１〜３である。

In the formula _{(8), R} 15 ~R ₁₇ is a hydrogen or an organic radical, they are independent of one another, identical or different, respectively. n5 is an integer of 1 to 5, preferably 1 to 3.

  Examples of the aromatic group as Z in the formulas (3) and (6) include a phenylene group, a naphthylene group, an anthracenylene group, a phenanthrenylene group, a polycyclic aromatic group having 4 to 6 aromatic rings, and fluorenylene. Groups, diphenylfluorenylene groups, biphenylene groups, and the like, but are not limited thereto. The hydrogen atom in the aromatic group may be substituted with a fluorine atom, a methyl group, a methoxy group, a trifluoromethyl group, or the like.

As the aliphatic group as R ₈ in the formula R ₄ and in (3) (6), a methylene group, an ethylene group, a propylene group, butylene group, hexylene group, 1 carbon atoms, such as octylene group and decylene Examples include, but are not limited to, 10 chain aliphatic groups. The hydrogen atom in the aliphatic group is a halogen group such as a fluorine atom or a trifluoromethyl group; a carbon number such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, t-butyl, or a pentyl group. An alkyl group having 1 to 5 carbon atoms; an alkoxy group having 1 to 5 carbon atoms such as methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutyloxy group, t-butyloxy group and pentyloxy group; May be.

R ₅ in formula (3), R ₆ in formula (4), R ₇ in formula (5), R _{9 to} R ₁₁ in formula (6), R _{12 to} R ₁₄ in formula (7) are hydrogen or Examples of the organic group and the organic group as R _{15 to} R ₁₇ in Formula (8) include aliphatic groups such as chain aliphatic groups and cyclic aliphatic groups, and aromatic groups. Examples of the chain aliphatic group include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a heptyl group, and an octyl group; and the cyclic aliphatic group includes a cyclohexyl group, a cycloheptyl group, and a bicyclo [2 , 2, 1] heptyl group and adamantyl group. Examples of the aromatic group include a phenyl group, a naphthyl group, an anthracenyl group, a phenanthrenyl group, a phenoxyphenyl group, a polycyclic aromatic group having four or more aromatic rings, a fluorenyl group, a diphenylfluorenyl group, and a biphenyl group. However, it is not limited to these. Note that a hydrogen atom in the organic group may be substituted with a fluorine atom, a methyl group, a methoxy group, a trifluoromethyl group, an adamantyl group, a phenyl group, or the like.

  The cage structure in the cage structure compound has a structure having an adamantane structure as a minimum unit, and examples of such cage structures include an adamantane structure, a polyamantane structure, a polyadamantane structure, and a poly (polyamantane) structure. By having such a saddle type structure, a resin film having a lower dielectric constant can be obtained. Examples of the group having a cage structure include, for example, an adamantane structure, an adamantyl group; a polyamantane structure, a diamantyl group, a triamantyl group, a tetramantyl group, a pentamantyl group, a hexamantyl group, a heptamantyl group, an octamantyl group, a nonamantyl group, a decamantyl group, and Examples include a group having an (aliphatic) polycyclic skeleton structure such as an undecamantyl group, and further a group having a plurality of groups having the polycyclic skeleton structure.

  Examples of the group having a plurality of groups having a polycyclic skeleton structure include a group having a poly structure, and the polyadamantane structure is an adamantyl group as the group having the polycyclic skeleton structure. Biadamantyl groups such as di (1,3-adamantane) group and di (2,2-adamantane) group, triadamantyl groups such as tri (1,3-adamantane) group and tri (2,2-adamantane) group, A tetraadamantyl group such as a tetra (1,3-adamantane) group and a tetra (2,2-adamantane) group, a pentaadamantyl group such as a penta (1,3-adamantane) group and a penta (2,2-adamantane) group, Heptaadamantyl group such as hepta (1,3-adamantane) group and hepta (2,2-adamantane) group, hexaadamantyl group Oct adamantyl group, Nonaadamanchiru group, decamethylene adamantyl group, and the like undecapeptide adamantyl group, and the like more groups having more polyadamantane structures the number of the adamantyl group.

  In addition, in the case of a group other than an adamantyl group as the group having the polycyclic skeleton structure, a group having a poly (polyamantane) structure in which the adamantyl group is substituted with the polyamantane structure in the group having the polyadamantane structure is exemplified. For example, di- (diamantane) group, tri- (diamantane) group, tetra- (diamantane) group, penta- (diamantane) group, hexa- (diamantane) group, hepta- (diamantane) group, octa- (diamantane) A group having a plurality of diamantane groups such as a group, a non- (diamantane) group, a deca- (diamantane) group and an undeca- (diamantane) group, a di- (triamantane) group, a tri- (triamantane) group, a tetra -(Triamantane) group, penta- (triamantane) group, hexa- (triamant) ) Group, hepta- (triamantane) group, octa- (triamantane) group, nona- (triamantane) group, deca- (triamantane) group and undeca- (triamantane) group, etc. A plurality of groups, a di- (tetraamantane) group, a tri- (tetraamantane) group, a tetra- (tetraamantane) group, a penta- (tetraamantane) group, a hexa- (tetraamantane) group, Tetraamantane such as hepta- (tetraamantane) group, octa- (tetraamantane) group, nona- (tetraamantane) group, deca- (tetraamantane) group and undeca- (tetraamantane) group And a group having a plurality of groups.

  Hydrogen on the adamantane structure and the polyamantane structure may have an alkyl group having 1 to 20 carbon atoms. Examples of such an alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, A heptyl group, an octyl group, etc. are mentioned, Among these, a methyl group and an ethyl group are more preferable. By introducing an alkyl group into the adamantane structure, solubility in an organic solvent and heat resistance can be improved.

  The group having a polymerizable unsaturated bond and the cage structure compound having a cage structure having an adamantane structure as a minimum unit are used as the group having the polymerizable unsaturated bond and the compound having the cage structure. And having the cage structure in the main chain, the side chain, or both the main chain and the side chain, and the group containing the polymerizable unsaturated bond is directly bonded to the cage structure. It may be bonded to a group different from the cage structure.

The number of the groups containing a polymerizable unsaturated bond may be one or more, but preferably 2 to 4.
A preferable example of the cage compound is a compound having a structure represented by the general formula (1).

式（１）中、Ｘ_１及びＹ_１は、それぞれ、同一又は異なる重合性不飽和結合を含む１または２以上の基を示すが、具体例としては、上記重合性不飽和結合を含む基である。また、Ｒ_１は、それぞれ、アダマンタン構造又はポリアマンタン構造を有する基を示すが、前記アダマンタン構造又はポリアマンタン構造を有する多環式骨格構造を有する基が挙げられ、各単位ごとに独立しても良いし、同じであっても良い。ｍは１又は２以上の整数であり、ｍは９以下が好ましく、更に溶解性の点から３以下が好ましい。

In formula (1), X ₁ and Y ₁ each represent one or two or more groups containing the same or different polymerizable unsaturated bond. Specific examples thereof include a group containing the above polymerizable unsaturated bond. is there. R ₁ represents a group having an adamantane structure or a polyamantane structure, and examples thereof include groups having a polycyclic skeleton structure having the adamantane structure or the polyamantane structure, and may be independent for each unit. , May be the same. m is an integer of 1 or 2 or more, m is preferably 9 or less, and more preferably 3 or less from the viewpoint of solubility.

  Among the compounds having the structure represented by the general formula (1), a polyadamantane compound represented by the following general formula (2) is preferable in terms of heat resistance.

式（２）中、Ｘ_２及びＹ_２は、それぞれ、同一又は異なる重合性不飽和結合を含む１または２以上の基を示すが、具体例としては上記重合性不飽和結合を含む基である。Ｒ_２〜Ｒ_３は、それぞれ、水素又は有機基を示すが、各単位ごとに独立しても良いし、同じであっても良い。ｎ１は前記一般式（１）におけるｍと同じである。

In formula (2), X ₂ and Y ₂ each represent one or two or more groups containing the same or different polymerizable unsaturated bond, and specific examples thereof are groups containing the above polymerizable unsaturated bond. . R _{2 to} R ₃ each represent hydrogen or an organic group, but each unit may be independent or the same. n1 is the same as m in the general formula (1).

Examples of the organic group as R _{2 to} R _{3 in the} general formula (2) include an aliphatic group and an aromatic group, and examples of the aliphatic include a chain aliphatic group and a cyclic aliphatic group. Specific examples of the chain aliphatic group include a methyl group, an ethyl group, a propyl group, a butyl group, and a hexyl group. Specific examples of the cyclic aliphatic group include a cyclohexyl group, a bicyclo [2 , 2, 1] heptyl group and adamantyl group. Examples of the aromatic group include a phenyl group, a naphthyl group, an anthracenyl group, a phenanthrenyl group, a polycyclic aromatic group having 4 or more aromatic rings, a fluorenyl group, a diphenylfluorenyl group, and a biphenyl group. However, it is not limited to these. Among these, when the chain aliphatic group is, for example, a methyl group or an ethyl group, solubility in an organic solvent and heat resistance can be improved. The hydrogen atom in the organic group may be substituted with a fluorine atom, a methyl group, a methoxy group, a trifluoromethyl group, or the like. R _{2 to} R ₃ may be a group containing the polymerizable unsaturated bond.

Specific examples of the adamantane skeleton having a plurality of adamantane structures as the cage structure compound represented by the general formula (2) include a 1,1′-biadamantyl skeleton, a 2,2′-biadamantyl skeleton, and 1 , 2′-biadamantyl skeleton such as 1,1 ′: 3 ′, 1 ″ -triadamantyl skeleton, 1,2 ′: 5 ′, 1 ″ -triadamantyl skeleton, 1,2 ′: Tridamantyl skeletons such as 4 ′, 1 ″ -triadamantyl skeleton and 2,2 ′: 4 ′, 2 ″ -triadamantyl skeleton, 1,1 ′: 3 ′, 1 ″: 3 ″, 1 ′ '' -Tetraadamantyl skeleton, 1,2 ′: 5 ′, 1 ″: 3 ″, 1 ′ ″-tetraadamantyl skeleton, 1,2 ′: 4 ′, 1 ″: 3 ″, 1 ′ '' -Tetraadamantyl skeleton, 1,1 ′: 4 ′, 1 ″: 4 ″, 1 ′ ″-tetraadamantyl skeleton and 1,1 ′: 3 ′, 1 ″: 3 ″, 2 Tetraadamantyl skeletons such as''' -tetraadamantyl skeleton and 1,1 ': 3', 1 '': 3 '', 1 ''':3''', 1 ''''-pentaadamantyl skeleton, 1 , 1 ': 4', 1 ": 3", 1 '": 3'", 1 ""-pentaadamantyl skeleton, 1, 1 ': 4', 1 ": 4" , 1 ′ ″: 3 ′ ″, 1 ″ ″-pentaadamantyl skeleton and 1,1 ′: 3 ′, 1 ″: 4 ″, 2 ′ ″: 5 ′ ″, 1 ″ And pentaadamantyl skeleton such as '' -pentaadamantyl skeleton.
Among them, a biadamantane compound having a biadamantyl skeleton is preferable from the viewpoint of solubility in a solvent. Further, examples of the biadamantyl skeleton include those having a 1,1′-biadamantyl skeleton, a 2,2′-biadamantyl skeleton, and a 1,2′-biadamantyl skeleton, and an organic insulation having more heat resistance stability. In obtaining a film, a 1,1′-biadamantyl skeleton is preferable.

  The polymerization reaction of the group containing a polymerizable unsaturated bond and the cage structure compound having a cage structure having an adamantane structure as a minimum unit is not particularly limited, and a known polymerization method can be applied. Is possible.

  Examples of the polymerization method include a method by radical polymerization using radical initiators such as benzoyl peroxide, t-butyl peroxide and azobisisobutyronitrile, a method by photo radical polymerization using light irradiation, and the like, dichlorobis (Triphenylphosphine) palladium (II), bis (benzonitrile) palladium (II) dichloride, tetrakis (triphenylphosphine) palladium (0) and other polymerization methods using a palladium catalyst, heating without using a catalyst A method using thermal polymerization for reaction, a method using polymerization using a transition catalyst such as copper (II) acetate, and transition metal chlorides such as molybdenum chloride (V), tungsten chloride (VI) and tantalum chloride (V). Examples thereof include a polymerization method. Among these, the method by thermal polymerization is desirable because the desired polymer can be easily controlled and the removal of impurities due to the remaining catalyst and the like is unnecessary.

  The reaction conditions may be appropriately changed depending on the structure of the cage structure compound having a group containing a polymerizable unsaturated bond and a cage structure having an adamantane structure as a minimum unit. In particular, when the reactive group is a carbon-carbon unsaturated bond, the reaction temperature is usually about 50 ° C to 500 ° C. When thermal polymerization is performed, it is desirable that the group containing a polymerizable unsaturated bond and the cage structure compound having a cage structure having an adamantane structure as a minimum unit are dissolved in an organic solvent. The concentration of the group having a polymerizable unsaturated bond in the organic solvent and the cage structure compound having a cage structure having an adamantane structure as a minimum unit is usually about 1% by mass to 50% by mass. The reaction temperature and the group containing a polymerizable unsaturated bond at the time of the reaction and the concentration of the cage structure compound having a cage structure having the adamantane structure as a minimum unit can be used even outside the above range. It may become large and cause insolubilization in organic solvents.

  The organic solvent in the polymerization reaction is not particularly limited. For example, alcohol solvents such as methanol, ethanol, isopropanol, 1-butanol and 2-butanol, acetylacetone, methylethylketone, methylisobutylketone, cyclopentanone, cyclohexanone, cyclohexane Ketone solvents such as heptanone, 2-pentanone and 2-heptanone, ester solvents such as ethyl acetate, propyl acetate, butyl acetate, pentyl acetate, isoamyl acetate, γ-butyrolactone and propylene glycol monomethyl ether acetate, diisopropyl ether, di Butyl ether, tetrahydrofuran, anisole, ethoxybenzene, 1,2-dimethoxybenzene, 1,3-dimethoxybenzene, 1,4-dimethoxybenzene and di Ether solvents such as phenyl ether, aromatic hydrocarbon solvents such as benzene, toluene, xylene, mesitylene, ethylbenzene, diethylbenzene and propylbenzene, N-methylpyrrolidone, N, N-dimethylacetamide and N, N-dimethylformamide In addition, amide sulfoxide, dimethyl sulfoxide, propylene carbonate, diethyl carbonate and the like are suitable as the solvent, and these may be used alone or in admixture of two or more.

These polymerization reactions generally proceed when a group containing a polymerizable unsaturated bond and a part or all of a cage structure compound having a cage structure having an adamantane structure as a minimum unit react.
The polymer thus obtained is produced by reacting a polymerizable unsaturated bond with each other in a cage structure compound having a cage structure having a group containing the polymerizable unsaturated bond and an adamantane structure as a minimum unit. It is preferable that the polymer is a prepolymer having an unsaturated bond formed by reacting, or an unsaturated bond formed by a reaction between the polymerizable unsaturated bonds and an unreacted unsaturated bond.

  In the present invention, by using a prepolymer of a cage structure compound, a branched crosslinked structure is formed around the cage structure, and aggregation of molecular chains can be prevented. As a result, when the molecular density is sparse, a nano-vacancy structure is formed inside, and a low molecular component that fills the nano-vacancy structure is included at 5% or less, a film with the nano-vacancy structure retained can be obtained. It is assumed that it is possible. This is also suggested from a decrease in density. By reducing the number of low molecular components that fill the nanopore structure, the density can be further reduced, and the lower dielectric constant can be achieved by reducing the density.

  As a specific example of such a polymer, when the group containing a polymerizable unsaturated bond group is an ethynyl group, in the general formula (1), a group containing a terminal polymerizable unsaturated bond group is not an ethynyl group. When the polymer is described by a simplified chemical formula with the site being Z, a structure having a cage structure having a cage structure having a group containing a polymerizable unsaturated bond and an adamantane structure as a minimum unit by a polymerization reaction. Examples thereof include, but are not limited to, those having a repeating unit having a structure represented by the following formula (Formula 9).

The example shown by the above formula (Chemical formula 9) shows an example in which the carbon-carbon triple bond of the group containing one or two carbon-carbon triple bonds in the compound represented by the general formula (1) is reacted. However, a carbon-carbon triple bond of a group containing a plurality of carbon-carbon triple bonds may further react.
In addition, the prepolymer obtained by the polymerization reaction is shown in (Chemical Formula 9) for improving heat resistance and elastic modulus by a cross-linking reaction during resin film production and for improving solubility in an organic solvent. Thus, it is more desirable to leave unreacted carbon-carbon triple bonds so that they partially remain. The residual ratio of unreacted unsaturated bonds in the prepolymer is more preferably 20% or more and 80% or less.

The polymer thus obtained may be an oligomer or a polymer, but the peak area Ap of the peak P for detecting the polymer and the residual monomer at the molecular weight peak measured by gel permeation chromatography. For the total peak area (Ap + Am), which is the sum of the peak areas Am of the peaks M to detect the peaks, the molecular weight peaks are detected at an elution time later than the elution time corresponding to a polystyrene equivalent weight average molecular weight of 9000. The ratio of the peak area Al of the peak L in the region is 0 to 5% or less, preferably 3% or less, more preferably 1% or less. It is speculated that a film having more nanopore structures can be formed by reducing the number of low-molecular components that fill the nanopore structure. As a result, the density of the film is lowered and a low dielectric constant is expected.
Here, the definition of the molecular weight peak in terms of polystyrene measured by gel permeation chromatography is shown in FIG.

  The peak P has a polystyrene-equivalent number average molecular weight of 9,000 to 500,000, a preferred lower limit is 10,000, and a preferred upper limit is 400,000. A more preferred lower limit is 15,000, and a more preferred upper limit is 200,000. When the upper limit of the number average molecular weight is exceeded, insolubilization in an organic solvent may be caused. When the value falls below the lower limit of the number average molecular weight, there is a possibility that an increase in dielectric constant presumed to be caused by an increase in low molecular weight components and an appearance defect during coating film preparation.

  The peak P preferably has a polystyrene-equivalent weight average molecular weight to number average molecular weight ratio (Mw / Mn) of 20 or less, more preferably 15 or less, and even more preferably 10 or less. The smaller the Mw / Mn, the narrower the molecular weight distribution and the better the filterability.

  In the present invention, the peak top of the peak M for detecting the residual monomer is preferably detected at an elution time slower than an elution time corresponding to a polystyrene-equivalent weight average molecular weight of 1500. Thereby, it becomes easy to control the conversion molecular weight of the polymer at the time of polymerization.

  In order to do this, the polymer may be polymerized such that the area of the peak area Al is 0 to 5% or less, but the area of the peak area Al exceeds 5% at the end of the polymerization. In this case, the area ratio can be adjusted by removing the component having a weight average molecular weight of less than 9000.

As this removal method, a known method can be adopted. For example, when the volatility of the component having a weight average molecular weight of less than 9000 is high, it can be removed by distillation.
Further, when there is a difference between the obtained polymer and the solubility of the component having a weight average molecular weight of less than 9000, the solubility difference can be used to remove it by a treatment such as precipitation fractionation represented by reprecipitation purification. it can.
In addition, removal by a centrifugal separation method using a molecular weight difference, a molecular sieve, or a membrane separation method represented by ultrafiltration is also possible.
Among these, the method using the difference in solubility is simple, and the precipitation fractionation method is particularly preferable.
The combination of the good solvent and the poor solvent used in the precipitation fractionation method can be determined by conducting a preliminary experiment or the like as appropriate before the polymerization depending on the compound used for the polymerization and the polymer thereof.

  Examples of the good solvent include aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as dichloromethane, chloroform and carbon tetrachloride; ethers such as diethyl ether, tetrahydrofuran and dioxane; Among these, aromatic hydrocarbons and ethers are preferable in that they do not contain halogen, and ethers are more preferable.

  Examples of the poor solvent include alcohols such as methanol, ethanol, isopropanol, 1-butanol, 2-ethoxyethanol and 3-methoxypropanol; acetylacetone, methylethylketone, methylisobutylketone, 2-pentanone, 3-pentanone, 2-heptanone and 3 -Ketones such as heptanone; Hydrocarbons such as n-hexane, cyclohexane and n-heptane; Among these, alcohols and ketones having low volatility are preferable, and alcohols having low solubility are preferable, but it is desirable to select a good solvent and a poor solvent depending on the polymer and the compound to be separated.

  Further, in the process of this separation operation, atmospheric oxygen or the like is mixed in the system, and the polymer further reacts to increase the molecular weight. However, the peak area Al of the polymer after the separation operation is increased. The area may be 0 to 5% or less.

The resin composition used in the present invention contains the polymer obtained above.
The resin composition of the present invention contains the polymer obtained above, and generally forms a resin film by coating on a support as a varnish for a resin film, as will be described later. Therefore, a solvent for dissolving or dispersing the polymer can be included. In making the resin film varnish, the polymer obtained above may be dissolved in an organic solvent to form a resin film varnish, or the reaction solution obtained when producing the polymer may be directly used as a resin film. It may be used as a varnish for use, and another organic solvent may be mixed in the reaction solution.

The organic solvent used for the resin film varnish is not particularly limited as long as it can dissolve or disperse the polymer.
Examples of the organic solvent include alcohol solvents such as methanol, ethanol, isopropanol, 1-butanol and 2-butanol; acetylacetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, 2-pentanone and 2-heptanone. Ketone solvents; ester solvents such as ethyl acetate, propyl acetate, butyl acetate, pentyl acetate and propylene glycol monomethyl ether acetate; ether solvents such as diisopropyl ether, dibutyl ether, tetrahydrofuran, anisole and 1,3-dimethoxybenzene; benzene , Toluene, mesitylene, ethylbenzene, diethylbenzene, propylbenzene and other aromatic hydrocarbon solvents; N-methylpyrrolidone and other amide solvents ; Etc., it is suitable as industrially solvent because it is available, without limitation. These may be used alone or in admixture of two or more.

  The concentration of the polymer in the resin film varnish may be appropriately determined depending on the structure and molecular weight of the polymer, but the polymer is preferably 0.1% by mass to 50% by mass in the resin film varnish. Furthermore, 0.5 to 15% by mass is more preferable.

  The resin composition of the present invention includes a surfactant, an adhesion promoter such as a coupling agent typified by a silane coupling agent, a radical initiator that generates oxygen radicals or sulfur radicals upon heating, disulfide, if necessary. It may contain additives such as catalysts.

The resin composition of the present invention can reduce the dielectric constant of the resin film even if it does not substantially contain the pore-forming agent, but the pore-forming agent can be used as long as the effect of the present invention is not affected.
Examples of the pore-forming agent include carbon nanotubes and fullerenes having a hollow structure, cage silsesquioxane, cyclodextrin, organic compounds having a high melting point, surfactants, azobis compounds, organic peroxides, and polyamidoamine structures. And the like, and polymethacrylic acid hyperbranched polymers. Among these, surfactants or hyperbranched polymers are preferable. Thereby, it becomes possible to disperse | distribute a void | hole formation agent uniformly in a resin composition. If the pore-forming agent can be uniformly dispersed, a resin film having uniform fine pores can be obtained by further heating and extraction treatment.

  When a resin film is obtained by forming a nanofoam using such a resin composition, if the crosslink density of the resin film can be increased, the nanofoam can be retained without agglomeration. The dielectric constant of the resin film can be further reduced.

Next, the resin film will be described.
The resin film of the present invention can be obtained using the resin composition. For example, as described above, the resin composition is applied to a support such as a substrate as a varnish for a resin film, and this is heated or activated. It can be manufactured by processing such as energy beam irradiation. Alternatively, the resin composition may be heated and dissolved, and applied to a support.

  Regarding the method for producing a resin film of the present invention, a specific example in the case of using the resin film varnish will be described. First, the resin film varnish is made into an appropriate support, for example, an organic substrate such as a polyester film, copper, and the like. A coating film is formed by coating on a base material such as a metal plate such as a foil or a semiconductor substrate such as a silicon wafer or a ceramic substrate. Examples of the coating method include spin coating using a spinner, spray coating using a spray coater, dipping, printing, roll coating, and the like. Then, the coating film is dried, subjected to a treatment such as heating, followed by solvent removal, followed by a crosslinking reaction by a method using heating, a method of irradiating active energy rays, a method using both of these methods, and the like. A resin film having excellent characteristics can be obtained.

In the heating method, for example, the heating can be performed at 150 to 425 ° C. for 5 minutes to 24 hours using a hot plate such as a hot plate, a furnace, an oven, a vacuum oven, or the like. Examples of the active energy rays include active energy rays such as visible light, ultraviolet light, infrared light, and laser light, X-rays, electron beams, and microwaves.
When irradiating these active energy rays, they may be heated simultaneously or separately from the heating. Although there is no particular limitation on heating and irradiation with active energy rays, the concentration of an oxidizing gas such as oxygen in the atmosphere should be 1% or less, preferably 100 ppm or less, in order to suppress oxidation of the insulating film. Is preferred.

The resin film of the present invention may be formed by directly applying to a substrate such as a semiconductor substrate by the above method, or by peeling the resin film formed on a support such as an organic base material from the support. It can also be used as a dry film.
Moreover, in order to improve the adhesiveness between a support such as a substrate and a resin film, a resin film may be formed thereon after forming an adhesion promoter layer on the substrate with an adhesion promoter.

  The resin film is used as, for example, a semiconductor interlayer insulating film or surface protective film, a multilayer circuit interlayer insulating film, a flexible copper-clad cover coat, a solder resist film, a liquid crystal alignment film, an etching protective film, an adhesive, or the like. be able to. Among these, it is suitably used as an interlayer insulating film for semiconductors, a surface protective film, and an etching protective film.

The thickness of the resin film is not particularly limited, but is preferably 0.01 to 20 μm, particularly preferably 0.02 to 10 μm, and most preferably 0.05 to 0.7 μm in a semiconductor interlayer insulating film or the like. When the thickness is within the above range, the semiconductor manufacturing process compatibility is excellent.
The thickness of the protective film is not particularly limited, but is preferably 0.01 to 70 μm, and particularly preferably 0.2 to 50 μm. When the thickness is within the above range, both the protective properties and workability of the semiconductor element are particularly excellent.

  When the resin film is used as an interlayer insulating film for a semiconductor, for example, the varnish for resin film is directly applied to a predetermined position such as a silicon wafer or a ceramic substrate to form a coating film. Examples of the coating method include spin coating using a spinner, spray coating using a spray coater, dipping, printing, roll coating, and the like. Thereafter, the coating film is dried, the solvent is removed, and an interlayer insulating film can be formed by a crosslinking reaction by a method using heating, a method of irradiating active energy rays, a method using both of these methods, and the like. . Alternatively, the resin film varnish may be used in advance to form a dry film, which may be laminated at a predetermined position.

  Also, when the resin film is used as the semiconductor protective film, the resin film varnish is directly applied to a predetermined position such as a silicon wafer or a ceramic substrate in the same manner as the semiconductor interlayer insulating film. Examples of the coating method include spin coating using a spinner, spray coating using a spray coater, dipping, printing, roll coating, and the like. Thereafter, the coating film is dried, the solvent is removed, and a protective film composed of the resin film is crosslinked by a heating method, a method of irradiating active energy rays, a method using both of these methods, and the like. It can be.

As shown in FIG. 2, the resin film obtained in the present invention has a positron annihilation lifetime first peak top (A) corresponding to the pore size obtained by the positron annihilation lifetime measurement method of 1 nm or more. It is in the area of
Here, the first peak top is for clearly distinguishing from other peak tops described later, and has a different meaning from the first peak and the like. As a result, a large number of nano-level pores can be formed inside the resin structure constituting the resin film, thereby reducing the dielectric constant of the resin film.

  Further, the second peak top (B) having a pore size is present in a region of less than 1 nm. A pore size of less than 1 nm is a skeleton-derived peak and is a peak that always appears.

  Moreover, although the intensity | strength of the said 1st peak top (A) is not specifically limited, It is preferable that it is stronger than the intensity | strength of the said 2nd peak top (B). Thereby, it can have many nano level void | holes, and the reduction | decrease of a dielectric constant is realizable.

  The pore size in the first peak top (A) is preferably 1 nm or more and 3 nm or less, preferably 1.1 nm or more and 2.7 nm or less, and 1.2 nm or more and 2.4 nm or less. It is more preferable. When the positron annihilation lifetime at the first peak top (A) is within the above range, the balance between reduction of dielectric constant and retention of mechanical strength is excellent.

  Further, with respect to the resin film, a spectrum obtained by measuring with a positron annihilation lifetime measurement method is analyzed by a positron annihilation lifetime analysis program, and the I4 corresponding to the ratio of the nano-level vacancy component to the total vacancies obtained. The (%) term is not particularly limited, but is preferably 5 to 40%, particularly preferably 10 to 30%. When the I4 (%) term is within the above range, the balance between reduction of dielectric constant and mechanical strength retention is particularly excellent.

Here, the positron annihilation lifetime is measured by, for example, an electromagnetic wave (annihilation γ-ray) generated when the positron annihilates by using a positron / positronium lifetime measurement / nanopore measuring device (manufactured by Fuji Imback Co., Ltd.). The pore size distribution can be obtained by subjecting the obtained positron annihilation lifetime spectrum to inverse Laplace transform processing using an analysis program.
In the measurement, a film having a thickness of 300 nm prepared by applying the above-described varnish for resin film on a silicon wafer by spin coating and further performing a curing treatment was used.

  The density of the resin film obtained in the present invention is preferably 0.7 or more and 1.0 or less, more preferably 0.75 or more and 0.95 or less, further preferably 0.8 or more, 0.9 or less. Although it can be used outside the density range, if the upper limit of the density is exceeded, the amount of pores contained in the resin film decreases and the dielectric constant may not be reduced. Below the lower limit of the density, the mechanical strength becomes weak, and there is a possibility that the resin film will crack in the process of manufacturing the semiconductor device having the resin film.

  The density of the resin film can be determined by an X-ray reflectance measurement method. A film obtained by subjecting a resin film to X-ray irradiation at an extremely low angle, for example, in the range of 0.2 degrees to 2 degrees, measuring the reflectance, and obtaining the obtained reflectance curve from the Fresnel equation. The density of the resin film can be obtained by fitting to the equation of the reflectance of the sample.

  Next, the present invention is a semiconductor device including the resin film obtained above, and a preferred embodiment of the semiconductor device will be described with reference to FIG. However, the present invention is not limited to this form.

FIG. 3 is a cross-sectional view schematically showing an example of the semiconductor device of the present invention.
The semiconductor device 100 includes a semiconductor substrate 1 on which elements are formed, and a wiring structure provided on the upper side (upper side in FIG. 3) of the semiconductor substrate 1. First, a first interlayer insulating film 2 is formed on a semiconductor substrate 1 in which an element such as a transistor is formed. As the interlayer insulating film 2, a resin film (organic insulating film) formed from the above resin composition, an inorganic insulating film formed by a chemical vapor deposition (CVD) method, or the like is used.
A recess corresponding to the pattern to be wired is formed in the interlayer insulating film 2, and a copper wiring layer 3 is provided inside the recess.
Further, a barrier metal layer 4 may be provided between the interlayer insulating film 2 and the copper wiring layer 3. In order to improve the adhesion between the interlayer insulating film 2 and the barrier metal layer 4 or between the interlayer insulating film 2 and the copper wiring layer 3, for example, a modified layer may be provided on the inner surface of the wiring groove by plasma processing or the like.
A hard mask layer 5 is formed on the upper side of the interlayer insulating film 2 (on the side surface opposite to the semiconductor substrate 1). A wiring layer is further formed above the first layer wiring, and an interlayer insulating film or the like is formed in the same manner as described above, so that a multilayer wiring structure can be obtained.

As an example of a manufacturing method of the semiconductor device 100, first, a semiconductor substrate 1 on which a device such as a transistor is manufactured is prepared on a silicon wafer, and an interlayer insulating film 2 and a hard mask layer 5 are formed thereon. Further, a photoresist layer is formed thereon, and a wiring groove (concave portion) penetrating into a predetermined position of the insulating layer composed of the interlayer insulating film 2 and the hard mask layer 5 is processed by dry etching. Next, a barrier metal layer 4 made of Ta, Ti, TaN, TiN, WN or the like is formed on the inner surface of the wiring groove by a method such as PVD or CVD. Further, a copper wiring layer 3 to be a wiring layer is formed by an electroplating method or the like, and then the copper layer and the barrier metal layer other than the wiring portion are polished and removed and planarized by a CMP method, thereby manufacturing the semiconductor device 100. be able to.
Further, when the wiring layers are stacked, the wiring layers can be basically formed by the same method as the first wiring formation.

  As a method for forming the interlayer insulating film 2, a resin film varnish for forming the interlayer insulating film 2 can be directly applied on the semiconductor substrate 1. And the interlayer insulating film 2 can be formed by laminating it on the semiconductor substrate 1. More specifically, the resin film varnish obtained above may be directly applied onto the semiconductor substrate 1 to form a coating film, and then heated and / or irradiated with active energy rays to be cured. it can. When using a dry film, using the above-described resin film varnish, a resin layer is formed on a base material and dried to form a dry film, which is formed on the semiconductor substrate 1. It can be formed by laminating and curing by irradiation with heat and / or active energy rays. Note that the position where the interlayer insulating film is formed is not limited thereto.

In the present embodiment, the semiconductor device 100 using the interlayer insulating film 2 has been described. However, the present invention is not limited to this. The semiconductor device of the present invention uses the interlayer insulating film 2 as described above. Excellent dimensional accuracy and sufficient insulation can be achieved, thereby improving connection reliability.
Further, since the interlayer insulating film 2 as described above is excellent in dielectric characteristics, wiring delay can be reduced.

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

[Polymer synthesis example]
(Synthesis Example 1)
[Synthesis of 1,7-bis (3,5-diethynylphenyl) -3,5-dimethyladamantane]
A 200 ml flask was charged with 5.5 g (17 mmol) of 1,7-dibromo-3,5-dimethyladamantane, 2.3 g (9 mol) of aluminum bromide and 100 ml of m-dibromobenzene, and stirred at 60 ° C. for 10 hours. After cooling, the reaction solution was added to 150 g of ice water in which 10 g of concentrated hydrochloric acid was dissolved, and the aqueous layer was removed after stirring. After excess dibromobenzene was removed by distillation under reduced pressure, 100 ml of methylene chloride was added to the residue and dissolved, washed with water and brine, and dried over magnesium sulfate. After magnesium sulfate was filtered off, methylene chloride was concentrated with an evaporator, and 100 ml of methanol was added and stirred. The precipitated crystals were separated by filtration and dried under reduced pressure. 6.0 g of this crystal was charged into a 200 ml flask, 200 mg of dichlorobis (triphenylphosphine) palladium, 400 mg of triphenylphosphine, 180 mg of copper (I) iodide and 100 ml of triethylamine were added, and the temperature was raised to 80 ° C. Trimethylsilylacetylene 6.7g was dripped over 1 hour, and it was made to react at 80 degreeC for 4 hours. After cooling, the solvent was distilled off, 200 ml of diethyl ether was added to the residue, and the insoluble salt was filtered off. The filtrate was washed with 1 mol / L hydrochloric acid, saturated brine and water, and the ether layer was dried over magnesium sulfate. The desiccant was filtered off, the ether was distilled off and the residue was purified on a column. 5.8 g of the product was dissolved in 150 ml of methanol and 100 ml of tetrahydrofuran, 0.5 g of potassium carbonate was added, and the mixture was stirred at room temperature for 4 hours. The solvent was distilled off under reduced pressure, and 200 ml of methylene chloride and 100 ml of 1 mol / L hydrochloric acid were added to the residue. After stirring, the hydrochloric acid phase was removed. The methylene chloride layer was washed three times with 100 ml of pure water, the solvent was distilled off from the methylene chloride phase, and the residue was dried under reduced pressure, whereby 1,7-bis (3,5-diethynylphenyl) -3,5- 3.0 g (7.3 mmol: 43% yield) of dimethyladamantane was obtained.

[Polymerization of 1,7-bis (3,5-diethynylphenyl) -3,5-dimethyladamantane]
5.0 g of 1,7-bis (3,5-diethynylphenyl) -3,5-dimethyladamantane obtained by repeating the above operation was dissolved in 45 g of anisole, and the resultant was dried at 155 ° C. for 18 hours under a dry nitrogen atmosphere. The reaction solution was dropped into 10 times volume of methanol and precipitated. The precipitate was collected and dried to obtain 4.4 g of the polymer (A).

(Synthesis Example 2)
From the precipitate obtained by the same operation as in Synthesis Example 1, the monomer was further removed using preparative high performance liquid chromatography (HPLC) to obtain 1.0 g of the polymer (B).

(Synthesis Example 3)
In the polymerization of Synthesis Example 1, 4.2 g of the polymer (C) was obtained by the same operation as the polymerization of Synthesis Example 1 except that methanol was changed to a methanol / tetrahydrofuran = 2/1 mixed solvent.

(Synthesis Example 4)
In the polymerization of Synthesis Example 1, 3.8 g of the polymer (D) was obtained by the same operation as the polymerization of Synthesis Example 1 except that methanol was changed to a methanol / dioxane = 4/3 mixed solvent.

(Synthesis Example 5)
[Synthesis of 7,7′-bis (3,5-bis (phenylethynyl) phenyl) -3,3 ′, 5,5′-tetramethyl-1,1′-biadamantane]
1) Synthesis of 3,3 ′, 5,5′-tetramethyl-1,1′-biadamantane Into a 4-neck 1000 mL flask equipped with a thermometer, a stirrer and a reflux tube, 14 g (0.6 mol) of sodium metal ) And 600 ml of n-octane were added, and the internal temperature was cooled to 0 ° C. With vigorous stirring, 73.0 g (0.3 mol) of 1-bromo-3,5-dimethyladamantane previously dissolved in 300 ml of n-octane was gradually added dropwise. During the dropping, the internal temperature was kept at 0 ° C to 5 ° C. When the temperature did not rise after completion of the dropwise addition, the reaction was continued for 1 hour. Then, it poured into about 1500 mL of cold water, the crude product was separated by filtration, washed with pure water, and dried. Further, the crude product was recrystallized with hot hexane. The obtained recrystallized product was dried under reduced pressure to obtain 78.0 g (0.24 mol: yield 80%) of the product.
From the result that the absorption of Br group (around 690-515 cm ⁻¹ ) disappeared by infrared spectroscopic analysis (IR) and the molecular weight by mass spectrometry was 326, the product was 3,3 ′, 5,5′-tetramethyl. It was shown to be −1,1′-biadamantane.

2) Synthesis of 7,7′-dibromo-3,3 ′, 5,5′-tetramethyl-1,1′-biadamantane In a 4-neck 2000 mL flask equipped with a thermometer, stirrer and reflux tube, 700 mL of carbon tetrachloride and 35 g (0.22 mol) of bromine were added, and while stirring, 65.3 g (0.2 mol) of 3,3 ′, 5,5′-tetramethyl-1,1′-biadamantane obtained above. ) Was added in small portions. During the addition, the internal temperature was kept at 20 ° C to 30 ° C. When the temperature did not rise after completion of the addition, the reaction was continued for 1 hour. Thereafter, it was poured into about 2000 mL of cold water, and the crude product was filtered off, 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 64.9 g (0.13 mol: yield 65%) of the product.
From the result that the absorption of bromo group is observed at 690 to 515 cm ⁻¹ by IR analysis and the molecular weight by mass spectrometry is 482, the product is 7,7′-dibromo-3,3 ′, 5,5′-tetra. It was shown to be methyl-1,1′-biadamantane.

3) Synthesis of 7,7′-bis (3,5-dibromophenyl) -3,3 ′, 5,5′-tetramethyl-1,1′-biadamantane 7,7-synthesized above in a 3 L eggplant flask 7′-Dibromo-3,3 ′, 5,5′-tetramethyl-1,1′-biadamantane 48.4 g (100 mmol), 1,3-dibromobenzene 1180 g (500 mmol) and a stir bar were added, and nitrogen was added. While stirring at room temperature under an air stream, 26.7 g (100 mmol) of aluminum (III) bromide was added little by little. After completion of the addition, the mixture was stirred at 50 ° C. for 7 hours. The reaction solution was added to 2 L of a 1 mol / L hydrochloric acid aqueous solution, and the aqueous layer was separated and removed. Then, 1 L of acetone was added and the extracted solid was collected by filtration and dried under reduced pressure to obtain 7,7′-bis (3 , 5-Dibromophenyl) -3,3 ′, 5,5′-tetramethyl-1,1′-biadamantane (71.4 g, 89.9 mmol; yield 90%) was obtained.

4) Synthesis of 7,7′-bis (3,5-bis (phenylethynyl) phenyl) -3,3 ′, 5,5′-tetramethyl-1,1′-biadamantane Next, in a 3 L eggplant flask 7,7′-bis (3,5-dibromophenyl) -3,3 ′, 5,5′-tetramethyl-1,1′-biadamantane obtained in the above, 39.7 g (50.0 mmol), ethynyl Benzene 40.9 g (400 mmol), dichlorobistriphenylphosphine palladium 3.5 g (5.0 mmol), copper (I) iodide 3.8 g (20.0 mmol), triphenylphosphine 5.2 g (20.0 mmol), triethylamine 1 L and a stirring bar were added, and the mixture was stirred at 95 ° C. for 6 hours under a nitrogen stream. The reaction solution was poured into 1 L of acetone, and the precipitated solid was washed with 1 L of 2 mol / L hydrochloric acid aqueous solution and 1 L of acetone and then dried under reduced pressure to obtain 26.3 g (29.9 mmol: yield 60%) of the product.

The appearance, mass spectrometry (MS) and elemental analysis results of the product obtained above are shown below. These data show that the obtained compound is 7,7′-bis (3,5-bis (phenylethynyl) phenyl) -3,3 ′, 5,5′-tetramethyl-1,1′-biadamantane. It shows that there is.
Appearance: White solid MS (FD) (m / z): 878 (M ⁺ )
Elemental analysis: Theoretical value (/%) C; 92.89, H; 7.11
Found (/%) C; 92.95, H; 7.05

[Polymerization of 7,7′-bis (3,5-bis (phenylethynyl) phenyl) -3,3 ′, 5,5′-tetramethyl-1,1′-biadamantane]
The 7,7'-bis (3,5-bis (phenylethynyl) phenyl) -3,3 ', 5,5'-tetramethyl-1,1'-biadamantane (5.0 g) obtained above was dissolved in toluene. Dissolved in 95 g, added 0.5 g of tantalum chloride (V), reacted at 30 ° C. for 24 hours under dry nitrogen, dropped the reaction solution into 10 times volume of methanol, collected the precipitate and dried, 4.4 g of polymer (E) was obtained.

(Synthesis Example 6)
5.0 g of 7,7′-bis (3,5-bis (phenylethynyl) phenyl) -3,3 ′, 5,5′-tetramethyl-1,1′-biadamantane obtained in Synthesis Example 5 was used. , Dissolved in 45 g of 1,3-dimethoxybenzene, 0.1 g of bis (benzonitryl) palladium (II) dichloride was added, and the mixture was reacted at 190 ° C. for 6 hours under dry nitrogen. The precipitate was collected by dropwise addition to methanol and dried to obtain 4.6 g of polymer (F).

(Synthesis Example 7)
In the polymerization of Synthesis Example 5, 3.8 g of the polymer (G) was obtained by the same operation as the polymerization of Synthesis Example 5 except that methanol was a mixed solvent of methanol / dioxane = 4/3.

(Synthesis Example 8)
In the polymerization of Synthesis Example 5, 2.9 g of the polymer (H) was obtained by the same operation as the polymerization of Synthesis Example 5 except that methanol was changed to a methanol / tetrahydrofuran = 1/1 mixed solvent.

(Synthesis Example 9)
[Synthesis of 7,7′-bis (3,5-diethynylphenyl) -3,3 ′, 5,5′-tetramethyl-1,1′-biadamantane]
1) According to the method described in Synthesis Example 5-3), 7,7′-bis (3,5-dibromophenyl) -3,3 ′, 5,5′-tetramethyl-1,1′-biadamantane was obtained. Synthesized.
Next, 7,7′-bis (3,5-dibromophenyl) -3,3 ′, 5,5′-tetramethyl-1,1′-biadamantane 50 g (63 mmol), dichlorobistriphenylphosphine palladium3. 53 g (5.0 mmol), 6.60 g (25.2 mmol) of triphenylphosphine, 4.79 g (25.2 mmol) of copper (II) iodide, and 750 ml of triethylamine were added to the flask and stirred. After the temperature was raised 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. After returning to room temperature, 1000 ml of dichloromethane was added to the reaction solution and stirred for 20 minutes. Precipitates in the reaction solution were removed by filtration, and 1000 ml of 5% hydrochloric acid aqueous solution was added to the filtrate for liquid separation. The organic layer obtained by liquid separation was washed with 1000 ml of water three times, and then the solvent of the organic layer was removed under reduced pressure to obtain a compound. The obtained compound was dissolved in 1500 ml of hexane, insoluble matters were removed by filtration, and hexane in the filtrate was removed under reduced pressure. To this, 1000 ml of acetone was added, and the precipitate was washed three times with acetone, whereby 7,7′-bis (3,5-ditrimethylsilylethynylphenyl) -3,3 ′, 5,5′-tetramethyl. 43 g (50 mmol: 79% yield) of -1,1′-biadamantane was obtained.
Furthermore, 47.5 g of 7,7′-bis (3,5-ditrimethylsilylethynylphenyl) -3,3 ′, 5,5′-tetramethyl-1,1′-biadamantane obtained by repeating the above operation. (55 mmol) and 1.46 g (10.6 mmol) of potassium carbonate were stirred in a mixed solvent of tetrahydrofuran (600 ml) and methanol (300 ml) at room temperature for 4 hours in a nitrogen atmosphere. This was poured into 1000 ml of a 10% aqueous hydrochloric acid solution, the precipitate was filtered, and the resulting precipitate was washed with 1000 ml of water, further washed with 1000 ml of acetone and then dried to obtain 21.2 g (36. 9 mmol: 67% yield).
Below, the external appearance of the product obtained above, the result of mass spectrometry and elemental analysis are shown. These data indicate that the resulting compound is 7,7′-bis (3,5-diethynylphenyl) -3,3 ′, 5,5′-tetramethyl-1,1′-biadamantane. Show.
Appearance: White solid MS (FD) (m / z): 574 (M ⁺ )
Elemental analysis: Theoretical value (/%): C, 91.93; H, 8.07
Found (/%): C, 91.89; H, 8.11

[Polymerization of 7,7′-bis (3,5-diethynylphenyl) -3,3 ′, 5,5′-tetramethyl-1,1′-biadamantane]
The 7,7′-bis (3,5-diethynylphenyl) -3,3 ′, 5,5′-tetramethyl-1,1′-biadamantane (5.0 g) obtained above was replaced with 1,3- Dissolve in 45 g of dimethoxybenzene, add 0.1 g of bis (benzonitryl) palladium (II) dichloride, react at 170 ° C. for 2 hours under dry nitrogen, and add 10 times the volume of methanol / tetrahydrofuran = 3 / 1 and the precipitate was collected and dried to obtain 3.9 g of the polymer (I).

(Synthesis Example 10)
5.0 g of 7,7′-bis (3,5-diethynylphenyl) -3,3 ′, 5,5′-tetramethyl-1,1′-biadamantane obtained in Synthesis Example 9 was added to 45 g of anisole. The reaction solution was reacted at 155 ° C. for 18 hours under dry nitrogen, and the reaction solution was added dropwise to a 10 times volume of a mixed solvent of methanol / dioxane = 3/2, and the precipitate was collected and dried. A polymer (J) was obtained.

(Synthesis Example 11)
[Synthesis of 9,9′-bis (3,5-diethynylphenyl) -4,4′-bidiamantane]
1) Synthesis of 4,4′-bi (diamantane) 14 g (0.6 mol) of metallic sodium and 600 ml of n-octane were placed in a four-necked 500 mL flask equipped with a thermometer, a stirrer and a reflux tube, and the internal temperature Was cooled to 0 ° C. With vigorous stirring, 80.2 g (0.3 mol) of 4-bromodiamantane previously dissolved in 300 ml of n-octane was gradually added dropwise. During the dropping, the internal temperature was kept at 0 ° C to 5 ° C. When the temperature did not rise after completion of the dropwise addition, the reaction was continued for 1 hour. Then, it poured into about 1500 mL of cold water, the crude product was separated by filtration, washed with pure water, and dried. The crude product was recrystallized from hot hexane. The obtained recrystallized product was dried under reduced pressure to obtain 78.6 g (0.21 mol: yield 70%) of the product.
Absorption of Br group (near 690-515 cm ⁻¹ ) disappeared by IR analysis, and the result of mass spectrometry having a molecular weight of 374 showed that the product was 4,4′-bi (diamantane).

2) Synthesis of 9,9′-dibromo-4,4′-bidiamantane 74.9 g (0.2 mmol) of 4,4′-bi (diamantane) obtained above was treated in the same manner as in Synthesis Example 5-2). To obtain 63.9 g (0.12 mol: yield 60%) of 9,9′-dibromo-4,4′-bidiamantane.
The IR analysis shows that the absorption of the bromo group is observed at 690 to 515 cm ^−1, and the molecular weight by mass analysis is 530, which indicates that the product is 9,9′-dibromo-4,4′-bidiamantane. It was done.

3) Synthesis of 9,9′-bis (3,5-diethynylphenyl) -4,4′-bidiamantane 40 g (75 mmol) of 9,9′-dibromo-4,4′-bidiamantane obtained above was synthesized. By reacting in the same manner as in Example 9-1), 21.8 g (35 mmol: yield 47%) of 9,9′-bis (3,5-diethynylphenyl) -4,4′-bidiamantane was synthesized. did.
The appearance of the product, the results of mass spectrometry and elemental analysis are shown below. These data indicate that the resulting compound is 9,9′-bis (3,5-diethynylphenyl) -4,4′-bidiamantane.
Appearance: White solid MS (FD) (m / z): 622 (M ⁺ )
Elemental analysis: Theoretical value (/%): C; 92.56, H; 7.44
Found (/%): C; 92.68, H; 7.32.

[Polymerization of 9,9′-bis (3,5-diethynylphenyl) -4,4′-bidiamantane]
In the polymerization of Synthesis Example 10, instead of 5.0 g of 7,7′-bis (3,5-diethynylphenyl) -3,3 ′, 5,5′-tetramethyl-1,1′-biadamantane, By reacting in the same manner as in the polymerization of Synthesis Example 10 except that 5.0 g of 9,9′-bis (3,5-diethynylphenyl) -4,4′-bidiamantane obtained above was used, 3 .8 g of polymer (K) was obtained.

(Synthesis Example 12)
[3,3 ′ ″-dimethylethynyl-5,7,5 ′, 7 ′, 5 ″, 7 ″, 5 ′ ″, 7 ′ ″-octamethyl-1,1 ′: 3 ′, 1 '': 3 '', 1 '''-Synthesis of Tetoaladamantane]
1) In a flask, 3,3 ′ ″-dibromo-5,7,5 ′, 7 ′, 5 ″, 7 ″, 5 ′ ″, 7 ′ ″-octamethyl-1,1 ′: 3 ′, 1 ″: 3 ″, 1 ′ ″-tetraadamantane 56.5 g (70 mmol) and bromoethene 18 ml (256 mmol) were dissolved in dichloromethane 240 ml, and the aluminum chloride (III ) 3.0 g (22 mmol) was added dropwise and stirred for 1 hour. Furthermore, at −15 ° C., 40 ml of water was added dropwise, and then returned to room temperature to obtain a reaction solution. The reaction solution was added to 400 ml of 10% aqueous hydrochloric acid, extracted with 80 ml of dichloromethane three times, washed with 80 ml of water, dried over magnesium sulfate, and the organic layer was concentrated to 3,3 ′ ″. -Bis (dibromoethyl) -5,7,5 ', 7', 5 '', 7 '', 5 ''',7'''-octamethyl-1,1':3', 1 '': 3 As a result, 49.8 g (49 mmol: yield 70%) of ”, 1 ′ ″-tetoaladamantane was obtained.
From the result that the absorption of bromo group is observed at 690 to 515 cm ⁻¹ by IR analysis and the molecular weight by mass spectrometry is 1018, the product is 3,3 ′ ″-bis (dibromoethyl) -5,7,5. ', 7', 5 '', 7 '', 5 ''',7'''-octamethyl-1,1':3', 1 '': 3 '', 1 '''-tetoaladamantan It was shown that there is.

2) Furthermore, 3,3 ′ ″-bis (dibromoethyl) -5,7,5 ′, 7 ′, 5 ″, 7 ″, 5 ′ ″, 7 ′ ″-octamethyl obtained above -1,1 ′: 3 ′, 1 ″: 3 ″, 1 ′ ″-Tetraadamantane 49.8 g (49 mmol) was dissolved in 400 ml of dimethyl sulfoxide, and potassium tert-butoxide 28 g (250 mmol) was dissolved at room temperature. This was added and stirred for 48 hours. Furthermore, the reaction solution was added to 800 ml of water, extracted with 400 ml of dichloromethane each time, extracted three times, washed with 400 ml of water, dried over magnesium sulfate, and the organic layer was concentrated to 3,3 ′ ″ − Diethynyl-5,7,5 ′, 7 ′, 5 ″, 7 ″, 5 ′ ″, 7 ′ ″-octamethyl-1,1 ′: 3 ′, 1 ″: 3 ″, 1 ′ 30.8 g (44 mmol: yield 90%) of ″ -tetoaradamantane was obtained.

3) 3,3 ′ ″-diethynyl-5,7,5 ′, 7 ′, 5 ″, 7 ″, 5 ′ ″, 7 ′ ″-octamethyl-1,1 ′ obtained above : 3 ′, 1 ″: 3 ″, 1 ′ ″-tetoaradamantane 30.8 g (44 mmol) and methyl iodide 22.7 g (160 mmol) were dissolved in triethylamine 80 ml and pyridine 40 ml, and copper iodide ( II) 0.124 g (0.66 mmol) and 0.48 g (1.82 mmol) of triphenylphosphine were added. Furthermore, 0.116 g (0.164 mmol) of dichlorobis (triphenylphosphine) palladium (II) was added and reacted at 110 ° C. for 5 hours in a dry nitrogen atmosphere. After the reaction, triethylamine and pyridine were distilled off, and 1000 ml of 2 mol / L hydrochloric acid aqueous solution was added to precipitate a precipitate. The precipitate was filtered, washed with 1000 ml of water and 1000 ml of methanol, and dried in an atmosphere at 60 ° C. for 24 hours using a vacuum dryer to obtain 3,3 ′ ″-dimethylethynyl-5,7,5 ′, 7 ′, 5 ″, 7 ″, 5 ′ ″, 7 ′ ″-octamethyl-1, 1 ′: 3 ′, 1 ″: 3 ″, 1 ′ ″-tetoaladamantan 27.1 g (38 mmol: 86% yield) was obtained.
The appearance of the product, the results of mass spectrometry and elemental analysis are shown below. These data indicate that the resulting compound is 3,3 ′ ″-dimethylethynyl-5,7,5 ′, 7 ′, 5 ″, 7 ″, 5 ′ ″, 7 ′ ″-octamethyl- 1, 1 ′: 3 ′, 1 ″: 3 ″, 1 ′ ″ — denotes Tetoaladamantane.
Appearance: White solid MS (FD) (m / z): 727 (M ⁺ )
Elemental analysis: Theoretical value (/%): C; 89.19, H; 10.81
Actual value (/%): C; 89.25, H; 10.75

[3,3 ′ ″-dimethylethynyl-5,7,5 ′, 7 ′, 5 ″, 7 ″, 5 ′ ″, 7 ′ ″-octamethyl-1,1 ′: 3 ′, 1 '': 3 '', 1 '''-polymerization of tetaradamantane]
In the polymerization of Synthesis Example 10, instead of 5.0 g of 7,7′-bis (3,5-diethynylphenyl) -3,3 ′, 5,5′-tetramethyl-1,1′-biadamantane, 3,3 ′ ″-dimethylethynyl-5,7,5 ′, 7 ′, 5 ″, 7 ″, 5 ′ ″, 7 ′ ″-octamethyl-1,1 ′: 3 obtained above ', 1 ″: 3 ″, 1 ′ ″-3.7 g of polymer (L) by reacting in the same manner as the polymerization of Synthesis Example 10 except that 5.0 g of tetaradamantane was used. Got.

  Table 1 shows the results obtained by evaluating the polymers obtained in the above synthesis examples by the following molecular weight distribution measurement method.

The molecular weight distribution was measured using a gel permeation chromatograph (GPC) device (HLC-8220GPC, manufactured by Tosoh Corporation), and as a column, TSKgel GMH _XL (polystyrene conversion exclusion limit 4 × 10 ² (estimated)) × 2 And TSKgel G2000H _XL (polystyrene conversion exclusion limit 1 × 10 ⁴ ) × 2 in series, and using a refractometer (RI) or an ultraviolet / visible detector (UV (254 nm)) as a detector, under the following conditions: The results obtained by RI or UV were analyzed for the molecular weight of the polymer.
The measurement conditions were mobile phase: tetrahydrofuran, temperature: 40 ° C., flow rate: 1.00 mL / min, sample concentration: 0.1 wt% tetrahydrofuran solution.

[Manufacture of resin film]
(Example 1)
3 g of the polymer (C) obtained in Synthesis Example 3 described above was dissolved in 27 g of cyclopentanone and filtered through a filter having a pore size of 0.05 μm to obtain a resin film varnish. The resin film varnish was applied onto 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 resin film after the heat treatment was about 0.3 μm. After application, dry on a hot plate at 200 ° C for 1 minute. Thereafter, the resin film (cured film) of a curable resin was obtained by curing in an oven at 400 ° C. for 30 minutes in a nitrogen atmosphere.

(Examples 2 to 8)
About the polymers D and GL obtained by the synthesis examples 4 and 7-12, the resin film (cured film) of curable resin was obtained by performing operation similar to Example 1, respectively.

(Comparative Examples 1-3)
Resin films (cured films) of curable resins were obtained by performing the same operations as in Example 1 for the polymers A, B, and E obtained in Synthesis Examples 1, 2, and 5, respectively.

(Comparative Example 4)
The polymer F obtained in Synthesis Example 6 was subjected to the same operation as in Example 1. As a result, it was insoluble in cyclopentanone and thus could not be evaluated.

(Comparative Example 5)
Example 1 except that 1.5 g of the polymer (A) obtained in Synthesis Example 1 and 1.5 g of polystyrene (manufactured by Aldrich) having a weight average molecular weight of 4000 as a pore-forming agent were dissolved in 27 g of cyclopentanone. A resin film (cured film) of a curable resin was obtained by performing the same operation as.

  Evaluation of resin film

About the resin film obtained by each Example and the comparative example, each characteristic of a film thickness, a dielectric constant, a space | gap diameter, a density, a glass transition temperature, and an elasticity modulus was evaluated with the following evaluation method.
The obtained results are shown in Table 2.

1. Film thickness The film thickness was evaluated by irradiating light with a wavelength of 633 nm using an n & k analyzer 1500 manufactured by n & k Technology.

2. Dielectric constant The dielectric constant was evaluated using an automatic mercury probe CV measuring device SSM495 manufactured by Japan SMM Co., Ltd.

3. Void Diameter Void diameter was evaluated by a positron annihilation lifetime measurement method.
Here, the positron annihilation lifetime is measured by, for example, an electromagnetic wave (annihilation γ-ray) generated when the positron annihilates by using a positron / positronium lifetime measurement / nanopore measuring device (manufactured by Fuji Imback Co., Ltd.). The pore size distribution was obtained by analyzing the obtained spectrum by inverse Laplace transform analysis using a positron annihilation lifetime analysis program.

4). Density Density was evaluated by X-ray reflectometry.
X-ray reflectivity measurement pattern obtained in SAXS (small angle X-ray diffuse scattering measurement) mode (measurement wavelength 0.154 nm) is analyzed using an X-ray film thickness / structure evaluation apparatus (BedeMetrix ^™ -L manufactured by bede). Was determined by

5. Glass transition temperature (Tg)
Tg was evaluated by using a DSC-Q1000 apparatus manufactured by TA Instruments Co., Ltd. The measurement temperature range was 250 ° C. to 450 ° C., and the temperature increase rate was 2 ° C./min. The glass transition temperature was evaluated by analyzing whether there is an inflection point in the reverse heat flow in the temperature range of 250 ° C to 450 ° C.

6). Elastic Modulus The elastic modulus was evaluated in a region where a signal with an indentation depth of up to 1/10 of the film thickness was stable using a program for measuring a thin film with a nano indenter manufactured by MST.

  As is clear from Table 2, the resin films of Examples 1 to 8 had a low dielectric constant, a high glass transition temperature, excellent heat resistance, a high elastic modulus, and excellent mechanical strength.

[Manufacture of semiconductor devices]
Next, the signal delay of the semiconductor devices using the resin films obtained in Examples 3 and 6 and Comparative Example 5 was evaluated.
A silicon nitride layer is formed on a semiconductor substrate, and the resin film varnishes obtained in Examples 3 and 6 and Comparative Example 5 are applied to the silicon nitride layer, followed by heat treatment at 400 ° C. for 30 minutes. Then, an interlayer insulating film having a thickness of 0.1 μm was formed.
Next, metal wiring was formed on the interlayer insulating film so as to form a predetermined pattern, thereby obtaining a semiconductor device. When the resin film of Comparative Example 5 was used as an interlayer insulating film, a crack was generated in the process of manufacturing the semiconductor device, and it was not possible to proceed to evaluation of signal delay.
Further, the degree of wiring delay was compared with a semiconductor device having a SiO ₂ insulating film with the same configuration as this semiconductor device. As the evaluation standard, the signal delay time obtained by conversion from the transmission frequency of the ring oscillator was adopted. As a result of comparing the two, it was confirmed that the semiconductor device obtained by the present invention has less wiring delay than the semiconductor device having the SiO ₂ insulating film, and an average speed improvement of about 25%.
The semiconductor device using the insulating film obtained in Examples 3 and 6 as an interlayer insulating film was excellent in the effect of reducing the signal delay because the dielectric constant of the interlayer insulating film was low.

DESCRIPTION OF SYMBOLS 1 Semiconductor substrate 2 Interlayer insulating film 3 Copper wiring layer 4 Barrier metal layer 5 Hard mask layer 100 Semiconductor device

Claims (20)

A resin composition used for forming a resin film, comprising a group containing a polymerizable unsaturated bond and a polymer of a cage structure compound having a cage structure having an adamantane structure as a minimum unit,
In the molecular weight peak measured by gel permeation chromatography, the polymer has a peak total area (Ap + Am) obtained by adding the peak area Ap of the peak P for detecting the polymer and the peak area Am of the peak M for detecting the residual monomer. On the other hand, the ratio of the peak area Al of the peak L in the region detected in the elution time slower than the elution time corresponding to the weight average molecular weight in terms of polystyrene of 9000 among the molecular weight peaks is 0 to 5% or less. A resin composition characterized by the above.   The resin composition according to claim 1, wherein the ratio of the peak area Al of the peak L is 0 to 3% or less.   The resin composition according to claim 1, wherein the polymer is a prepolymer of the cage structure compound. The group containing a polymerizable unsaturated bond and the cage structure compound having a cage structure having an adamantane structure as a minimum unit are compounds represented by the following formula (1). 2. The resin composition according to item 1.

(In Formula (1), X ₁ and Y ₁ each represent one or two or more groups containing the same or different polymerizable unsaturated bond. R ₁ represents a group having an adamantane structure or a polyamantane structure. When m is 2 or more, they may be the same or different, and m is 1 or an integer of 2 or more.) The group containing the polymerizable unsaturated bond and the cage structure compound having a cage structure having an adamantane structure as a minimum unit is a compound represented by the following formula (2). 2. The resin composition according to item 1.

(In formula (2), X ₂ and Y ₂ each represent one or more groups containing the same or different polymerizable unsaturated bonds. R ₂ and R ₃ each represent hydrogen or an organic group. However, when n ¹ is 2 or more, it may be the same or different for each repeating unit. N ¹ is 1 or an integer of 2 or more.)   The resin composition according to any one of claims 1 to 5, wherein the cage structure having the adamantane structure as a minimum unit is an adamantane structure, a polyamantane structure, or a polyadamantane structure.   The resin composition according to any one of claims 1 to 6, wherein the group containing a polymerizable unsaturated bond is a group containing a carbon-carbon triple bond.   The resin according to any one of claims 1 to 7, wherein the peak P for detecting the polymer measured by gel permeation chromatography has a polystyrene-equivalent number average molecular weight of 9,000 or more and 500,000 or less. Composition.   The resin composition according to any one of claims 1 to 8, wherein the peak P for detecting the polymer measured by gel permeation chromatography has a polystyrene-equivalent number average molecular weight of 15,000 or more and 200,000 or less. object.   The peak P for detecting the polymer measured by gel permeation chromatography has a polydispersity (Mw / Mn) which is a ratio of the weight average molecular weight and number average molecular weight in terms of polystyrene of 20 or less. 10. The resin composition according to any one of 9 above.   The peak P for detecting the polymer measured by gel permeation chromatography has a polydispersity (Mw / Mn), which is a ratio of a weight average molecular weight in terms of polystyrene and a number average molecular weight, of 10 or less. 11. The resin composition according to any one of 10 above.   The peak top of the peak M for detecting the residual monomer measured by gel permeation chromatography is detected at an elution time slower than an elution time corresponding to a polystyrene-equivalent weight average molecular weight of 1500. 2. The resin composition according to item 1.   In the resin composition formed using the resin composition, a first peak top having a vacancy size corresponding to a positron annihilation lifetime obtained by measurement by a positron annihilation lifetime measurement method is in a region of 1 nm or more. It is a thing, The resin composition of any one of Claims 1-12.   The resin composition according to claim 13, wherein the resin film further has a pore size second peak top in a region of less than 1 nm.   The resin composition according to claim 14, wherein the intensity of the first peak top is stronger than the intensity of the second peak top.   The resin composition according to any one of claims 13 to 15, wherein a pore size in the first peak top is 1 nm or more and 3 nm or less.   The resin composition according to claim 1, wherein a density of the resin film is 0.7 or more and 1.0 or less.   The resin composition according to any one of claims 1 to 17, wherein the resin composition does not substantially contain a pore-forming agent.   A resin obtained by subjecting a coating film formed by applying the resin composition according to any one of claims 1 to 18 to a crosslinking reaction by heating, active energy rays, or heating and active energy ray irradiation. film.   A semiconductor device comprising the resin film according to claim 19.

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