JP2007177042A - Composition for forming film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain an insulating film having excellent film properties such as dielectric constant, metal diffusion barrier property, etc., and a composition for forming a film for obtaining an electronic device using the insulating film. <P>SOLUTION: The composition for a forming film comprises a polymer of a compound represented by general formula (I) (Q is a group containing a ring structure composed of carbon atoms or a group containing a basket structure composed of carbon atoms; l is an integer of 1-10; m is an integer of 0-10; n is an integer of 1-10; X is an arbitrary substituent group; Y is a group containing a carbon-carbon unsaturated bond; R is a group containing a functional group containing atoms such as O, N, S, P, etc.). <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a film-forming composition, and more particularly to a composition for forming an insulating film having good film properties such as dielectric constant, metal diffusion barrier property, mechanical strength, heat resistance and the like used for electronic devices, Furthermore, the present invention relates to an insulating film obtained by using the composition, a metal diffusion barrier film, and an electronic device having the insulating film.

  In recent years, in the field of electronic materials, with the progress of higher integration, more functions, and higher performance, circuit resistance and capacitor capacity between wirings have increased, leading to an increase in power consumption and delay time. In particular, an increase in delay time is a major factor in reducing the signal speed of the device and the occurrence of crosstalk. Therefore, in order to reduce the delay time and speed up the device, it is necessary to reduce parasitic resistance and parasitic capacitance. It has been. As one specific measure for reducing this parasitic capacitance, an attempt is made to cover the periphery of the wiring with an interlayer insulating film having a low dielectric constant (relative dielectric constant of 3.0 or less). (See Patent Document 1)

  When manufacturing semiconductor devices, it is necessary that metals (copper, etc.) used for wiring do not diffuse into the insulating film even when heated to about 400 ° C. A normal low-k insulating film is a diffusion barrier for wiring metal. In order to avoid diffusion of metal into the insulating film, an insulating barrier film is used between the insulating film and the metal. As such a barrier film, for example, silicon nitride, silicon carbide, or the like is used, and since these generally have a relative dielectric constant of 4.0 or more, the effective dielectric constant of the interlayer insulating film increases. It is the cause.

Thus, it has been desired to develop an insulating film having a small relative dielectric constant and a high effect of suppressing metal diffusion.
JP 2002-534546 A

  The present invention relates to a film-forming composition for solving the above-described problems, and more specifically, a film for forming an insulating film having good film characteristics such as dielectric constant and metal diffusion barrier property, which is used in electronic devices and the like. More particularly, the present invention relates to an insulating film, a metal diffusion barrier film, and an electronic device having the insulating film obtained by using the film forming composition.

一般式（Ｉ）中、
Ｑは、炭素原子で形成された環構造を含む基または炭素原子で形成されたカゴ構造を含む基を表す。
ｌは１〜１０の整数を表し、
ｍは０〜１０の整数を表し、
ｎは１〜１０の整数を表す。
Ｘは任意の置換基を表す。
Ｙは下記一般式（Ｙ−１）〜（Ｙ−６）のいずれかで表される基を表す。
Ｒは下記一般式（Ｒ−１）〜（Ｒ−１０）のいずれかで表される基を表す。

一般式（Ｙ−１）〜（Ｙ−６）中、
Ｚは水素原子または任意の置換基を表す。
Ｘ¹はＣ(Ｘ^２)₂、ＮＸ^２、Ｏ、Ｓから選ばれる原子または基を表す。
Ｘ²は水素原子または任意の置換基を表す。
Ｑ²は炭素原子で形成された環構造を含む基または炭素原子で形成されたカゴ構造を含む基またはSiX^３ (3-n²)を表す。
Ｘ^３は水素原子または任意の置換基を表す。
ｎ²は１〜１０の整数を表す。ただし、Ｑ²がSiX^３ (3-n²)を表すとき、ｎ²は１〜３の整数を表す。

一般式（Ｒ−１）〜（Ｒ−１０）中、
Ｒ^２は水素原子または任意の置換基を表す。
Ｒ、Ｒ^２、Ｘ、Ｙ、Ｚ、Ｘ¹、Ｘ^３およびＱ²は複数存在する場合は、各々同一でも異なっていてもよい。
＜２＞
一般式（Ｉ）で表される化合物において、Ｑの表す基が一般式（Ｑ−１）〜（Ｑ−７）のいずれかで表される基であることを特徴とする請求項１に記載の膜形成用組成物。

式中、Ａは各々独立に一般式（Ｉ）のＸ、Ｙ、Ｒおよび水素原子から選ばれる基を表す。
＜３＞
一般式（Ｉ）で表される化合物において、Ｑの表す基が一般式（Ｑ−１）または（Ｑ−５）で表される構造を含む基であることを特徴とする上記＜２＞に記載の膜形成用組成物。
＜４＞
一般式（Ｉ）で表される化合物を遷移金属触媒存在下または重合開始剤存在下で重合して得られることを特徴とする上記＜１＞〜＜３＞のいずれかに記載の膜形成用組成物。
＜５＞
さらに有機溶剤を含むことを特徴とする上記＜１＞〜＜４＞のいずれかに記載の膜形成用組成物。
＜６＞
上記＜１＞〜＜５＞のいずれかに記載の膜形成用組成物を用いて形成した絶縁膜。
＜７＞
上記＜１＞〜＜５＞のいずれかに記載の膜形成用組成物を用いて形成した金属拡散バリア膜。
＜８＞
上記＜６＞に記載の絶縁膜又は請求項７に記載の金属拡散バリア膜を有する電子デバイス。 It has been found that the above problems are solved by the following <1> to <8> configurations.
<1>
A film-forming composition comprising a compound represented by formula (I) or a polymer thereof.

In general formula (I),
Q represents a group containing a ring structure formed of carbon atoms or a group containing a cage structure formed of carbon atoms.
l represents an integer of 1 to 10,
m represents an integer of 0 to 10,
n represents an integer of 1 to 10.
X represents an arbitrary substituent.
Y represents a group represented by any one of the following general formulas (Y-1) to (Y-6).
R represents a group represented by any one of the following general formulas (R-1) to (R-10).

In general formulas (Y-1) to (Y-6),
Z represents a hydrogen atom or an arbitrary substituent.
X ¹ represents an atom or group selected from C (X ² ) ₂ , NX ² , O, and S.
X ² represents a hydrogen atom or an arbitrary substituent.
Q ² represents a group containing a ring structure formed of carbon atoms, a group containing a cage structure formed of carbon atoms, or SiX ³ (3-n ² ).
X ³ represents a hydrogen atom or an arbitrary substituent.
n ² represents an integer of 1 to 10. However, when Q ² represents SiX ³ (3-n ² ), n ² represents an integer of 1 to 3.

In general formulas (R-1) to (R-10),
R ² represents a hydrogen atom or an arbitrary substituent.
When a plurality of R, R ² , X, Y, Z, X ¹ , X ³ and Q ² are present, they may be the same or different.
<2>
2. The compound represented by general formula (I), wherein the group represented by Q is a group represented by any one of general formulas (Q-1) to (Q-7). A film forming composition.

In the formula, each A independently represents a group selected from X, Y, R and a hydrogen atom in the general formula (I).
<3>
In the compound represented by the general formula (I), the group represented by Q is a group including a structure represented by the general formula (Q-1) or (Q-5); The composition for film formation as described.
<4>
It is obtained by polymerizing the compound represented by formula (I) in the presence of a transition metal catalyst or in the presence of a polymerization initiator, for film formation as described in any one of <1> to <3> above Composition.
<5>
Furthermore, the organic solvent is contained, The film formation composition in any one of said <1>-<4> characterized by the above-mentioned.
<6>
An insulating film formed using the film forming composition according to any one of <1> to <5>.
<7>
A metal diffusion barrier film formed using the film forming composition according to any one of <1> to <5>.
<8>
An electronic device having the insulating film according to <6> or the metal diffusion barrier film according to claim 7.

  Since the film-forming composition of the present invention is uniform and does not precipitate impurities, and an insulating film formed using the composition has a low dielectric constant and a high metal diffusion barrier property, an interlayer insulating film in electronic devices and the like can be obtained. Suitable as

  Hereinafter, the present invention will be described in detail.

  The film-forming composition of the present invention is characterized by containing a compound represented by the general formula (I) or a polymer thereof.

In general formula (I),
Q represents a group containing a ring structure formed of carbon atoms or a group containing a cage structure formed of carbon atoms.
l represents an integer of 1 to 10, an integer of 1 to 6 is preferable, an integer of 1 to 4 is more preferable, and an integer of 1 to 2 is most preferable.
m represents an integer of 0 to 10, an integer of 0 to 5 is preferable, and an integer of 0 to 2 is more preferable.
n represents an integer of 1 to 10, an integer of 1 to 6 is preferable, and an integer of 2 to 4 is more preferable.
X represents an arbitrary substituent, for example, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, a hydroxyl group, a mercapto group, an amino group having 0 to 10 carbon atoms, or an acylamino group having 1 to 10 carbon atoms. Group, carboxyl group and the like. These groups may further have an arbitrary substituent.
Y represents a group represented by any one of the following general formulas (Y-1) to (Y-6).
R represents a group represented by any one of the following general formulas (R-1) to (R-10).

In general formulas (Y-1) to (Y-6),
Q ² represents a group containing a ring structure formed of carbon atoms, a group containing a cage structure formed of carbon atoms, or SiX ³ (3-n ² ).
X ³ each independently represents a hydrogen atom or an arbitrary substituent.
Examples of the group represented by Q ² include an aromatic ring (such as a benzene ring and a naphthalene ring), a cycloalkyl ring (such as cyclohexane), and a cage hydrocarbon (such as adamantane), and a benzene ring or adamantane is preferable. The group represented by Q ² may further have an arbitrary substituent, and examples of the further substituent include an alkyl group, an amino group, an acylamino group, a hydroxyl group, and a mercapto group.
X ¹ represents an atom or group selected from C (X ² ) ₂ , NX ² , O, and S.
X ² each independently represents a hydrogen atom or an arbitrary substituent, and the optional substituent includes an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an acyl group having 1 to 10 carbon atoms. , Etc.
Z represents a hydrogen atom or an arbitrary substituent. Z is preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms, more preferably a hydrogen atom, a methyl group or a phenyl group, and preferably a hydrogen atom. Most preferred.
X ³ is preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms, and most preferably a methyl group.
n ² represents an integer of 1 to 10. n ² is preferably an integer of 1 to 5, more preferably 1 to 2 integer. However, when Q ² represents SiX ³ (3-n ² ), n ² represents an integer of 1 to 3, and n ² is more preferably an integer of 1 to 2.

In general formulas (R-1) to (R-10),
R ² each independently represents a hydrogen atom or an arbitrary substituent. The group represented by R ² is a hydrogen atom or an arbitrary substituent, and preferred substituents include, for example, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and 1 to 10 carbon atoms. Acyl group, hydroxyl group, carbamoyl group, thiocarbamoyl group, and the like. More preferred are hydrogen atom, methyl group, phenyl group, acetyl group, benzoyl group and the like. These groups may further have an arbitrary substituent.
When a plurality of R, X, Y, Z, X ¹ , X ² , X ³ and Q ² are present, they may be the same or different.

  In the compound represented by the general formula (I), the group represented by Q is represented by any one of the general formulas (Q-1) to (Q-7) from the viewpoints of dielectric constant, heat resistance and solubility. It is preferably a group.

  In the formula, A represents a group selected from X, Y, R and a hydrogen atom in the general formula (I).

  In the compound represented by the general formula (I), groups represented by Q are represented by the general formulas (Q-1) to (Q-4) in that the heat resistance of the insulating film to be formed is particularly high. A group including a structure is preferable, and a group including a structure represented by (Q-1) is more preferable. Moreover, it is more preferable that the insulating film is a group including a structure represented by the general formulas (Q-5) to (Q-7) in that the dielectric constant of the formed insulating film is low, and represented by (Q-5). It is more preferable that the group includes a structure to be formed.

  In the compound represented by the general formula (I), the group represented by Y is preferably a group represented by (Y-1), (Y-2) or (Y-3), It is more preferably a group represented by 1) or (Y-2).

  The “ring structure formed of carbon atoms” described in the present invention is a saturated or unsaturated hydrocarbon ring. These rings may have a substituent, and these substituents may further form a ring. Preferred examples include a benzene ring, a naphthalene ring, and a cyclohexane ring.

The “cage structure” described in the present invention is such that the volume is determined by a plurality of rings formed of covalently bonded atoms, and a point located within the volume cannot be separated from the volume without passing through the ring. Refers to a molecule. For example, an adamantane structure is considered a cage structure. In contrast, a cyclic structure having a single bridge such as norbornane (bicyclo [2,2,1] heptane) is not considered a cage structure because the ring of a single bridged cyclic compound does not define volume. .
The “cage structure formed of carbon atoms” is preferably composed of 11 to 30, more preferably 12 to 20, and still more preferably 12 to 14 carbon atoms. When a cage structure having 11 or more carbon atoms is used, the electronic polarization of the film is lowered, and the bulk of the cage structure is increased, so that a space is formed in the film and a sufficiently low dielectric constant is obtained. Moreover, there is an unexpected excellent effect that the mechanical strength of the film increases as the number of carbon atoms increases.
The carbon atom here does not include a linking group substituted with a cage structure or a carbon atom of the substituent. For example, 1-methyladamantane is composed of 10 carbon atoms.
The cage structure having 11 or more carbon atoms of the present invention is preferably a saturated aliphatic hydrocarbon from the viewpoint of a low dielectric constant, and examples thereof include diamantane, triamantane, tetramantane, dodecahedrane, and the like. Of these, diamantane is particularly preferable from the viewpoints of high mechanical strength, good solubility in a coating solvent, and suitability for production.
The cage structure in the present invention may contain either a saturated or unsaturated bond, and may contain a heteroatom such as oxygen, nitrogen or sulfur.

  The molecular weight of the compound represented by the general formula (I) is preferably 100 to 1500, more preferably 120 to 1000, and particularly preferably 150 to 500 from the viewpoint of solubility.

  Although the specific example of a compound represented with general formula (I) below is described, this invention is not limited to these.

The compound represented by the general formula (I) is, for example, Synth. Commun. 32; 14; 2004; 2549-2556,
J.Org.Chem.; 68; 18; 2003; 6952-6958, Chimica; 56; 10; 2002; 494-499, J.Organomet.Chem.; 587; 1; 1999; 67-73, Chem.Europ. J.; 7; 23; 2002; 5118-5134 and the like.
In still another method, it can be synthesized by converting an acetyl group or a vinyl group into an ethynyl group by a known method.

  Although the composition of this invention contains the compound or its polymer represented by general formula (I), it is preferable that the polymer of the compound represented by general formula (I) is included.

The reaction when the compound of the general formula (I) is polymerized to synthesize the polymer contained in the composition of the present invention is preferably a reaction of a polymerizable group substituted on the compound. Here, the polymerizable group refers to a reactive substituent that polymerizes the compound, and examples thereof include a group containing a polymerizable carbon-carbon double bond or carbon-carbon triple bond.
The polymerization reaction may be any polymerization reaction, and examples thereof include radical polymerization, cationic polymerization, anionic polymerization, ring-opening polymerization, polyaddition, transition metal catalyst polymerization, and thermal polymerization. A radical polymerization reaction is preferred.

  In producing an insoluble and infusible insulating film from the composition of the present invention, the reaction used is also preferably a reaction of a polymerizable group substituted with the compound. Here, the polymerizable group refers to a reactive substituent that polymerizes the compound, and examples thereof include a group containing a polymerizable carbon-carbon double bond or carbon-carbon triple bond. The polymerization reaction may be any polymerization reaction, and examples thereof include radical polymerization, cationic polymerization, anionic polymerization, ring-opening polymerization, polyaddition, and transition metal catalyst polymerization. Radical polymerization and thermal polymerization are preferred.

  The polymer of the compound used in the present invention is preferably a compound other than polyimide, that is, a compound having no polyimide bond, from the viewpoint of dielectric constant and hygroscopicity of the film.

The polymerization reaction of the compound used in the present invention is preferably carried out in the presence of a transition metal catalyst or in the presence of a polymerization initiator.
In the present invention, the polymerization reaction is preferably performed in the presence of a nonmetallic polymerization initiator. For example, a compound having a polymerizable carbon-carbon double bond or carbon-carbon triple bond may be polymerized in the presence of a polymerization initiator that exhibits activity by generating free radicals such as carbon radicals and oxygen radicals by heating. I can do it.
As the polymerization initiator, an organic peroxide or an organic azo compound is preferably used, and an organic peroxide is particularly preferable.
Examples of the organic peroxide include ketone peroxides such as perhexa H, peroxyketals such as perhexa TMH, hydroperoxides such as perbutyl H-69, park mill D, and perbutyl C, which are commercially available from Nippon Oil & Fats Co., Ltd. , Dialkyl peroxides such as perbutyl D, diacyl peroxides such as niper BW, peroxyesters such as perbutyl Z and perbutyl L, peroxydicarbonates such as perroyl TCP, diisobutyryl peroxide, cumylperoxyneodeca Noate, di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, di-sec-butyl peroxydicarbonate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, di (4 -T-Buchi Chlohexyl) peroxydicarbonate, di (2-ethylhexyl) peroxydicarbonate, t-hexylperoxyneodecanoate, t-butylperoxyneodecanoate, t-butylperoxyneoheptanoate, t- Hexyl peroxypivalate, t-butyl peroxypivalate, di (3,5,5-trimethylhexanoyl) peroxide, dilauroyl peroxide, 1,1,3,3-tetramethylbutylperoxy-2- Ethylhexanoate, disuccinic acid peroxide, 2,5-dimethyl-2,5-di (2-ethylhexanoylperoxy) hexane, t-hexylperoxy-2-ethylhexanoate, di (4-methylbenzoyl) ) Peroxide, t-butylperoxy-2-ethylhexanoate, (3-methylbenzoyl) peroxide, benzoyl (3-methylbenzoyl) peroxide, dibenzoyl peroxide, dibenzoyl peroxide, 1,1-di (t-butylperoxy) -2-methylcyclohexane, 1,1 -Di (t-hexylperoxy) -3,3,5-trimethylcyclohexane, 1,1-di (t-hexylperoxy) cyclohexane, 1,1-di (t-butylperoxy) cyclohexane, 2,2 -Di (4,4-di- (t-butylperoxy) cyclohexyl) propane, t-hexylperoxyisopropyl monocarbonate, t-butylperoxymaleic acid, t-butylperoxy-3,5,5,- Trimethylhexanoate, t-butylperoxylaurate, t-butylperoxyisopropyl Rumonocarbonate, t-butylperoxy 2-ethylhexyl monocarbonate, t-hexylperoxybenzoate, 2,5-di-methyl-2,5-di (benzoylperoxy) hexane, t-butylperoxyacetate, 2, 2-di (t-butylperoxy) butane, t-butylperoxybenzoate, n-butyl 4,4-di-t-butylperoxyvalerate, di (2-t-butylperoxyisopropyl) benzene, dicumyl Peroxide, di-t-hexyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, t-butylcumyl peroxide, di-t-butyl peroxide, p-methane Hydroperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, Diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide, 2,3-dimethyl-2,3-diphenylbutane, 2,4-dichloro Benzoyl peroxide, o-chlorobenzoyl peroxide, p-chlorobenzoyl peroxide, tris- (t-butylperoxy) triazine, 2,4,4-trimethylpentylperoxyneodecanoate, α-cumylperoxyneo Decanoate, t-amylperoxy 2-ethylhexanoate, t-butylperoxyisobutyrate, di-t-butylperoxyhexahydroterephthalate, di-t-butylperoxytrimethyladipate, di-3-methoxy Butyl peru Sidicarbonate, di-isopropylperoxydicarbonate, t-butylperoxyisopropylcarbonate, 1,6-bis (t-butylperoxycarbonyloxy) hexane, diethylene glycol bis (t-butylperoxycarbonate), t-hexylper Oxyneodecanoate or the like is preferably used.

  As organic azo compounds, azonitrile compounds such as V-30, V-40, V-59, V-60, V-65, and V-70, which are commercially available from Wako Pure Chemical Industries, Ltd., VA-080, Azoamide compounds such as VA-085, VA-086, VF-096, VAm-110 and VAm-111, cyclic azoamidine compounds such as VA-044 and VA-061, and azoamidine compounds such as V-50 and VA-057 2,2-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2-azobis (2,4-dimethylvaleronitrile), 2,2-azobis (2-methylpropionitrile), 2,2-azobis (2,4-dimethylbutyronitrile), 1,1-azobis (cyclohexane-1-carbonitrile), 1-[(1-cyano-1-methylethyl) azo Formamide, 2,2-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide}, 2,2-azobis [2-methyl-N- (2-hydroxy) Butyl) propionamide], 2,2-azobis [N- (2-propenyl) -2-methylpropionamide], 2,2-azobis (N-butyl-2-methylpropionamide), 2,2-azobis (N -Cyclohexyl-2-methylpropioamide), 2,2-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, 2,2-azobis [2- (2-imidazolin-2-yl) Propane] disulfate dihydrate, 2,2-azobis {2- [1- (2-hydroxyethyl) -2-imidazolin-2-yl] propane} dihy Drochloride, 2,2-azobis [2- [2-imidazolin-2-yl] propane], 2,2-azobis (1-imino-1-pyrrolidino-2-methylpropane) dihydrochloride, 2,2-azobis (2 -Methylpropionamidine) dihydrochloride, 2,2-azobis [N- (2-carboxyethyl) -2-methylpropionamidine] tetrahydrate, dimethyl 2,2-azobis (2-methylpropionate), 4, 4-Azobis (4-cyanovaleric acid), 2,2-azobis (2,4,4-trimethylpentane) and the like are preferably used.

In the present invention, the polymerization initiator may be used alone or in combination of two or more.
In the present invention, the amount of the polymerization initiator used is preferably 0.001 to 2 mol, more preferably 0.01 to 1 mol, particularly preferably 0.05 to 0.5 mol, relative to 1 mol of the compound.

The polymerization reaction of the compound used in the present invention is also preferably performed in the presence of a transition metal catalyst. Any transition metal catalyst may be used as long as it can cause the polymerization reaction of the compound used in the present invention to proceed. For example, a compound having a polymerizable carbon-carbon double bond or carbon-carbon triple bond, for example, Pd-based catalyst such as Pd (PPh ₃ ) ₄ , Pd (OAc) ₂ , Ziegler-Natta catalyst, nickel acetylacetonate, etc. polymerized using a Ni-based catalyst, W-based catalyst such as WCl _6, Mo-based catalysts such as MoCl _5, Ta catalysts such as TaCl _5, Nb-based catalyst such as NbCl _5, Rh-based catalyst, a Pt-based catalyst and the like It is preferable.

In the present invention, only one transition metal catalyst or a mixture of two or more transition metal catalysts may be used.
In the present invention, the amount of the transition metal catalyst used is preferably 0.001 to 2 mol, more preferably 0.01 to 1 mol, and particularly preferably 0.05 to 0.5 mol, relative to 1 mol of the compound.

  The polymerization reaction for producing the film-forming composition of the present invention from the compound represented by the general formula (I) is more preferably performed in the presence of a nonmetallic polymerization initiator.

  Two or more kinds of the compounds represented by the general formula (I) may be copolymerized, and have a compound represented by the general formula (I) and a reactive group (such as an ethynyl group, a vinyl group, or a diene functional group). Other reactive compounds may be copolymerized.

A solvent may be used for the polymerization reaction, and any solvent can be used as long as the raw material compound can be dissolved at a necessary concentration and does not adversely affect the characteristics of the film formed from the obtained polymer. Such a thing may be used. For example, alcohol solvents such as water, methanol, ethanol, propanol, etc., ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, acetophenone, ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, γ-butyrolactone, methyl benzoate, etc. Ester solvents, ether solvents such as dibutyl ether, anisole, tetrahydrofuran, aromatic hydrocarbon solvents such as toluene, xylene, mesitylene, 1,3,5-triisopropylbenzene, N-methylpyrrolidinone, dimethylacetamide, etc. Amide solvents, carbon tetrachloride, dichloromethane, chloroform, 1,2-dichloroethane, chlorobenzene, 1,2-dichlorobenzene, 1,2,4-trichlorobenzene Halogen-based solvents, hexane, heptane, octane, and aliphatic hydrocarbon solvents such as cyclohexane can be used for. Among these, preferred solvents are acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, acetophenone, ethyl acetate, propylene glycol monomethyl ether acetate, γ-butyrolactone, anisole, tetrahydrofuran, toluene, xylene, mesitylene, 1,3,5-trimethyl. Isopropylbenzene, 1,2-dichloroethane, chlorobenzene, 1,2-dichlorobenzene, 1,2,4-trichlorobenzene, more preferably tetrahydrofuran, γ-butyrolactone, anisole, toluene, xylene, mesitylene, 1,3,4 5-triisopropylbenzene, 1,2-dichloroethane, chlorobenzene, 1,2-dichlorobenzene, 1,2,4-trichlorobenzene, particularly preferably γ-butyl Lactones, anisole, mesitylene, 1,3,5-triisopropylbenzene, 1,2-dichlorobenzene, 1,2,4-trichlorobenzene. These may be used alone or in admixture of two or more.
The concentration of the compound in the reaction solution is preferably 1 to 50% by mass, more preferably 5 to 30% by mass, and particularly preferably 10 to 20% by mass.

Optimum conditions for the polymerization reaction in the present invention vary depending on the polymerization initiator, the compound, the type of solvent, the concentration, etc., but the internal temperature is preferably 0 ° C to 220 ° C, more preferably 40 ° C to 210 ° C, and particularly preferably 80 C. to 200.degree. C., preferably 1 to 50 hours, more preferably 2 to 20 hours, and particularly preferably 3 to 10 hours.
Moreover, in order to suppress the inactivation of the polymerization initiator by oxygen, it is preferable to make it react under inert gas atmosphere (for example, nitrogen, argon, etc.). The oxygen concentration during the reaction is preferably 100 ppm or less, more preferably 50 ppm or less, and particularly preferably 20 ppm or less.
The preferred range of the weight average molecular weight of the polymer obtained by polymerization is 1000 to 500000, more preferably 2000 to 300000, and particularly preferably 6000 to 200000.
The polymer of this invention may be used individually or may be used in mixture of 2 or more types.

The film-forming composition of the present invention may contain an organic solvent, and can also be used as a coating solution. Although it does not specifically limit as an organic solvent, For example, alcohol solvents, such as methanol, ethanol, 2-propanol, 1-butanol, 2-ethoxymethanol, 3-methoxypropanol, 1-methoxy-2-propanol, acetone, acetylacetone, methyl ethyl ketone , Ketone solvents such as methyl isobutyl ketone, 2-pentanone, 3-pentanone, 2-heptanone, 3-heptanone, cyclopentanone, cyclohexanone, ethyl acetate, propyl acetate, butyl acetate, isobutyl acetate, pentyl acetate, ethyl propionate , Ester solvents such as propyl propionate, butyl propionate, isobutyl propionate, propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate, γ-butyrolactone, diisopropyl Ether solvents such as pyr ether, dibutyl ether, ethyl propyl ether, anisole, phenetol, veratrol, aromatic hydrocarbon solvents such as mesitylene, ethylbenzene, diethylbenzene, propylbenzene, t-butylbenzene, N-methylpyrrolidinone, dimethylacetamide Examples of these solvents include amide solvents, and the like. These may be used alone or in admixture of two or more.
More preferable organic solvents are 1-methoxy-2-propanol, 2-propanol, acetylacetone, cyclohexanone, propylene glycol monomethyl ether acetate, butyl acetate, methyl lactate, ethyl lactate, γ-butyrolactone, anisole, mesitylene, and t-butylbenzene. Particularly preferred are 1-methoxy-2-propanol, cyclohexanone, propylene glycol monomethyl ether acetate, ethyl lactate, γ-butyrolactone, t-butylbenzene, and anisole.
The solid content concentration of the film forming composition of the present invention is preferably 0.2 to 30% by mass, more preferably 0.5 to 20% by mass, and particularly preferably 1 to 10% by mass.
Here, solid content is equivalent to all the components which comprise the insulating film obtained using this composition.

  The compound represented by the general formula (I) or a polymer thereof preferably has sufficient solubility in an organic solvent. The solubility is preferably 3% by mass or more, more preferably 5% by mass or more, and particularly preferably 10% by mass or more in cyclohexanone or anisole at 25 ° C.

The film-forming composition of the present invention preferably has a sufficiently low metal content such as impurities. The metal concentration of the film-forming composition can be measured with high sensitivity by the ICP-MS method. In that case, the metal content other than the transition metal is preferably 30 ppm or less, more preferably 3 ppm or less, particularly preferably 300 ppb or less. It is. In addition, the transition metal has a high catalytic ability to promote oxidation, and from the viewpoint of increasing the dielectric constant of the film obtained in the present invention by an oxidation reaction in the prebaking and thermosetting processes, the content is preferably smaller. Preferably it is 10 ppm or less, More preferably, it is 1 ppm or less, Most preferably, it is 100 ppb or less.
The metal concentration of the film forming composition can also be evaluated by performing total reflection X-ray fluorescence measurement on the film obtained using the film forming composition of the present invention. When W line is used as the X-ray source, K, Ca, Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn, and Pd can be observed as metal elements, and each of them is 100 × 10 ¹⁰ atoms · cm ^{−. It} is preferably ² or less, more preferably 50 × 10 ¹⁰ atoms · cm ⁻² or less, and particularly preferably 10 × 10 ¹⁰ atoms · cm ⁻² or less. Further, Br which is halogen can be observed, and the residual amount is preferably 10,000 × 10 ¹⁰ atoms · cm ⁻² or less, more preferably 1000 × 10 ¹⁰ atoms · cm ⁻² or less, and particularly preferably 400 × 10 ¹⁰ atoms / cm ^{2. -It} is cm- ² or less. Further, although Cl can be observed as halogen, the remaining amount is preferably 100 × 10 ¹⁰ atoms · cm ⁻² or less, more preferably 50 × 10 ¹⁰ atoms · cm ·, from the viewpoint of damaging the CVD apparatus, the etching apparatus, and the like. cm ⁻² or less, particularly preferably 10 × 10 ¹⁰ atoms · cm ⁻² or less.

  Furthermore, the composition for forming a film of the present invention includes a radical generator, colloidal silica, and the like within a range that does not impair the properties of the obtained insulating film (heat resistance, dielectric constant, mechanical strength, coatability, adhesion, etc.). You may add additives, such as surfactant, a silane coupling agent, and an adhesion promoter.

  The radical generator refers to a compound that generates radicals such as carbon, oxygen, and nitrogen by irradiation with heat or light energy, and has a function of accelerating the dural reaction.

Any colloidal silica may be used in the present invention. For example, it is a dispersion in which high-purity silicic acid is dispersed in a hydrophilic organic solvent or water, and usually has an average particle size of 5 to 30 nm, preferably 10 to 20 nm, and a solid content concentration of about 5 to 40% by mass. Can be used.
The colloidal silica used in the present invention may be one type or two or more types.

  Any surfactant may be used in the present invention, and examples thereof include nonionic surfactants, anionic surfactants, cationic surfactants, silicone surfactants, and fluorine-containing interfaces. Activators, polyalkylene oxide surfactants, and acrylic surfactants can be mentioned. The surfactant used in the present invention may be one type or two or more types. As the surfactant, silicone surfactants, nonionic surfactants, fluorine-containing surfactants, and acrylic surfactants are preferable, and silicone surfactants are particularly preferable.

  The addition amount of the surfactant used in the present invention is preferably 0.01% by mass or more and 1% by mass or less, and 0.1% by mass or more and 0.5% by mass or less with respect to the total amount of the film-forming coating solution. More preferably.

  In the present invention, the silicon-based surfactant is a surfactant containing at least one Si atom. The silicon-based surfactant used in the present invention may be any silicon-based surfactant, and preferably has a structure containing alkylene oxide and dimethylsiloxane. A structure including the following chemical formula is more preferable.

In the formula, R ³ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, x is an integer of 1 to 20, and m ′ and n ′ are each independently an integer of 2 to 100. A plurality of R ³ may be the same or different.

  Examples of the silicon-based surfactant used in the present invention include BYK306, BYK307 (manufactured by Big Chemie), SH7PA, SH21PA, SH28PA, SH30PA (manufactured by Toray Dow Corning Silicone), Troysol S366 (manufactured by Troy Chemical). Can be mentioned.

  Any nonionic surfactant may be used as the nonionic surfactant used in the present invention. For example, polyoxyethylene alkyl ethers, polyoxyethylene aryl ethers, polyoxyethylene dialkyl esters, sorbitan fatty acid esters, fatty acid-modified polyoxyethylenes, polyoxyethylene-polyoxypropylene block copolymers, etc. Can do.

  As the fluorine-containing surfactant used in the present invention, any fluorine-containing surfactant may be used. For example, perfluorooctyl polyethylene oxide, perfluorodecyl polyethylene oxide, perfluorodecyl polyethylene oxide and the like can be mentioned.

  The acrylic surfactant used in the present invention may be any acrylic surfactant. For example, a (meth) acrylic acid type copolymer etc. are mentioned.

Any silane coupling agent may be used in the present invention. For example, 3-glycidyloxypropyltrimethoxysilane, 3-aminoglycidyloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3- Glycidyloxypropylmethyldimethoxysilane, 1-methacryloxypropylmethyldimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N -(2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-triethoxysilylpropyltriethylenetriamine, 10- Trimethoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6 -Diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyl Triethoxysilane, - bis (oxyethylene) -3-aminopropyltrimethoxysilane, N- bis (oxyethylene) -3-aminopropyltriethoxysilane and the like. The silane coupling agent used in the present invention may be one type or two or more types.
The preferred amount of the silane coupling agent is 10 parts by mass or less, particularly 0.05 to 5 parts by mass with respect to 100 parts by mass of the total solid content.

Any adhesion promoter may be used in the present invention. For example, trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane , Γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, trimethoxyvinylsilane, γ-aminopropyltriethoxysilane, aluminum monoethylacetoacetate diisopropylate, vinyltris (2 -Methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3- Chloropropyltrimethoxy Sisilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, trimethylchlorosilane, dimethylvinylchlorosilane, methyldiphenylchlorosilane, chloromethyldimethylchlorosilane, trimethylmethoxysilane, dimethyldiethoxysilane, methyldimethoxysilane, dimethyl Vinylethoxysilane, diphenyldimethoxysilane, phenyltriethoxysilane, hexamethyldisilazane, N, N′-bis (trimethylsilyl) urea, dimethyltrimethylsilylamine, trimethylsilylimidazole, vinyltrichlorosilane, benzotriazole, benzimidazole, indazole, Imidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-merca DOO benzoxazole, urazole, thiouracil, mercaptoimidazole, mercaptopyrimidine, 1,1-dimethylurea, 1,3-dimethylurea, may be mentioned thiourea compounds.
The preferable use amount of the adhesion promoter is preferably 10 parts by mass or less, particularly 0.05 to 5 parts by mass with respect to 100 parts by mass of the total solid content.

  A film obtained using the film forming composition of the present invention is obtained by applying the film forming composition to a substrate by any method such as spin coating, roller coating, dip coating, or scanning, and then using a solvent. Can be formed by heat treatment. Heating for drying the solvent is preferably performed at 100 to 250 ° C. for 1 to 5 minutes. As a method of applying to the substrate, a spin coating method or a scanning method is preferable. Particularly preferred is the spin coating method. For spin coating, commercially available equipment can be used. For example, the clean track series (manufactured by Tokyo Electron), D-spin series (manufactured by Dainippon Screen), SS series or CS series (manufactured by Tokyo Ohka Kogyo) can be preferably used. The spin coating conditions may be any rotational speed, but from the viewpoint of in-plane uniformity of the film, a rotational speed of about 1300 rpm is preferable for a 300 mm silicon substrate. The film forming composition solution discharging method may be either dynamic discharging for discharging the composition solution onto a rotating substrate or static discharging for discharging the composition solution onto a stationary substrate. Dynamic discharge is preferable from the viewpoint of in-plane uniformity. Further, from the viewpoint of suppressing the consumption of the film-forming composition, it is also possible to use a method in which only the solvent is preliminarily discharged onto the substrate to form a liquid film, and then the composition is discharged from the liquid film. . The spin coating time is not particularly limited, but is preferably within 180 seconds from the viewpoint of throughput. Further, from the viewpoint of transporting the substrate, it is also preferable to perform processing (edge rinse, back rinse) so as not to leave the film at the edge portion of the substrate. The method of heat treatment is not particularly limited, but it is possible to apply commonly used hot plate heating, heating method using a furnace, light irradiation heating using a xenon lamp by RTP (Rapid Thermal Processor), etc. Can do. A heating method using hot plate heating or furnace is preferable. A commercially available device can be preferably used as the hot plate, and the clean track series (manufactured by Tokyo Electron), D-Spin series (manufactured by Dainippon Screen), SS series or CS series (manufactured by Tokyo Ohka Kogyo) can be preferably used. As the furnace, α series (manufactured by Tokyo Electron) and the like can be preferably used.

It is particularly preferable that the compound of the general formula (I) or a polymer thereof is cured by heat treatment after coating on the substrate. For example, a polymerization reaction during post-heating of the carbon triple bond remaining in the polymer can be used. The conditions for this post-heat treatment are preferably 100 to 450 ° C., more preferably 200 to 420 ° C., particularly preferably 350 to 400 ° C., preferably 1 minute to 2 hours, more preferably 10 minutes to 1.5 ° C. Time, particularly preferably in the range of 30 minutes to 1 hour. The post-heating treatment may be performed in several times. Further, this post-heating is particularly preferably performed in a nitrogen atmosphere in order to prevent thermal oxidation by oxygen.
Moreover, in this invention, you may make it harden | cure by raise | generating the polymerization reaction of the carbon triple bond which remains in a polymer by irradiating a high energy ray instead of heat processing. Examples of high energy rays include electron beams, ultraviolet rays, and X-rays, but are not particularly limited to these methods.
The energy when an electron beam is used as the high energy beam is preferably 50 keV or less, more preferably 30 keV or less, and particularly preferably 20 keV or less. The total dose of the electron beam is preferably 5 μC / cm ² or less, more preferably ² μC / cm ² or less, and particularly preferably 0 to 1 μC / cm ² or less. The substrate temperature at the time of irradiation with an electron beam is preferably 0 to 450 ° C, more preferably 0 to 400 ° C, and particularly preferably 0 to 350 ° C. The pressure is preferably 0 to 133 kPa, more preferably 0 to 60 kPa, and particularly preferably 0 to 20 kPa. From the viewpoint of preventing oxidation of the polymer of the present invention, the atmosphere around the substrate is preferably an inert atmosphere such as Ar, He, or nitrogen. Further, a gas such as oxygen, hydrocarbon, or ammonia may be added for the purpose of reaction with plasma, electromagnetic waves, or chemical species generated by interaction with an electron beam. The electron beam irradiation in the present invention may be performed a plurality of times. In this case, the electron beam irradiation conditions need not be the same each time, and may be performed under different conditions each time.
Ultraviolet rays may be used as the high energy rays. The irradiation wavelength region when using ultraviolet rays is preferably 190 to 400 nm, and the output is preferably 0.1 to 2000 mWcm ⁻² immediately above the substrate. The substrate temperature at the time of ultraviolet irradiation is preferably 250 to 450 ° C., more preferably 250 to 400 ° C., and particularly preferably 250 to 350 ° C. From the viewpoint of preventing oxidation of the polymer of the present invention, the atmosphere around the substrate is preferably an inert atmosphere such as Ar, He, or nitrogen. Further, the pressure at that time is preferably 0 to 133 kPa.

  The film obtained by using the film forming composition of the present invention may be used alone as an interlayer insulating film having a copper diffusion barrier property, or in combination with another interlayer insulating film as a copper diffusion barrier film. Although it may be used, it is preferable to form the insulating film of the present invention as the copper diffusion barrier film after forming the copper wiring in the interlayer insulating film having a low dielectric constant from the viewpoint of lowering the effective dielectric constant.

  The film obtained using the film forming composition of the present invention can be used for various purposes. For example, it is suitable as an insulating film for semiconductor devices such as LSI, system LSI, DRAM, SDRAM, RDRAM, and D-RDRAM, and electronic parts such as multichip module multilayer wiring boards, interlayer insulating film for semiconductor, etching stopper film, surface protection In addition to films, buffer coat films, LSI passivation films, alpha ray blocking films, flexographic printing plate cover lay films, overcoat films, flexible copper clad cover coats, solder resist films, liquid crystal alignment films, etc. I can do it.

  The following examples illustrate the invention and are not intended to limit its scope.

<Synthesis Example 1>
Macromolecules, 36, 16 (2003), 5947-5959 (1a) synthesized according to the method described in 5947-5959 and Acta. Chem. Scand. Ser. B; 42; 7; 1988; 448-454 13.1 g of (Ib) synthesized according to the method was added to 100 ml of dimethylacetamide, 9 ml of pyridine was further added, and the mixture was stirred at room temperature for 5 hours. The reaction solution was poured into 200 ml of 1N hydrochloric acid and extracted with 200 ml of ethyl acetate.
After dehydration with anhydrous magnesium sulfate, concentration under reduced pressure, and purification by column chromatography, 8.92 g of Exemplified Compound (I-9) was obtained.

  Next, 2 g of Exemplified Compound (I-9), 0.19 g of dicumyl peroxide (Perk Mill D, manufactured by NOF Corporation) and 5 ml of t-butylbenzene were stirred and polymerized at an internal temperature of 150 ° C. for 7 hours under a nitrogen stream. . After the reaction solution was brought to room temperature, it was added to 30 ml of isopropyl alcohol, and the precipitated solid was filtered and thoroughly washed with isopropyl alcohol. 0.30 g of polymer (A) having a weight average molecular weight of about 6000 was obtained.

<Example 1-1>
A coating solution was prepared by completely dissolving 0.30 g of the polymer (A) in 10 g of cyclohexanone. The solution was filtered through a 0.1 μm tetrafluoroethylene filter, spin-coated on a silicon wafer, the coating was heated on a hot plate at 200 ° C. for 60 seconds under a nitrogen stream, and the solvent was dried. Furthermore, as a result of baking for 40 minutes in a 400 ° C. oven purged with nitrogen, a uniform film having a thickness of 0.2 μm and no defects was obtained. The relative dielectric constant of the film was calculated from the capacitance value at 1 MHz by using a mercury probe manufactured by Four Dimensions and an HP4285ALCR meter manufactured by Yokogawa Hewlett-Packard.

<Example 1-2>
A silicon wafer is used which is first coated by sputtering with a Ti-W adhesion promoter layer (100 ml) and then with copper (500 nm).
The coating solution was applied to the wafer (Cu surface) in the same manner as in Example 1-1, and this coating film was heated on a hot plate at 200 ° C. for 60 seconds under a nitrogen stream to dry the solvent, followed by further nitrogen substitution. Baking for 50 minutes in an oven at 400 ° C. The surface of the membrane obtained in this manner was found to be smooth by microscopic examination. Copper particles or clusters could not be detected on this surface.

<Comparative Example 1-1>
Using the resin solution A of Example 2 as a coating solution, the same test as in Example 1-1 was performed.
A uniform film having no film thickness of 0.2 μm was obtained. The relative dielectric constant of the film was 2.86.

<Comparative Example 1-2>
Using the resin solution A of Example 2 as a coating solution, the same test as in Example 1-2 was performed. After heating, the surface of the obtained film was examined with a microscope, and diffused copper was visible.

  It can be seen that the insulating film produced from the composition of the present invention has superior performance as a metal diffusion barrier film compared to the comparative example.

Claims (8)

A film-forming composition comprising a compound represented by formula (I) or a polymer thereof.

In general formula (I),
Q represents a group containing a ring structure formed of carbon atoms or a group containing a cage structure formed of carbon atoms.
l represents an integer of 1 to 10,
m represents an integer of 0 to 10,
n represents an integer of 1 to 10.
X represents an arbitrary substituent.
Y represents a group represented by any one of the following general formulas (Y-1) to (Y-6).
R represents a group represented by any one of the following general formulas (R-1) to (R-10).

In general formulas (Y-1) to (Y-6),
Z represents a hydrogen atom or an arbitrary substituent.
X ¹ represents an atom or group selected from C (X ² ) ₂ , NX ² , O, and S.
X ² represents a hydrogen atom or an arbitrary substituent.
Q ² represents a group containing a ring structure formed of carbon atoms, a group containing a cage structure formed of carbon atoms, or SiX ³ (3-n ² ).
X ³ represents a hydrogen atom or an arbitrary substituent.
n ² represents an integer of 1 to 10. However, when Q ² represents SiX ³ (3-n ² ), n ² represents an integer of 1 to 3.

In general formulas (R-1) to (R-10),
R ² represents a hydrogen atom or an arbitrary substituent.
When a plurality of R, R ² , X, Y, Z, X ¹ , X ³ and Q ² are present, they may be the same or different. 2. The compound represented by general formula (I), wherein the group represented by Q is a group represented by any one of general formulas (Q-1) to (Q-7). A film forming composition.

In the formula, each A independently represents a group selected from X, Y, R and a hydrogen atom in the general formula (I).   3. The compound represented by the general formula (I), wherein the group represented by Q is a group including a structure represented by the general formula (Q-1) or (Q-5). A film forming composition.   The film-forming composition according to any one of claims 1 to 3, which is obtained by polymerizing the compound represented by formula (I) in the presence of a transition metal catalyst or in the presence of a polymerization initiator.   Furthermore, the organic solvent is contained, The composition for film formation in any one of Claims 1-4 characterized by the above-mentioned.   The insulating film formed using the film forming composition in any one of Claims 1-5.   A metal diffusion barrier film formed by using the film-forming composition according to claim 1.   An electronic device having the insulating film according to claim 6 or the metal diffusion barrier film according to claim 7.