JPH11200048A - Forming material of copper alloy film and forming method of copper alloy film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enable filling of wiring holes having a small diameter and a high aspect ratio, to improve the efficiency and to increase the EM life by constituting the copper alloy of a Cu-coordinated complex and an org. metal or metal complex of one or more kinds of metals selected from Zr, Sn, Mg, Cr, Ni, Cd and Mn. SOLUTION: The Cu-coordinated complex is a (+1) coordinated complex stabilized with ligands, or a complex with coordination of β-diketone to Cu. Especially, the complex has β-diketone coordinated to Cu and at least one stabilizing ligand bonded to Cu. As for the β-diketone, trifluoroacetylacetone or hexafluoroacetylacetone can be used. As the stabilizing ligand, 1,5- cyclooctadiene or alkyl-substd. 1,5-cyclooctadiene can be used. Tetrakis dimethylaminozirconium or the like is cited as the org. metal or metal complex of Zr or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a copper alloy film forming material and a copper alloy film forming method.

[0002]

At present, in the field of semiconductor devices, miniaturization is progressing in order to improve signal processing speed. 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. In addition, power consumption increases with higher functionality and higher performance of devices, and Pent
Some have reached up to 30W, such as ium-Pro. The operating environment of the device is 100 to 1 temperature.
It has reached 20 ° C. Therefore, the electromigration (E
M) causes a problem of reduced reliability.

Therefore, a Cu wiring having high EM resistance has been studied instead of the conventional Al-Si-Cu wiring. That is, the adoption of copper makes it possible to reduce the wiring width to 0.25 μm or less. However, when the wiring width is 0.25 μm or less, since the crystal grains are almost the same as the wiring width, it has been found that the life of the wiring is as short as several years in an environment where the temperature is 120 ° C.

Therefore, in order to solve this problem, Cu-Z
r alloy proposed (Symposium, June 24, 1996,
Exploring the direction of the future wiring process, hosted by Realize, presenter: Yasushi Igarashi). That is, while the EM life of pure copper is 3.9 years,
It is said that the EM life of a u-Zr alloy is extended to 144 years.

[0005] A sputtering method is employed for producing the Cu-Zr alloy film. However, according to the study of the present inventor, there is a limit in the sputtering method in order to achieve the burying of the wiring hole having the diameter of 0.25 μm or less and the high aspect ratio (the depth is deeper than the diameter). I understand that. In other words, while studying thin-film formation technology, if the sputtering method is used to form a copper alloy film that is said to have a long EM life, there is a limit to the embedding of wiring holes with a high aspect ratio. I knew it.

Further, the film formation efficiency is low in the sputtering method.
Therefore, the problem to be solved by the present invention is that the caliber is 0.
It is an object of the present invention to provide a technique for forming a copper alloy film which is capable of filling a wiring hole having a high aspect ratio of 25 μm or less, is efficient, and has a long EM life.

[0007]

As the study for solving the above-mentioned problems has been earnestly promoted, the formation of a copper alloy film by a chemical vapor deposition (CVD) method instead of a sputtering method has a large diameter. It has been found that, when the thickness is 0.25 μm or less, wiring holes having a high aspect ratio can be embedded.

Further, according to the CVD method, the film forming efficiency is good. However, the problem of what material must be used to form a copper alloy film having a long EM life by the CVD method has not been solved. As a result of further study on this problem, a coordination complex of copper and an organic metal or metal complex of at least one metal selected from the group of zirconium, tin, magnesium, chromium, nickel, cadmium, and manganese It turns out that it can be solved by using.

The present invention has been accomplished on the basis of such findings, and the above-mentioned problem is a material for forming a copper alloy film, which comprises a copper coordination complex, zirconium, tin,
The problem is solved by a copper alloy film forming material comprising an organic metal or a metal complex of at least one metal selected from the group consisting of magnesium, chromium, nickel, cadmium, and manganese.

[0010] In particular, a material for forming a copper alloy film by chemical vapor deposition, which is selected from the group of a coordination complex of copper and zirconium, tin, magnesium, chromium, nickel, cadmium, and manganese. The problem is solved by a copper alloy film forming material characterized by comprising an organic metal or a metal complex of at least one metal.

Further, a coordination complex of copper, zirconium, tin,
A method for forming a copper alloy film using an organic metal or a metal complex of at least one metal selected from the group consisting of magnesium, chromium, nickel, cadmium, and manganese, wherein the substrate on which the copper alloy film is formed is heated. The process of
A step of attaching an organometallic or metal complex of at least one metal selected from the group of the copper coordination complex, zirconium, tin, magnesium, chromium, nickel, cadmium and manganese onto the substrate, Forming a copper alloy film by decomposing the copper coordination complex and the metal organic metal or metal complex.

In particular, a coordination complex of copper, zirconium,
Tin, magnesium, chromium, nickel, cadmium, a method of forming a copper alloy film by chemical vapor deposition using an organic metal or metal complex of at least one metal selected from the group of manganese,
A step of heating a substrate for forming a copper alloy film, and a coordination complex of the copper, and zirconium, tin, magnesium, chromium, nickel, cadmium, and an organic metal or metal of at least one metal selected from the group of manganese A step of attaching a complex to a substrate, and a step of decomposing the copper coordination complex and the metal organometallic or metal complex attached to the substrate to form a copper alloy film. The problem is solved by a copper alloy film forming method.

The copper coordination complex used in the "copper alloy film forming material and copper alloy film forming method" of the present invention is preferably a (+1) coordination complex stabilized by a ligand. Further, those in which a β-diketone is coordinated to copper are preferable. In particular, those having a β-diketone coordinated to copper and at least one stabilizing ligand bonded to copper are preferable. Above all, β-diketone is coordinated to copper, and the β-diketone is represented by the general formula R′COCHRCOR ″ [where R is H, F, Cl, Br, I, a methyl group, and an ethyl group. R ′ and R ″ are C
_{n H 2n + 1, C n} F 2n + 1 (n is an integer from 1 to 4) selected from the group consisting of, aryl group and substituted aryl group. ] Is preferable. Further, β-diketone is a coordination bond to copper, and the β-diketone has a general formula R′C
OCH ₂ COR ″, wherein R ′ and R ″ are —CH ₃ , —CF ₃ , —C ₂ H ₅ , —C
_{2 F 5, -C 3 H 7} , -C 3 F 7, -C 4 H 9 and -C
Which is preferably one selected from the group consisting of ₄ F _9. In particular, β
-It is preferred that the diketone is coordinated to copper and the β-diketone is trifluoroacetylacetone or hexafluoroacetylacetone.

The copper coordination complex has at least one stabilizing ligand bonded to copper, and the stabilizing ligand is substituted or unsubstituted alkyne, olefin, diene, and phosphine. Those selected from the group of are preferred. Among them, one having at least one stabilizing ligand bonded to copper, wherein the stabilizing ligand is 1,5-
Cyclooctadiene, alkyl-substituted 1,5-cyclooctadiene, fluoro-1,5-cyclooctadiene, cyclooctene, methylcyclooctene, cyclooctatetraene, norbornene, norbornadiene, tricyclo [5.2.1.0] -Deca-2,6-diene, 1,4
Those selected from the group consisting of cyclohexadiene, acetylene, alkyl-substituted acetylene, halogen-substituted acetylene and trimethylphosphine are preferred. Further, it has at least one stabilizing ligand bonded to copper, wherein the stabilizing ligand is selected from the group of trimethylvinylsilane, methyltrivinylsilane, dimethyldivinylsilane, and bistrimethylsilylacetylene. Is preferred.

Particularly preferred coordination complexes of copper are hexafluoroacetylacetonato copper (I) 1,5-cyclooctadiene, hexafluoroacetylacetonato copper (I) dimethyl-1,5-cyclooctadiene, or these. Is a mixture of Alternatively, hexafluoroacetylacetonato copper (I) trimethylvinylsilane, tris (hexafluoroacetylacetonatocopper (I)) methyltrivinylsilane, bis (hexafluoroacetylacetonatocopper (I)) dimethyldivinylsilane, hexafluoroacetylacetate Nato copper (I) bistrimethylsilylacetylene, or a mixture thereof. Or, copper (I) hexafluoroacetylacetonate 1,5-cyclooctadiene, copper (I) hexafluoroacetylacetonate dimethyl-1,5-cyclooctadiene, copper (I) hexafluoroacetylacetonatodiethyl-1 , 5-cyclooctadiene, hexafluoroacetylacetonato copper (I) trimethylvinylsilane, tris (hexafluoroacetylacetonato copper (I)) methyltrivinylsilane, bis (hexafluoroacetylacetonato copper (I)) dimethyldivinylsilane , Hexafluoroacetylacetonato copper (I) bistrimethylsilylacetylene, or a mixture thereof.

The organometallic or metal complex of zirconium used in the above-mentioned "copper alloy film forming material and copper alloy film forming method" is tetrakisdimethylaminozirconium, tetrakisdiethylaminozirconium, zirconium tetraboron hydride, zirconium tetrabromide, zirconium. Those selected from the group of tetrachlorides are preferred.

According to the present invention, "a copper alloy film forming material and a copper alloy film"
Organometallic or Metal Complex of Tin Used in "Formation Method"
The body is R¹R^TwoR^ThreeR^FourSn (R¹, R^Two, R^Three, R^Four
Is an alkyl group or an aryl group.
May be used), tetrakisdimethylaminotin, te
Trakis diethylamino tin, tin bromide, tin chloride, iodide
Tin, R_nSnX_4-n(R is an alkyl group or aryl
X is H, F, Cl, Br or I, n is an integer of 0 to 3
Those selected from the group of (number) are preferred. Among them, one
General formula R¹R^TwoR^ThreeR^FourAnd represented by Sn
R¹, R^Two, R^Three, R ^FourIs H, -CH_Three, -CF_Three, −
C_TwoH_Five, -C_TwoF_Five, -C_ThreeH₇, -C_ThreeF ₇, -C
_FourH₉, -C_FourF₉, -C₆H_FiveSelected from the group of
Are preferred.

The organometallic or metal complex of magnesium used in the "material for forming a copper alloy film and the method for forming a copper alloy film" of the present invention is preferably bis (alkylcyclopentadienyl) magnesium. Among them, the general formula (RC ₅
H ₄ ) ₂ Mg, bis (alkylcyclopentadienyl) magnesium, wherein R is H, —CH ₃ ,
_{-C 2 H 5, -C 3 H} 7, those selected from the group of -C ₄ H ₉ is preferred. Octamethyldialuminum magnesium (CH ₃ ) ₈ Al ₂ Mg is also preferred.

According to the present invention, "a material for forming a copper alloy film, a copper alloy film"
Of chromium used in the method of formation
Is a metal complex, bis (alkylcyclopentadienyl)
Chromium, bis (alkyl-substituted benzene) chromium
Group of bismuth and bis (ethylbenzene) chromium
Those selected from among them are preferred. Among them, the general formula (RC_FiveH
_Four)_TwoBis (alkylcyclopentadie represented by Cr
Nyl) chromium, wherein R is H, -CH_Three, -C
_TwoH_Five, -C_ThreeH₇, -C_FourH₉Selected from the group of
Are preferred.

The organic metal or metal complex of nickel used in the "copper alloy film forming material and copper alloy film forming method" of the present invention is preferably bis (alkylcyclopentadienyl) nickel. Among them, the general formula (RC ₅ H ₄ ) ₂ N
a bis (alkyl cyclopentadienyl) nickel represented by i, the R is _{H, -CH 3, -C 2 H} 5, -
C ₃ H _7, those selected from the group of -C ₄ H ₉ is preferred.

The organic metal or metal complex of cadmium used in the "copper alloy film forming material and copper alloy film forming method" of the present invention is preferably dimethyl cadmium. The organometallic or metal complex of manganese used in the above-mentioned "copper alloy film forming material and copper alloy film forming method" is preferably bis (alkylcyclopentadienyl) manganese. Among them, bis (alkylcyclopentadienyl) manganese represented by the general formula (RC ₅ H ₄ ) ₂ Mn,
Wherein R is _{H, -CH 3, -C 2 H} 5, -C 3 H 7, -C
Which is preferably one selected from the group consisting of ₄ H _9.

The above-mentioned coordination complex of copper and an organic metal or metal complex of at least one metal selected from the group consisting of zirconium, tin, magnesium, chromium, nickel, cadmium and manganese are used on a substrate. When forming a copper alloy film on the substrate, the coordination complex of copper attached on the substrate, and decomposition of the organic metal or metal complex of the metal, heating, laser induction heating, laser induction heating using ultraviolet light,
This is performed by a plasma method.

In particular, when the decomposition is carried out at a temperature of 100 to 1000 ° C., the resistance of the wiring is increased by containing components other than Cu, but the resistance is reduced by the heat treatment, which is preferable.

[0024]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Copper alloy film (wiring film) according to the present invention
The material to be formed is a material for forming a copper alloy film, and a copper coordination complex and at least one organic metal selected from the group consisting of zirconium, tin, magnesium, chromium, nickel, cadmium, and manganese. It consists of a metal or a metal complex. In particular, a material for forming a copper alloy film by chemical vapor deposition, and a copper coordination complex, zirconium, tin, magnesium, chromium, nickel, cadmium, at least one selected from the group of manganese It consists of an organic metal or a metal complex of a metal.

The method for forming a copper alloy film (wiring film) according to the present invention is a method of forming a copper coordination complex and at least one metal selected from the group consisting of zirconium, tin, magnesium, chromium, nickel, cadmium and manganese. A method of forming a copper alloy film using an organic metal or a metal complex,
A step of heating a substrate for forming a copper alloy film, and a coordination complex of the copper, and zirconium, tin, magnesium, chromium, nickel, cadmium, and an organic metal or metal of at least one metal selected from the group of manganese A step of contacting the complex simultaneously or alternately and attaching it to the substrate, and a step of decomposing the copper coordination complex attached to the substrate and the organometallic or metal complex of the metal to form a copper alloy film. Have. In particular, copper coordination complexes, zirconium, tin,
Magnesium, chromium, nickel, cadmium, a method of forming a copper alloy film by chemical vapor deposition using an organic metal or metal complex of at least one metal selected from the group of manganese, Heating the substrate to be formed and the coordination complex of copper, and zirconium, tin, magnesium, chromium, nickel, cadmium, and an organic metal or metal complex of at least one metal selected from the group of manganese simultaneously or The method comprises the steps of alternately contacting and attaching to the substrate, and decomposing the copper coordination complex and the metal organic metal or metal complex attached to the substrate to form a copper alloy film. Forming a copper alloy film on a substrate using a coordination complex of copper and an organic metal or metal complex of at least one metal selected from the group of zirconium, tin, magnesium, chromium, nickel, cadmium, and manganese When
The decomposition of the coordination complex of copper and the organometallic or metal complex of the metal on the substrate is performed by heating, laser induction heating, laser induction heating using ultraviolet light, or a plasma method. The decomposition takes place in particular at a temperature of from 100 to 1000 ° C.

For example, a copper alloy film is formed on a substrate by using an apparatus as shown in FIG. That is,
The copper coordination complex solution 1a is put into the vaporization vessel 2a, and the copper coordination complex is vaporized by bubbling a gas. The metal organic metal (or metal complex) solution 1b is put in the vaporization vessel 2b, and the metal organic metal (or metal complex) is vaporized by bubbling a gas. The vaporized raw material (coordination complex of copper, organic metal (or metal complex)) is introduced into the decomposition reactor 5 through the pipes 4 and 4.
A silicon substrate 7 on which a film is formed is placed in a reaction furnace 5,
The silicon substrate 7 is heated by the heating means 6. Then, the copper coordination complex and the metal organic metal (or metal complex) introduced into the reaction furnace 5 adhere to the surface of the silicon substrate 7 and are decomposed at 100 to 1000 ° C. to form a copper alloy film. You.

The copper coordination complex is a ligand-stabilized (+1) coordination complex. Also, β-diketone is coordinated to copper. In particular, it has a β-diketone coordinated to copper and at least one stabilizing ligand bonded to copper. Among them, a β-diketone is a coordination bond to copper, and the β-diketone has a general formula R ′
COCHRCOR "[where R is H, F, Cl, Br,
It is selected from the group consisting of I, methyl group, and ethyl group.
R ′ and R ″ are selected from the group _consisting of C _n H _{2n + 1} , C _n F _{2n + 1} (n is an integer of 1 to 4), an aryl group and a substituted aryl group. Further, β-diketone is a coordination bond to copper, and the β-diketone is represented by the general formula R′COCH ₂ COR ″, wherein R ′ and R ″ are —CH _3, -CF _3, -C ₂ H
_{5, -C 2 F 5, -C} 3 H 7, -C 3 F 7, -C 4 H 9
And those selected from the group of -C ₄ F _9. In particular, the β-diketone is coordinated to copper, and the β-diketone is trifluoroacetylacetone or hexafluoroacetylacetone.

The copper coordination complex has at least one stabilizing ligand bonded to copper, and the stabilizing ligand is substituted or unsubstituted alkyne, olefin, diene, and phosphine. Is selected from the group of Among them, those having at least one stabilizing ligand bonded to copper, wherein the stabilizing ligand is 1,5-cyclooctadiene, alkyl-substituted 1,5-cyclooctadiene, fluoro-1,5. -Cyclooctadiene, cyclooctene, methylcyclooctene, cyclooctatetraene, norbornene, norbornadiene, tricyclo [5.2.1.0] -deca-2,6-diene, 1,4-
It is selected from the group consisting of cyclohexadiene, acetylene, alkyl-substituted acetylene, halogen-substituted acetylene, and trimethylphosphine. Further, it has at least one stabilizing ligand bonded to copper,
The stabilizing ligand is selected from the group consisting of trimethylvinylsilane, methyltrivinylsilane, dimethyldivinylsilane, and bistrimethylsilylacetylene.

Specific examples of the copper coordination complex include hexafluoroacetylacetonato copper (I) 1,5-cyclooctadiene, hexafluoroacetylacetonato copper (I) dimethyl-1,5-cyclooctadiene, or There are these mixtures. Alternatively, hexafluoroacetylacetonato copper (I) trimethylvinylsilane, tris (hexafluoroacetylacetonatocopper (I)) methyltrivinylsilane, bis (hexafluoroacetylacetonatocopper (I)) dimethyldivinylsilane, hexafluoroacetylacetate There are natocopper (I) bistrimethylsilylacetylene, or mixtures thereof. Or, copper (I) hexafluoroacetylacetonate 1,5-cyclooctadiene, copper (I) hexafluoroacetylacetonate dimethyl-1,5-cyclooctadiene, copper (I) hexafluoroacetylacetonatodiethyl-1 , 5-cyclooctadiene, hexafluoroacetylacetonato copper (I) trimethylvinylsilane, tris (hexafluoroacetylacetonato copper (I)) methyltrivinylsilane, bis (hexafluoroacetylacetonato copper (I)) dimethyldivinylsilane , Hexafluoroacetylacetonato copper (I) bistrimethylsilylacetylene, or a mixture thereof.

As zirconium organometallic or metal complex
Is tetrakisdimethylamino zirconium, tetra
Kiss diethylamino zirconium, zirconium tetra
Boron hydride, zirconium tetrabromide,
There is zirconium tetrachloride. Tin organometallic or
Is a metal complex, R¹R^TwoR^ThreeR^FourSn (R¹, R
^Two, R ^Three, R^FourIs an alkyl or aryl group.
May be the same or different), tetrakis
Tylaminotin, tetrakisdiethylaminotin, tin bromide,
Tin chloride, tin iodide, R_nSnX_4-n(R is an alkyl group
X is H, F, Cl, Br or I, and n is
(An integer of 0 to 3). Among them, the general formula R¹R^TwoR ^ThreeR
^FourSn, wherein R¹, R^Two, R^Three,
R^FourIs H, -CH_Three, -CF_Three, -C_TwoH_Five, -C_TwoF
_Five, -C_ThreeH₇, -C_ThreeF₇, -C_FourH₉, -C
_FourF₉, -C₆H_FiveAre selected from the group of
It is.

As the organometallic or metal complex of magnesium, there is bis (alkylcyclopentadienyl) magnesium. Above all, the general formula (RC ₅ H ₄₎ is a bis (alkyl cyclopentadienyl) magnesium which is represented by ₂ Mg, wherein R is _{H, -CH 3, -C 2 H} 5, -C
₃ H _7, include those which are selected from the group consisting of -C ₄ H _9. Also, there is octamethyldialuminum magnesium (CH ₃ ) ₈ Al ₂ Mg.

As the organometallic or metal complex of chromium, there are bis (alkylcyclopentadienyl) chromium, bis (alkyl-substituted benzene) chromium, and bis (ethylbenzene) chromium. Above all, the general formula (RC ₅ H ₄₎ bis represented by ₂ Cr (alkyl cyclopentadienyl) and chromium, wherein R is H, -
CH ₃ , —C ₂ H ₅ , —C ₃ H ₇ , and —C ₄ H ₉ .

As an organometallic or metal complex of nickel
Is bis (alkylcyclopentadienyl) nickel
is there. Among them, the general formula (RC_FiveH_Four)_TwoRepresented by Ni
Bis (alkylcyclopentadienyl) nickel
R is H, -CH_Three, -C _TwoH_Five, -C_ThreeH₇,
-C_FourH₉And those selected from the group of. Mosquito
As an organic metal or metal complex of domium, dimethylca
There is domium.

As an organometallic or metal complex of manganese
Is bis (alkylcyclopentadienyl) manganese
is there. Among them, the general formula (RC_FiveH_Four)_TwoRepresented by Mn
Bis (alkylcyclopentadienyl) manganese
R is H, -CH_Three, -C _TwoH_Five, -C_ThreeH₇,
-C_FourH₉And those selected from the group of. Up
As described above, a wiring film made of a copper alloy is formed. This
In the case of a Cu—Sn alloy, the composition of the wiring film
90-99.995wt%, Sn 0.005-10w
t%. In the case of Cu-Zr alloy, Cu
99.995wt%, Zr 0.005-10wt%
is there. In the case of a Cu—Mg alloy, Cu is 90 to 99.
999 wt%, and Mg is 0.001 to 10 wt%.
In the case of a Cu—Cr alloy, Cu is 90 to 99.999.
wt% and Cr are 0.001 to 10 wt%. Cu-
In the case of a Mn alloy, Cu is 80 to 99.995 wt.
%, Mn is 0.005 to 20 wt%. Cu-Cd
In the case of an alloy, Cu is 90 to 99.999 wt%, C
d is 0.001 to 10 wt%. Cu-Ni alloy
In the case, Cu is 70 to 99.995 wt%, and Ni is
0.005 to 30 wt%. Cu-Cr-Zr alloy
In the case of, Cu is 80 to 99.999 wt%, and Cr is
0.0005-10 wt%, Zr 0.0005-10
wt%. Same as above for other three-component systems
Is the ratio of

The proportion of the alloy composition is controlled by controlling the amount of the raw material of each component to obtain a copper alloy film having a desired composition. Hereinafter, some specific examples will be described, but the present invention is not limited thereto. That is, the wiring film having the alloy composition described in the present embodiment can be obtained according to the description of the examples described below.

[0036]

Example 1 A copper-tin alloy film was formed by a CVD method using hexafluoroacetylacetonato copper (I) trimethylvinylsilane and tetraethyltin. That is, using the apparatus of FIG. 1, hexafluoroacetylacetonato copper (I) trimethylvinylsilane was charged into the vaporization container 2a, and hydrogen was vaporized by bubbling at a flow rate of 100 ml / min. Tetraethyltin was placed in the vaporization vessel 2b, and the solution was vaporized by bubbling hydrogen at a flow rate of 5 ml / min. At this time, the temperature of the vaporization container 2a was controlled at 27.5 ° C, and the temperature of the vaporization container 2b was controlled at -10 ° C.

The vaporized raw materials (copper hexafluoroacetylacetonate (I) trimethylvinylsilane, tetraethyltin) were introduced into the decomposition reactor 5 through the pipes 4 and 4. A silicon substrate 7 on which a film is to be formed is placed in a reaction furnace 5, and the whole is heated to 450 ° C. by a heating means 6. Hexafluoroacetylacetonato copper (I) trimethylvinylsilane and tetraethyltin are used as silicon substrate 7
After adhering to the surface, it was heat-treated at 500 ° C. for several minutes.

As a result, a copper-tin alloy having a thickness of 0.2
A μm low-resistance film was formed.

[0039]

Example 2 A copper-tin alloy film was formed by a CVD method using hexafluoroacetylacetonato copper (I) trimethylvinylsilane and tetrakisdimethylaminotin. That is, using the apparatus of FIG. 1, hexafluoroacetylacetonato copper (I) trimethylvinylsilane was charged into the vaporization container 2a, and hydrogen was vaporized by bubbling at a flow rate of 100 ml / min. Tetrakisdimethylaminotin was put in the vaporization vessel 2b, and the solution was vaporized by bubbling hydrogen at a flow rate of 5 ml / min. At this time, the temperature of the vaporization containers 2a and 2b was controlled at 27.5 ° C.

The vaporized raw materials (copper (I) hexafluoroacetylacetonate trimethylvinylsilane, tetrakisdimethylaminotin) are passed through pipes 4 and 4 to a decomposition reactor 5.
Was introduced. A silicon substrate 7 on which a film is to be formed is placed in a reaction furnace 5, and the whole is heated to 450 ° C. by a heating means 6.

After copper hexafluoroacetylacetonate (I) trimethylvinylsilane and tetrakisdimethylaminotin adhere to the surface of the silicon substrate 7, the mixture
Heat treatment was performed at 00 ° C. As a result, a 0.2 μm-thick low-resistance film made of a copper-tin alloy was formed.

[0042]

Example 3 A copper-zirconium alloy film was formed by a CVD method using hexafluoroacetylacetonato copper (I) trimethylvinylsilane and zirconium tetraboron hydride. That is, using the apparatus of FIG. 1, hexafluoroacetylacetonato copper (I) trimethylvinylsilane was charged into the vaporization container 2a, and hydrogen was vaporized by bubbling at a flow rate of 100 ml / min. Zirconium tetraboron hydride was placed in the vaporization vessel 2b, and hydrogen was supplied into the powder at a flow rate of 1 ml / min to sublime. At this time, the temperature of the vaporization vessels 2a and 2b is 2
The temperature was controlled at 7.5 ° C.

The vaporized and sublimed raw materials (copper hexafluoroacetylacetonato trimethylvinylsilane, zirconium tetraboron hydride) were introduced into the decomposition reactor 5 through the pipes 4 and 4. A silicon substrate 7 on which a film is to be formed is placed in a reaction furnace 5, and the whole is heated to 450 ° C. by a heating means 6.

After copper hexafluoroacetylacetonate (I) trimethylvinylsilane and zirconium tetraboron hydride were adhered to the silicon substrate 7, a heat treatment was performed at 500 ° C. for several minutes. As a result, a 0.2 μm-thick low-resistance film made of a copper-zirconium alloy was formed.

[0045]

Example 4 A copper-zirconium alloy film was formed by a CVD method using hexafluoroacetylacetonato copper (I) trimethylvinylsilane and tetrakisdimethylaminozirconium. That is, using the apparatus of FIG. 1, hexafluoroacetylacetonato copper (I) trimethylvinylsilane was charged into the vaporization container 2a, and hydrogen was vaporized by bubbling at a flow rate of 100 ml / min. Tetrakisdimethylaminozirconium was put in the vaporization vessel 2b, and the solution was vaporized by bubbling hydrogen at a flow rate of 50 ml / min. Vaporization container 2 at this time
The temperatures of a and 2b were controlled at 27.5 ° C.

The vaporized raw materials (copper (I) hexafluoroacetylacetonate trimethylvinylsilane, tetrakisdimethylaminozirconium) were introduced into the decomposition reactor 5 through the pipes 4 and 4. A silicon substrate 7 on which a film is to be formed is placed in the reaction furnace 5,
Heated to 0 ° C.

After hexafluoroacetylacetonato copper (I) trimethylvinylsilane and tetrakisdimethylaminozirconium were adhered to the surface of the silicon substrate 7, a heat treatment was performed at 500 ° C. for several minutes. As a result, a 0.2 μm-thick low-resistance film made of a copper-zirconium alloy was formed.

[0048]

Example 5 A copper-magnesium alloy film was formed by a CVD method using bis (hexafluoroacetylacetonato copper (I)) dimethyldivinylsilane and bis (cyclopentadienyl) magnesium. That is, using the apparatus of FIG. 1, bis (hexafluoroacetylacetonato copper (I)) dimethyldivinylsilane was charged into the vaporization container 2a, and hydrogen was vaporized by bubbling at a flow rate of 100 ml / min. Bis (cyclopentadienyl) magnesium is charged into the vaporization vessel 2b, and hydrogen is supplied at a flow rate of 50 ml /
In minutes and sublimated. Vaporization container 2 at this time
The temperatures of a and 2b were controlled at 27.5 ° C.

The vaporized and sublimated raw materials (bis (hexafluoroacetylacetonatocopper (I)) dimethyldivinylsilane and bis (cyclopentadienyl) magnesium) were introduced into the decomposition reactor 5 through the pipes 4 and 4. . Reactor 5
A silicon substrate 7 on which a film is to be formed is placed, and the whole is heated to 450 ° C. by a heating means 6.

After bis (hexafluoroacetylacetonato copper (I)) dimethyldivinylsilane and bis (cyclopentadienyl) magnesium were adhered to the surface of the silicon substrate 7, a heat treatment was performed at 500 ° C. for several minutes. As a result, a 0.2 μm-thick low-resistance film made of a copper-magnesium alloy was formed.

[0051]

Example 6 A copper-chromium alloy film was formed by a CVD method using hexafluoroacetylacetonato copper (I) trimethylvinylsilane and bis (methylcyclopentadienyl) chromium. That is, using the apparatus of FIG. 1, hexafluoroacetylacetonato copper (I) trimethylvinylsilane was charged into the vaporization container 2a, and hydrogen was vaporized by bubbling at a flow rate of 100 ml / min. Bis (methylcyclopentadienyl) chromium was charged into the vaporization vessel 2b, and the solution was vaporized by bubbling hydrogen at a flow rate of 1 ml / min. At this time, the temperature of the vaporization containers 2a and 2b was controlled at 40 ° C.

The vaporized raw materials (copper (I) hexafluoroacetylacetonate trimethylvinylsilane, bis (methylcyclopentadienyl) chromium) were supplied to pipes 4 and 4
And introduced into the decomposition reaction furnace 5. A silicon substrate 7 on which a film is to be formed is placed in a reaction furnace 5, and the whole is heated to 450 ° C. by a heating means 6.

After hexafluoroacetylacetonato copper (I) trimethylvinylsilane and bis (methylcyclopentadienyl) chromium were adhered to the surface of the silicon substrate 7, a heat treatment was performed at 500 ° C. for several minutes. As a result, a 0.2 μm-thick low-resistance film made of a copper-chromium alloy was formed.

[0054]

Example 7 A copper-manganese alloy film was formed by a CVD method using hexafluoroacetylacetonato copper (I) trimethylvinylsilane and bis (cyclopentadienyl) manganese. That is, using the apparatus shown in FIG. 1, hexafluoroacetylacetonato copper (I) trimethylvinylsilane is charged into the vaporization vessel 2a, and hydrogen is supplied at a flow rate of 10%.
Vaporized by bubbling at 0 ml / min. Bis (cyclopentadienyl) manganese was charged into the vaporization vessel 2b, and hydrogen was supplied into the powder at a flow rate of 50 ml / min to sublime. At this time, the temperature of the vaporization containers 2a and 2b is 27.
The temperature was controlled at 5 ° C.

The vaporized and sublimated raw materials (copper hexafluoroacetylacetonate (I) trimethylvinylsilane, bis (cyclopentadienyl) manganese) were introduced into the decomposition reactor 5 through the pipes 4 and 4. A silicon substrate 7 on which a film is to be formed is placed in a reaction furnace 5, and the whole is heated to 450 ° C. by a heating means 6.

After hexafluoroacetylacetonato copper (I) trimethylvinylsilane and bis (cyclopentadienyl) manganese were adhered to the surface of the silicon substrate 7, a heat treatment was performed at 500 ° C. for several minutes. As a result, a 0.2 μm-thick low-resistance film made of a copper-manganese alloy was formed.

[0057]

Example 8 A copper-cadmium alloy film was formed by a CVD method using hexafluoroacetylacetonato copper (I) trimethylvinylsilane and dimethylcadmium. That is, using the apparatus of FIG. 1, hexafluoroacetylacetonato copper (I) trimethylvinylsilane was charged into the vaporization container 2a, and hydrogen was vaporized by bubbling at a flow rate of 100 ml / min. Dimethylcadmium was charged into the vaporization vessel 2b, and the solution was vaporized by bubbling hydrogen at a flow rate of 1 ml / min. At this time, the temperature of the vaporization container 2a was controlled at 50 ° C, and the temperature of the vaporization container 2b was controlled at 5 ° C.

The vaporized raw materials (copper (I) hexafluoroacetylacetonate trimethylvinylsilane, dimethylcadmium) were introduced into the decomposition reactor 5 through the pipes 4 and 4. A silicon substrate 7 on which a film is formed is placed in a reaction furnace 5, and the whole is heated to 300 ° C. by a heating means 6.

After the hexafluoroacetylacetonato copper (I) trimethylvinylsilane and dimethylcadmium were adhered to the surface of the silicon substrate 7, a heat treatment was performed at 500 ° C. for several minutes. As a result, a 0.2 μm-thick low-resistance film made of a copper-cadmium alloy was formed.

[0060]

Embodiment 9 Copper (I) copper (I) trimethylvinylsilane and bis (methylcyclopentadienyl) nickel were used by the CVD method.
A nickel alloy film was formed. That is, using the apparatus of FIG. 1, hexafluoroacetylacetonato copper (I) trimethylvinylsilane was charged into the vaporization container 2a, and hydrogen was vaporized by bubbling at a flow rate of 100 ml / min. Bis (methylcyclopentadienyl) nickel was charged into the vaporization vessel 2b, and the solution was vaporized by bubbling hydrogen at a flow rate of 1 ml / min. At this time, the temperature of the vaporization containers 2a and 2b was controlled at 50 ° C.

The vaporized raw materials (copper (I) hexafluoroacetylacetonate trimethylvinylsilane, bis (methylcyclopentadienyl) nickel) were introduced into the decomposition reactor 5 through the pipes 4 and 4. A silicon substrate 7 on which a film is formed is placed in a reaction furnace 5, and the whole is heated to 300 ° C. by a heating means 6.

After hexafluoroacetylacetonato copper (I) trimethylvinylsilane and bis (methylcyclopentadienyl) nickel were adhered to the surface of the silicon substrate 7, a heat treatment was performed at 500 ° C. for several minutes. As a result, copper
A low-resistance film made of a nickel alloy and having a thickness of 0.2 μm was formed.

[0063]

Example 10 A copper-zirconium-chromium alloy film was formed by a CVD method using hexafluoroacetylacetonato copper (I) trimethylvinylsilane, zirconium tetraboron hydride and bis (methylcyclopentadienyl) chromium.

That is, using the apparatus shown in FIG.
a) Hexafluoroacetylacetonato copper (I) trimethylvinylsilane 1a is charged, and hydrogen is supplied at a flow rate of 100 ml.
Vaporized by bubbling at / min. Zirconium tetraboron hydride 1b was placed in the vaporization vessel 2b, and hydrogen was supplied into the powder at a flow rate of 1 ml / min to sublime. Bis (methylcyclopentadienyl) chromium 1c was put in the vaporization vessel 2c, and hydrogen was vaporized by bubbling hydrogen at a flow rate of 1 ml / min.

The vaporized and sublimated raw materials (copper (I) trimethylvinylsilane hexafluoroacetylacetonate, zirconium tetraboron hydride, bis (methylcyclopentadienyl) chromium) are passed through pipes 4, 4, and 4 to a decomposition reaction furnace 5. Was introduced. A silicon substrate 7 on which a film is to be formed is placed in a reaction furnace 5, and the whole is heated to 450 ° C. by a heating means 6.

After hexafluoroacetylacetonato copper (I) trimethylvinylsilane, zirconium tetraboron hydride and bis (methylcyclopentadienyl) chromium were adhered to the silicon substrate 7, it was heat-treated at 500 ° C. for several minutes. As a result, a 0.2 μm-thick low-resistance film made of a copper-zirconium-chromium alloy was formed.

[0067]

According to the present invention, a copper alloy film having a diameter of 0.25 μm or less, a wiring hole having a high aspect ratio can be filled, and a long EM life can be efficiently formed.

[Brief description of the drawings]

FIG. 1 is a schematic diagram of a copper alloy film forming apparatus.

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

[Explanation of symbols]

1a Coordination complex of copper 1b, 1c Organometallic or metal complex of metal such as tin 2a, 2b, 2c Vaporization vessel 3 Gas flow controller 4 Gas-phase transport pipe 5 Decomposition reactor 6 Heating means 7 Silicon substrate

Claims (34)

[Claims] 1. A material for forming a copper alloy film, comprising a copper coordination complex and at least one metal selected from the group consisting of zirconium, tin, magnesium, chromium, nickel, cadmium and manganese. A copper alloy film forming material comprising an organic metal or a metal complex. 2. A material for forming a copper alloy film by chemical vapor deposition, wherein the material is selected from the group of a coordination complex of copper and zirconium, tin, magnesium, chromium, nickel, cadmium, and manganese. A copper alloy film-forming material comprising an organic metal or a metal complex of at least one metal. 3. The copper alloy film forming material according to claim 1, wherein the copper coordination complex is a (+1) coordination complex stabilized by a ligand. 4. The copper alloy film forming material according to claim 1, wherein the copper coordination complex is a coordination bond of β-diketone to copper. 5. The coordination complex of copper is β-coordinated to copper.
The copper alloy film forming material according to any one of claims 1 to 4, comprising a diketone and at least one stabilizing ligand bonded to copper. 6. The coordination complex of copper is a coordination bond of β-diketone to copper, and the β-diketone has a general formula R ′
COCHRCOR "[where R is H, F, Cl, Br,
It is any one selected from the group consisting of I, a methyl group, and an ethyl group. R ′ and R ″ are C _n H _{2n + 1} , C _n F
_{2n + 1} (n is an integer of 1 to 4), any one selected from the group consisting of an aryl group and a substituted aryl group. The material for forming a copper alloy film according to any one of claims 1 to 5, characterized in that: 7. The coordination complex of copper is a coordination bond of β-diketone to copper, and the β-diketone has the general formula R′C
OCH ₂ COR ″, wherein R ′ and R ″ are —CH ₃ , —CF ₃ , —C ₂ H ₅ , —C
_{2 F 5, -C 3 H 7} , -C 3 F 7, -C 4 H 9 and -C
Claims 1 to 6 or of a copper alloy film forming material which is characterized in that any one selected from the group of ₄ F _9. 8. The coordination complex of copper is a β-diketone coordinated to copper, and the β-diketone is any one selected from the group consisting of trifluoroacetylacetone and hexafluoroacetylacetone. The copper alloy film forming material according to any one of claims 1 to 7, wherein: 9. A copper coordination complex having at least one stabilizing ligand bound to copper, wherein the stabilizing ligand is a substituted or unsubstituted alkyne, olefin, diene, and phosphine. The copper alloy film forming material according to any one of claims 1 to 8, wherein the material is one selected from a group. 10. A copper coordination complex having at least one stabilizing ligand bound to copper, wherein said stabilizing ligand is 1,5-cyclooctadiene, alkyl-substituted 1,5- Cyclooctadiene, fluoro-1,5-cyclooctadiene, cyclooctene, methylcyclooctene, cyclooctatetraene, norbornene, norbornadiene, tricyclo [5.2.1.0] -deca-2,
10. A compound selected from the group consisting of 6-diene, 1,4-cyclohexadiene, acetylene, alkyl-substituted acetylene, halogen-substituted acetylene, and trimethylphosphine. Copper alloy film forming material. 11. A copper coordination complex having at least one stabilizing ligand bound to copper, wherein said stabilizing ligand is trimethylvinylsilane, methyltrivinylsilane, dimethyldivinylsilane, and bistrimethylsilyl. The copper alloy film forming material according to any one of claims 1 to 8, wherein the material is any one selected from the group of acetylene. 12. The coordination complex of copper is copper (I) hexafluoroacetylacetonate 1,5-cyclooctadiene,
Hexafluoroacetylacetonato copper (I) dimethyl-
1,5-cyclooctadiene, hexafluoroacetylacetonato copper (I) diethyl-1,5-cyclooctadiene, hexafluoroacetylacetonato copper (I) trimethylvinylsilane, tris (hexafluoroacetylacetonato copper (I) 2) methyltrivinylsilane, bis (hexafluoroacetylacetonatocopper (I)) dimethyldivinylsilane, hexafluoroacetylacetonatocopper (I) bistrimethylsilylacetylene, or a mixture thereof. Item 11
Any copper alloy film forming material. 13. The method according to claim 1, wherein the organometallic or metal complex of zirconium is selected from the group consisting of tetrakisdimethylaminozirconium, tetrakisdiethylaminozirconium, zirconium tetraboron hydride, zirconium tetrabromide, and zirconium tetrachloride. The material for forming a copper alloy film according to claim 1 or 2, wherein 14. The organometallic or metal complex of tin is represented by R¹R
^TwoR^ThreeR^FourSn (R ¹, R^Two, R^Three, R^FourIs an alkyl group
Or the same or different aryl groups
Good), tetrakisdimethylaminotin, tetrakisdie
Tylaminotin, tin bromide, tin chloride, tin iodide, R_nSnX
_4-n(R is an alkyl or aryl group, X is H, F,
Cl, Br or I and n are integers from 0 to 3).
2. The method according to claim 1, wherein
The material for forming a copper alloy film according to claim 2. 15. An organometallic or metal complex of tin having the general formula
R¹R^TwoR^ThreeR^FourAnd represented by Sn
R¹, R^Two, R^Three, R^FourIs H, -CH_Three, -CF _Three, −
C_TwoH_Five, -C_TwoF_Five, -C_ThreeH₇, -C_ThreeF₇, -C
_FourH₉, -C_FourF ₉, -C₆H_FiveSelected from the group of
3. The method according to claim 1, wherein the first value is one of:
Copper alloy film forming material. 16. The copper alloy film forming material according to claim 1, wherein the organometallic or metal complex of magnesium is bis (alkylcyclopentadienyl) magnesium. 17. An organometallic or metal complex of magnesium
Is the general formula (RC_FiveH _Four)_TwoBis (Alky) represented by Mg
Rucyclopentadienyl) magnesium;
Is H, -CH_Three, -C_TwoH_Five, -C_ThreeH₇, -C_FourH₉
Characterized by being selected from the group of
The material for forming a copper alloy film according to claim 1. 18. The organic metal or metal complex of magnesium may be magnesium octamethyldialuminum (CH ₃ ).
3. The copper alloy film forming material according to claim 1, wherein the material is ₈ Al ₂ Mg. 19. The organic metal or metal complex of chromium is selected from the group consisting of bis (alkylcyclopentadienyl) chromium, bis (alkyl-substituted benzene) chromium, and bis (ethylbenzene) chromium. The material for forming a copper alloy film according to claim 1 or 2, wherein 20. The organic metal or metal complex of chromium is bis (alkylcyclopentadienyl) chromium represented by the general formula (RC ₅ H ₄ ) ₂ Cr, wherein R is H, —CH ₃ , —C _{2 H 5, -C 3 H 7} , the copper alloy film forming material according to claim 1 or claim 2, characterized in that at any one selected from the group of -C ₄ H _9. 21. The copper alloy film forming material according to claim 1, wherein the organic metal or metal complex of nickel is bis (alkylcyclopentadienyl) nickel. 22. The organic metal or metal complex of nickel is one of
General formula (RC_FiveH_Four) _TwoBis (alkyl
Clopentadienyl) nickel, wherein R is H,-
CH_Three, -C_TwoH_Five, -C_ThreeH₇, -C_FourH₉In the group of
2. The method according to claim 1, wherein the selected one is selected from the group consisting of:
Or the copper alloy film forming material according to claim 2. 23. The copper alloy film forming material according to claim 1, wherein the organic metal or metal complex of cadmium is dimethyl cadmium. 24. The copper alloy film forming material according to claim 1, wherein the organometallic or metal complex of manganese is bis (alkylcyclopentadienyl) manganese. 25. An organic metal or metal complex of manganese,
General formula (RC_FiveH_Four) _TwoBis (alkylalkyl) represented by Mn
Clopentadienyl) manganese, wherein R is H,-
CH_Three, -C_TwoH_Five, -C_ThreeH₇, -C_FourH₉In the group of
2. The method according to claim 1, wherein the selected one is selected from the group consisting of:
Or the copper alloy film forming material according to claim 2. 26. The copper alloy film forming material according to claim 1, which is used for wiring. 27. A coordination complex of copper, zirconium, tin,
A method of forming a copper alloy film using an organic metal or a metal complex of at least one metal selected from the group consisting of magnesium, chromium, nickel, cadmium, and manganese, wherein the substrate on which the copper alloy film is formed is heated. And the step of applying the copper coordination complex, and zirconium, tin, magnesium, chromium, nickel, cadmium, at least one metal organic metal or metal complex selected from the group of manganese on the substrate, Forming a copper alloy film by decomposing the copper coordination complex and an organic metal or metal complex of the metal on a substrate. 28. A coordination complex of copper, zirconium, tin,
A method of forming a copper alloy film by chemical vapor deposition using an organic metal or a metal complex of at least one metal selected from the group consisting of magnesium, chromium, nickel, cadmium, and manganese, Heating the substrate to be formed; and coordinating complex of copper and an organic metal or metal complex of at least one metal selected from the group of zirconium, tin, magnesium, chromium, nickel, cadmium, and manganese on the substrate. Forming a copper alloy film by decomposing the copper coordination complex and the metal organometallic or metal complex attached to the substrate to form a copper alloy film. Method. 29. The method for forming a copper alloy film according to claim 27, wherein the coordination complex of copper and the organometallic or metal complex attached to the substrate are decomposed by heating. 30. The method for forming a copper alloy film according to claim 27, wherein the decomposition of the coordination complex of copper and the organometallic or metal complex on the substrate is performed by laser induction heating. 31. The copper alloy film according to claim 27, wherein the coordination complex of copper and the organometallic or metal complex attached to the substrate are decomposed by laser induction heating using ultraviolet rays. Forming method. 32. The method for forming a copper alloy film according to claim 27, wherein the decomposition of the coordination complex of copper and the organometallic or metal complex on the substrate is performed by a plasma method. 33. Decomposition of the copper coordination complex and the organometallic or metal complex of the metal on the substrate is from 100 to 1
The method is carried out at 000 ° C.
2. Any one of the copper alloy film forming methods. 34. The method for forming a copper alloy film according to claim 27, wherein the compound according to any one of claims 3 to 26 is used.