JP5817593B2 - Aluminum body forming composition and aluminum body forming method - Google Patents

Description

  The present invention relates to an aluminum body forming composition and an aluminum body forming method.

The metal aluminum material is widely used for the application of the electrode wiring of the semiconductor device represented by DRAM, the application of the reflection film of the optical device, etc. because of its high conductivity and high optical characteristics.
In general, sputtering methods, vapor deposition methods, and chemical vapor deposition methods have been the mainstream methods for forming aluminum films (Patent Document 1). However, these methods are expensive because they require expensive devices such as a vacuum chamber and a high-voltage current device. In addition, there is a problem that it is difficult to apply to a large-diameter substrate. Furthermore, with the recent miniaturization of semiconductor devices and the complication of the shape of optical devices, these conventional methods also have the problem of generating defects in the film and reducing step coverage.
On the other hand, the film formation method by coating does not require an expensive apparatus, the film formation cost is relatively low, and good film formation on a narrow trench substrate is also possible using the penetration force of the liquid material. I can expect.
For example, a conductive film-forming composition containing a complex of an amine compound and aluminum hydride (hereinafter also referred to as “alane-amine complex”) and an organic solvent, and the conductive film-forming composition on the substrate A method of forming an aluminum film by applying the coating onto the substrate and then heating and / or irradiating with light has been reported (Patent Document 2).
In addition, a liquid composition containing a titanium compound or the like is applied to a substrate under a first pressure, the substrate is heated under a second pressure, and then a complex of an amine compound and aluminum hydride is formed on the substrate. In addition, an aluminum film forming method in which a composition for forming an aluminum film containing a solvent and a solvent is applied and the substrate is subjected to heat treatment has been reported (Patent Document 3).

JP 2000-86673 A Japanese Patent Laid-Open No. 2004-6197 JP 2006-237392 A

J. et al. K. Ruff et al. Amer. Chem. Soc. 82, 2141 pages, 1960

However, when a conventional alane / amine complex (for example, a complex of triethylamine and aluminum hydride) is used, the vapor pressure of the alane / amine complex is high. There was a problem that the amount of the amine complex was increased. When the volatilization amount of the alane-amine complex increases, there arises a problem that the coating film becomes uneven in the coating process or the film forming apparatus is contaminated. Furthermore, contamination of the film forming apparatus has caused the resulting aluminum film to be contaminated.
In view of the above problems, the object of the present invention is to form an aluminum body that does not cause unevenness in the coating film and does not contaminate the film forming apparatus because the amount of the alan-amine complex that volatilizes in the coating step and the heating step is small. It is to provide a composition for use.

（上記一般式（１）においてＲ^１は炭素数１〜８のアルキル基、アルケニル基、もしくはアルキニル基、または炭素数３〜６の脂環式基である。Ｒ^２およびＲ^３はそれぞれ独立して、炭素数１〜８のアルキル基、アルケニル基、もしくはアルキニル基、または炭素数３〜６の脂環式基でもよく、Ｒ^２およびＲ^３が互いに連結して炭素数４以上の環状構造を有する一つの炭化水素基を形成していてもよい。ただし、Ｒ^２およびＲ^３がアルキル基、アルケニル基、アルキニル基、または脂環式基である場合、Ｒ^１、Ｒ^２、Ｒ^３のうち少なくとも１つは炭素数３以上の基である。また、Ｒ^１、Ｒ^２、Ｒ^３の全てが炭素数４以下のアルキル基、アルケニル基、もしくはアルキニル基の場合、Ｒ ^１ 、Ｒ ^２ 、Ｒ ^３ の全てが炭素数３〜４でかつ直鎖状のアルキル基、アルケニル基、もしくはアルキニル基である。）
［２］ さらに、錯体を形成していない第二のアミン化合物を含有する前記［１］に記載のアルミニウム体形成用組成物。
［３］ さらに、チタン化合物を含有する前記［１］または［２］に記載のアルミニウム体形成用組成物。
［４］ 基体上に、前記［１］〜［３］のいずれかに記載されたアルミニウム体形成用組成物を塗布し、次いで加熱及び／又は光照射することにより、前記基体上にアルミニウム体を形成する、アルミニウム体形成方法。
［５］ 上記基体が、予め、基体本体に、チタン、パラジウム、及びアルミニウムからなる群より選ばれる少なくとも一種の金属原子を含む有機金属化合物（ただし、アミン化合物と水素化アルミニウムとの錯体を除く。）を含有する下地膜形成用組成物を塗布し、次いで該下地膜形成用組成物を加熱してなるものである、前記［４］に記載のアルミニウム体形成方法。 As a result of intensive studies to solve the above problems, the present inventor is a composition for forming an aluminum body containing a complex of a specific first amine compound and aluminum hydride, and an organic solvent, According to the aluminum body forming composition having a vapor pressure of 5.0 Torr or less at 50 ° C., it was found that the above-mentioned problems can be solved, and the present invention was completed.
That is, the present invention provides the following [1] to [5].
[1] A composition for forming an aluminum body containing a complex of a first amine compound and aluminum hydride, and an organic solvent, wherein the complex has a vapor pressure of 5.0 Torr or less at 50 ° C., and A composition for forming an aluminum body, wherein the first amine compound is represented by the following general formula (1).

(In the general formula (1), R ¹ is an alkyl group having 1 to 8 carbon atoms, an alkenyl group, or an alkynyl group, or an alicyclic group having 3 to 6 carbon atoms. R ² and R ³ are each independently selected. An alkyl group having 1 to 8 carbon atoms, an alkenyl group, or an alkynyl group, or an alicyclic group having 3 to 6 carbon atoms, and R ² and R ³ are connected to each other to form a cyclic structure having 4 or more carbon atoms. One of the hydrocarbon groups may be formed, provided that when R ² and R ³ are an alkyl group, an alkenyl group, an alkynyl group, or an alicyclic group, among R ¹ , R ² , and R ³ At least one is a group having 3 or more carbon atoms, and when all of R ¹ , R ² , and R ³ are alkyl groups, alkenyl groups, or alkynyl groups having 4 or less carbon atoms, R ¹ , R ² , R in all of ³ 3 to 4 carbon atoms One straight chain alkyl group, an alkenyl group or alkynyl group.)
[2] The composition for forming an aluminum body according to [1], further including a second amine compound not forming a complex.
[3] The composition for forming an aluminum body according to [1] or [2], further including a titanium compound.
[4] An aluminum body is formed on the substrate by applying the aluminum body-forming composition described in any one of [1] to [3] on the substrate and then heating and / or irradiating with light. A method for forming an aluminum body.
[5] An organic metal compound containing at least one metal atom selected from the group consisting of titanium, palladium, and aluminum (excluding a complex of an amine compound and aluminum hydride). The composition for forming an aluminum body according to [4], wherein the composition for forming a base film is applied, and then the composition for forming the base film is heated.

  The composition for forming an aluminum body of the present invention does not cause unevenness in the coating film in the coating step because the amount of the alane / amine complex that volatilizes in the coating step and the heating step is small. In addition, contamination of the film forming apparatus can be prevented.

The composition for forming an aluminum body of the present invention contains a complex of a first amine compound and aluminum hydride, and an organic solvent.
Here, aluminum hydride (often commonly referred to as “alane”) is a compound composed of aluminum and a hydrogen atom, and is generally represented by AlH ₃ .

The complex of the first amine compound and aluminum hydride contained in the composition for forming an aluminum body of the present invention is, for example, J.A. K. Ruff et al. Amer. Chem. Soc. 82, page 2141, 1960, G.C. W. Fraser et al. Chem. Soc. 3742, 1963 and J. Am. L. Atwood et al., J. MoI. Amer. Chem. Soc. 113, 8133, 1991 and the like.
Specifically, for example, a hydrochloride of an amine compound is added to a suspension of lithium aluminum hydride in diethyl ether and reacted, for example, in N ₂ gas with stirring at room temperature. The reaction temperature, reaction solvent, and the like are appropriately selected according to the desired type of complex of the first amine compound and aluminum hydride.

（上記一般式（１）においてＲ^１は炭素数１〜８のアルキル基、アルケニル基、もしくはアルキニル基、または炭素数３〜６の脂環式基である。Ｒ^２およびＲ^３はそれぞれ独立して、炭素数１〜８のアルキル基、アルケニル基、もしくはアルキニル基、または炭素数３〜６の脂環式基でもよく、Ｒ^２およびＲ^３が互いに連結して炭素数４以上の環状構造を有する一つの炭化水素基を形成していてもよい。ただし、Ｒ^２およびＲ^３がアルキル基、アルケニル基、アルキニル基、または脂環式基である場合、Ｒ^１、Ｒ^２、Ｒ^３のうち少なくとも１つは炭素数３以上の基である。また、Ｒ^１、Ｒ^２、Ｒ^３の全てが炭素数４以下のアルキル基、アルケニル基、もしくはアルキニル基の場合、Ｒ ^１ 、Ｒ ^２ 、Ｒ ^３ の全てが炭素数３〜４でかつ直鎖状のアルキル基、アルケニル基、もしくはアルキニル基である。）
上記Ｒ^１、Ｒ^２、Ｒ^３で表される炭素数１〜８のアルキル基としては、具体的には、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基等を挙げることができる。
上記炭素数１〜８のアルケニル基としては、具体的にはビニル基、アリル基、クロチル基等を挙げることができる。
上記炭素数１〜８のアルキニル基としては、具体的にはエチニル基等を挙げることができる。
Ｒ^１、Ｒ^２、Ｒ^３の全てが炭素数４以下のアルキル基、アルケニル基、もしくはアルキニル基の場合、全てが直鎖状のアルキル基、アルケニル基、もしくはアルキニル基である。Ｒ^１、Ｒ^２、Ｒ^３の全てが炭素数４以下の分枝鎖状のアルキル基、アルケニル基、もしくはアルキニル基であると、得られる錯体の蒸気圧が、５０℃において５．０Ｔｏｒｒを超える場合がある。
上記Ｒ^１、Ｒ^２、またはＲ^３が炭素数１〜８のアルキル基、アルケニル基、もしくはアルキニル基の場合、蒸気圧を低くする観点から直鎖状が好ましい。また、蒸気圧を低くする観点から炭素数は、より好ましくは２〜８であり、特に好ましくは３〜８である。また、アルキル基、アルケニル基、及びアルキニル基の中でも、蒸気圧を低くする観点から、アルキル基が好ましい。
上記Ｒ^１、Ｒ^２、Ｒ^３で表される炭素数３〜６の脂環式基としては、具体的にはシクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基等を挙げることができる。 The first amine compound contained in the composition for forming an aluminum body of the present invention is represented by the following general formula (1).

(In the general formula (1), R ¹ is an alkyl group having 1 to 8 carbon atoms, an alkenyl group, or an alkynyl group, or an alicyclic group having 3 to 6 carbon atoms. R ² and R ³ are each independently selected. An alkyl group having 1 to 8 carbon atoms, an alkenyl group, or an alkynyl group, or an alicyclic group having 3 to 6 carbon atoms, and R ² and R ³ are connected to each other to form a cyclic structure having 4 or more carbon atoms. One of the hydrocarbon groups may be formed, provided that when R ² and R ³ are an alkyl group, an alkenyl group, an alkynyl group, or an alicyclic group, among R ¹ , R ² , and R ³ At least one is a group having 3 or more carbon atoms, and when all of R ¹ , R ² , and R ³ are alkyl groups, alkenyl groups, or alkynyl groups having 4 or less carbon atoms, R ¹ , R ² , R in all of ³ 3 to 4 carbon atoms One straight chain alkyl group, an alkenyl group or alkynyl group.)
Specific examples of the alkyl group having 1 to 8 carbon atoms represented by R ¹ , R ² and R ³ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, An octyl group etc. can be mentioned.
Specific examples of the alkenyl group having 1 to 8 carbon atoms include a vinyl group, an allyl group, and a crotyl group.
Specific examples of the alkynyl group having 1 to 8 carbon atoms include an ethynyl group.
When all of R ¹ , R ² , and R ³ are alkyl groups, alkenyl groups, or alkynyl groups having 4 or less carbon atoms , all are linear alkyl groups, alkenyl groups, or alkynyl groups. When all of R ¹ , R ² , and R ³ are branched alkyl groups, alkenyl groups, or alkynyl groups having 4 or less carbon atoms, the vapor pressure of the resulting complex exceeds 5.0 Torr at 50 ° C. There is a case.
When R ¹ , R ² , or R ³ is an alkyl group, alkenyl group, or alkynyl group having 1 to 8 carbon atoms, a straight chain is preferable from the viewpoint of lowering the vapor pressure. Further, from the viewpoint of lowering the vapor pressure, the carbon number is more preferably 2 to 8, particularly preferably 3 to 8. Of the alkyl group, alkenyl group, and alkynyl group, an alkyl group is preferred from the viewpoint of lowering the vapor pressure.
Specific examples of the alicyclic group having 3 to 6 carbon atoms represented by R ¹ , R ² , and R ³ include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.

Specific examples of the amine compound represented by the general formula (1) include, for example, tri-n-propylamine, tri-n-butylamine, tri-2-methylbutylamine, tri-n-hexylamine, and tricyclohexylamine. , Tri (2-ethylhexyl) amine, trioctylamine, dimethyloctylamine, dimethylcyclohexylamine, N-methylpyrrolidine and the like.
Among these, tri-n-propylamine, tri-n-butylamine, dimethyloctylamine, dimethylcyclohexylamine, and N-methylpyrrolidine are preferable.
These amine compounds can be used alone or in combination of two or more.

The vapor pressure of the complex of the first amine compound and aluminum hydride is 5.0 Torr or less at 50 ° C., more preferably 4.5 Torr or less, and particularly preferably 4.0 Torr or less.
When the vapor pressure of the complex exceeds 5.0 Torr, the amount of amine-alanine complex that volatilizes increases in the coating step and the heating step. As a result, the obtained film thickness is reduced, the uniformity of the film is inferior, and the obtained film-like aluminum body is easily peeled off from the substrate. Further, the deposition apparatus is contaminated by the volatilized amine-alanic complex.

  The organic solvent contained in the composition for forming an aluminum body used in the method of the present invention dissolves the complex of the first amine compound and aluminum hydride, and any additional components described below, and If it does not react with these, it will not specifically limit. For example, a hydrocarbon solvent, an ether solvent, other polar solvents, etc. can be used.

  Examples of the hydrocarbon solvent include n-pentane, cyclopentane, n-hexane, cyclohexane, n-heptane, cycloheptane, n-octane, cyclooctane, decane, cyclodecane, dicyclopentadiene hydride, benzene, toluene, Xylene, durene, indene, tetrahydronaphthalene, decahydronaphthalene, squalane and the like can be mentioned.

Examples of the ether solvent include diethyl ether, dipropyl ether, dibutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol methyl ethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, tetrahydrofuran, tetrahydropyran, and bis. (2-methoxyethyl) ether, p-dioxane, anisole, 2-methylanisole, 3-methylanisole, 4-methylanisole, fentol, 2-methylfentol, 3-methylfentol, 4-methylfentol, Examples include veratrol, 2-ethoxyanisole, and 1,4-dimethoxybenzene.
Examples of the polar solvent include methylene chloride and chloroform.
These organic solvents can be used alone or in admixture of two or more.

  Among these, it is preferable to use a hydrocarbon solvent or a mixed solvent of a hydrocarbon solvent and an ether solvent from the viewpoints of solubility and stability of the formed solution. At that time, hydrocarbon solvents include n-pentane, cyclopentane, n-hexane, cyclohexane, n-heptane, cycloheptane, n-octane, benzene, toluene, xylene, cumene, n-butylbenzene, and s-butylbenzene. , T-butylbenzene, cymene, t-butylxylene, and tetralin are preferably used. As ether solvents, diethyl ether, dipropyl ether, dibutyl ether, ethylene glycol diethyl ether, ethylene glycol methyl ethyl ether, tetrahydrofuran, tetrahydropyran, anisole, 2-methylanisole, 3-methylanisole, 4-methylanisole, fentol , Veratrol, 2-ethoxyanisole and 1,4-dimethoxybenzene are preferably used.

The composition for forming an aluminum body of the present invention may further contain a second amine compound not forming a complex. By containing the second amine compound, storage stability and material stability at high temperatures can be improved.
The second amine compound is a monoamine compound or a polyamine compound.
As the monoamine compound, for example, the same amine compound as the first amine compound described above can be used.
Furthermore, a monoamine compound represented by the following general formula (2) (excluding the amine compound represented by the above general formula (1)) and other monoamine compounds can also be used.
R ⁴ R ⁵ R ⁶ N (2)
(In the general formula (2), R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or an aralkyl group.)
The alkyl group, alkenyl group, or alkynyl group of R ⁴ , R ^5, and R ^{6 in} the general formula (2) may be linear, cyclic, or branched.
As said alkyl group, Preferably it is C1-C12, More preferably, a C1-C8 alkyl group can be mentioned. Specifically, for example, methyl group, ethyl group, propyl group, cyclopropyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, cyclohexyl group, 2 -A methylbutyl group, 2-ethylhexyl group, etc. can be mentioned.
As said alkenyl group, Preferably it is C2-C12, More preferably, a C2-C4 alkenyl group can be mentioned. Specifically, a vinyl group, an allyl group, a crotyl group, etc. can be mentioned, for example.
As said alkynyl group, Preferably it is C2-C12, More preferably, a C2-C8 alkynyl group can be mentioned. Specific examples include an ethynyl group and a phenylethynyl group.
As said aryl group, Preferably it is C6-C30, Preferably C6-C12 aryl group can be mentioned. Specific examples include a phenyl group.
Preferred examples of the aralkyl group include aralkyl groups having 7 to 30 carbon atoms, more preferably 7 to 13 carbon atoms. Specific examples include a benzyl group.

  Specific examples of the monoamine compound represented by the general formula (1) or (2) include trimethylamine, triethylamine, tri-n-propylamine, tri-isopropylamine, tricyclopropylamine, tri-n-butylamine, Triisobutylamine, tri-t-butylamine, tri-2-methylbutylamine, tri-n-hexylamine, tricyclohexylamine, tri (2-ethylhexyl) amine, trioctylamine, triphenylamine, tribenzylamine, dimethylphenyl Amine, diethylphenylamine, diisobutylphenylamine, methyldiphenylamine, ethyldiphenylamine, isobutyldiphenylamine, dimethylamine, diethylamine, di-n-propylamine, diisopropylamine Dicyclopropylamine, di-n-butylamine, diisobutylamine, di-t-butylamine, methylethylamine, methylbutylamine, di-n-hexylamine, dicyclohexylamine, di (2-ethylhexyl) amine, dioctylamine, diphenylamine, di Benzylamine, methylphenylamine, ethylphenylamine, isobutylphenylamine, methylallylamine, methylvinylamine, methyl (phenylethynyl) amine, phenyl (phenylethynyl) amine, methylamine, ethylamine, n-propylamine, isopropylamine, cyclo Propylamine, n-butylamine, isobutylamine, t-butylamine, 2-methylbutylamine, n-hexylamine, cyclohexylamine, 2-ethylhexene Shiruamin, octylamine, phenylamine, benzylamine, dimethyl octylamine, dimethyl cyclohexylamine, mention may be made of diethylaniline, N- methylpyrrolidine, or the like.

  Specific examples of the monoamine compound other than the monoamine compound represented by the general formula (1) or (2) include, for example, 1-aza-bicyclo [2.2.1] heptane, 1-aza-bicyclo [2.2. .2] octane (quinuclidine), 1-aza-cyclohexane, 1-aza-cyclohexane-3-ene, N-methyl-1-aza-cyclohexane-3-ene, and the like.

As said polyamine compound, a diamine compound, a triamine compound, a tetraamine compound etc. can be mentioned, for example.
Examples of the diamine compound include ethylenediamine, N, N′-dimethylethylenediamine, N, N′-diethylethylenediamine, N, N′-diisopropylethylenediamine, N, N′-di-t-butylethylenediamine, and N, N′—. Examples thereof include diphenylethylenediamine, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetraethylethylenediamine, and phenylenediamine.
Examples of the triamine compound include diethylenetriamine, 1,7-dimethyl-1,4,7-triazaheptane, 1,7-diethyl-1,4,7-triazaheptane, N, N ′, N ″ — And trimethyl-1,3,5-triazacyclohexane.
Examples of the tetraamine compound include trimethylenetetraamine and triethylenetetraamine.

Among these amine compounds, it is preferable to use a monoamine compound represented by the general formula (1). Of these, tri-n-propylamine, dimethyloctylamine, dimethylcyclohexylamine, and N-methylpyrrolidine are more preferable.
These 2nd amine compounds can be used individually by 1 type or in combination of 2 or more types.

The composition for forming an aluminum body used in the method of the present invention may further contain a titanium compound (hereinafter also referred to as “titanium catalyst” in the present specification). By containing the titanium compound, the adhesion at the interface between the substrate and aluminum can be improved.
As said titanium compound, the compound represented by following General formula (3)-(7) can be mentioned, for example.

Ti (OR ⁷ ) ₄ (3)
(In the general formula (3), R ⁷ is an alkyl group having 1 to 10 carbon atoms, a phenyl group, a halogenated alkyl group, or a halogenated phenyl group.)

Ti (OR ⁸ ) _x L _4-x (4)
(In the general formula (4), R ⁸ is the same as R ^{7 in the} general formula (3). L is a group represented by the following general formula (8), and R ⁹ and R ¹⁰ are the same or different. C 1-10 alkyl group, phenyl group, alkoxy group, halogenated alkyl group, or halogenated phenyl group, x is an integer of 0-3.)

Ti (OR ¹¹ ) _y (X) _4-y (5)
(In the general formula (5), R ¹¹ is an alkyl group or a phenyl group. X is a halogen atom. Y is an integer of 0 to 3.)

Ti (NR ¹² ) ₄ (6)
(In the general formula (6), R ¹² is an alkyl group or a phenyl group.)

Ti (Cp) _n (Y) _4-n (7)
(In the general formula (7), Cp is a cyclopentadienyl group. Y is a halogen atom or an alkyl group. N is an integer of 1 to 4.)

In the general formulas (3) and (4), R ⁷ and R ⁸ are preferably a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a t-butyl group, a methoxy group, An ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, a t-butoxy group, a hexyl group, a cyclohexyl group, a phenoxy group, a methylphenoxy group, and a trifluoromethyl group, more preferably a methyl group, an ethyl group Group, n-propyl group, i-propyl group, n-butyl group, t-butyl group, hexyl group, cyclohexyl group and phenyl group.
In the general formula (8), R ⁹ and R ¹⁰ are preferably a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a t-butyl group, a methoxy group, or an ethoxy group. N-propoxy group, i-propoxy group, n-butoxy group, t-butoxy group, phenoxy group, methylphenoxy group, and trifluoromethyl group. More preferred are methyl group, ethyl group, i-propyl group, t-butyl group, methoxy group, ethoxy group, i-propoxy group, t-butoxy group and trifluoromethyl group.

  Specific examples of the titanium compound represented by the general formula (3) include, for example, titanium methoxide, titanium ethoxide, titanium-n-propoxide, titanium-n-nonyl oxide, titanium stearyl oxide, titanium isopropoxide, Titanium-n-butoxide, titanium isobutoxide, titanium-t-butoxide, titanium trimethylsiloxide, titanium-2-ethylhexoxide, titanium methoxypropoxide, titanium phenoxide, titanium methylphenoxide, titanium fluoromethoxide and titanium chlorophenoxide Etc.

  Specific examples of the titanium compound represented by the general formula (4) include, for example, tetrakis (penta-2,4-diketo) titanium, tetrakis (2,2,6,6-tetramethylhepta-3,5-diketo. ) Titanium, tetrakis (1-ethoxybutane-1,3-diketo) titanium, tetrakis (1,1,1,5,5,5-hexafluoropenta-2,4-diketo) titanium, (2,2-dimethyl) Hexa-3,5-diketo) titanium, bis (penta-2,4-diketo) titanium dimethoxide, bis (2,2,6,6-tetramethylhepta-3,5-diketo) titanium dimethoxide, bis ( 1-ethoxybutane-1,3-diketo) titanium dimethoxide, bis (1,1,1,5,5,5-hexafluoropenta-2,4-diketo) titanium Methoxide, (2,2-dimethylhexa-3,5-diketo) titanium dimethoxide, bis (penta-2,4-diketo) titanium di-propoxide, bis (2,2,6,6-tetramethylhepta -3,5-diketo) titanium di i-propoxide, bis (1-ethoxybutane-1,3-diketo) titanium di i-propoxide, bis (1,1,1,5,5,5-hexafluoro Examples include penta-2,4-diketo) titanium dii-propoxide and (2,2-dimethylhexa-3,5-diketo) titanium dii-propoxide.

  Specific examples of the titanium compound represented by the general formula (5) include, for example, trimethoxytitanium chloride, triethoxytitanium chloride, tri-n-propoxytitanium chloride, tri-i-propoxytitanium chloride, tri-n-butoxy. Titanium chloride, tri-t-butoxytitanium chloride, triisostearoyl titanium chloride, dimethoxytitanium dichloride, diethoxytitanium dichloride, di-n-propoxytitanium dichloride, di-i-propoxytitanium dichloride, di-n-butoxytitanium dichloride, Di-t-butoxy titanium dichloride, diisostearoyl titanium dichloride, methoxy titanium trichloride, ethoxy titanium trichloride Roraido, n- propoxytitanium trichloride, i- propoxytitanium trichloride, n- butoxytitanium trichloride, t-butoxy titanium trichloride, isostearoyl trichloride, can be mentioned titanium tetrachloride and the like.

  Specific examples of the titanium compound represented by the general formula (6) include tetrakis (dimethylamino) titanium, tetrakis (diethylamino) titanium, tetrakis (di-t-butoxyamino) titanium, tetrakis (di-i-propoxy). Amino) titanium and tetrakis (diphenylamino) titanium can be mentioned.

  Specific examples of the titanium compound represented by the general formula (7) include, for example, dicyclopentadienyl titanium dichloride, dicyclopentadienyl titanium dibromide, cyclopentadienyl titanium trichloride, and cyclopentadienyl titanium trichloride. Examples include bromide, dicyclopentadienyldimethyltitanium, dicyclopentadienyldiethyltitanium, dicyclopentadienyldi-t-butyltitanium, dicyclopentadienylphenyltitanium chloride, dicyclopentadienylmethyltitanium chloride, etc. be able to.

  When the composition for forming an aluminum body of the present invention contains a second amine compound, the concentration of the second amine compound is such that the complex of the first amine compound and aluminum hydride, and the second amine compound. Is preferably 70% by mass or less, more preferably 50% by mass or less, and particularly preferably 3% by mass to 50% by mass with respect to 100% by mass in total.

  When the composition for forming an aluminum body of the present invention contains a titanium compound, the concentration of the titanium compound is preferably 1 mol% with respect to the total of the complex of the first amine compound and aluminum hydride and the titanium compound. It is below, More preferably, it is 0.00001-1 mol%, More preferably, it is 0.00005-0.01 mol%. By setting the content of the titanium compound in this range, it is possible to achieve both good embedding and adhesion to the substrate.

  The proportion of the total mass of the composition excluding the organic solvent in the composition for forming an aluminum body and the second amine compound (hereinafter referred to as “nonvolatile component content”) should be formed. It is preferable to vary according to the film thickness of the film-like aluminum body. For example, when the film-like aluminum body has a film thickness of less than 200 nm, the content of non-volatile components in the aluminum body-forming composition is preferably 5 to 55 mass%, more preferably 10 to 50 mass%. is there. When the film thickness of the film-like aluminum body is 200 nm or more, it is preferably 55 to 90% by mass, more preferably 70 to 85% by mass.

  The manufacturing method of the composition for forming an aluminum body of the present invention is not particularly limited. For example, a solution obtained by synthesizing a complex of the first amine compound and aluminum hydride in the presence of an organic solvent and then removing insolubles such as by-products with a filter or the like is used as it is as a composition for forming an aluminum body. Can do. Alternatively, after adding a desired organic solvent to this solution, the solvent used in the reaction, for example, diethyl ether, may be removed under reduced pressure to obtain an aluminum body-forming composition.

  When the composition for forming an aluminum body of the present invention further contains a second amine compound and / or a titanium compound, the composition for forming an aluminum body contains, for example, a complex of the above amine compound and aluminum hydride. A predetermined amount of the second amine compound and / or titanium compound solution can be added to the solution while stirring. The temperature of the solution at the time of addition becomes like this. Preferably it is 0-150 degreeC, More preferably, it is 5-100 degreeC. The stirring time is preferably 0.1 to 120 minutes, more preferably 0.2 to 60 minutes. By mixing under such conditions, a stable composition can be obtained.

<Method for forming aluminum body>
In the method for forming an aluminum body of the present invention, a coating film is formed by applying the above-described composition for forming an aluminum body on a substrate, and the coating film is subjected to at least one treatment of heating and light irradiation to form a substrate. By converting the coating film into a film-like aluminum body, an aluminum body is formed on the substrate.
There are no particular limitations on the material, shape, etc. of the material constituting the substrate (substrate body in the case of having a base film described later). The material of the substrate is preferably one that can withstand the heat treatment when the heat treatment is employed in the step of converting the coating film into an aluminum body. The shape of the substrate on which the coating film is formed is not particularly limited by a block shape, a plate shape, a film shape, or the like, and the surface of the substrate on which the coating film is formed may be a flat surface or a non-planar surface having a step. Moreover, the base | substrate may have a recessed part on the surface. The “concave portion” includes both a wiring groove or electrode groove (trench) formed on the substrate and a wiring connection hole (hole).
Specific examples of the material of the substrate include glass, metal, plastic, ceramics and the like. Examples of the glass that can be used include quartz glass, borosilicate glass, soda glass, and lead glass. Examples of the metal that can be used include gold, silver, copper, nickel, silicon, aluminum, iron, and other stainless steel. Examples of the plastic include polyimide and polyethersulfone.

The base is previously an organometallic compound containing at least one metal atom selected from the group consisting of titanium, palladium, and aluminum in the base body (except for the complex of the first amine compound and aluminum hydride). It may have a base film formed by applying a solution containing the above (hereinafter also referred to as “a composition for forming a base film”), followed by heat treatment. When the base has the base film, the film formability of the film-like aluminum body on the base can be improved.
Examples of the organometallic compound containing a titanium atom include a titanium alkoxide, a titanium compound having an amino group, a β-diketone complex of titanium, a titanium compound having a cyclopentadienyl group, and a titanium compound having a halogen atom. Can do.
Examples of the organometallic compound containing a palladium atom include a palladium complex having a halogen atom, palladium acetate, a palladium β-diketone complex, a complex of palladium and a compound having a conjugated carbonyl group, and a palladium phosphine complex. be able to.
The organometallic compound containing an aluminum atom excludes the complex of the first amine compound and aluminum hydride, and examples thereof include aluminum alkoxide, aluminum alkylate, and aluminum β-diketone complex.

Specific examples of such an organometallic compound include, for example, the same titanium compound as the above-described titanium compound as an organometallic compound containing a titanium atom.
Among organometallic compounds containing a palladium atom, palladium complexes having a halogen atom include, for example, allyl palladium chloride, dichlorobis (acetonitrile) palladium, dichlorobis (benzonitrile) palladium and the like;
Examples of palladium acetate include palladium acetate;
As a β-diketone complex of palladium, for example, pentane-2,4-dionatopalladium, hexafluoropentanedionatopalladium and the like;
As a complex of palladium and a compound having a conjugated carbonyl group, for example, bis (dibenzylideneacetone) palladium and the like;
Examples of palladium phosphine complexes include bis [1,2-bis (diphenylphosphino) ethane] palladium, bis (triphenylphosphine) palladium chloride, bis (triphenylphosphine) palladium acetate, and diacetate bis (triphenylphosphine) palladium. Dichloro [1,2-bis (diphenylphosphine) ethane] palladium, trans-dichlorobis (tricyclohexylphosphine) palladium, trans-dichlorobis (triphenylphosphine) palladium, trans-dichlorobis (tri-o-tolylphosphine) palladium, tetrakis (Triphenylphosphine) palladium etc. can be mentioned, respectively.

Examples of the organometallic compound containing an aluminum atom include aluminum alkoxides such as aluminum ethoxide, aluminum isopropoxide, aluminum-n-butoxide, aluminum-s-butoxide, aluminum-t-butoxide, aluminum ethoxyethoxyethoxide, and aluminum. Phenoxide, etc .;
Examples of aluminum alkylates include aluminum acetate, aluminum acrylate, aluminum methacrylate, aluminum cyclohexane butyrate and the like;
Examples of aluminum β-diketone complexes include pentane-2,4-diketoaluminum, hexafluoropentane-2,4-diketoaluminum, 2,2,6,6-tetramethylheptane-3,5-diketoaluminum. Bis (ethoxybutane-1,3-diketo) aluminum s-butoxide, (ethoxybutane-1,3-diketo) aluminum di-s-butoxide, (ethoxybutane-1,3-diketo) aluminum diisopropoxide, etc. Can be mentioned respectively.
Of these, titanium isopropoxide, aluminum isopropoxide, bis (ethoxybutane-1,3-diketo) titanium diisopropoxide, tetra (pentane-2,4-diketo) titanium, pentane-2,4-di It is preferred to use ketopalladium, hexafluoropentane-2,4-diketopalladium, pentane-2,4-diketoaluminum or hexafluoropentane-2,4-diketoaluminum.

As the solvent used for the solution of the organometallic compound containing at least one metal atom selected from the group consisting of titanium, palladium and aluminum, any solvent can be used as long as the organometallic compound can be dissolved. Examples of these solvents include ethers, ether-containing esters, hydrocarbons, alcohols, aprotic polar solvents, and the like, and mixed solvents thereof.
Examples of the ether include tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether and the like;
Examples of the ester having an ether group include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 2-acetoxy-1-methoxypropane and the like;
Examples of the hydrocarbon include toluene, xylene, hexane, cyclohexane, octane, decalin, tetralin, durene and the like;
Examples of the alcohol include methanol, ethanol, propanol and the like;
Examples of the aprotic polar solvent include N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, hexamethylphosphoamide, and γ-butyrolactone.
Content of the said organometallic compound in a solution becomes like this. Preferably it is 0.1-10 mass%, More preferably, it is 0.1-5 mass%. Note that it is desirable to use a solvent from which water and oxygen have been removed.

The base film forming composition can be applied to the substrate body by an appropriate method such as spin coating, roll coating, curtain coating, dip coating, spraying, or droplet discharge. When the substrate body has a trench structure, when the opening width is 300 nm or less and the aspect ratio of the trench is 5 or more, the substrate is applied for a while after the base film forming composition is applied to the substrate body. The composition for forming a base film can be applied more uniformly in the trenches by placing it under a pressure lower than the environmental pressure at the time of application. As a specific method, under pressure (hereinafter referred to as “second pressure”) lower than the pressure (hereinafter referred to as “first pressure”) when the base film forming composition is applied onto a substrate having a trench. .) Hold the substrate. The second pressure is preferably 1 to 70%, more preferably 10 to 40% with respect to the first pressure. For example, the second pressure when the application pressure is 1.01 × 10 ⁵ Pa (normal pressure) is preferably 1.01 × 10 ^{3 to} 7.09 × 10 ⁴ Pa, more preferably Is 1.01 × 10 ^{4 to} 4.05 × 10 ⁴ Pa. The time for holding the substrate under the second pressure is preferably 10 seconds to 10 minutes, more preferably 10 seconds to 1 minute. After holding the substrate at the second pressure, the pressure is preferably returned using an inert gas, and then subjected to the next heating step. After this pressure is reduced and held at the same pressure, the pressure is reduced. The series of operations for returning may be repeated several times. The pressure increase time for returning from the second pressure to the first pressure is preferably 3 seconds to 5 minutes, and more preferably 5 seconds to 1 minute. Further, the number of repetitions is preferably 10 times or less from the viewpoint of both film uniformity and workability, and more preferably 5 times or less in view of workability. The coating film (hereinafter, also referred to as “undercoat film”) made of the composition for forming an undercoat film thus formed is then heated. The heating temperature is preferably 30 to 350 ° C, more preferably 40 to 300 ° C. The heating time is preferably 5 to 90 minutes, more preferably 10 to 60 minutes. The ambient atmosphere from the coating process to the end of the heating process is preferably made of an inert gas such as nitrogen, helium, or argon. Furthermore, it may be carried out in an atmosphere mixed with a reducing gas such as hydrogen or an oxidizing gas such as oxygen, if necessary.
The thickness of these base films is preferably 0.001 to 5 μm, more preferably 0.005 to 0.5 μm, as the film thickness after heating.

Examples of the method for applying the aluminum body-forming composition of the present invention on the substrate described above include appropriate methods such as spin coating, roll coating, curtain coating, dip coating, spraying, and droplet discharge. The method can be used. In these coating steps, coating conditions are adopted such that the composition for forming an aluminum body reaches every corner of the substrate depending on the shape and size on the substrate. For example, when the spin coating method is employed as the coating method, the spinner rotation speed can be set to 300 to 2,500 rpm, and further to 500 to 2,000 rpm. In addition, when the substrate has a concave portion, the above-described variation in the environmental pressure after coating may be employed in the coating of the base film forming composition.
After the coating step, heat treatment may be performed to remove low-boiling components such as a solvent contained in the coated aluminum body-forming composition. The temperature and time for heating vary depending on the type of solvent used and the boiling point (vapor pressure), but can be, for example, 100 to 350 ° C. and 1 to 90 minutes. At this time, the solvent can be removed at a lower temperature by reducing the pressure of the entire system. The conditions for the heat treatment under reduced pressure are preferably 100 to 250 ° C. and 10 to 60 minutes.

Next, the coating film formed as described above is subjected to at least one treatment of heating and light irradiation to convert the coating film into a film-like aluminum body, and the film-like aluminum is formed on the substrate. The body is formed.
The temperature of the heat treatment is preferably 60 ° C or higher, more preferably 70 ° C to 600 ° C, and particularly preferably 100 ° C to 400 ° C. The heating time is preferably 30 seconds to 120 minutes, more preferably 1 to 90 minutes, and particularly preferably 10 to 60 minutes.
Examples of the light source used for the light treatment include a mercury lamp, a deuterium lamp, a rare gas discharge light, a YAG laser, an argon laser, a carbon dioxide gas laser, and a rare gas halogen excimer laser. Examples of the mercury lamp include a low-pressure mercury lamp and a high-pressure mercury lamp. Examples of the rare gas used for the discharge light of the rare gas include argon, krypton, and xenon. Examples of the rare gas halogen used in the rare gas halogen excimer laser include XeF, XeCl, XeBr, KrF, KrCl, ArF, ArCl, and the like.
The output of these light sources is preferably 10 to 5,000 W, more preferably 100 to 1,000 W. Although the wavelength of these light sources is not specifically limited, Preferably it is 170 nm-600 nm. In addition, the use of laser light is particularly preferable from the viewpoint of the film quality of the formed aluminum film.
The atmosphere at the time of performing the coating step, the heating step, and the light irradiation step is preferably an inert atmosphere or a reducing atmosphere. The inert atmosphere can be realized by using an inert gas such as nitrogen, helium, or argon. The reducing atmosphere can be realized by using a reducing gas such as hydrogen or by using the reducing gas and the inert gas in combination.
Only one of the heat treatment and the light treatment may be performed, or both the heat treatment and the light treatment may be performed. When both heat treatment and light treatment are performed, the heat treatment and light treatment may be performed at the same time regardless of the order. Among these, it is preferable to perform only heat treatment or perform both heat treatment and light treatment.

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. The following operations were all performed in a dry nitrogen atmosphere unless otherwise specified. All the solvents used were dehydrated in advance with Molecular Sieves 4A (manufactured by Union Showa Co., Ltd.) and degassed by bubbling nitrogen gas. Further, various tertiary alkylamine hydrochlorides used in the synthesis were obtained by reacting 35% by mass of hydrochloric acid with the corresponding tertiary alkylamine, followed by desolubilization, recrystallization, and drying under reduced pressure. .
The vapor pressure of the alane / amine complex was measured according to the following method.
[Method for measuring vapor pressure of alane-amine complexes]
The vapor pressure was measured by the static method. Specifically, 30 g of alane / amine complex is filled in a sealed vessel (with a capacity of 100 ml) with a precision pressure gauge and a gas introduction valve in a nitrogen atmosphere, and after sealing, the entire vessel is temporarily filled with liquid nitrogen in the atmosphere. Cool for hours. Then, while continuing cooling, the inside of the container was depressurized (10 ⁻³ torr or less) with a high vacuum pump via a gas introduction valve, and the internal pressure at a stable time was set to zero. Next, after the decompression was stopped, the gas introduction valve of the container was closed to make the container a closed system. Thereafter, the cooling was stopped, and the mixture was allowed to stand at room temperature overnight, and then the temperature at that time and the pressure inside the container (the vapor pressure of the alan / amine complex) were measured. Further, the entire container including the pressure gauge was placed in a constant temperature bath at 50 ° C., and the pressure inside the container after three hours (the vapor pressure of the Alane / amine complex) was measured.

[Preparation of composition for forming undercoat film]
Take 0.30 g of titanium (IV) bis (acetoacetato) diisopropoxide and 64 μL of tetrakis (dimethylamino) titanium in a 20 mL glass container, and add 2-acetoxy-1-methoxypropane to this to give a total amount of 18.00 g. did. These mixtures were sufficiently stirred and allowed to stand at room temperature for 2 hours. Subsequently, this was filtered using a membrane filter (manufactured by Whatman Inc.) having a pore diameter of 0.1 μm made of polytetrafluoroethylene to obtain a composition for forming a base film.

[Preparation of composition for forming aluminum body]
(1-1) Synthesis of complex of first amine compound and aluminum hydride 50 g of lithium aluminum hydride was charged into a 3 L three-necked flask containing a magnetic stirrer. A 500 mL powder addition funnel, a suction stopper three-way cock connected to a nitrogen stream, and a glass stopper were connected to the three connection ports of the three-neck flask. After charging 213 g of tripropylamine hydrochloride into a powder addition funnel, the three-necked flask was placed under a nitrogen seal via a suction stopper three-way cock. Next, 550 ml of cyclohexane was added to the three-necked flask using a glass syringe. While stirring with a magnetic stirrer at 500 rpm, tripropylamine hydrochloride was gradually dropped into a three-necked flask over 2 hours at room temperature, and stirring was continued for another 4 hours. At this time, the temperature in the liquid was 40 ° C. at the maximum and 28 ° C. at the end of the addition.
Then, using a tube made of polytetrafluoroethylene filled with quartz wool (manufactured by Tosoh), the reaction mixture was taken out into another container by pressure feeding, and the taken out liquid was a glass filter having a diameter of 30 μm in a nitrogen atmosphere. And filtered under reduced pressure. The filtrate was received in a 3 L eggplant-shaped flask. After completion of filtration, a magnetic stirrer was inserted, and a suction stopper three-way cock was attached.
The suction stopper three-way cock was connected to a vacuum pump through a trap, and the solvent was removed under reduced pressure while stirring the flask at 35 ° C. with a magnetic stirrer while heating the flask to 35 ° C. In about 1 hour, a white solid precipitated in the flask, and the residue of the solvent was no longer observed with the naked eye. Therefore, the solvent removal under reduced pressure was continued after the stirring was stopped. Thereafter, the mass of the flask was measured every hour, and the removal of the reduced-pressure solvent was terminated when the weight loss was within 0.5 g.
In this synthesis example, it took 5 hours from the start to the end of the removal of the solvent under reduced pressure. The obtained solid was confirmed to be a complex of tripropylamine and aluminum hydride by proton NMR analysis and elemental analysis. The mass of the obtained complex was 144 g, and the yield was 70%.
Moreover, as a result of measuring the vapor pressure of this complex by the said method, it turned out that it is 1.4 torr at 25 degreeC and 2.7 torr at 50 degreeC.
(1-2) Preparation of Composition A for Forming Aluminum Body 6.0 g of the complex obtained in 1-1 was dissolved in 14.0 g of t-butylbenzene to prepare a solution having 30% by mass of the complex. Next, this solution was filtered using a membrane filter (manufactured by Whatman Inc.) made of polytetrafluoroethylene having a pore size of 0.1 μm to obtain a filtrate of an amine / alanine complex solution. Next, 0.11 g of cyclopentadienyltitanium trichloride and 24.89 g of t-butylbenzene were mixed in another container, stirred well and allowed to stand at room temperature for 4 hours, and then this was made of polytetrafluoroethylene. Filtration was performed using a membrane filter (manufactured by Whatman Inc.) having a pore diameter of 0.1 μm to obtain a filtrate of a titanium complex solution containing 20 μmol / g of cyclopentadienyl titanium trichloride. 1.75 g (35 μmol) of the titanium complex solution filtrate was added to the total amount of the amine-alanine complex filtrate prepared above (35 mmol of amine-alanine complex) with stirring at room temperature, and then the stirring was continued for 1 minute. By doing this, the composition A for forming an aluminum body was prepared.

(2-1) Synthesis of complex of first amine compound and aluminum hydride 50 g of lithium aluminum hydride was charged into a 3 L three-necked flask containing a magnetic stirrer. A 500 mL powder addition funnel, a suction stopper three-way cock connected to a nitrogen stream, and a glass stopper were connected to the three connection ports of the three-neck flask. After charging 144 g of N-methylpyrrolidine hydrochloride into the powder addition funnel, the three-necked flask was placed under a nitrogen seal through a suction stopper three-way cock. Next, 550 ml of toluene was added to the three-necked flask using a glass syringe. While stirring with a magnetic stirrer at a rotation speed of 500 rpm, N-methylpyrrolidine hydrochloride was gradually dropped into a three-necked flask over 2 hours at room temperature, and stirring was further continued for 4 hours. At this time, the temperature in the liquid was 35 ° C. at the maximum and 25 ° C. at the end of the addition.
Thereafter, in the same manner as in (1-1) above, the reaction mixture was filtered, and then the solvent was removed. The solvent was removed by measuring the mass of the flask every hour, and when the weight loss was within 0.5 g, the removal of the solvent under reduced pressure was terminated to obtain a colorless and transparent liquid.
In this synthesis example, it took 3 hours from the start to the end of removal of the solvent under reduced pressure. The obtained solid was confirmed to be a complex of N-methylpyrrolidine and aluminum hydride by proton NMR analysis and elemental analysis. The mass of the obtained complex was 132 g, and the yield was 64%. Moreover, as a result of measuring the vapor pressure of this complex by the said method, it turned out that it is 1.3 torr at 25 degreeC and 3.0 torr at 50 degreeC.
(2-2) Preparation of aluminum body-forming composition B 0.20 g of N-methylpyrrolidine was added to 4.0 g of the complex obtained in 2-1 above, and this was dissolved in 15.8 g of t-butylbenzene. A solution having 20% by mass of the complex was prepared. Except using the solution which has this complex, it carried out similarly to said (1-2), and prepared the composition B for aluminum body formation.

(3-1) Synthesis of Complex of First Amine Compound and Aluminum Hydride 40 g of lithium aluminum hydride was charged into a 3 L three-necked flask containing a magnetic stirrer. A 500 mL powder addition funnel, a suction stopper three-way cock connected to a nitrogen stream, and a glass stopper were connected to the three connection ports of the three-neck flask. After charging 210 g of tributylamine hydrochloride into a powder addition funnel, the three-necked flask was placed under a nitrogen seal through a suction stopper three-way cock. Next, 1500 ml of hexane was added to the three-necked flask using a glass syringe. While stirring at 500 rpm with a magnetic stirrer, tributylamine hydrochloride was gradually dropped into the three-necked flask over 2 hours at room temperature, and stirring was continued for further 4 hours. At this time, the temperature in the liquid was 42 ° C. at the maximum, and 29 ° C. at the end of the addition.
Thereafter, the reaction mixture was filtered in the same manner as in (1-1), and the solvent was removed. As a result, a white solid precipitated in the flask in about 1 hour, and the solvent residue was no longer observed visually. After the stirring was stopped, the solvent removal under reduced pressure was continued. Thereafter, the mass of the flask was measured every hour, and the removal of the reduced-pressure solvent was terminated when the weight loss was within 0.5 g.
In this synthesis example, it took 3.5 hours from the start to the end of the vacuum solvent removal. The obtained solid was confirmed to be a complex of tributylamine and aluminum hydride by proton NMR analysis and elemental analysis. The obtained complex had a mass of 198 g and a yield of 97%.
Moreover, as a result of measuring the vapor pressure of this complex by the said method, it turned out that it is 0.8 torr at 25 degreeC and 1.4 torr at 50 degreeC.
(3-2) Preparation of Composition C for Forming Aluminum Body 7.5 g of the complex obtained in 3-1 above was dissolved in 12.5 g of t-butylbenzene to prepare a solution having 38% by mass of the complex. Next, this solution was used to obtain a filtrate of an amine / alanine complex solution using a membrane filter (manufactured by Whatman Inc.) made of polytetrafluoroethylene having a pore size of 0.1 μm (amine / alane complex 35 mmol). C.

(4-1) Synthesis of Complex of First Amine Compound and Aluminum Hydride 38 g of lithium aluminum hydride was charged into a 3 L three-necked flask containing a magnetic stirrer. A 500 mL powder addition funnel, a suction stopper three-way cock connected to a nitrogen stream, and a glass stopper were connected to the three connection ports of the three-neck flask. After charging 174 g of dimethyloctylamine hydrochloride into the addition funnel for powder, the three-necked flask was placed under a nitrogen seal through a suction stopper three-way cock. Next, 560 ml of hexane was added to the three-necked flask using a glass syringe. While stirring at 500 rpm with a magnetic stirrer, dimethyloctylamine hydrochloride was gradually dropped into the three-necked flask over 2 hours at room temperature, and then stirring was continued for another 4 hours. At this time, the temperature in the liquid was 35 ° C. at the maximum, and 28 ° C. at the end of the addition.
Then, using a tube made of polytetrafluoroethylene filled with quartz wool (manufactured by Tosoh), the reaction mixture was taken out into another container by pressure feeding, and the taken out liquid was a glass filter having a diameter of 30 μm in a nitrogen atmosphere. And filtered under reduced pressure. The filtrate was received in a 2 L eggplant-shaped flask, and after completion of the filtration, a magnetic stirrer was inserted and a suction stopper three-way cock was attached.
The suction stopper three-way cock was connected to a vacuum pump through a trap, and the solvent was removed under reduced pressure while stirring the flask at 35 ° C. with a magnetic stirrer while heating the flask to 35 ° C. The mass of the flask was measured every hour, and when the weight loss was within 0.5 g, the removal of the vacuum solvent was terminated, and a colorless and transparent liquid was obtained.
In this synthesis example, it took 4 hours from the start to the end of removal of the solvent under reduced pressure. The obtained liquid was confirmed to be a complex of dimethyloctylamine and aluminum hydride by proton NMR analysis and elemental analysis. The obtained complex had a mass of 120 g and a yield of 71%. Moreover, as a result of measuring the vapor pressure of this complex by the said method, it turned out that it is 2.0 torr at 25 degreeC and 4.0 torr at 50 degreeC.
(4-2) Preparation of aluminum body-forming composition D 0.33 g of dimethyloctylamine was added to 6.6 g of the complex obtained in 4-1 above, and this was dissolved in 13.1 g of t-butylbenzene. A solution having 33% by mass of the complex was prepared. Except using the solution which has this complex, it carried out similarly to said (1-2), and prepared the composition D for aluminum body formation.

(5-1) Synthesis of Complex of First Amine Compound and Aluminum Hydride 38 g of lithium aluminum hydride was charged into a 3 L three-necked flask containing a magnetic stirrer. A 500 mL powder addition funnel, a suction stopper three-way cock connected to a nitrogen stream, and a glass stopper were connected to the three connection ports of the three-neck flask. After charging 147 g of dimethylcyclohexylamine hydrochloride into a powder addition funnel, the three-necked flask was placed under a nitrogen seal through a suction stopper three-way cock. Next, 560 ml of hexane was added to the three-necked flask using a glass syringe. While stirring at 500 rpm with a magnetic stirrer, dimethylcyclohexylamine hydrochloride was gradually dropped into the three-necked flask over 2 hours at room temperature, and stirring was further continued for 4 hours. At this time, the temperature in the liquid was 31 ° C. at the maximum and 24 ° C. at the end of the addition.
Thereafter, in the same manner as in (4-1) above, the reaction mixture was filtered, and then the solvent was removed. The solvent was removed by measuring the mass of the flask every hour, and when the weight loss was within 0.5 g, the removal of the solvent under reduced pressure was terminated to obtain a white solid.
In this synthesis example, it took 4 hours from the start to the end of removal of the solvent under reduced pressure. The obtained solid was confirmed to be a complex of dimethylcyclohexylamine and aluminum hydride by proton NMR analysis and elemental analysis. The obtained complex had a mass of 95 g and a yield of 67%. Moreover, as a result of measuring the vapor pressure of this complex by the said method, it turned out that it is 2.2 torr at 25 degreeC and 4.4 torr at 50 degreeC.
(5-2) Preparation of Composition E for Forming Aluminum Body 5.5 g of the complex obtained in the above 5-1 was dissolved in 14.5 g of t-butylbenzene to prepare a solution having 28% by mass of the complex. Except using the solution which has this complex, it carried out similarly to said (1-2), and prepared the composition E for aluminum body formation.

(6-1) Synthesis of complex of first amine compound and aluminum hydride 150 g of lithium aluminum hydride was charged into a 3 L three-necked flask containing a magnetic stirrer. The three connection ports of the three-necked flask were each connected with a 3000 mL addition funnel for powder, a suction stopper three-way cock connected to a nitrogen stream, and a glass stopper. After charging 368 g of ethyldimethylamine hydrochloride into a powder addition funnel, the three-necked flask was placed under a nitrogen seal through a suction stopper three-way cock. Next, 1500 ml of hexane was added to the three-necked flask using a glass syringe. While stirring at a rotational speed of 500 rpm with a magnetic stirrer, ethyldimethylamine hydrochloride was gradually dropped into the three-necked flask over 2 hours at room temperature, and stirring was continued for another 4 hours. At this time, the temperature in the liquid was 38 ° C. at the maximum and 32 ° C. at the end of the addition.
Thereafter, in the same manner as in (1-1) above, the reaction mixture was filtered, and then the solvent was removed. The solvent was removed by measuring the mass of the flask every hour, and when the weight loss was within 0.5 g, the removal of the solvent under reduced pressure was terminated to obtain a colorless and transparent liquid.
In this synthesis example, 4.5 hours were required from the start to the end of removal of the solvent under reduced pressure. The obtained solid was confirmed to be a complex of ethyldimethylamine and aluminum hydride by proton NMR analysis and elemental analysis. The mass of the obtained complex was 243 g, and the yield was 70%. Moreover, as a result of measuring the vapor pressure of this complex by the said method, it turned out that it is 2.9 torr at 25 degreeC and 12.5 torr at 50 degreeC.
(6-2) Preparation of composition F for forming aluminum body 3.6 g of the complex obtained in 6-1 above was dissolved in 16.4 g of t-butylbenzene to prepare a solution having 18% by mass of the complex. Except using the solution which has this complex, it carried out similarly to the said (1-2), and prepared the composition F for aluminum body formation.

(7-1) Synthesis of Complex of First Amine Compound and Aluminum Hydride 170 g of lithium aluminum hydride was charged into a 3 L three-necked flask containing a magnetic stirrer. The three connection ports of the three-neck flask were each connected with a 1500 mL powder addition funnel, a suction stopper three-way cock connected to a nitrogen stream, and a glass stopper. After charging 555 g of triethylamine hydrochloride into an addition funnel for powder, the three-necked flask was placed under a nitrogen seal through a suction stopper three-way cock. Next, 1500 ml of hexane was added to the three-necked flask using a glass syringe. While stirring at 500 rpm with a magnetic stirrer, triethylamine hydrochloride was gradually dropped into the three-necked flask over 2 hours at room temperature, and stirring was continued for further 4 hours. At this time, the temperature in the liquid was 35 ° C. at the maximum and 30 ° C. at the end of the addition.
Thereafter, in the same manner as in (1-1) above, the reaction mixture was filtered, and then the solvent was removed. The solvent was removed by measuring the mass of the flask every hour, and when the weight loss was within 0.5 g, the removal of the solvent under reduced pressure was terminated to obtain a colorless and transparent liquid.
In this synthesis example, 4.5 hours were required from the start to the end of removal of the solvent under reduced pressure. The obtained solid was confirmed to be a complex of triethylamine and aluminum hydride by proton NMR analysis and elemental analysis. The obtained complex had a mass of 406 g and a yield of 77%. Moreover, as a result of measuring the vapor pressure of this complex by the said method, it turned out that it is 2.1 torr at 25 degreeC and 6.5 torr at 50 degreeC.
(7-2) Preparation of aluminum body-forming composition G 0.23 g of triethylamine was added to 4.6 g of the complex obtained in 7-1 above, and further dissolved with 13.17 g of t-butylbenzene to obtain 23 mass of the complex. % Solution was prepared. Except using the solution which has this complex, it carried out similarly to said (1-2), and prepared the composition G for aluminum body formation.

The following film forming experiment was conducted using the above-described composition for forming an aluminum body.
[Example 1]
The following operations were all performed under a nitrogen atmosphere.
A 12-inch silicon pattern wafer having a large number of linear trenches (aspect ratio = about 5) having a width of 200 nm, a depth of 1000 nm, and a length of 3 mm at intervals of 200 nm (pitch 400 nm) was prepared. The trench is formed on one of the surfaces of the substrate. The 12-inch silicon substrate was mounted on a spin coater, and 1 mL of the above-described composition for forming an underlayer was dropped in a nitrogen gas atmosphere, and was spun at 3,000 rpm for 10 seconds. This substrate was placed on a hot plate set at 150 ° C. and heated for 2 minutes.
This substrate was mounted on the spin coater again with the surface having the trench up, and the entire amount of the aluminum body-forming composition A prepared in (1-2) above was placed on the substrate with the surface having the trench up. The solution was dropped and spun at 1000 rpm for 10 seconds, and then heated on a hot plate at 100 ° C. for 2 minutes. Thereafter, when the temperature was further raised to 400 ° C. and held at that temperature for 30 minutes, the substrate surface was covered with a film having a metallic luster. Among these films, when the ESCA spectrum was observed for a portion formed where the substrate did not have a trench, a peak attributed to Al 2p was observed in eV, and it was found that this film was an aluminum film. .
This substrate is cut in a direction perpendicular to the trench, and a cross section thereof is observed with a field emission scanning electron microscope “S-4200” manufactured by Hitachi, Ltd. (A) A portion of the substrate having no trench, B) The portion of the trench wall surface that is 200 nm down from the opening (upper wall surface of the trench) (C) The portion that is 800 nm down from the opening (lower wall surface of the trench) (D) The film thickness of the bottom surface of the trench is measured . Further, the presence or absence of film peeling at the top of the trench pattern portion was measured. The results are shown in Table 1.
Also, a 12-inch blanket silicon wafer having no trench is subjected to the same film forming process as that for the silicon pattern wafer, and a straight line area of 30 cm from the notch portion of the silicon wafer to the opposite end through the center portion of the wafer. The sheet resistance was measured with a resistivity meter “Loresta-GP MCP-T600” manufactured by Mitsubishi Chemical Analytic at intervals of 1 cm, and the average value and standard deviation were calculated. The results are shown in Table 1.

[Example 2]
Evaluation was performed under the same conditions as in Example 1 except that the aluminum body-forming composition B prepared in (2-2) above was used as the aluminum body-forming composition. The results are shown in Table 1.
[Example 3]
Evaluation was performed under the same conditions as in Example 1 except that the aluminum body-forming composition C prepared in (3-2) above was used as the aluminum body-forming composition. The results are shown in Table 1.
[Example 4]
Evaluation was performed under the same conditions as in Example 1 except that the aluminum body-forming composition D prepared in (4-2) above was used as the aluminum body-forming composition. The results are shown in Table 1.
[Example 5]
Evaluation was performed under the same conditions as in Example 1 except that the aluminum body-forming composition E prepared in (5-2) above was used as the aluminum body-forming composition. The results are shown in Table 1.

[Comparative Example 1]
Evaluation was performed under the same conditions as in Example 1 except that the aluminum body-forming composition F prepared in (6-2) above was used as the aluminum body-forming composition. The results are shown in Table 1.
[Comparative Example 1]
Evaluation was performed under the same conditions as in Example 1 except that the aluminum body-forming composition G prepared in (7-2) above was used as the aluminum body-forming composition. The results are shown in Table 1.

From the results shown in Table 1, when the molar concentration of the amine / arane complex contained in the composition for forming an aluminum body is compared under a unified condition, the vapor pressure of the amine / arane complex is 5.0 Torr or less at 50 ° C. It can be seen that the film thickness is large and the step coverage in the trench is good. Furthermore, since the variation of the sheet resistance value in the 12-inch wafer is low, it can be seen that the film quality is uniform in the plane.
On the other hand, when the vapor pressure of the amine / alane complex exceeds 5.0 Torr at 50 ° C., the step coverage inside the trench is good, but the film thickness is thin, and the film tends to peel off from the substrate. Further, due to this, the in-plane uniformity of the sheet resistance value is inferior.
From the above, when the vapor pressure of the amine / alane complex contained in the composition for forming an aluminum body exceeds 5.0 Torr, volatilization of the complex molecules becomes severe in the coating process and the heating process, which causes a decrease in film thickness, It is thought that this is connected to the phenomenon of peeling and deterioration of in-plane uniformity of the film quality. This also means that the proportion of amine / alane complex supplied at the time of coating is effectively used, and from this point of view, the vapor pressure of the amine / alanine complex used as the aluminum body forming composition is It was found that a reasonably low value is better, specifically, 5.0 torr or less at 50 ° C. is good.

Claims (5)

A composition for forming an aluminum body, comprising a complex of a first amine compound and aluminum hydride, and an organic solvent, wherein the vapor pressure of the complex is 5.0 Torr or less at 50 ° C., and the first The composition for forming an aluminum body is represented by the following general formula (1).

(In the general formula (1), R ¹ is an alkyl group having 1 to 8 carbon atoms, an alkenyl group, or an alkynyl group, or an alicyclic group having 3 to 6 carbon atoms. R ² and R ³ are each independently selected. An alkyl group having 1 to 8 carbon atoms, an alkenyl group, or an alkynyl group, or an alicyclic group having 3 to 6 carbon atoms, and R ² and R ³ are connected to each other to form a cyclic structure having 4 or more carbon atoms. One of the hydrocarbon groups may be formed, provided that when R ² and R ³ are an alkyl group, an alkenyl group, an alkynyl group, or an alicyclic group, among R ¹ , R ² , and R ³ At least one is a group having 3 or more carbon atoms, and when all of R ¹ , R ² , and R ³ are alkyl groups, alkenyl groups, or alkynyl groups having 4 or less carbon atoms, R ¹ , R ² , R in all of ³ 3 to 4 carbon atoms One straight chain alkyl group, an alkenyl group or alkynyl group.)   Furthermore, the composition for aluminum body formation of Claim 1 containing the 2nd amine compound which has not formed the complex.   Furthermore, the composition for aluminum body formation of Claim 1 or 2 containing a titanium compound.   An aluminum body is formed on the substrate by applying the aluminum body-forming composition described in any one of claims 1 to 3 on the substrate, and then heating and / or irradiating with light. Body formation method.   The substrate previously contains an organometallic compound containing at least one metal atom selected from the group consisting of titanium, palladium, and aluminum (excluding a complex of an amine compound and aluminum hydride) in the substrate body. The aluminum body forming method according to claim 4, wherein the base film forming composition is applied, and then the base film forming composition is heated.