JP2008001670A - Low dielectric material consisting of cyclic aromatic compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a low dielectric material excellent as an interlayer insulation membrane material without requiring the introduction of an empty hole to dissolve various problems caused by the increase of the introduction of empty holes into the interlayer insulation membrane. <P>SOLUTION: This low dielectric material comprises a cyclic aromatic compound expressed by formula (1) [wherein, Ar<SP>1</SP>is a 6-52C substituted or non-substituted divalent aromatic group; X is a substituent for bonding the aromatic groups expressed by the Ar<SP>1</SP>with each other, and two Ar<SP>1</SP>s may be bonded through 1 to 3 pieces of the X; (n) is 4 to 8 integer; and each of a multiple number of Ar<SP>1</SP>and X may be the same or different]. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a low dielectric material. More specifically, the present invention relates to a low dielectric material that is made of a cyclic aromatic compound having a specific structure and that is suitably used as a semiconductor interlayer insulating film material or the like in the electric / electronic field.

  Low dielectric materials are widely used as materials in electric and electronic parts in order to solve problems such as charging and resistance value increase. In particular, a low dielectric material is useful as a material for a semiconductor interlayer insulating film, and a material having a low dielectric constant has been actively developed.

  Currently, siloxane compounds are mainly used as semiconductor interlayer insulating film materials, which are the main applications of low dielectric materials. Siloxane compounds are mainly composed of silicon and oxygen. However, since the dielectric constant increases as the dipole moment of the molecule increases, a siloxane compound having many unshared electron pairs is disadvantageous. However, until now, the required value of the dielectric constant is good at k = 3 to 4, and the siloxane compound has been used from the viewpoint of the balance of adhesion to the silicon wafer.

In recent years, there has been a demand for finer semiconductor circuit widths due to the demand for higher performance of semiconductors, and it has become necessary to further lower the dielectric constant. On the other hand, from the viewpoint of lowering the dielectric constant, siloxane compounds have been introduced from the inorganic siloxane compounds to the organic siloxane compounds, and the introduction of controlled nanometer-level vacancies and techniques have progressed.
For example, Patent Document 1 proposes an organic / inorganic polymer such as a borazine-silicon polymer. However, although it has a low dielectric constant, there is no process for removing the platinum catalyst necessary for polymerization, so that problems remain in terms of dielectric breakdown caused by residual platinum atoms and low stability.

On the other hand, naphthylene polymers have been proposed as organic low dielectric materials (Patent Documents 2 and 3). Patent Document 2 discloses an interlayer insulating film having a low dielectric constant from which residual catalyst has been removed. However, there is a possibility that there is a portion having a dielectric constant distribution depending on a measurement portion of the insulating film and not a low dielectric constant. was there. In Patent Document 3, a low dielectric constant material is obtained, but there is room for improvement in terms of surface roughness. The occurrence of the dielectric constant distribution and the surface roughness are all attributable to the use of the polymer as the insulating film material.
JP 2002-359240 A International Publication WO2004 / 083278 Pamphlet International Publication WO2005 / 092946 Pamphlet

In order to lower the dielectric constant found in known interlayer insulating film materials, there is a technique for increasing the amount of introduction of holes at the nanometer level by introducing a pyrolyzable porogen (substance that is the source of holes). It is used. However, since an increase in the amount of introduced holes causes a decrease in the strength of the interlayer insulating film, there is a limit in reducing the dielectric constant without a decrease in the strength.
An object of the present invention is to provide a low dielectric material suitable as an interlayer insulating film material that does not require introduction of holes.

（式中、Ａｒ^１は、置換又は非置換の炭素数６〜５２の２価の芳香族基であり、Ｘは、Ａｒ^１で表される芳香族基同士を結合させる置換基であり、２つのＡｒ^１は１〜３個のＸを介して結合しても良く、ｎは、４〜８の整数を表し、複数のＡｒ^１、Ｘは同一でも異なってもよい。）
２．下記式（２）で表される構造を有する環状芳香族化合物からなる低誘電材料。

（式中、Ａｒ^２は、置換又は非置換の炭素数６〜５２の４価の芳香族基であり、Ａｒ^２’は、置換又は非置換の炭素数６〜５２の３価の芳香族基であり、Ｘは、Ａｒ^２で表される芳香族基を結合させる置換基であり、Ｙ^１は、単結合、二重結合、エーテル基、置換もしくは非置換のアセタール基、又は置換もしくは非置換のメチレン基である。Ｙ^１に結合する［ ］内の環状芳香族化合物は互いに積層して筒状の構造を構成する。ｎは、４〜８の整数を表し、複数のＡｒ^２、Ａｒ^２’、Ｘ、Ｙ^１は同一でも異なってもよく、ｍは、０〜３の整数を表し、複数のｎは同じでも異なってもよい。）
３．前記式（２）で表される環状芳香族化合物が、下記式（３）で表される環状芳香族化合物である２に記載の低誘電材料。

（式中、Ａｒ^３は、式（２）のＡｒ^２と同じであり、Ａｒ^４は、Ａｒ^２’と同じであり、Ｘは、Ａｒ^３で表される芳香族基を結合させる置換基であり、Ｙ^１は上記のＹ^１と同様である。Ｙ^２は３価の置換基であり、置換又は非置換の、炭素数３〜２０の脂環式置換基、炭素数６〜１４の芳香族基、アセタール基、メチリジン基、アミノ基であり、Ｚは、Ａｒ^４で表される芳香族基を結合させる置換基であり、ｎは４〜８の整数を表し、それぞれ同一でも異なっていてもよく、複数のＡｒ^３，Ａｒ^４、Ｘ、Ｙ^１、Ｙ^２、Ｚはそれぞれ同一でも異なってもよい。）
４．前記式（３）で表される環状芳香族化合物が、下記式（４）で表される環状芳香族化合物である３に記載の低誘電材料。

（式中、Ｒ^１は、置換もしくは非置換の炭素数６〜１４の芳香族基、又は置換もしくは非置換の炭素数５〜５０の脂環式置換基であり、Ｒ^２は、水素、置換もしくは非置換の炭素数１〜２０の直鎖状脂肪族基、置換もしくは非置換の炭素数３〜２０の分岐状脂肪族基、置換もしくは非置換の炭素数５〜５０の脂環式置換基、又は置換もしくは非置換の炭素数６〜３０の芳香族基である。Ｒ^３は、それぞれ置換もしくは非置換の炭素数１〜２０の直鎖状脂肪族基、置換もしくは非置換の炭素数３〜２０の分岐状脂肪族基、又は置換もしくは非置換の炭素数４〜５０の脂環式置換基であり、ｋは０〜２の整数を表し、ｌは０〜３の整数を表し、ｋが１又はｌが１〜２である場合、Ｒ^３の位置はいずれでもよく、ｋが２又はｌが２〜３である場合、複数のＲ^３は同一でも異なってもよく、ｎは４〜８の整数を表し、それぞれ同一でも異なっていてもよく、複数のＲ^１、Ｒ^２はそれぞれ同一でも異なってもよい。）
５．下記式（５）で表される環状芳香族化合物。

（式中、Ｒ^１は、置換もしくは非置換の炭素数６〜１４の芳香族基、又は置換もしくは非置換の炭素数５〜５０の脂環式置換基であり、Ｒ^２は、水素、置換もしくは非置換の炭素数１〜２０の直鎖状脂肪族基、置換もしくは非置換の炭素数３〜２０の分岐状脂肪族基、置換もしくは非置換の炭素数５〜５０の脂環式置換基、又は置換もしくは非置換の炭素数６〜３０の芳香族基である。Ｒは、それぞれ置換もしくは非置換の炭素数５〜５０の脂環式置換基であり、ｊは０以上の整数を表し、ｋは０〜２の整数を表し、ｌは０〜３の整数を表し、化合物全体のｊ、ｋ及びｌの合計は１以上である。ｋが１又はｌが１〜２である場合、Ｒの位置はいずれでもよく、ｋが２又はｌが２〜３である場合、複数のＲは同一でも異なってもよく、ｎは４〜８の整数を表し、それぞれ同一でも異なっていてもよく、複数のＲ^１、Ｒ^２はそれぞれ同一でも異なってもよい。）
６．上記１〜４のいずれかに記載の低誘電材料からなる半導体用層間絶縁膜材料。
７．上記１〜４のいずれかに記載の低誘電材料を有機溶媒に溶解させた塗料。
８．上記１〜４のいずれかに記載の低誘電材料からなる薄膜。
９．上記８に記載の薄膜を含む半導体装置。
１０．上記８に記載の薄膜を含む電子回路装置。 According to the present invention, the following low dielectric materials and the like are provided.
1. A low dielectric material comprising a cyclic aromatic compound represented by the following formula (1).

(In the formula, Ar ¹ is a substituted or unsubstituted divalent aromatic group having 6 to 52 carbon atoms, X is a substituent that bonds the aromatic groups represented by Ar ¹ , and 2 One Ar ¹ may be bonded through ¹ to 3 Xs, n represents an integer of 4 to 8, and a plurality of Ar ¹ and X may be the same or different.)
2. A low dielectric material comprising a cyclic aromatic compound having a structure represented by the following formula (2).

(In the formula, Ar ² is a substituted or unsubstituted tetravalent aromatic group having 6 to 52 carbon atoms, and Ar ^{2 ′} is a substituted or unsubstituted trivalent aromatic group having 6 to 52 carbon atoms. X is a substituent for bonding an aromatic group represented by Ar ² , and Y ¹ is a single bond, a double bond, an ether group, a substituted or unsubstituted acetal group, or a substituted or unsubstituted group The cyclic aromatic compounds in [] bonded to Y ¹ are laminated together to form a cylindrical structure, and n represents an integer of 4 to 8, and a plurality of Ar ² and Ar ^{2. '} , X and Y ¹ may be the same or different, m represents an integer of 0 to 3, and a plurality of n may be the same or different.)
3. 3. The low dielectric material according to 2, wherein the cyclic aromatic compound represented by the formula (2) is a cyclic aromatic compound represented by the following formula (3).

(In the formula, Ar ³ is the same as Ar ² in formula (2), Ar ⁴ is the same as Ar ^{2 ′} , and X is a substituent for bonding the aromatic group represented by Ar ^3. Y ¹ is the same as Y ¹ above Y ² is a trivalent substituent, substituted or unsubstituted alicyclic substituent having 3 to 20 carbon atoms, aromatic having 6 to 14 carbon atoms A group, an acetal group, a methylidyne group, an amino group, Z is a substituent for bonding an aromatic group represented by Ar ⁴ , and n is an integer of 4 to 8, each being the same or different. The plurality of Ar ³ , Ar ⁴ , X, Y ¹ , Y ² , and Z may be the same or different.
4). 4. The low dielectric material according to 3, wherein the cyclic aromatic compound represented by the formula (3) is a cyclic aromatic compound represented by the following formula (4).

(In the formula, R ¹ is a substituted or unsubstituted aromatic group having 6 to 14 carbon atoms, or a substituted or unsubstituted alicyclic substituent having 5 to 50 carbon atoms, and R ² is hydrogen or substituted. Or an unsubstituted linear aliphatic group having 1 to 20 carbon atoms, a substituted or unsubstituted branched aliphatic group having 3 to 20 carbon atoms, and a substituted or unsubstituted alicyclic substituent having 5 to 50 carbon atoms. Or a substituted or unsubstituted aromatic group having 6 to 30 carbon atoms, R ³ is a substituted or unsubstituted linear aliphatic group having 1 to 20 carbon atoms, substituted or unsubstituted carbon number 3; A branched aliphatic group of -20, or a substituted or unsubstituted alicyclic substituent having 4 to 50 carbon atoms, k represents an integer of 0 to 2, l represents an integer of 0 to 3, k Is 1 or l is 1 to 2, the position of R ³ may be any, k is 2 or l is 2 to 3 The plurality of R ³ may be the same or different, n represents an integer of 4 to 8, may be the same or different, and the plurality of R ¹ and R ² may be the same or different.)
5. The cyclic aromatic compound represented by following formula (5).

(In the formula, R ¹ is a substituted or unsubstituted aromatic group having 6 to 14 carbon atoms, or a substituted or unsubstituted alicyclic substituent having 5 to 50 carbon atoms, and R ² is hydrogen or substituted. Or an unsubstituted linear aliphatic group having 1 to 20 carbon atoms, a substituted or unsubstituted branched aliphatic group having 3 to 20 carbon atoms, and a substituted or unsubstituted alicyclic substituent having 5 to 50 carbon atoms. Or a substituted or unsubstituted aromatic group having 6 to 30 carbon atoms, R is a substituted or unsubstituted alicyclic substituent having 5 to 50 carbon atoms, and j represents an integer of 0 or more. , K represents an integer of 0 to 2, l represents an integer of 0 to 3, and the total of j, k, and l of the whole compound is 1 or more, when k is 1 or 1 is 1 to 2, The position of R may be any, and when k is 2 or l is 2 to 3, a plurality of R may be the same or different, and n is 4 Represents an 8 integer, which may be the same as or different from each other, a plurality of R ^1, R ² may be the same or different.)
6). 5. A semiconductor interlayer insulating film material comprising the low dielectric material according to any one of 1 to 4 above.
7). 5. A paint obtained by dissolving the low dielectric material according to any one of 1 to 4 in an organic solvent.
8). A thin film comprising the low dielectric material according to any one of 1 to 4 above.
9. 9. A semiconductor device comprising the thin film as described in 8 above.
10. 9. An electronic circuit device comprising the thin film according to 8 above.

  According to the present invention, a low dielectric material suitable as an interlayer insulating film material that does not require introduction of holes can be provided.

One of the low dielectric materials of the present invention is a cyclic aromatic compound represented by the following formula (1).

In Formula (1), Ar ¹ represents a substituted or unsubstituted divalent aromatic group having 6 to 52 carbon atoms.
Ar ¹ is preferably a substituted or unsubstituted phenylene group or naphthylene group. Specifically, phenylene group, methylphenylene group, methoxyphenylene group, ethoxyphenylene group, phenoxyphenylene group, naphthylene group, methylnaphthylene group, dimethylnaphthylene group, ethylnaphthylene group, diethylnaphthylene group, hydroxyphenylene group, dihydroxy Preferable examples include a phenylene group and a trihydroxyphenylene group. Particularly preferred is a substituted or unsubstituted phenylene group.

In the formula (1), X is a substituent for bonding Ar ^{1 to} each other, specifically, a single bond, a double bond, an ether group (—O—), a substituted or unsubstituted acetal group (—OCR ¹¹ ₂ O—) or a substituted or unsubstituted methylene group (—CR ¹¹ ₂ —).
X is preferably an ether group (—O—), a substituted or unsubstituted acetal group (—OCR ¹¹ ₂ O—), or a substituted or unsubstituted methylene group (—CR ¹¹ ₂ —).

Here, R ¹¹ is hydrogen, an aromatic group having 6 to 40 carbon atoms, a substituted or unsubstituted linear aliphatic group having 1 to 20 carbon atoms, a substituted or unsubstituted branched fatty acid having 3 to 20 carbon atoms. Or a substituted or unsubstituted alicyclic substituent having 3 to 50 carbon atoms. Preferably, it is an aromatic group having 6 to 20 carbon atoms, a substituted or unsubstituted linear aliphatic group having 1 to 12 carbon atoms, or a substituted or unsubstituted branched aliphatic group having 3 to 12 carbon atoms. is there.
When R ¹¹ is an unsaturated cyclic substituent having 5 or less carbon atoms, such as a dicyclopentadienyl group, it may be difficult to form a thin film because it has low solubility in an organic solvent such as chloroform. . An aromatic-containing group having 21 or more carbon atoms is not preferable in forming a thin film because the crystallinity is high. In addition, a linear or branched aliphatic group having 13 or more carbon atoms may be unfavorable for forming a thin film because of its high crystallinity.

  Specific examples of the aromatic group having 6 to 40 carbon atoms include phenyl group, benzyl group, phenethyl group, phenylpropyl group, phenylbutyl group, phenylpentyl group, phenylhexyl group, phenylheptyl group, phenyloctyl group, phenyldecyl. Group, substituted or unsubstituted aromatic group such as phenyldodecyl group, phenoxymethyl group, phenoxyethyl group, phenoxypropyl group, phenoxybutyl group, phenoxypentyl group, phenoxyhexyl group, phenoxyheptyl group, phenoxyoctyl group, phenoxydecyl group Preferred examples include an aryloxy group-containing group such as a group and a phenoxide decyl group.

  Examples of the substituted or unsubstituted linear aliphatic group having 1 to 20 carbon atoms or the substituted or unsubstituted branched aliphatic group having 3 to 20 carbon atoms include methyl group, ethyl group, n-propyl group, iso -Propyl group, n-butyl group, iso-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-decyl group, undecyl group, dodecyl group, A methylhexyl group, ethylhexyl, methylpentyl group, ethylpentyl group, methoxypentyl group, ethoxypentyl group, methoxyhexyl group, ethoxyhexyl group and the like are preferable. When it has a substituent, the position of the substituent is not limited.

  Preferred examples of the substituted or unsubstituted alicyclic substituent having 3 to 50 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclohexyl group, an adamantyl group, a biadamantyl group, a diamantyl group, and a norbornyl group.

X is particularly preferably an unsubstituted methylene group or a —CR ¹² H-type substituted methylene group. In this case, R ¹² is in particular methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, phenethyl, phenyl, A benzyl group and the like are preferable.

One Ar ¹ and another Ar ¹ may be bonded via 1 to 3 Xs. When two or more X are bonded, each X may be the same or different. For example, —Ar ¹ —CH ₂ —O—CH ₂ —Ar ¹ — (a structure in which Ar ¹ is bonded by a combination of two methylene groups and one ether bond) may be mentioned.

In Formula (1), n represents an integer of 4 to 8. A plurality of Ar ¹ may be the same or different. From the viewpoint of ease of production, n = 4 is preferable.

Preferred examples of the formula (1) include calixarenes of the following formula (1-a) and calix resorcinalenes of the following formula (1-b).

In formulas (1-a) and (1-b), R ¹³ , R ¹⁴ , and R ¹⁵ are the same as R ¹¹ described above.
In formula (1-a), i is an integer of 0-3. In formula (1-b), h is an integer of 0-2.

In the formulas (1-a) and (1-b), R ¹³ is preferably a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, or a decyl group. , Undecyl group, dodecyl group, phenethyl group, phenyl group, and benzyl group.
In the formulas (1-a) and (1-b), preferably, i and h are 0, or R ¹⁴ is a substituted or unsubstituted alicyclic substituent having 3 to 50 carbon atoms.
As the alicyclic substituent, a cyclohexyl group, an adamantyl group, a biadamantyl group, and a biadamantyl group having an aliphatic group are preferable.
In the formulas (1-a) and (1-b), R ¹⁵ is preferably hydrogen.
In the formulas (1-a) and (1-b), n is preferably 4 from the viewpoint of ease of synthesis.

Another embodiment of the low dielectric material of the present invention is a cyclic aromatic compound represented by the following formula (2).

The compound of the formula (2) has a structure in which the cyclic aromatic compound of the formula (1) described above is laminated.
In Formula (2), Ar ² is a substituted or unsubstituted tetravalent aromatic group having 6 to 52 carbon atoms, and Ar ^{2 ′} is a substituted or unsubstituted trivalent aromatic group having 6 to 52 carbon atoms. It is a family group.
Ar ² and Ar ^{2 ′} are a trivalent or tetravalent group having the same structure as the group exemplified as Ar ¹ in the above-described formula (1).
X is a substituent that bonds Ar ^{2 to} each other or Ar ^{2 ′ to} each other, and is specifically the same as X in the formula (1).

In Formula (2), Y ¹ represents a single bond, a double bond, an ether group, a substituted or unsubstituted acetal group, or a substituted or unsubstituted methylene group. Specifically, it is the same as X in the formula (1) described above. The cyclic aromatic compounds in [] bonded to Y ¹ are laminated together to form a cylindrical structure.
Y ¹ is more preferably a substituted or unsubstituted acetal group (—OCR ¹⁶ ₂ O—), and still more preferably an acetal group represented by —OCHR ¹⁶ O—.

R ¹⁶ is preferably an aromatic group having 6 to 20 carbon atoms. Specifically, phenyl group, benzyl group, phenethyl group, phenylpropyl group, phenylbutyl group, phenylpentyl group, phenylhexyl group, phenylheptyl group, phenyloctyl group, phenyldecyl group, phenyldodecyl group, tolyl group, phenyl Substituted or unsubstituted aromatic group such as phenyl group, naphthyl group, phenoxymethyl group, phenoxyethyl group, phenoxypropyl group, phenoxybutyl group, phenoxypentyl group, phenoxyhexyl group, phenoxyheptyl group, phenoxyoctyl group, phenoxydecyl Preferred examples include an aryloxy group-containing group such as a group and a phenoxide decyl group. More preferred are a phenyl group, a tolyl group, a phenylphenyl group, and a naphthyl group.

In Formula (2), n represents an integer of 4 to 8. From the viewpoint of ease of synthesis, n = 4 is preferable. A plurality of Ar ² , Ar ^{2 ′} , X, and Y ¹ may be the same or different.

In Formula (2), m represents an integer of 0 to 3. Preferably m = 2.
Each n may be the same or different.

The cyclic aromatic compound represented by the formula (2) is preferably a cyclic aromatic compound represented by the formula (3).

In Formula (3), Ar ³ is the same as Ar ^{2 in} Formula (2), and Ar ⁴ is the same as Ar ^{2 ′ in} Formula (2).
In Formula (3), X is the same as X in Formula (1) and Formula (2).
In the formula (3), ^{Y 1} is the same as ^{Y 1} in the formula (2).
In Formula (3), Y ² is a trivalent substituent, which is a substituted or unsubstituted alicyclic substituent having 3 to 20 carbon atoms, an aromatic group having 6 to 14 carbon atoms, an acetal group, or a methylidyne group. (Note: trivalent CH), amino group, group having the following structure (a), and the like. Preferably, it is a substituent having a methyl group, an adamantyl group, a biadamantyl group or a diamantyl group instead of hydrogen in the following structure (a) and the following structure (a).

In Formula (3), Z is a substituent for bonding Ar ⁴ and Ar ⁴ , and specific examples thereof are the same as Y ^{1 in} Formula (2).
n represents an integer of 4 to 8. A plurality of n, Ar ³ , Ar ⁴ , X, Z, and Y ² may be the same or different.

The cyclic aromatic compound represented by the formula (2) is particularly preferably a cyclic aromatic compound represented by the formula (4).

In formula (4), R ¹ is an aromatic group having 6 to 14 carbon atoms, or a substituted or unsubstituted alicyclic substituent having 5 to 50 carbon atoms, preferably an aromatic group having 6 to 14 carbon atoms. It is a group.
Specific examples of the aromatic group include a phenylene group, a methylphenylene group, a methoxyphenylene group, an ethoxyphenylene group, a phenoxyphenylene group, a naphthylene group, a methylnaphthylene group, a dimethylnaphthylene group, an ethylnaphthylene group, and a diethylnaphthylene group. Substituted or unsubstituted aromatic group, substituted or unsubstituted hydroxy group-containing aromatic group such as hydroxynaphthylene group, substituted or unsubstituted alkoxy group-containing aromatic group such as methoxynaphthylene group and ethoxynaphthylene group A preferred group is a substituted or unsubstituted aryloxy group-containing aromatic group such as a phenoxynaphthylene group. The aromatic group is particularly preferably a phenylene group or a naphthylene group.
In addition, since an aromatic group having 16 or more carbon atoms has a large strain, it is not always preferable from the viewpoint of molecular stability.

  The alicyclic substituent is preferably a cyclohexyl group, an adamantyl group, a biadamantyl group, a diamantyl group, or a norbornyl group.

In the formula (4), R ² is hydrogen, a substituted or unsubstituted linear aliphatic group having 1 to 20 carbon atoms, a substituted or unsubstituted branched aliphatic group having 3 to 20 carbon atoms, substituted or unsubstituted. These are an aromatic group having 6 to 30 carbon atoms, or a substituted or unsubstituted alicyclic substituent having 5 to 50 carbon atoms.
Preferably, it is an aromatic group having 6 to 20 carbon atoms, a substituted or unsubstituted linear aliphatic group having 1 to 12 carbon atoms, or a substituted or unsubstituted branched aliphatic group having 3 to 12 carbon atoms. .
If it is an aromatic group having 6 or less carbon atoms, it may have low solubility in an organic solvent such as chloroform, and if it is an aromatic group having 21 or more carbon atoms, the crystallinity may be high. Moreover, crystallinity may become high in it being a C13 or more linear or branched aliphatic group.

  Specific examples of the aromatic group having 6 to 20 carbon atoms include phenyl group, benzyl group, phenethyl group, phenylpropyl group, phenylbutyl group, phenylpentyl group, phenylhexyl group, phenylheptyl group, phenyloctyl group, phenyldecyl. Group, substituted or unsubstituted aromatic group such as phenyldodecyl group, phenoxymethyl group, phenoxyethyl group, phenoxypropyl group, phenoxybutyl group, phenoxypentyl group, phenoxyhexyl group, phenoxyheptyl group, phenoxyoctyl group, phenoxydecyl group Preferred examples include substituted or unsubstituted phenoxy group-containing aromatic groups such as a group and a phenoxide dodecyl group. Particularly preferred is a phenethyl group.

  A substituted or unsubstituted linear aliphatic group having 1 to 12 carbon atoms or a substituted or unsubstituted branched aliphatic group having 3 to 12 carbon atoms is preferably a methyl group, an ethyl group, an n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-decyl group, undecyl group, dodecyl group Methylhexyl group, ethylhexyl, methylpentyl group, ethylpentyl group, methoxypentyl group, ethoxypentyl group, methoxyhexyl group, ethoxyhexyl group and the like. Particularly preferred are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl and dodecyl. In addition, when it has a substituent, the substitution position is not limited.

  Preferred examples of the substituted or unsubstituted alicyclic substituent having 3 to 50 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclohexyl group, an adamantyl group, a biadamantyl group, a diamantyl group, and a norbornyl group.

In the formula (4), R ³ represents a substituted or unsubstituted linear aliphatic group having 1 to 20 carbon atoms, a substituted or unsubstituted branched aliphatic group having 3 to 20 carbon atoms, and an alkoxy group-containing aliphatic group. Or a substituted or unsubstituted alicyclic substituent having 4 to 50 carbon atoms.
Preferably, it is a substituted or unsubstituted linear aliphatic group having 1 to 12 carbon atoms, a substituted or unsubstituted branched aliphatic group having 3 to 12 carbon atoms, a substituted or unsubstituted fatty acid having 4 to 50 carbon atoms. A cyclic substituent.

  Specific examples of the substituted or unsubstituted linear aliphatic group having 1 to 12 carbon atoms and the substituted or unsubstituted branched aliphatic group having 3 to 12 carbon atoms include a methyl group, an ethyl group, and n-propyl. Group, iso-propyl group, n-butyl group, iso-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-decyl group, undecyl group, A dodecyl group is mentioned.

  The alkoxy group-containing aliphatic group is preferably a methoxypentyl group, an ethoxypentyl group, a methoxyhexyl group, an ethoxyhexyl group or the like.

  Preferred examples of the substituted or unsubstituted alicyclic substituent having 4 to 50 carbon atoms include a cyclopentyl group, a cyclohexyl group, an adamantyl group, a biadamantyl group, a diamantyl group, and a norbornyl group.

In Formula (4), k is an integer of 0-2. L is an integer of 0-3. When k is 1 or l is 1 to 2, the position of R ³ may be any. When k is 2 or l is 2 to 3, a plurality of R ³ may be the same or different.

In the formula (4), n is an integer of 4 to 8, preferably 4. Each n may be the same or different.
At this time, the plurality of R ¹ and R ² may be the same or different.

Of the formula (4), the cyclic aromatic compound represented by the following formula (5) is a novel substance, and particularly a compound having a low dielectric constant.

In the formula, each substituent except R and j is the same as the above formula (4). j is an integer of 0 or more. However, the sum of j + k + 1 of the whole compound is 1 or more. That is, one or more R is bonded to one compound molecule. R is a substituted or unsubstituted alicyclic substituent having 5 to 50 carbon atoms, specifically, the same as the alicyclic substituent exemplified for R ³ in the above formula (4). In particular, a substituted or unsubstituted cyclohexyl group, adamantyl group or a beadamantyl group represented by the following formula is preferable.

（式中、Ｒ^２１は炭素数１〜２０の脂肪族炭化水素基であり、ビアダマンチル基の任意の位置に０．１〜１７個の範囲で結合している。）

(In the formula, R ²¹ is an aliphatic hydrocarbon group having 1 to 20 carbon atoms, and is bonded to an arbitrary position of the biadamantyl group in a range of 0.1 to 17).

As the aliphatic hydrocarbon group having 1 to 20 carbon atoms, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a decyl group, and the like are preferable. The number of substitution is particularly preferably 0.5-6.
In the above, the number of substituents may not be an integer for the following reason. That is, when using the Friedel-Craft reaction described later, which is preferably used as a method for producing the compound of the present invention, the resulting compound is recovered as a mixture of those substituted with R ²¹ and unsubstituted ones. For this reason, the average number of substitutions per molecule may be a small number instead of an integer.

  By introducing the alicyclic substituent as R, a compound having a particularly low dielectric constant can be obtained. This is because the intermolecular distance between the molecules constituting the thin film is relatively long and the intermolecular voids can be secured when entering as a pendant as compared to the case where the alicyclic substituent enters the main chain structure. Therefore, it is considered that the dielectric constant decreases because the density of electronic polarization that leads to an increase in dielectric constant decreases. Further, although all molecules have electronic polarization, it is considered that alicyclic substituents have low electronic polarization, so that it is difficult to contribute to an increase in dielectric constant when introduced as a pendant.

  In the present invention, the alicyclic substituent which is R is preferably directly bonded to the aromatic ring. When bonded via an alkyl group or the like, the side chain bends at the intervening group portion, making it difficult to sufficiently separate the intermolecular distance. Also, from the viewpoint of heat resistance, it may be undesirable because it causes molecular movement due to rotation during heating.

The low dielectric material of the present invention comprises a cyclic aromatic compound having a so-called bowl-shaped structure. By using this cyclic aromatic compound, it is possible to provide an interlayer insulating film material that leads to a result of dramatically improving the performance of a semiconductor such as ULSI without introducing vacancies.
The current method of introducing pores at the nanometer level by introducing a thermally decomposable pore is limited in reducing the dielectric constant without reducing the strength. For this reason, it is necessary to introduce angstrom-level holes. That is to say, increasing atomic size vacancies, ie intermolecular free volume.
In particular, by using a cyclic compound represented by the calix resorcinarene compound as a molecular component, by combining multiple bonds with single bonds, ether bonds, etc., it has a cage-like molecular structure, so that vacancies with a large angstrom level can be formed in the molecule. The dielectric constant can be lowered.

  The cyclic aromatic compound of the formula (1) can be efficiently synthesized by a condensation reaction between an aldehyde and a phenol derivative or resorcinol in the presence of hydrochloric acid. As a specific synthesis method, J. et al. Am. Chem. Soc. , 1981, 103, 3782-3792, J. et al. Org. Chem. , 1980, 45, 4498-4500, etc. can be used.

  The cyclic aromatic compound of the formula (2) can be efficiently obtained by any one of a) condensation reaction of aldehyde and resorcinol in the presence of hydrochloric acid, b) acetalization reaction, and c) etherification reaction by Ullmann reaction. Can be synthesized. As a specific synthesis method, Org. Lett. , Vol. 2, no. 24, 3845-3848, 2000, J. MoI. Am. Chem. Soc. , 2003, 125, 650-651 can be used.

In order to introduce the above-described alicyclic substituent as R in the formula (5), the halide of R (R—X) and the base compound are reacted by Friedel-Craft reaction in the presence of Lewis acid. Can be obtained.
As the halide of R (R—X), for example, 3-bromo-5,5′-dibutyl-1,1′-biadamantane is preferable.
As the Lewis acid, a compound having a known Lewis acidity can be used.
Specifically, aluminum chloride, aluminum bromide, aluminum fluoride, boron trifluoride, boron trichloride, boron tribromide, tris (pentafluorophenyl) boron, phosphorus pentafluoride, scandium triflate, titanium, zirconium Known compounds such as metal alkoxide compounds are exemplified.
Aluminum chloride and aluminum bromide are preferred. You may use combining these.

  The amount of Lewis acid added is preferably 0.001 equivalent to 10 equivalents relative to the halogenated alicyclic compound used. Preferably it is 0.01 equivalent-1 equivalent.

  The preferred Lewis acid type and amount to be added vary depending on the combination of aromatic compound and halogenated alicyclic compound and reaction conditions of the substrate, but from the viewpoint of reactivity and economy, aluminum chloride and / or aluminum bromide is used. 0.01 equivalent to 1 equivalent is used.

  Depending on the reaction substrate used and the reaction conditions, the reaction can be carried out with or without a solvent. In general, the solvent may be used because the concentration of the reaction substrate and the catalyst may decrease due to the solvent, and the reaction rate may decrease, or the solvent itself may participate in the reaction and decrease the selectivity of the reaction. There are many examples where it is preferable not to. However, a halogenated hydrocarbon solvent is generally used when it is preferable to use a solvent due to the form of the substrate or the like due to reaction limitations or post-treatment limitations. The halogenated hydrocarbon is preferably 1,1,2,2-tetrachloroethane.

  When carrying out the Friedel-Crafts reaction, alcohol-based solvents and basic organic solvents such as pyridine are not preferred because they suppress the catalytic action of Lewis acids. An aromatic solvent is not preferable because it reacts with a halogenated alicyclic compound as a reaction substrate to give a by-product.

  The reaction temperature for carrying out the Friedel-Crafts reaction is preferably −100 ° C. to 200 ° C., more preferably −78 ° C. to 100 ° C. If it is less than −78 ° C., a sufficient reaction rate may not be obtained, and if it exceeds 100 ° C., side reactions may progress and the yield of the desired compound may be reduced.

By performing such a reaction, the compound of the formula (5) is obtained. In addition, the compound obtained by this method is actually recovered as a mixture of a substituted product represented by the formula (5) and an unsubstituted product in which R is not bonded at all. A substituted product and an unsubstituted product may be purified and separated, but for practical use, the mixture may be used as it is. The number of substitutions per compound (total of j + k + 1 of the whole compound) is, for example, 0.01 to 88, preferably 0.05 to 44 when R ¹ is naphthylene. If the number of substitutions is less than 0.05, significant improvement in performance such as reduction in dielectric constant may not be expected.

  The low dielectric material of the present invention can be suitably used as a semiconductor interlayer insulating film material. For example, when it is used as an interlayer insulating film material of a ULSI multilayer wiring structure in the manufacture of a semiconductor device, heat resistance and stability are required. However, since the required values of each characteristic differ depending on the part where a low dielectric material is used, Cannot be defined. However, when used as an interlayer insulating film material, it is generally desirable that the dielectric constant and the like are low and the heat resistance and stability are high. In particular, the dielectric constant is desirably 3.0 or less. The low dielectric material of the present invention has these properties.

The low dielectric material of the present invention can be dissolved in an organic solvent and used as a paint.
The low dielectric material of the present invention can be dissolved in a general organic solvent. Specific organic solvents include dichloromethane, chloroform, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, DMF, NMP, DMSO, propylene glycol methyl ether acetate (PGMEA), ethyl lactate, cyclohexanone toluene, benzene , Acetone and the like.
The blending amount of the low dielectric material in the paint can be appropriately adjusted in consideration of the thickness of the thin film to be produced, the viscosity of the paint, and the like, but is generally about 0.01 wt% to 50 wt%.

The low dielectric material of the present invention is preferably used in the form of a thin film such as an interlayer insulating film. A thin film made of the low dielectric material of the present invention can be formed by a generally known method such as a coating method such as a spin coating method or a spray coating method, or a CVD method using the above-described paint. A thin film having a thickness of 10 nm to 10 μm can be formed.
In addition, the low dielectric material of the present invention does not need to be cured at a high temperature after forming a thin film, and does not require a catalyst or a cross-linking material required for thermosetting, so that these materials do not remain.
The thin film made of the low dielectric material of the present invention can be suitably used as an interlayer insulating film for a semiconductor device (integrated circuit) or an electronic circuit device.

  Since the low dielectric material of the present invention has a low dielectric constant, a thin film made from the low dielectric material of the present invention is formed by patterning a semiconductor device such as a CPU, DRAM, flash memory, etc., and drawing a circuit. Small electronic circuit devices for information processing typified by thin film transistors, electronic circuit devices such as high-frequency communication electronic circuit devices, members of image display devices, optical communication devices, surface protective films, heat-resistant films, etc. Can do.

The dielectric constant of the low dielectric material of the present invention varies depending on the type of substituent, the substitution position, and the number of substitutions of the cyclic aromatic compound to be used, and thus cannot be defined unconditionally. Range, more preferably 2.6 or less, and still more preferably 2.4 or less. Although it is not necessary to specify the lower limit value of the dielectric constant k, a practical value is about 1.5.
The dielectric constant k is a value obtained by the mercury probe method.
The cyclic aromatic compound used as the low dielectric material of the present invention can appropriately adjust the main chain structure, molecular weight, type of substituent, substitution position, and number of substitutions within the above dielectric constant range.

The dielectric constant k varies depending on the structure of the cyclic aromatic compound represented by the above formulas (1) to (4), particularly the type of substituent and the substitution position. For example, if R ² , R ³ , R ¹³ and R ¹⁴ are long chain aliphatic groups such as n-heptyl group, adamantyl groups, biadamantyl groups, diamantyl groups, norbornyl groups, etc. The dielectric constant is low.

Example 1
(1) Synthesis of 3,5-dibromobenzalbromide (following formula)

  J. et al. Org. Chem. , 1999, 64, 9286, and synthesized with reference to the synthesis method described in Experimental Section. That is, 10 g (37.9 mmol) of 3,5-dibromobenzalaldehyde was added to a 500 mL flask and dissolved in 150 mL of anhydrous dichloromethane. The system was placed in a nitrogen atmosphere, and light-shielded, 57 mL (56.8 mmol) of 1M boron tribromide was added dropwise. The reaction was allowed to stir at room temperature for 24 hours. The reaction was stopped by adding 150 mL of acetone. Methylene chloride was removed by distillation under reduced pressure. Methylene chloride / pure water was added, and the organic layer was extracted with a separatory funnel. Water was removed with magnesium sulfate, and purification by chromatography on a silica gel column (methylene chloride: hexane = 1: 3) gave 13.6 g of 3,5-dibromobenzalbromide (yield: 89%). It was.

(2) Synthesis of calixresorcinalene represented by the following formula (6)

  50.0 g (454.5 mmol) of resorcinol was added to a 1 L flask and dissolved in 272 mL of methanol. Concentrated hydrochloric acid (45.4 mL) was added, and the mixture was cooled to 10 to 15 ° C. in an ice water bath. The inside of the system was put into a nitrogen atmosphere, and 70 mL (454.5 mmol) of octanal was added dropwise for 50 minutes. The internal temperature was raised to 60 ° C. in an oil bath, and the mixture was heated and stirred for 2 hours. The reaction solution was dropped into 1.0 L of pure water and reprecipitated. The resulting precipitate was filtered. The precipitate was again washed with 1.5 L of pure and filtered. As a result, 89.1 g (yield: 89%) of calix resorcinalene represented by the formula (6) was obtained.

Example 2
(1) Synthesis of intermediate compound (following formula (7))

Org. Lett. , Vol. 2, no. 24, 3845-3848 (2000).
In a 1 L flask, 6.08 g (6.9 mmol) of calix resornacilene synthesized in Example 1 (2) and 12.4 g of 3,5-dibromobenzalbromide synthesized in Example 1 (1) (30 .4 mmol) was dissolved in 365 mL of dimethylacetamide (DMA), and 8.2 mL (55.2 mmol) of diazabicycloundecene was added. The system was put in a nitrogen atmosphere, heated to an internal temperature of 65 ° C. with an oil bath, and reacted by heating and stirring for 3 days. DMA was removed by distillation under reduced pressure, methylene chloride / water was added, and the organic layer was extracted with a separatory funnel. Water was removed with magnesium sulfate, and purification by chromatography on a silica gel column (methylene chloride: hexane = 1: 3) gave 3.01 g (yield: 23%) of the compound represented by formula (7).

(2) Synthesis of a cyclic aromatic compound represented by the following formula (8)

J. et al. Am. Chem. Soc. , 2003, 125, 650, with reference to the synthesis method described in the literature.
16.20 g (3.24 mmol) of the compound of formula (7) synthesized in the above (1), 5.19 g (32.40 mmol) of 2,7-dihydroxynaphthalene, 9.00 g (65.12 mmol) of potassium carbonate, 720 mL of pyridine To give a suspension solution. Nitrogen bubbling was performed for 15 minutes, and copper (II) oxide (5.32 g, 66.92 mmol) was added. The system was put into a nitrogen atmosphere, heated in an oil bath, and reacted by heating and stirring for 7 days under reflux of pyridine. Pyridine was removed by distillation under reduced pressure, dissolved in 200 mL of methylene chloride, and filtered using celite. Methylene chloride was removed by distillation under reduced pressure, dissolved in 200 mL of methanol, and filtered. Methylene chloride / water was added to the insoluble material, and the organic layer was extracted with a separatory funnel. Water was removed with magnesium sulfate, and fractionation was performed by chromatography on a silica gel column (methylene chloride: hexane = 1: 3) to obtain 1.8 g (yield: 30%) of a mixture of the 3 and 4 substituents. It was.

  Add 2.0 g (1.08 mmol) of a mixture of 3-substituted and 4-substituted products, 358 mg (2.12 mmol) of 2,7-dihydroxynaphthalene, 1.22 g (8.48 mmol) of potassium carbonate, 240 ml of pyridine, and a suspension solution. I made it. Nitrogen bubbling was performed for 15 minutes, and 421.6 g (5.3 mmol) of copper (II) oxide was added. The system was put in a nitrogen atmosphere, heated in an oil bath, and reacted by heating and stirring for 3 days under reflux of pyridine. Pyridine was removed by distillation under reduced pressure, dissolved in 100 ml of methylene chloride, and filtered using celite. Methylene chloride was removed by distillation under reduced pressure, dissolved in 100 ml of methanol, and filtered. Methylene chloride / water was added to the insoluble material, and the organic layer was extracted. Water was removed with magnesium sulfate, and purification by chromatography on a silica gel column (methylene chloride: hexane = 1: 3) gave 0.63 g (yield: 34%) of the compound represented by formula (8) (deep cavitand). Got.

Example 3
A cyclic aromatic compound represented by the following formula (9) was synthesized.

  In Example 2 (2), except that resorcinol was used instead of 2,7-dihydroxynaphthalene, a compound represented by formula (9) was obtained by the same synthesis method as in Example 2 (44% yield).

Example 4
A compound having a dibutylbiadamantyl group introduced on the phenyl ring of the cyclic aromatic compound of the above formula (8) synthesized in Example 2 was synthesized by the following procedure.
Under a nitrogen atmosphere, in a 100-ml flask, a cyclic aromatic compound represented by the formula (8) and 3-bromo-5,5′-dibutyl-1,1′-biadamantane (0.23 g, 0.50 mmol), 1,1,2,2-tetrachloroethane (15 ml) was added and stirred to obtain a homogeneous solution. The solution was cooled to 0 ° C. with stirring in an ice bath, then anhydrous aluminum bromide (0.13 g, 0.50 mmol) was added under a nitrogen atmosphere and stirred for 3 hours while cooling to 0 ° C., The reaction was carried out. Next, the reaction is stopped by adding methanol (1 ml) dropwise with cooling and stirring, and by adding methanol (50 ml), the product is precipitated as a white solid, filtered and washed with methanol. A dibutylbiadamantyl-substituted cyclic aromatic compound was obtained (0.40 g, yield 88%).

The structure of the obtained dibutylbiadamantyl-substituted cyclic aromatic compound was confirmed by ¹ H-NMR. FIG. 1 shows a ¹ H-NMR spectrum of a dibutylbiadamantyl-substituted cyclic aromatic compound.
From this spectrum, 0.73 mol of dibutylbiadamantyl groups were bonded to 1 mol of the cyclic aromatic compound represented by the formula (8).

Example 5
[Insulating film formation and dielectric constant measurement]
Using the compound (8) synthesized in Example 2, a tetrachloroethane solution having a concentration of 10 wt% was prepared. This was rotated at 2000 rpm for 60 seconds using a spin coater and applied onto a silicon wafer to form an adhesive thin film. A silicon wafer (2 cm square) on which this adhesive thin film was formed was heated at 250 ° C. for 60 minutes and then vacuum dried at 200 ° C. to form a non-adhesive thin film having a uniform surface shape. This film thickness was measured to be 0.5 μm by a stylus type film thickness meter, and the dielectric constant k was 2.9 measured by the mercury probe method. For measuring the dielectric constant, a mercury prober (manufactured by Four Dimensions) was used.

Example 6
The compound (9) synthesized in Example 3 was formed into a film by the same method as in Example 5. When the dielectric constant of the obtained thin film was measured in the same manner as in Example 4, the relative dielectric constant k was 2.4.

Example 7
The compound (6) synthesized in Example 1 was formed into a film by the same method as in Example 5. When the dielectric constant of the obtained thin film was measured in the same manner as in Example 4, the relative dielectric constant k was 2.9.

Example 8
A dibutylbiadamantyl-substituted product of compound (8) synthesized in Example 4 was formed into a film by the same method as in Example 5. When the dielectric constant of the obtained thin film was measured in the same manner as in Example 5, the relative dielectric constant k was 2.7.

Comparative Example 1
130 g (1.38 mol) of phenol, 13 mL of water, 92.4 g (1.14 mol) of 37% aqueous formaldehyde solution and 1 g of oxalic acid dihydrate were added, and the mixture was heated to reflux with stirring for 30 minutes. 1 g of oxalic acid dihydrate was added, and the mixture was further heated under reflux for 1 hour, and then 400 mL of water was added and cooled. After allowing the resin to settle for 30 minutes, the aqueous phase was separated by decantation to obtain 140 g (1.31 mol, yield 95%) of a novolak resin.
The obtained novolac resin was formed into a film by the same method as in Example 4. The dielectric constant k of the obtained thin film was measured in the same manner as in Example 4. This novolac resin had a relative dielectric constant k of 4.8.

  The low dielectric material of the present invention can be used as an electronic material used in a semiconductor device, an electronic circuit device or the like, a semiconductor interlayer insulating film material, a transparent material, a high strength material, a heat resistant material, or the like.

2 is a ¹ H-NMR chart of a dibutylbiadamantyl-substituted cyclic aromatic compound obtained in Example 4. FIG.

Claims (10)

A low dielectric material comprising a cyclic aromatic compound represented by the following formula (1).

(In the formula, Ar ¹ is a substituted or unsubstituted divalent aromatic group having 6 to 52 carbon atoms, X is a substituent that bonds the aromatic groups represented by Ar ¹ , and 2 One Ar ¹ may be bonded through ¹ to 3 Xs, n represents an integer of 4 to 8, and a plurality of Ar ¹ and X may be the same or different.) A low dielectric material comprising a cyclic aromatic compound having a structure represented by the following formula (2).

(In the formula, Ar ² is a substituted or unsubstituted tetravalent aromatic group having 6 to 52 carbon atoms, and Ar ^{2 ′} is a substituted or unsubstituted trivalent aromatic group having 6 to 52 carbon atoms. X is a substituent for bonding an aromatic group represented by Ar ² , and Y ¹ is a single bond, a double bond, an ether group, a substituted or unsubstituted acetal group, or a substituted or unsubstituted group The cyclic aromatic compounds in [] bonded to Y ¹ are laminated together to form a cylindrical structure, and n represents an integer of 4 to 8, and a plurality of Ar ² and Ar ^{2. '} , X and Y ¹ may be the same or different, m represents an integer of 0 to 3, and a plurality of n may be the same or different.) The low dielectric material according to claim 2, wherein the cyclic aromatic compound represented by the formula (2) is a cyclic aromatic compound represented by the following formula (3).

(In the formula, Ar ³ is the same as Ar ² in formula (2), Ar ⁴ is the same as Ar ^{2 ′} , and X is a substituent for bonding the aromatic group represented by Ar ^3. Y ¹ is the same as Y ¹ above Y ² is a trivalent substituent, substituted or unsubstituted alicyclic substituent having 3 to 20 carbon atoms, aromatic having 6 to 14 carbon atoms A group, an acetal group, a methylidyne group, and an amino group, Z is a substituent for bonding an aromatic group represented by Ar ⁴ , and n is an integer of 4 to 8, each being the same or different. The plurality of Ar ³ , Ar ⁴ , X, Y ¹ , Y ² , and Z may be the same or different. The low dielectric material according to claim 3, wherein the cyclic aromatic compound represented by the formula (3) is a cyclic aromatic compound represented by the following formula (4).

(In the formula, R ¹ is a substituted or unsubstituted aromatic group having 6 to 14 carbon atoms, or a substituted or unsubstituted alicyclic substituent having 5 to 50 carbon atoms, and R ² is hydrogen or substituted. Or an unsubstituted linear aliphatic group having 1 to 20 carbon atoms, a substituted or unsubstituted branched aliphatic group having 3 to 20 carbon atoms, and a substituted or unsubstituted alicyclic substituent having 5 to 50 carbon atoms. Or a substituted or unsubstituted aromatic group having 6 to 30 carbon atoms, R ³ is a substituted or unsubstituted linear aliphatic group having 1 to 20 carbon atoms, substituted or unsubstituted carbon number 3; A branched aliphatic group of -20, or a substituted or unsubstituted alicyclic substituent having 4 to 50 carbon atoms, k represents an integer of 0 to 2, l represents an integer of 0 to 3, k Is 1 or l is 1 to 2, the position of R ³ may be any, k is 2 or l is 2 to 3 The plurality of R ³ may be the same or different, n represents an integer of 4 to 8, may be the same or different, and the plurality of R ¹ and R ² may be the same or different.) The cyclic aromatic compound represented by following formula (5).

(In the formula, R ¹ is a substituted or unsubstituted aromatic group having 6 to 14 carbon atoms, or a substituted or unsubstituted alicyclic substituent having 5 to 50 carbon atoms, and R ² is hydrogen or substituted. Or an unsubstituted linear aliphatic group having 1 to 20 carbon atoms, a substituted or unsubstituted branched aliphatic group having 3 to 20 carbon atoms, and a substituted or unsubstituted alicyclic substituent having 5 to 50 carbon atoms. Or a substituted or unsubstituted aromatic group having 6 to 30 carbon atoms, R is a substituted or unsubstituted alicyclic substituent having 5 to 50 carbon atoms, and j represents an integer of 0 or more. , K represents an integer of 0 to 2, l represents an integer of 0 to 3, and the total of j, k, and l of the whole compound is 1 or more, when k is 1 or 1 is 1 to 2, The position of R may be any, and when k is 2 or l is 2 to 3, a plurality of R may be the same or different, and n is 4 Represents an 8 integer, which may be the same as or different from each other, a plurality of R ^1, R ² may be the same or different.)   The interlayer insulating film material for semiconductors which consists of a low dielectric material as described in any one of Claims 1-4.   The coating material which melt | dissolved the low dielectric material as described in any one of Claims 1-4 in the organic solvent.   The thin film which consists of a low dielectric material as described in any one of Claims 1-4.   A semiconductor device comprising the thin film according to claim 8. An electronic circuit device comprising the thin film according to claim 8.

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