JP3169934B2 - Conductive Ta-based film forming material, conductive Ta-based film forming method, wiring film forming method, and ULSI - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a conductive Ta-based film forming material, a method for forming a conductive Ta-based film, a method for forming a wiring film, and an ULSI on which a copper wiring film is formed.

[0002]

At present, progress in the field of semiconductors is remarkable, and LSIs are moving to ULSIs. In order to improve the signal processing speed, miniaturization is progressing. In particular, a conductive portion (wiring) for transmitting an electric signal is required to be thin. However, when the wiring is made thinner, the electric resistance naturally becomes higher. Therefore, a wiring material having a lower resistance has been demanded. For example, it has moved from a W wiring film to an Al wiring film. And in the next generation,
Attention has been paid to Cu wiring films.

[0003] However, Cu diffuses strongly into a silicon substrate. Therefore, it is difficult to form a wiring film as it is. Therefore, a conceivable means is to provide a diffusion prevention film (barrier film) on a substrate and form a copper film thereon. Tantalum metal, tantalum carbide, tantalum nitride, tantalum silicide, tantalum silicide nitride, and the like have been proposed as materials for the barrier film. In particular, Ta-based films such as tantalum nitride and tantalum have high barrier properties and are expected.

By the way, with the miniaturization of ULSI, it is required that the wiring width of copper be 0.18 μm or less. For this reason, a Ta-based film as a barrier film is required to be thin, and a chemical vapor deposition (CV)
It has become necessary to form a Ta-based film according to D). However, there are only a few reports on the formation of Ta-based films by CVD, and no satisfactory results have been obtained.

[0005] This is because there was no satisfactory CVD raw material for forming a Ta-based film. For example, a stable and good vaporizable material as a CVD material has not been obtained.
In other words, the vaporization of the compound is low, and the vapor of the compound cannot be stably transported over a long period of time. For example, since it is a solid, compound vapor cannot be transported stably for a long period of time. Therefore, stable vaporization can be obtained even when used many times and for a long time, and C has good vaporizability even at low temperature heating.
Development of VD raw materials is desired.

Although a Ta-based compound is unlikely to exhibit a favorable effect as a CVD raw material, it is difficult to use a metal tantalum,
Tantalum carbide, tantalum nitride, tantalum silicide, tantalum silicide, etc. show conductivity differently from tantalum oxide, and when a copper film is provided thereon, it is difficult for copper to diffuse into the substrate Excellent barrier properties. Therefore, it is important to form a conductive Ta-based film such as metal tantalum, tantalum carbide, tantalum nitride, tantalum silicide, and tantalum silicide.

[0007] Therefore, while repeating the thinking and error, the Ta-based compound is dissolved in a hydrocarbon or amine-based solvent, and when the Ta-based compound is dissolved and the solution is vaporized, the Ta-based compound is dissolved. The compound can be vaporized together with the solvent or separately from the solvent, the Ta-based compound can be stably transported, and a conductive Ta-based film such as metal tantalum, tantalum carbide, tantalum nitride, tantalum silicide, tantalum silicate silicide, etc. Have been found to be able to be formed efficiently.

Accordingly, a first object of the present invention is to provide a conductive Ta-based film forming material which is easy to use. A second problem to be solved by the present invention is to provide a method for forming a conductive Ta-based film using the above-described material for forming a conductive Ta-based film. A third problem to be solved by the present invention is to provide an ULSI in which a copper wiring film is formed on a conductive Ta-based film as a barrier film formed by the above-described method for forming a conductive Ta-based film. It is.

[0009]

A first object of the present invention is to provide a material for forming a conductive Ta-based film, which comprises a compound having Ta and a hydrocarbon-based solvent. The problem is solved by the conductive Ta-based film forming material.

[0010] In particular, a material for forming a conductive Ta-based film provided as a base film of a copper (including copper alloy) wiring film, comprising a compound having Ta and a hydrocarbon-based solvent. The problem is solved by a characteristic conductive Ta-based film forming material.

Further, the problem is solved by a material for forming a conductive Ta-based film, which comprises a compound having Ta and an amine-based solvent. In particular, a material for forming a conductive Ta-based film provided as a base film of a copper (including a copper alloy) wiring film, comprising a compound having Ta and an amine-based solvent. The problem is solved by the conductive Ta-based film forming material.

In the present invention, the conductive Ta-based film means a film of tantalum metal, tantalum carbide, tantalum nitride, tantalum silicide, tantalum silicide nitride, or the like. However, the tantalum oxide film is not a conductive Ta-based film. In the present invention, the compound having Ta is particularly preferably a compound represented by the following general formula (1).

Formula (1) R _n TaX _5-n · L _m [where R is H, an alkyl group, a halogenated alkyl group,
Alkene group, halogenated alkene group, alkyne group, halogenated alkyne group, aryl group, substituted aryl group, Si
Or an alkene group having Si, an alkyne group having Si, an aryl group having Si, or a substituted aryl group having Si.

N is an integer of 0-5. X is H, F, C
It is any one selected from the group of l, Br and I.
L is any one selected from the group consisting of alkyl-substituted sulfur, halogen-substituted sulfur, alkyl-substituted phosphine, and halogen-substituted phosphine. m is an integer of 0 to 4 when n is an integer of 1 to 5, and an integer of 1 to 4 when n is 0.

When n is 2 or more, all Rs in R _n may be the same or different. When n is 3 or less, all Xs in X _5-n may be the same or different. When m is 2 or more, all L in L _m
May be the same or different. ] The alkyl group (the n 1 or more integer) -C _n H _{2n + 1} is a group represented by. And the halogenated alkyl group is
The alkyl group is a group in which one or more hydrogen atoms have been replaced with halogen atoms. Alkene group is -C _n H _2n-1 group (n is an integer greater than or equal to 2) is represented by. The halogenated alkene group is a group in which one or more hydrogen atoms of the alkene group are substituted with a halogen atom. The alkyne group is-
It is a group represented by C _n H _{2n -3} (n is an integer of 2 or more).
The halogenated alkyne group is a group in which one or more hydrogen atoms of the alkyne group are substituted with a halogen atom. The aryl group is an atomic group obtained by removing one hydrogen atom from an aromatic hydrocarbon. A substituted aryl group is a compound in which one or more hydrogen atoms of the above aryl group are other groups (eg, an alkyl group, a halogenated alkyl group, an alkene group, a halogenated alkene group, an alkyne group, a halogenated alkyne group, a halogen atom, and the like). Is a group substituted with The alkyl group having Si, the alkene group having Si, the alkyne group having Si, the aryl group having Si, and the substituted aryl group having Si are each a group (alkyl group, alkene group, alkyne group,
(Aryl group, substituted aryl group) has Si. Alkyl-substituted sulfur is, for example, R ₂ S or R
SH (R is any one selected from the group consisting of an alkyl group, an alkene group, an alkyne group, an aryl group, and a substituted aryl group). The halogen-substituted sulfur is, for example, SX ₂ or S ₂ X ₂ (X is any one selected from the group consisting of F, Cl, Br and I) or SF ₆ . Alkyl-substituted phosphines include, for example, R ₃ P,
R ₂ PH, RPH ₂ (R is any one selected from the group consisting of an alkyl group, an alkene group, an alkyne group, an aryl group, and a substituted aryl group). Halogen-substituted phosphines include, for example, PX ₃ , PX ₅ (X is F, Cl,
(Any one selected from the group consisting of Br and I).

"When n is 2 or more, all R in R _n
May be the same or different "means that, for example, in the case of R ₂ , there are two Rs, and these two Rs may be the same alkyl group, It means that it may be. For others,
The same is true. The alkyl group represented by R in the above general formula is
Those having 1 to 10 carbon atoms are preferred. The alkene group represented by R preferably has 2 to 10 carbon atoms. The alkyne group represented by R preferably has 2 to 10 carbon atoms. R
The aryl group represented by has preferably 6 to 20 carbon atoms. The substituted aryl group represented by R has 7 to 20 carbon atoms.
Are preferred. The alkyl group having Si represented by R preferably has 1 to 10 carbon atoms. S represented by R
The alkene group having i preferably has 2 to 10 carbon atoms. The alkyne group having Si represented by R has 2 to 2 carbon atoms.
Ten are preferred. The aryl group having Si represented by R preferably has 6 to 20 carbon atoms. The substituted aryl group having Si represented by R preferably has 7 to 20 carbon atoms.

The Ta-based film forming material represented by the above general formula
Among them, R is -CH_Three, -CF_Three, -C_TwoH_Five, -C_Two
F_Five, -C_ThreeH₇, -C_ThreeF₇, -C_FourH₉, -C_FourF
₉, -CH = CH_TwoAnd -CH_TwoCH = CH_TwoIn the group of
Any of the conductive Ta-based film forming materials selected from
It is a new thing. L is (CH_Three)_TwoS, (C
_TwoH_Five)_TwoS, (C_ThreeH₇)_TwoS and (C_FourH ₉)_TwoS
Conductive Ta-based film forming material selected from the group consisting of
Charges are preferred.

Among the compounds represented by the above general formula (1),
Particularly preferred compounds are TaCl _Five・ S (C_TwoH_Five)
_Two, CH_ThreeTaCl_Four, (CH_Three)_TwoTaCl_Three, (C
H_Three)_ThreeTaCl_Two, CH_ThreeTaCl_Four・ S (C
_TwoH_Five)_Two, (CH_Three)_TwoTaCl _Three・ S (C_TwoH_Five)
_Two, (CH_Three)_ThreeTaCl_Two・ S (C_TwoH_Five)_TwoIn
You. Therefore, one or two selected from these groups
The above are particularly preferred compounds.

In the present invention, the above-mentioned general formula (1)
In addition to the compound having Ta represented by the following general formula:
The compound represented by (2) is also particularly preferred. General formula (2) TaC_iH_jN_kSi_lX_m [However, i is an integer of 2 to 40, j is an integer of 6 to 90, k
Is an integer of 0 to 9, l is an integer of 0 to 2, m is an integer of 0 to 4, X is
It is a halogen atom. Particularly preferred among the compounds represented by the above general formula (2)
Compound is [(CH _Three)_TwoN]_FiveTa, [(CH_Three)
_TwoN]_FourTaCl, [(CH_Three)_TwoN]_ThreeTaCl_Two,
[(CH_Three)_TwoN]_TwoTaCl_Three, [(CH_Three)_TwoN]
TaCl_Four, [(CH_Three)_TwoN]_FourTa [CH_TwoSi
(CH_Three)_Three], [(CH_Three)_TwoN]_ThreeTa [CH_TwoS
i (CH_Three)_Three]_Two, C_TwoH_FiveN = Ta [N (C
_TwoH_Five)_Two]_Three, Ta [N (C_TwoH_Five)_Two]_Four, C_FourH
₉N = Ta [N (C_TwoH_Five)_Two]_Three, (C _FiveH_Five)_TwoT
aH_Three, (CH_ThreeC_FiveH_Four)_TwoTaH_Three, (C_TwoH_FiveC
_FiveH_Four)_TwoTaH_Three, (C_ThreeH₇C_FiveH_Four)_TwoTa
H_Three, (C_FourH₉C_FiveH_Four)_TwoTaH_Three, [C_Five(CH
_Three)_Five]_TwoTaH_Three, (CH_ThreeC_FiveH_Four) TaC
₇H₇, (C_FiveH_Five)_TwoTa (N_Three)_Three, (CH_ThreeC_Five
H_Four)_TwoTa (N_Three)_Three, (C_TwoH_FiveC _FiveH_Four)_TwoTa
(N_Three)_Three, (C_ThreeH₇C_FiveH_Four)_TwoTa (N_Three)_Three,
(C_FourH ₉C_FiveH_Four)_TwoTa (N_Three)_Three, [C_Five(CH
_Three)_Five]_TwoTa (N_Three)_Three, (C _FiveH_Five)_TwoTa
(N_Three)_Two, (CH_ThreeC_FiveH_Four)_TwoTa (N_Three)_Two,
(C_TwoH_FiveC_FiveH_Four)_TwoTa (N_Three)_Two, (C_ThreeH₇C
_FiveH_Four)_TwoTa (N_Three)_Two, (C_FourH₉C_FiveH_Four)_TwoT
a (N_Three)_Two, [C_Five(CH_Three)_Five]_TwoTa (N_Three)_Two
It is. Therefore, a kind selected from these groups or
Two or more are particularly preferred compounds.

In the present invention, the Ta compound represented by the general formula (1) or (2) is dissolved in a hydrocarbon solvent and / or an amine solvent. Here, the hydrocarbon solvent is particularly preferably one having 5 to 40 carbon atoms. Among them, pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, heptadecane, octadecane, nonadecane, eicosan, heenicosan, docosan, trichosan, cyclohexane, decalin, toluene, xylene, mesitylene, Tetralin, petroleum ether, ligroin, cyclopentadiene, cyclopentadiene dimer, methylcyclopentadiene, methylcyclopentadiene dimer,
Ethylcyclopentadiene, ethylcyclopentadiene dimer, propylcyclopentadiene, propylcyclopentadiene dimer, butylcyclopentadiene,
Butylcyclopentadiene dimer, cycloheptatriene, cyclooctadiene, cyclooctatetraene are preferred solvents. In particular, a preferred solvent is hexane,
Heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, heptadecane, toluene and xylene. One or two or more selected from these groups are used.

The amine-based solvent preferably has a carbon atom in the molecule and has 2 to 40 carbon atoms. Among them, acetonitrile, dimethylethylamine, diethylamine, diethylmethylamine, triethylamine, propylamine, dipropylamine, dipropylmethylamine, dipropylethylamine, ethylenediamine,
N, N, N ', N'-tetramethylethylenediamine,
Diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine,
2,2 ′, 2 ″ -triaminotriethylamine, methylhydrazine, dimethylhydrazine, ethylhydrazine,
Diethylhydrazine, butylhydrazine, phenylhydrazine, ethyl azide, propyl azide, butyl azide, phenyl azide, piperidine, N-methylpiperidine, aniline, N, N-dimethylaniline, pyridine,
Quinoline is a preferred solvent. Particularly preferred solvents are dimethylethylamine, diethylamine, diethylmethylamine, triethylamine, propylamine, dipropylamine, ethylenediamine, N, N, N ', N'-.
It is tetramethylethylenediamine. One or two or more selected from these groups are used.

The second object is a method of forming a conductive Ta-based film, comprising the steps of: applying the above-described conductive Ta-based film forming material on a substrate;
Forming a conductive Ta-based film by decomposing the system-film forming material.

Also, a method of forming a conductive Ta-based film by chemical vapor deposition (CVD),
The problem is solved by a method for forming a conductive Ta-based film, comprising a step of forming a conductive Ta-based film on a substrate by decomposing the conductive Ta-based film forming material.

It is preferable that the method of forming a conductive Ta-based film further includes a step of heating a substrate on which the conductive Ta-based film is formed. The decomposition of the conductive Ta-based film forming material is performed by employing a heating means, a light irradiation means, and a plasma means. The decomposition of the Ta-based film forming material is particularly preferably performed in a reducing atmosphere. For example, hydrogen, hydrogen plasma, nitrogen, nitrogen plasma, ammonia, hydrazine, hydrazine derivatives (eg, CH ₃ NHNH ₂ ,
(CH ₃ ) ₂ NNH ₂ , CH ₃ NHNHCH ₃ , RNH
Hydrazine derivatives such as NH ₂ (R is a functional group such as an alkyl group), silane, and silane derivatives (for example, R _n Si
Y _4-n (R is a functional group such as an alkyl group, Y is H, F, C
silane derivatives such as l, Br or I), borane, and borane derivatives (eg, R _n BY _3-n (R is a functional group such as an alkyl group, Y is H, F, Cl, Br or I), etc. It is preferable to decompose the Ta-based film-forming material under an air current containing one or more selected from the group of borane derivatives).

In addition, simultaneously with the decomposition of a compound containing one or more compounds selected from the group consisting of ammonia, hydrazine, hydrazine derivatives and alkyl azides, or before and / or after the decomposition of the compound, a Ta-based compound can be used. The decomposition of the film-forming material is preferably performed. In particular, compounds containing one or more selected from the group of methylhydrazine, dimethylhydrazine, ethylhydrazine, diethylhydrazine, butylhydrazine, phenylhydrazine, ethyl azide, propyl azide, butyl azide, phenyl azide Preferably, the Ta-based film-forming material is decomposed simultaneously with or before and / or after the decomposition of the compound. Thus, a conductive Ta-based nitride film is formed.

The third object is to provide a conductive Ta-based film forming step and a copper (including copper alloy) wiring film on the conductive Ta-based film formed by the conductive Ta-based film forming step. And a step of forming a copper wiring film. Further, a copper (including copper alloy) wiring film is formed on the conductive Ta-based film formed by the above-described conductive Ta-based film forming method.
Solved by LSI.

In particular, copper (including a copper alloy) is formed on a Ta nitride-based film formed by using the above-described conductive Ta-based film forming method.
The problem is solved by a ULSI in which a wiring film is formed.

[0028]

BEST MODE FOR CARRYING OUT THE INVENTION A conductive Ta-based film according to the present invention (for example, a film of tantalum metal, tantalum carbide, tantalum nitride, tantalum silicide, tantalum silicide nitride, etc.) A tantalum oxide film shows conductivity. The conductive Ta of the present invention
Not applicable to system membranes. The formation material includes a compound having Ta and a hydrocarbon-based solvent. In particular, it is a material for forming a conductive Ta-based film provided as a base film of a copper (including copper alloy) wiring film, and includes a compound having Ta and a hydrocarbon-based solvent.

The conductive Ta-based film according to the present invention (for example, a film of metal tantalum, tantalum carbide, tantalum nitride, tantalum silicide, tantalum silicide silicide, etc.) Since tantalum oxide film does not show conductivity. This does not correspond to the conductive Ta-based film of the present invention.) The forming material includes a compound having Ta and an amine-based solvent. In particular, it is a material for forming a conductive Ta-based film provided as a base film of a copper (including copper alloy) wiring film, and includes a compound having Ta and an amine-based solvent.

The compound having Ta is, in particular, a compound represented by the following general formulas (1) and (2). Formula (1) R _n TaX _5-n · L _m [where R is H, an alkyl group, a halogenated alkyl group,
Alkene group, halogenated alkene group, alkyne group, halogenated alkyne group, aryl group, substituted aryl group, Si
Or an alkene group having Si, an alkyne group having Si, an aryl group having Si, or a substituted aryl group having Si.

N is an integer of 0-5. X is H, F, C
It is any one selected from the group of l, Br and I.
L is any one selected from the group consisting of alkyl-substituted sulfur, halogen-substituted sulfur, alkyl-substituted phosphine, and halogen-substituted phosphine. m is an integer of 0 to 4 when n is an integer of 1 to 5, and an integer of 1 to 4 when n is 0.

When n is 2 or more, all Rs in R _n may be the same or different. When n is 3 or less, all Xs in X _5-n may be the same or different. When m is 2 or more, all L in L _m
May be the same or different. ] The alkyl group (the n 1 or more integer) -C _n H _{2n + 1} is a group represented by. And the halogenated alkyl group is
The alkyl group is a group in which one or more hydrogen atoms have been replaced with halogen atoms. Alkene group is -C _n H _2n-1 group (n is an integer greater than or equal to 2) is represented by. The halogenated alkene group is a group in which one or more hydrogen atoms of the alkene group are substituted with a halogen atom. The alkyne group is-
It is a group represented by C _n H _{2n -3} (n is an integer of 2 or more).
The halogenated alkyne group is a group in which one or more hydrogen atoms of the alkyne group have been substituted with halogen atoms. The aryl group is an atomic group obtained by removing one hydrogen atom from an aromatic hydrocarbon. The substituted aryl group is such that one or more hydrogen atoms of the aryl group are other groups (eg, an alkyl group, a halogenated alkyl group, an alkene group, a halogenated alkene group, an alkyne group, a halogenated alkyne group, a halogen atom, and the like). Is a group substituted with The alkyl group having Si, the alkene group having Si, the alkyne group having Si, the aryl group having Si, and the substituted aryl group having Si are each a group (alkyl group, alkene group, alkyne group,
(Aryl group, substituted aryl group) has Si. Alkyl-substituted sulfur is, for example, R ₂ S or R
SH (R is any one selected from the group consisting of an alkyl group, an alkene group, an alkyne group, an aryl group, and a substituted aryl group). The halogen-substituted sulfur is, for example, SX ₂ or S ₂ X ₂ (X is any one selected from the group consisting of F, Cl, Br, and I) or SF ₆ . Alkyl-substituted phosphines include, for example, R ₃ P,
R ₂ PH, RPH ₂ (R is any one selected from the group consisting of an alkyl group, an alkene group, an alkyne group, an aryl group, and a substituted aryl group). Halogen-substituted phosphines include, for example, PX ₃ , PX ₅ (X is F, Cl,
(Any one selected from the group consisting of Br and I).

The alkyl group represented by R in the above general formula is
In particular, those having 1 to 10 carbon atoms. The alkene group represented by R particularly has 2 to 10 carbon atoms. R
The alkyne group represented by is particularly one having 2 to 10 carbon atoms. The aryl group represented by R particularly has 6 to 20 carbon atoms. The substituted aryl group represented by R particularly has 7 to 20 carbon atoms. The alkyl group having Si represented by R particularly has 1 to 10 carbon atoms. The alkene group having Si represented by R particularly has 2 to 10 carbon atoms. Si represented by R
Are particularly those having 2 to 10 carbon atoms. The aryl group having Si represented by R particularly has 6 to 20 carbon atoms. The substituted aryl group having Si represented by R particularly has 7 to 20 carbon atoms.

Among the Ta-based film forming materials represented by the above general formula, R represents —CH ₃ , —CF ₃ , —C ₂ H ₅ , and —C _{2.
F 5, -C 3 H 7,} -C 3 F 7, -C 4 H 9, -C 4 F
_9, either Ta-based film forming material selected from the group of -CH = CH ₂ and -CH ₂ CH = CH ₂ are preferred. L is (CH ₃ ) ₂ S, (C ₂ H ₅ )
Any Ta-based film forming material selected from the group consisting of ₂ S, (C ₃ H ₇ ) ₂ S and (C ₄ H ₉ ) ₂ S is preferable.

Among the compounds represented by the above general formula (1),
Particularly preferred compounds are TaCl _Five・ S (C_TwoH_Five)
_Two, CH_ThreeTaCl_Four, (CH_Three)_TwoTaCl_Three, (C
H_Three)_ThreeTaCl_Two, CH_ThreeTaCl_Four・ S (C
_TwoH_Five)_Two, (CH_Three)_TwoTaCl _Three・ S (C_TwoH_Five)
_Two, (CH_Three)_ThreeTaCl_Two・ S (C_TwoH_Five)_TwoIn
You. And one or two selected from these groups
The above are particularly preferred compounds.

General formula (2) TaC_iH_jN_kSi_lX_m [However, i is an integer of 2 to 40, j is an integer of 6 to 90, k
Is an integer of 0 to 9, l is an integer of 0 to 2, m is an integer of 0 to 4, X is
It is a halogen atom. Particularly preferred among the compounds represented by the above general formula (2)
Compound is [(CH _Three)_TwoN]_FiveTa, [(CH_Three)
_TwoN]_FourTaCl, [(CH_Three)_TwoN]_ThreeTaCl_Two,
[(CH_Three)_TwoN]_TwoTaCl_Three, [(CH_Three)_TwoN]
TaCl_Four, [(CH_Three)_TwoN]_FourTa [CH_TwoSi
(CH_Three)_Three], [(CH_Three)_TwoN]_ThreeTa [CH_TwoS
i (CH_Three)_Three]_Two, C_TwoH_FiveN = Ta [N (C
_TwoH_Five)_Two]_Three, Ta [N (C_TwoH_Five)_Two]_Four, C_FourH
₉N = Ta [N (C_TwoH_Five)_Two]_Three, (C _FiveH_Five)_TwoT
aH_Three, (CH_ThreeC_FiveH_Four)_TwoTaH_Three, (C_TwoH_FiveC
_FiveH_Four)_TwoTaH_Three, (C_ThreeH₇C_FiveH_Four)_TwoTa
H_Three, (C_FourH₉C_FiveH_Four)_TwoTaH_Three, [C_Five(CH
_Three)_Five]_TwoTaH_Three, (CH_ThreeC_FiveH_Four) TaC
₇H₇, (C_FiveH_Five)_TwoTa (N_Three)_Three, (CH_ThreeC_Five
H_Four)_TwoTa (N_Three)_Three, (C_TwoH_FiveC _FiveH_Four)_TwoTa
(N_Three)_Three, (C_ThreeH₇C_FiveH_Four)_TwoTa (N_Three)_Three,
(C_FourH ₉C_FiveH_Four)_TwoTa (N_Three)_Three, [C_Five(CH
_Three)_Five]_TwoTa (N_Three)_Three, (C _FiveH_Five)_TwoTa
(N_Three)_Two, (CH_ThreeC_FiveH_Four)_TwoTa (N_Three)_Two,
(C_TwoH_FiveC_FiveH_Four)_TwoTa (N_Three)_Two, (C_ThreeH₇C
_FiveH_Four)_TwoTa (N_Three)_Two, (C_FourH₉C_FiveH_Four)_TwoT
a (N_Three)_Two, [C_Five(CH_Three)_Five]_TwoTa (N_Three)_Two
It is. And a kind selected from these groups or
Two or more are particularly preferred compounds.

In the present invention, the Ta compound represented by the general formula (1) or (2) is dissolved in a hydrocarbon or an amine solvent. At this time, the concentration of the Ta-based compound may be within the range in which it is dissolved. Incidentally, the Ta-based compound may be present as a precipitate. Here, the hydrocarbon-based solvent particularly has 5 to 40 carbon atoms. Among them, pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, heptadecane, octadecane, nonadecane, eicosan, heenicosan, docosan, trichosan, cyclohexane, decalin, toluene, xylene, mesitylene, Tetralin, petroleum ether, ligroin, cyclopentadiene, cyclopentadiene dimer, methylcyclopentadiene, methylcyclopentadiene dimer, ethylcyclopentadiene, ethylcyclopentadiene dimer, propylcyclopentadiene, propylcyclopentadiene dimer, butylcyclopentadiene, butylcyclopentadiene dimer, Cycloheptatriene, cyclooctadiene, cycloo Tatetoraen is the preferred solvent. Particularly preferred solvents are hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, heptadecanetoluene, xylene. One or two or more selected from these groups are used.

The amine solvent particularly has a carbon atom in the molecule and has 2 to 40 carbon atoms. Among them, acetonitrile, dimethylethylamine, diethylamine, diethylmethylamine, triethylamine, propylamine, dipropylamine, dipropylmethylamine, dipropylethylamine, ethylenediamine,
N, N, N ', N'-tetramethylethylenediamine,
Diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine,
2,2 ′, 2 ″ -triaminotriethylamine, methylhydrazine, dimethylhydrazine, ethylhydrazine,
Diethylhydrazine, butylhydrazine, phenylhydrazine, ethyl azide, propyl azide, butyl azide, phenyl azide, piperidine, N-methylpiperidine, aniline, N, N-dimethylaniline, pyridine,
Quinoline is a preferred solvent. Particularly preferred solvents are dimethylethylamine, diethylamine, diethylmethylamine, triethylamine, propylamine, dipropylamine, ethylenediamine, N, N, N ', N'-.
It is tetramethylethylenediamine. One or two or more selected from these groups are used.

The method for forming a conductive Ta-based film according to the present invention comprises:
The method includes a step of applying the Ta-based film-forming material on a substrate, and a step of decomposing the Ta-based film-forming material on the substrate to form a Ta-based film. In particular, the conductive Ta
A method for forming a base film by CVD, wherein the Ta
A step of decomposing the base film forming material to form a Ta base film on the substrate.

For example, an apparatus as shown in FIGS. 1 and 2 is used.
Forming a conductive Ta-based thin film on the substrate.
It is. That is, in a hydrocarbon or amine solvent, R_n
TaX_5-n・ L_mOr TaC_iH_jN_kSi_lX_mDissolve
The scraped solution is placed in a container and allowed to evaporate. Vaporized
Raw material (R_nTaX_5-n・ L_mOr TaC_iH_jN_kS
i_lX_mIs introduced into the decomposition reactor via piping. reaction
A silicon substrate on which a film is formed is placed in the furnace,
This silicon substrate is heated by the heating means. So
And the R introduced into the reactor_nTaX_5-n・ L_mOr
TaC_iH_jN _kSi_lX_mDecomposes near silicon substrate
To form a conductive Ta-based film, for example, conductive nitride.
A Ta-based film is formed. In addition, silicon in the form of the solution
It may be transported on a substrate.

1 and 2, reference numerals 1a, 1b, and 1c denote containers each containing a solution containing a compound having Ta.
2 is a vaporizer, 3 is a heater, 4 is a decomposition reactor, 5 is a silicon substrate, 6 is a reaction gas such as hydrogen, hydrogen plasma, ammonia or silane, 7 is a gas flow controller, 8 is a liquid flow controller. It is. The method for forming a conductive Ta-based film includes a step of heating a substrate on which the conductive Ta-based film is formed. The decomposition of the Ta-based film forming material is performed by employing a heating means, a light irradiation means, and a plasma means. The decomposition of the Ta-based film forming material is particularly performed in a reducing atmosphere. For example, hydrogen, hydrogen plasma, nitrogen, nitrogen plasma, ammonia, hydrazine, hydrazine derivatives (for example, CH ₃
NHNH ₂ , (CH ₃ ) ₂ NNH ₂ , CH ₃ NHNHC
Hydrazine derivatives such as H ₃ , RNHNH ₂ (R is a functional group such as an alkyl group), silane, silane derivatives (for example, R _n SiY _4-n (R is a functional group such as an alkyl group, Y
Is a silane derivative such as H, F, Cl, Br or I)),
Borane and borane derivatives (for example, R _n BY _3-n (R
Is a functional group such as an alkyl group, and Y is a decomposition of a Ta-based film-forming material under an air current containing one or more members selected from the group consisting of borane derivatives such as H, F, Cl, Br and I). Is done. The Ta-based film-forming material may be formed simultaneously with the decomposition of a compound containing one or more compounds selected from the group consisting of ammonia, hydrazine, hydrazine derivatives, and alkyl azides, or before and / or after the decomposition of the compound. Is decomposed. In particular, compounds containing one or more selected from the group of methylhydrazine, dimethylhydrazine, ethylhydrazine, diethylhydrazine, butylhydrazine, phenylhydrazine, ethyl azide, propyl azide, butyl azide, phenyl azide Simultaneously with or before and / or after the decomposition of the compound
The decomposition of the system film forming material is performed. Thus, a conductive Ta-based nitride film is formed.

The method of forming a wiring film according to the present invention includes the step of forming a conductive Ta-based film and the step of forming copper (including a copper alloy) on the conductive Ta-based film formed by the conductive Ta-based film forming step. A) forming a copper wiring film for forming a wiring film. The ULSI according to the present invention is a ULSI in which a copper (including copper alloy) wiring film is formed on a conductive Ta-based film formed using the above-described Ta-based film forming method. In particular,
This is a ULSI in which a copper (including copper alloy) wiring film is formed on a conductive Ta-based nitride film formed using the Ta-based film forming method.

Hereinafter, the present invention will be described with reference to some specific examples, but the present invention is not limited to these examples.

[0044]

Example 1 The apparatus shown in FIG. 1 was used. In the container 1a, [(C
H ₃ ) ₂ N] ₅ Ta / toluene solution ([(CH ₃ )
₂ N] ₅ Ta at a concentration of 20 wt%).
Nothing is put in the containers 1b and 1c. The vaporizer 2 is heated to 80 to 130C.

Under the above conditions, [(CH ₃ ) ₂ N]
_The 5Ta / toluene solution was transported under control by the liquid flow controller 8, and [(CH ₃ ) ₂ N] ₅ Ta and toluene were both vaporized by the vaporizer 2. When the vapors were collected by a cooling trap, 90% or more of [(CH ₃ ) ₂ N] ₅ Ta could be recovered. Further, the vaporization experiment was continuously performed for several tens of hours, but the transport amount was constant.

[0046]

Comparative Example 1 The apparatus shown in FIG. 1 was used. [(C
H ₃ ) ₂ N] ₅ Ta (solid). Nothing is put in the containers 1a and 1b. Vaporizer 2 is 80
Heated to ~ 130 ° C. Under the above conditions,
[(CH ₃ ) ₂ N] ₅ Ta was sublimated and transported by a carrier gas. However, one hour later, the pipe was clogged and stopped.

In order to eliminate clogging, the entire piping must be maintained at 140 ° C.
The experiment was resumed with the temperature kept at that temperature. When the vaporized product was recovered by a cooling trap, only 40% of [(CH ₃ ) ₂ N] ₅ Ta could be recovered at most. When the container 1c is opened, [(CH
_{3) 2} N] degradation product ₅ Ta was observed. Further, as the vaporization experiment progressed, the transport amount was gradually reduced.

[0048]

Embodiment 2 The apparatus shown in FIG. 2 was used. TaC is used for the container 1a.
_{l 5 · S (C 2 H} 5) 2 / toluene solution (TaCl ₅ ·
The concentration of S (C ₂ H ₅ ) ₂ is 6 wt%. Nothing is put in the containers 1b and 1c. Hydrogen was used as a reaction gas, and helium was used as a carrier gas. The vaporizer 2 is heated to 80 to 130C. The silicon substrate 5 is heated to 200 to 450C. The deposition pressure in the decomposition reaction furnace 4 is 0.2 to 1.5 Torr
Is set to

Under the above conditions, TaCl ₅ .S (C
_{The 2} H ₅ ) ₂ / toluene solution is controlled and transported by the liquid flow rate controller 8, and both TaCl ₅ .S (C ₂ H ₅ ) ₂ and toluene are vaporized by the vaporizer 2.
Then, a thin film was formed. This thin film was metal tantalum and had a thickness of 0.01 to 0.2 μm.

[0050]

Embodiment 3 In Embodiment 2, the container 1a contains (C ₃ H
₇ C ₅ H ₄ ) ₂ TaH ₃ / xylene solution ((C ₃ H ₇ C
₅ H ₄ ) ₂ TaH ₃ concentration is 1 wt%), the vaporizer 2 is at 150 to 250 ° C., and the silicon substrate 5 is at 200 to 5
The same procedure was performed except that the temperature was changed to 00 ° C.

As a result, a thickness of 0.01
A .about.0.2 .mu.m metal tantalum thin film was formed.

[0052]

Fourth Embodiment In the second embodiment, (CH _{3
C 5 H 4) TaC 7 H} 7 / cycloheptatriene solution _{((CH 3 C 5 H 4} ) concentration of TaC ₇ H ₇ is 3 wt%)
Was carried out in the same manner except that hydrogen plasma was used as a reaction gas and hydrogen was used as a carrier gas.

As a result, a thickness of 0.01
A tantalum carbide thin film having a thickness of about 0.2 μm was formed.

[0054]

Fifth Embodiment In the second embodiment, the container 1a contains TaCl
₅ · S (C ₂ H ₅ ) ₂ / toluene solution (TaCl ₅ .S
(The concentration of (C ₂ H ₅ ) ₂ is 6 wt%), ammonia is used as a reaction gas, and nitrogen is used as a carrier gas.
The same procedure was performed except that the temperature was changed to 450 ° C.

As a result, a thickness of 0.01
A .about.0.2 .mu.m tantalum nitride thin film was formed.

[0056]

Embodiment 6 In Embodiment 2, the container 1a contains [(CH
₃ ) ₂ N] ₅ Ta / toluene solution ([(CH ₃ ) ₂ N]
₅ Ta concentration is 10 wt%), ethyl azide is charged in the container 1 c, no reaction gas is used, nitrogen is used as a carrier gas, the vaporizer 2 is at 80 to 100 ° C., and the silicon substrate 5 is at 300 to 300 ° C. The same procedure was performed except that the temperature was changed to 500 ° C.

As a result, a thickness of 0.01
A .about.0.2 .mu.m tantalum nitride thin film was formed.

[0058]

Embodiment 7 In Embodiment 2, the container 1a contains C ₂ H ₅
The concentration of N = Ta [N (C ₂ H ₅ ) ₂ ] ₃ / diethylamine solution (C ₂ H ₅ N = Ta [N (C ₂ H ₅ ) ₂ ] ₃ is 5
wt.), ammonia as a reaction gas, nitrogen as a carrier gas, and a vaporizer 2 at 40 to 90 ° C.
The same operation was performed except that the temperature of the silicon substrate 5 was set to 300 to 500 ° C.

As a result, a thickness of 0.01
A .about.0.2 .mu.m tantalum nitride thin film was formed.

[0060]

Embodiment 8 In Embodiment 2, the container 1a contains C ₂ H ₅
N = Ta [N (C ₂ H ₅ ) ₂ ] ₃ / heptane solution (C ₂
The concentration of H ₅ N = Ta [N (C ₂ H ₅ ) ₂ ] ₃ is 5 wt.
%), A monomethylhydrazine / heptane solution is placed in the container 1b, silane is used as a reaction gas, nitrogen is used as a carrier gas, and the vaporizer 2 is heated to 40 to 90 ° C.
The same operation was performed except that the temperature of the silicon substrate 5 was set to 300 to 500 ° C.

As a result, a thickness of 0.01
A tantalum nitride silicide thin film of about 0.2 μm was formed.

[0062]

Ninth Embodiment In the second embodiment, [(CH
₃ ) ₂ N] ₄ Ta [CH ₂ Si (CH ₃ ) ₃ ] / nonane solution ([(CH ₃ ) ₂ N] ₄ Ta [CH ₂ Si (C
H ₃ ) ₃ ] at a concentration of 5 wt%), using silane as a reaction gas, nitrogen as a carrier gas, the vaporizer 2 at 100 to 180 ° C., the silicon substrate 5 at 300 to 5 ° C.
The same procedure was performed except that the temperature was changed to 00 ° C.

As a result, a thickness of 0.01
A .about.0.2 .mu.m tantalum silicide thin film was formed.

[0064]

Embodiment 10 The silicon substrate 5 on which the tantalum nitride thin film formed in Embodiment 6 was formed was heated to 160.degree. Then, a hexafluoroacetylacetone copper trimethylvinylsilane (HfacCu: TMVS) heptadecane solution (0. 0) is formed on the tantalum nitride thin film on the silicon substrate 5.
2 mol / L). After pyrolysis for 20 seconds, cool, drain the solution and add
Washed twice.

As a result, the surface was changed from silver luster of the tantalum nitride thin film to red gold luster of copper. When the cross section of this silicon substrate 5 was observed with an electron microscope, it was 0.5 μm from the surface.
Deposits were observed to a depth of m. Subsequently, when the sediment of this cross-sectional image was subjected to elemental analysis, the surface layer was metallic copper, and below the metallic copper was tantalum nitride containing Ta and N as main components. And copper did not diffuse into the silicon substrate.

[0066]

Comparative Example 2 A silicon substrate on which a tantalum nitride thin film was not formed was heated to 160 ° C. Then, a heptadecane solution (0.2 mol / L) of hexafluoroacetylacetone copper trimethylvinylsilane (HfacCu: TMVS) was poured onto the silicon substrate. After pyrolysis for 20 seconds, it was cooled, the solution was drained and washed three times with normal hexane.

As a result, the surface was changed from dull silver luster to copper red gold luster. When a cross section of the silicon substrate was observed with an electron microscope, a deposit was observed to a depth of 0.4 μm from the surface. Subsequently, when the deposit of this cross-sectional image was subjected to elemental analysis, it was metallic copper at a depth of 0.4 μm from the surface, copper-silicon up to a depth of 2 μm from there, and silicon below. . Therefore, copper was diffused into the silicon substrate.

[0068]

Embodiment 11 A CVD using a solution of hexafluoroacetylacetone copper trimethylvinylsilane (HfacCu: TMVS) / trimethylvinylsilane as a CVD raw material on a tantalum nitride thin film of a silicon substrate 5 on which a tantalum nitride thin film formed in Example 6 is formed. To form a copper thin film.

As a result, the surface changed from silver luster of the tantalum nitride thin film to copper red gold luster. When the cross section of this silicon substrate 5 was observed with an electron microscope, it was 0.8 μm from the surface.
Deposits were observed to a depth of m. Subsequently, when the sediment of this cross-sectional image was subjected to elemental analysis, the surface layer was metallic copper, and below the metallic copper was tantalum nitride containing Ta and N as main components. And copper did not diffuse into the silicon substrate.

[0070]

Comparative Example 3 A thin copper film was formed on a silicon substrate on which no tantalum nitride thin film was formed by CVD using HfacCu: TMVS as a CVD raw material. As a result, the surface was changed from dull silver luster to copper red gold luster. When the cross section of the silicon substrate was observed with an electron microscope, a deposit was observed to a depth of 0.5 μm from the surface.

Subsequently, when the sediment of this cross-sectional image was subjected to elemental analysis, metallic copper was found at a depth of 0.5 μm from the surface, copper-silicon up to a depth of 2 μm therefrom, and silicon underneath. Met. Therefore, copper was diffused into the silicon substrate.

[0072]

According to the present invention, metal tantalum, tantalum carbide, tantalum nitride, tantalum silicide, tantalum silicide, and the like exhibit conductivity different from tantalum oxide, and when a copper film is provided thereon, copper is removed from the substrate. It is also excellent in barrier properties, which are difficult to diffuse into. An excellent conductive Ta-based film as such a barrier film can be efficiently and beautifully formed over a long period of time.

When a copper wiring film is formed on the conductive Ta-based film, copper hardly diffuses into the substrate. Therefore, in order to improve the signal processing speed, this is a very preferable technique in the ULSI in which the copper wiring width is reduced to 0.18 μm or less.

[Brief description of the drawings]

FIG. 1 is a schematic diagram of a vaporizer.

FIG. 2 is a schematic diagram of a film forming apparatus.

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁷ Identification code FI C23C 16/42 C23C 16/42 H01B 1/02 H01B 1/02 Z 5/14 5/14 Z 13/00 503 13/00 503Z H01L 21/285 H01L 21/285 C 301 301R 21/3205 21/88 R (56) Reference JP 2000-204095 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C23C 16/00-16/56 B01J 19/00 C07F 9/00 H01B 1/02 H01B 5/14 H01B 13/00 H01L 21/285 H01L 21/3205 INSPEC (DIALOG) JICST file (JOIS)

Claims (22)

(57) [Claims] 1. A conductive Ta-based material for forming a conductive Ta-based film, comprising: a Ta-containing compound; and a hydrocarbon-based solvent.
System film forming material. However, the following are excluded. Conductive Ta-based
The film is a tantalum nitride film, and the compound having Ta is Ta.
[N (CH ₃ ) C _n H _{2n + 1} ] ₅ (n is 2, 3 or 4),
Ta [N (CH ₃ ) ₂ ] ₅ or Ta [N (CH ₂ CH
₃ ) ₂ ] ₅ and the hydrocarbon solvent has 6, 7 or
Is a straight, branched or cyclic hydrocarbon of 8
Is an alkyl group having 3, 4, 5 or 6 carbon atoms
Mixture of Mi emissions, or methyl acetate, ethyl acetate,
Butyl, the group consisting of acetic acid Isobuchi Le and pentyl acetate
The selected acetate solvent. 2. A hydrocarbon solvent having a carbon number of 5 to 5.
The conductive T according to claim 1, wherein the conductive T is 40.
a-based film forming material. 3. A material for forming a conductive Ta-based film, comprising: a compound having Ta; and an amine-based solvent. However, the following are excluded. Conductive Ta-based film
Is a tantalum nitride film, and the compound having Ta is Ta.
[N (CH ₃ ) C _n H _{2n + 1} ] ₅ (n is 2, 3 or 4),
Ta [N (CH ₃ ) ₂ ] ₅ or Ta [N (CH ₂ CH
₃ ) ₂ ] ₅ and the amine solvent has 3, 4, 5 carbon atoms
Or the alkylamine of 6, or the above alkylamine
And C6, C7 or C8 linear, branched or cyclic
Solvents in mixtures with hydrocarbons. 4. The conductive Ta-based film forming material according to claim 3, wherein the amine-based solvent has a carbon atom in the molecule and has 2 to 40 carbon atoms. 5. The conductive Ta-based film forming material according to claim 1, wherein the compound having Ta is a compound represented by the following general formula. R _n TaX _5-n · L _m [where R is H, an alkyl group, a halogenated alkyl group,
Alkene group, halogenated alkene group, alkyne group, halogenated alkyne group, aryl group, substituted aryl group, Si
Or an alkene group having Si, an alkyne group having Si, an aryl group having Si, or a substituted aryl group having Si. n
Is an integer of 0 to 5. X is H, F, Cl, Br and I
Is any one selected from the group of L is alkyl-substituted sulfur, halogen-substituted sulfur, alkyl-substituted phosphine,
And halogen-substituted phosphines. m is an integer of 0 to 4 when n is an integer of 1 to 5, and an integer of 1 to 4 when n is 0. When n is 2 or more, all R in R _n may be the same or different. When n is 3 or less, all Xs in X _5-n may be the same or different. When m is 2 or more, all L in L _m may be the same or different. ] 6. The compound having Ta is TaCl ₅ .S.
(C ₂ H ₅ ) ₂ , CH ₃ TaCl ₄ , (CH ₃ ) ₂ Ta
Cl ₃ , (CH ₃ ) ₃ TaCl ₂ , CH ₃ TaCl _4.
S (C ₂ H ₅ ) ₂ , (CH ₃ ) ₂ TaCl ₃ .S (C _{2
H 5) 2, (CH 3} ) 3 TaCl 2 · S (C 2 H 5) 2
6. The conductive T according to claim 1, wherein the conductive T is one or more selected from the group consisting of
a-based film forming material. 7. The compound having Ta is an organometallic compound represented by the following general formula:
The material for forming a conductive Ta-based film according to any one of claims 1 to 4. _{TaC i H j N k Si l} X m [where, i is an integer of 2 to 40, j is an integer of 6 to 90, k
Is an integer of 0 to 9, 1 is an integer of 0 to 2, m is an integer of 0 to 4, and X is a halogen atom. ] 8. A compound having Ta is represented by [(CH_Three)_Two
N]_FiveTa, [(CH_Three)_TwoN]_FourTaCl, [(CH
_Three)_TwoN]_ThreeTaCl_Two, [(CH_Three)_TwoN]_TwoTaC
l_Three, [(CH_Three)_TwoN] TaCl_Four, [(CH_Three)_Two
N]_FourTa [CH_TwoSi (CH_Three)_Three], [(CH_Three)
_TwoN]_ThreeTa [CH_TwoSi (CH_Three) _Three]_Two, C_TwoH_Five
N = Ta [N (C_TwoH_Five)_Two]_Three, Ta [N (C
_TwoH_Five)_Two] _Four, C_FourH₉N = Ta [N (C
_TwoH_Five)_Two]_Three, (C_FiveH_Five)_TwoTaH_Three, (CH_ThreeC
_FiveH_Four)_TwoTaH_Three, (C_TwoH_FiveC_FiveH_Four)_TwoTa
H_Three, (C_ThreeH₇C_FiveH_Four)_TwoTaH_Three, (C_FourH₉C
_FiveH_Four)_TwoTaH_Three, [C_Five(CH_Three)_Five]_TwoTa
H_Three, (CH_ThreeC_FiveH_Four) TaC₇H₇, (C_FiveH_Five)
_TwoTa (N_Three)_Three, (CH_ThreeC_FiveH_Four)_TwoTa (N_Three)
_Three, (C_TwoH_FiveC_FiveH_Four)_TwoTa (N_Three)_Three, (C_ThreeH
₇C_FiveH_Four)_TwoTa (N_Three)_Three, (C_FourH₉C_FiveH_Four)
_TwoTa (N_Three)_Three, [C_Five(CH_Three)_Five]_TwoTa
(N_Three)_Three, (C_FiveH_Five)_TwoTa (N_Three)_Two, (CH_Three
C_FiveH_Four)_TwoTa (N_Three)_Two, (C_TwoH_FiveC_FiveH_Four)_Two
Ta (N_Three) _Two, (C_ThreeH₇C_FiveH_Four)_TwoTa (N_Three)
_Two, (C_FourH₉C_FiveH_Four)_TwoTa (N _Three)_Two, [C
_Five(CH_Three)_Five]_TwoTa (N_Three)_TwoFrom the group of
Claims characterized by one or more types
The conductive Ta-based film according to any one of claims 1 to 4 or 7.
Forming material. 9. The conductive Ta-based film forming material according to claim 1, which is a material for forming a conductive Ta-based film provided as a base film of a copper wiring film. 10. A method for forming a conductive Ta-based film, the method comprising: applying the conductive Ta-based film forming material according to claim 1 on a substrate; Decomposing the conductive Ta-based film forming material to form a conductive Ta-based film.
-Based film forming method. 11. A method for forming a conductive Ta-based film by chemical vapor deposition.
10. A method for forming a conductive Ta-based film, comprising a step of decomposing the material for forming a conductive Ta-based film according to claim 9 to form a conductive Ta-based film on a substrate. 12. The method for forming a conductive Ta-based film according to claim 10, further comprising a step of heating a substrate on which the conductive Ta-based film is formed. 13. The method for forming a conductive Ta-based film according to claim 10, wherein the decomposition of the conductive Ta-based film-forming material is performed by heating. 14. The method for forming a conductive Ta-based film according to claim 10, wherein the decomposition of the material for forming the conductive Ta-based film is performed by light. 15. The method according to claim 10, wherein the decomposition of the conductive Ta-based film forming material is performed by plasma.
4. Any of the conductive Ta-based film forming methods. 16. The method according to claim 10, wherein the decomposition of the conductive Ta-based film forming material is performed in a reducing atmosphere.
5. Any of the conductive Ta-based film forming methods. 17. In an air stream containing one or more selected from the group consisting of hydrogen, hydrogen plasma, nitrogen, nitrogen plasma, ammonia, hydrazine, hydrazine derivatives, silane, silane derivatives, borane, and borane derivatives, The method for forming a conductive Ta-based film according to any one of claims 10 to 16, wherein the material for forming the conductive Ta-based film is decomposed. 18. The method according to claim 1, wherein the compound having one or more of the group consisting of ammonia, hydrazine, a hydrazine derivative and an alkyl azide is decomposed simultaneously with, or before and / or after, the decomposition of the compound. 18. The Ta-based film forming material is decomposed.
Any of the conductive Ta-based film forming methods. 19. One or more selected from the group consisting of methylhydrazine, dimethylhydrazine, ethylhydrazine, diethylhydrazine, butylhydrazine, phenylhydrazine, ethyl azide, propyl azide, butyl azide, and phenyl azide. 19. The conductive Ta-based film-forming material is decomposed simultaneously with the decomposition of the compound containing, or before and / or after the decomposition of the compound. -Based film forming method. 20. A conductive Ta-based film forming step according to claim 10, and a copper wiring film is formed on the conductive Ta-based film formed in the conductive Ta-based film forming step. A method for forming a wiring film, comprising a step of forming a copper wiring film. 21. An ULSI in which a copper wiring film is formed on a conductive Ta-based film formed by the method for forming a conductive Ta-based film according to claim 10. 22. An ULSI in which a copper wiring film is formed on a Ta nitride-based film formed by using the method for forming a conductive Ta-based film according to claim 10.