JP2005079468A - Formation method of ruthenium-silicon mixed film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for preventing peeling in an interface between an insulating film layer of especially a low dielectric constant and a diffusion preventing film layer when wiring is formed on the insulating film layer of a low dielectric constant by a damascene method. <P>SOLUTION: A ruthenium-silicon mixed film is formed by a method wherein a specified ruthenium compound (A) and an annular silane compound (B) are used as a raw material. The specified ruthenium compound (A) is expressed by, for example, formula (1): (Cp')<SB>2</SB>Ru, wherein Cp' is a ligand expressed by formula (2) and the two Cp's can be the same or different from each other. Wherein, R<SP>1</SP>is a 1-6C alkyl group or fluoro-alkyl group, trimethylsilyl group or fluorine atom, a is an integer of 0 to 5, and when a plurality of R<SP>1</SP>s exist, they can be the same or different from each other. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a method for forming a ruthenium-silicon mixed film on a substrate.

In recent years, with the increase in the density of semiconductor devices, miniaturization of formed wirings has progressed. One of the methods attracting attention as a technique capable of achieving further miniaturization of the wiring is called a damascene method. In this method, a desired wiring is formed by embedding a wiring material in a groove or the like formed in an insulating material and then removing excess wiring material by chemical mechanical polishing.
The basic structure of such a typical wiring material is as follows: (1) an insulating layer in which a groove to be a wiring portion is formed in advance; (2) a diffusion preventing film layer that also serves as an excessive polishing preventing layer during chemical mechanical polishing; (3) A wiring material represented by copper is laminated.

As the insulating film, conventionally, an SiO ₂ film formed by a vacuum process such as chemical vapor deposition has been mainly used.
However, in recent years, attention has been focused on lowering the dielectric constant of insulating films for the purpose of improving the performance of semiconductor devices. As a substitute for the above-described SiO ₂ film having a high dielectric constant, silsesquioxane (relative dielectric constant: about 2.6 to 3.0), fluorine-added SiO ₂ (relative dielectric constant: about 3.3 to 3.5), polyimide resin (relative dielectric constant: about 2.4 to 3.6, trade name “PIQ” (manufactured by Hitachi Chemical Co., Ltd.), trade name “FLARE” (Allied Signal) ), Benzocyclobutene (relative dielectric constant: about 2.7, trade name “BCB” (manufactured by Dow Chemical)), hydrogen-containing SOG (relative dielectric constant: 2.5-3.5), organic SOG (relative permittivity: 1.9 to 3.0, trade name “HSGR7” (manufactured by Hitachi Chemical Co., Ltd.), trade name “Black Diamond” (manufactured by Applied Materials), trade name “Coral” (Novellus System Product name "Aurora" (manufactured by Japan ASM Co., Ltd.), product name "Nanoglass" (Honeywell), product name "LKD" Series (JSR (Ltd.)), etc.) and polyphenylene-based resin (dielectric constant; 2.2 to 2.9, trade name "SiLK" (Dow Chemical Co.)) consisting of an insulating film have been developed.
Of the above, “SOG” is an abbreviation for “Spin On Glass”. In general, after a solution obtained by dissolving or dispersing silicate compounds in an organic solvent is applied to a wafer or the like by a spin coating method or the like, It means an insulating film obtained by heat treatment.

However, if an attempt is made to form a damascene structure using an insulating film having such a low dielectric constant, an etching gas incorporated into the insulating film layer due to the heat treatment particularly when the above (2) diffusion preventing film layer is formed. Volatile components such as moisture evaporate, and peeling may occur at the interface between the insulating film layer and the diffusion prevention film layer, which causes the reliability of the semiconductor device and the yield of the semiconductor device manufacturing to decrease.
In order to solve such a problem, Patent Document 1 discloses a method of forming a diffusion prevention film layer after performing a cleaning process with a specific chemical on an insulating film having a low dielectric constant. Further, Patent Document 2 discloses a technique for preventing peeling by providing an opening above an insulating film layer having a low dielectric constant and releasing a volatile component generated in a later process from the opening.
However, although these techniques show a slight improvement effect, they do not fundamentally solve the problem, and a method for preventing interface peeling between the insulating film layer and the diffusion prevention film layer is still desired.
JP 2003-23072 A JP 2003-23073 A

  An object of the present invention is to prevent delamination that occurs at the material interface, particularly at the interface between a low dielectric constant insulating film layer and a diffusion barrier film layer, when wiring is formed on the low dielectric constant insulating film layer by a damascene method. It is to provide a method.

The present inventors have found that the above problem can be solved by forming a ruthenium-silicon mixed film between a low dielectric constant insulating film layer and a diffusion prevention film layer by a specific method, and have led to the present invention. It is.
That is, according to the present invention, the object of the present invention is (A) at least one ruthenium compound selected from the compounds represented by the following general formula (1), (3), (7) or (9) ( Hereinafter, it may be referred to as “specific ruthenium compound”), and (B) a method of forming a ruthenium-silicon mixed film characterized by using a cyclic silane compound as a raw material.
(Cp ′) ₂ Ru (1)
Here, Cp ′ is a ligand represented by the following formula (2), and two Cp ′ may be the same or different from each other.

Here, R ¹ is a C 1-6 alkyl group or fluorinated alkyl group, a trimethylsilyl group, or a fluorine atom, a is an integer of 0 to 5, and when a plurality of R ¹ are present, May be different.
(D) Ru (CO) ₃ (3)
Here, D is one selected from ligands represented by the following formulas (4) to (6).

(ACAC ') ₃ Ru (7)
Here, ACAC ′ is a ligand represented by the following formula (8), and the three ACAC ′ may be the same or different from each other.

Here, R ² is a hydrogen atom, a C 1 -C 6 alkyl group or fluorinated alkyl group, or a C 1 -C 6 alkoxyl group, and the two R ² may be the same or different from each other. Good. Moreover, the wavy line in Formula (8) represents a resonance structure.
(R ³ COO) ₃ Ru (9)
Here, R3 is an alkyl group of one prime number 1-6, a fluorinated alkyl group or a hydroxyalkyl group, there are three R ³ may be identical or different from each other.

  According to the present invention, when forming a wiring by a damascene method on an insulating film layer having a low dielectric constant, a method for preventing delamination that occurs at the interface of the material, particularly the interface between the insulating film layer having a low dielectric constant and the diffusion prevention film layer. Is provided.

The component (A) used in the method of the present invention is at least one ruthenium compound selected from the compounds represented by the general formula (1), (3), (7) or (9).
Examples of the ruthenium compound represented by the above formula (1) include biscyclopentadienyl ruthenium, bis (ethylcyclopentadienyl) ruthenium, bis (trimethylsilylcyclopentadienyl) ruthenium, bis (fluorocyclopentadienyl). ) Ruthenium, bis (trifluoromethylcyclopentadienyl) ruthenium, bis (isopropylcyclopentadienyl) ruthenium, (cyclopentadienyl) trimethylsilylcyclopentadienyl ruthenium, (cyclopentadienyl) trifluoromethylcyclopentadi Enyl ruthenium, (cyclopentadienyl) fluorocyclopentadienyl ruthenium, (ethylcyclopentadienyl) trimethylsilylcyclopentadienyl ruthenium, (ethylcyclopentadienyl) tri Examples include bromomethylcyclopentadienyl ruthenium, (ethylcyclopentadienyl) fluorocyclopentadienyl ruthenium, among which bis (trimethylsilylcyclopentadienyl) ruthenium, bis (ethylcyclopentadienyl) Ruthenium and bis (trifluoromethylcyclopentadienyl) ruthenium are preferred.

  Examples of the ruthenium compound represented by the general formula (7) include tris (penta-2,4-diketo) ruthenium (or trisacetylacetonate ruthenium), tris (2,2,6,6-tetramethylhepta). -3,5-diketo) ruthenium, tris (1-ethoxybutane-1,3-diketo) ruthenium, tris (1,1,1,5,5,5-hexafluoropenta-2,4-diketo) ruthenium, Tris (2,2-dimethylhexa-3,5-diketo) ruthenium, tris (1-ethoxy-4,4-dimethylpenta1,3-diketo) ruthenium, tris (1,1,1trifluoro-penta-2, 4-diketo) ruthenium and the like, among which tris (1-ethoxybutane-1,3-diketo) ruthenium, tris (penta-2,4 Diketo) ruthenium, tris (1-ethoxy-4,4-dimethyl-penta 1,3-diketo) ruthenium and (1,1,1-trifluoro - penta-2,4-diketo) ruthenium are preferred.

  Examples of the ruthenium compound represented by the general formula (9) include ruthenium acetate, ruthenium propionate, ruthenium trifluoroacetate, ruthenium tris (3-hydroxypropionate), ruthenium tris (2-hydroxypropionate), Examples thereof include ruthenium 2-ethylhexanoate, ruthenium acrylate, ruthenium methacrylate and the like, among which ruthenium trifluoroacetate, ruthenium 2-ethylhexanoate and ruthenium tris (3-hydroxypropionate) are preferable.

Component (B) used in the method of the present invention is a cyclic silane compound.
(B) The cyclic silane compound is a compound represented by the following general formula (10).
Si _n H _2n (10)
Here, n is an integer of 3 to 20, preferably an integer of 5 to 10, more preferably an integer of 5 to 7, and particularly an integer of 5 or 6.
Examples of the cyclic silane compound represented by the general formula (10) include cyclotrisilane, cyclotetrasilane, cyclopentasilane, silylcyclopentasilane, cyclohexasilane, cycloheptasilane, and the like. Of these, cyclopentasilane, silylcyclopentasilane, and cyclohexasilane are preferable.

  The method for forming the ruthenium-silicon mixed film of the present invention is not particularly limited as long as the above-described (A) specific ruthenium compound and (B) cyclic silane compound are used as raw materials. A phase growth method, a coating method, or the like can be used.

When the chemical vapor deposition method is employed as the method for forming the ruthenium-silicon mixed film of the present invention, as long as the above-described (A) specific ruthenium compound and (B) cyclic silane compound are used as raw materials. Although there is no particular limitation, for example, it can be carried out as follows.
(1) The above-mentioned (A) specific ruthenium compound and (B) cyclic silane compound are vaporized, then (2) the gas is heated to thermally decompose (A) the specific ruthenium compound and (B) cyclic silane compound. At least, a ruthenium-silicon mixed film is deposited on the substrate. In addition, in the said process (1), even if it is accompanied by decomposition | disassembly of (A) specific ruthenium compound and / or (B) cyclic silane compound, the effect of this invention is not diminished.

Here, an appropriate material such as glass, silicon semiconductor, quartz, metal, metal oxide, or synthetic resin can be used as the base, but an insulating film having a low dielectric constant that is to be an insulating layer of a damascene structure later is formed. It is preferable to use a silicon semiconductor, quartz, glass or the like. A ruthenium-silicon mixed film is formed on the upper surface of such a substrate by the method of the present invention, and a diffusion prevention layer film having a damascene structure is further formed on the upper surface thereof. Interfacial peeling between layers can be effectively suppressed.
Here, examples of the low dielectric constant insulating film include silsesquioxane (relative dielectric constant: about 2.6 to 3.0), fluorine-added SiO ₂ (relative dielectric constant: about 3.3 to 3.5). , Polyimide resin (relative dielectric constant: about 2.4 to 3.6, trade name “PIQ” (manufactured by Hitachi Chemical Co., Ltd.), trade name “FLARE” (made by Allied Signal), etc.), benzocyclobutene (Relative permittivity: about 2.7, trade name “BCB” (manufactured by Dow Chemical)), hydrogen-containing SOG (relative permittivity: 2.5 to 3.5), organic SOG (relative permittivity: 1. 9 to 3.0, trade name “HSGR7” (manufactured by Hitachi Chemical Co., Ltd.), trade name “Black Diamond” (manufactured by Applied Materials), trade name “Coral” (manufactured by Novellus System), trade name “Aurora” "(Nippon ASM Co., Ltd.), trade name" Nanoglass "(Honeywell), trade name" LKD "series (JSR) ) And polyphenylene resin (dielectric constant; 2.2 to 2.9, trade name "SiLK" (Dow Chemical Co.)), and the like.

In the step (1), (A) the specific ruthenium compound and (B) the cyclic silane compound may be vaporized from one vaporizer with or without being mixed in advance, and vaporized from separate vaporizers. May be.
In step (1), when the (A) specific ruthenium compound and the (B) cyclic silane compound are vaporized from one vaporizer, the ratio of the amount of the (A) specific ruthenium compound and (B) the cyclic silane compound used is ( A) The cyclic silane compound is preferably 0.5 to 200 mol, more preferably 1.5 to 50 mol, per 1 mol of the specific ruthenium compound. By using the ratio in this range, a ruthenium-silicon mixed film capable of effectively suppressing interfacial peeling is formed in forming a damascene structure using a low dielectric constant material for the insulating film layer. Can do.

The vaporization temperature when the (A) specific ruthenium compound and the (B) cyclic silane compound are vaporized from one vaporizer is preferably 100 to 300 ° C, more preferably 150 to 200 ° C.
In the above step (1), the vaporization temperature when vaporizing (A) the specific ruthenium compound and (B) the cyclic silane compound from a special vaporizer is preferably (A) the specific ruthenium compound, preferably 100 to 500 ° C. Preferably it is 150-400 degreeC, Preferably it is -30-300 degreeC about (B) cyclic silane compound, More preferably, it is 30-200 degreeC.

In the step (2), the temperature at which (A) the specific ruthenium compound and (B) the cyclic silane compound are thermally decomposed to deposit the ruthenium-silicon mixed film on the substrate is preferably 100 to 500 ° C. More preferably, it is 200-400 degreeC.
When a chemical vapor deposition method is employed as a method for forming the ruthenium-silicon mixed film of the present invention, the chemical vapor deposition method is performed in the presence or absence of an inert gas and in the presence of a reducing gas. It can be carried out under any conditions in the absence. Moreover, you may implement on the conditions in which both companies of an inert gas and a reducing gas exist.
Here, examples of the inert gas include nitrogen, argon, helium, and the like. Moreover, as reducing gas, hydrogen, ammonia, etc. can be mentioned, for example.
The chemical vapor deposition method can be carried out under pressure, normal pressure or reduced pressure, but is preferably carried out under normal pressure or reduced pressure, and is carried out under a pressure of 15,000 Pa or less. More preferably.

When the coating method is adopted as the method for forming the ruthenium-silicon mixed film of the present invention, as long as the above-mentioned (A) specific ruthenium compound and (B) cyclic silane compound are used as raw materials, there is a particular limitation. For example, it can be carried out by any of the following methods.
Application method (1)
A method of forming a ruthenium-silicon mixed film by preparing a composition containing the above-mentioned (A) specific ruthenium compound and (B) a cyclic silane compound, applying the composition onto a substrate, and then heat-treating it.
Application method (2)
The ruthenium-silicon is formed by forming a coating film of the (B) cyclic silane compound on the substrate and then forming a coating film of the specific ruthenium compound (A) on the film formed by heat treatment and then heat-treating. A method of forming a mixed film.

As the substrate that can be used in both the coating method (1) and the coating method (2), those exemplified as the substrate that can be used in the chemical vapor deposition method can be used.
The composition containing (A) specific ruthenium compound and (B) cyclic silane compound prepared in the coating method (1) contains (A) specific ruthenium compound and (B) cyclic silane compound as essential components, Preferably, it further contains a solvent. The solvent that can be used here is not particularly limited as long as it dissolves or disperses (A) the specific ruthenium compound and (B) the cyclic silane compound and does not react with them. Examples of such solvents include hydrocarbon solvents, ether solvents, halogen solvents and the like.

Specific examples thereof include n-pentane, cyclopentane, n-hexane, cyclohexane, n-heptane, cycloheptane, n-octane, cyclooctane, decane, cyclodecane, dicyclopentadiene hydride, and benzene as hydrocarbon solvents. , Toluene, xylene, durene, indene, tetrahydronaphthalene, decahydronaphthalene, squalane;
As ether solvents, diethyl ether, dipropyl ether, dibutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol methyl ethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, tetrahydrofuran, tetrahydropyran, bis (2- Methoxyethyl) ether, p-dioxane;
Examples of the halogen solvent include methylene chloride and chloroform. These solvents can be used alone or as a mixture of two or more.
Of these, a hydrocarbon solvent or a mixture of a hydrocarbon solvent and an ether solvent is used in view of the solubility of the above-mentioned (A) specific ruthenium compound and (B) cyclic silane compound and the stability of the resulting composition. It is preferable.

Ratio of the amount of (A) specific ruthenium compound and (B) cyclic silane compound used in the composition containing (A) specific ruthenium compound and (B) cyclic silane compound prepared in the coating method (1) The (B) cyclic silane compound is preferably 0.5 to 100 mol, more preferably 1.5 to 30 mol, per 1 mol of the (A) specific ruthenium compound. By using the ratio in this range, a ruthenium-silicon mixed film capable of effectively suppressing interfacial peeling is formed in forming a damascene structure using a low dielectric constant material for the insulating film layer. Can do.
In the case where the composition prepared in the coating method (1) contains, the amount of the solvent used is preferably 1 to 80% by weight of the total composition, excluding the solvent from the total amount of the composition, More preferably, it is 20 to 60% by weight.

In the coating method (1), when the composition as described above is coated on the substrate, the coating method is not particularly limited, and coating by spin coating, dip coating, curtain coating, roll coating, spray coating, ink jet method. The printing method can be used. The application may be performed only once, or may be repeated several times.
The thickness of the coating film can be preferably 3 to 3000 mm, more preferably 10 to 1000 mm.
This thickness should be understood as the thickness after removal of the solvent when the composition containing (A) the specific ruthenium compound and (B) the cyclic silane compound contains a solvent. .

In the coating method (1), a ruthenium-silicon mixed film can be formed by subsequent heat treatment.
About the said heat processing, it is preferable that the temperature shall be 30-500 degreeC, and it is more preferable to set it as 150-400 degreeC. The heating time is preferably about 5 to 90 minutes. The atmosphere during the heat treatment is preferably a non-oxidizing atmosphere, and it is more preferable to set the oxygen concentration as low as possible. In addition, it is preferable to perform heat treatment in an atmosphere containing hydrogen because a high-quality film can be obtained. Hydrogen in the above atmosphere may be used as a mixed gas with, for example, nitrogen, helium, argon, or the like.

In the coating method (2), a coating film of the (B) cyclic silane compound is formed on the substrate, and then a coating film of the specific ruthenium compound (A) is formed on the film formed by heat treatment. Next, a heat treatment is performed to form a ruthenium-silicon mixed film.
In the coating method (2), in the step of forming the coating film of the (B) cyclic silane compound on the substrate, the (B) cyclic silane compound may be applied as it is, but the (B) cyclic silane compound and solvent are used. It is preferable to prepare the composition to be contained and apply it. As a solvent which can be used here, the solvent illustrated as a solvent which can be used for preparation of the composition containing (A) specific ruthenium compound and (B) cyclic silane compound in the coating method (1) is used suitably. Can do.

In the composition containing the (B) cyclic silane compound and the solvent, the amount of the solvent used is preferably 1 to 70% by weight, more preferably the amount obtained by removing the solvent from the total amount of the composition. 20 to 50% by weight.
In the coating method (2), when the coating film of (B) the cyclic silane compound is formed on the substrate, it can be carried out in the same manner as in the coating method (1). Here, the thickness of the coating film can be preferably 3 to 2000 mm, and more preferably 10 to 1000 mm.
In addition, when forming the coating film of (B) cyclic silane compound, this thickness is the thickness after solvent removal in the case of applying the composition containing (B) cyclic silane compound and solvent. It should be understood.
In the coating method (2), heat treatment is then performed. About the said heat processing, it is preferable that the temperature shall be 50-500 degreeC, and it is more preferable to set it as 150-400 degreeC. The heating time is preferably about 5 to 90 minutes. The atmosphere during heating can be set in the same manner as in the case of the heat treatment in the coating method (1).

In the coating method (2), a ruthenium-silicon mixed film is then formed by further forming (A) a coating film of a specific ruthenium compound on the film formed as described above and then heat-treating it. be able to.
In the step of forming the coating film of the specific ruthenium compound (A), the composition containing (A) the specific ruthenium compound and a solvent is prepared and applied. As a solvent which can be used here, the solvent illustrated as a solvent which can be used for preparation of the composition containing (A) specific ruthenium compound and (B) cyclic silane compound in the coating method (1) is used suitably. Can do.

In the composition containing the (A) specific ruthenium compound and the solvent, the amount of the solvent used is preferably 10 to 80% by weight, more preferably the amount obtained by removing the solvent from the total amount of the composition. 20 to 50% by weight.
In the coating method (2), when the coating film of the specific ruthenium compound (A) is formed on the substrate, it can be carried out in the same manner as the coating method in the coating method (1). Here, the thickness of the coating film is preferably 1 to 2000 mm, and more preferably 10 to 1000 mm.
This thickness should be understood as the thickness after removal of the solvent.
In the coating method (2), a heat treatment is then performed to form a ruthenium-silicon mixed film. About the said heat processing, it is preferable that the temperature shall be 150-500 degreeC, and it is more preferable to set it as 200-400 degreeC. The heating time is preferably about 5 to 90 minutes. The atmosphere during heating can be set in the same manner as in the case of the heat treatment in the coating method (1).

When the ruthenium-silicon mixed film formed as described above is formed by the chemical vapor deposition method or the coating method (1), it becomes a mixed film having substantially the same composition over the entire film. In the coating method (2), the lower layer of the film is a silicon layer, the upper layer of the film is a ruthenium layer, and the intermediate layer of the film is a ruthenium-silicon mixed layer. In either case, the ruthenium-silicon mixed film formed by the method of the present invention is positioned between the low dielectric constant insulating film and the diffusion prevention film layer of the damascene structure, thereby insulating the damascene structure. Interfacial peeling between the film layer and the diffusion preventing layer can be effectively suppressed.
The thickness of the ruthenium-silicon mixed film formed as described above is preferably 10 to 2000 mm, and more preferably 50 to 1000 mm. If this value is less than 10 mm, the effect of suppressing interfacial delamination between the insulating film layer and the diffusion prevention layer may be insufficient when forming the damascene structure, while if it exceeds 2000 mm, formation of a fine damascene structure may be achieved. May be an obstacle.

Hereinafter, the present invention will be described more specifically with reference to examples. However, the following description shows the example of an aspect of this invention generally, and this invention is not limited by this description.
“Parts” and “%” in Examples and Comparative Examples mean parts by weight and% by weight, respectively, unless otherwise specified.
Various evaluations were performed as follows.
Relative permittivity The relative permittivity was measured by a CV method using a HP4284A precision LCR meter and a HP16451B electrode (both manufactured by Yokogawa and Hewlett-Packard Co., Ltd.) at a frequency of 100 kHz.
The “CV method” refers to a method of measuring the capacitance (C) of a sample at a specific applied voltage (V) and calculating the relative dielectric constant of the sample from the value.
The elastic modulus was measured by a continuous stiffness measurement method using Nanoindenter XP (manufactured by Nano Instruments).
The film thickness The film thickness was measured by grazing incidence X-ray analyzer (Philips, type "X'Pert MRD").
ESCA spectrum The ESCA spectrum was measured by JEOL Co., Ltd. model “JPS80”.
Adhesion Adhesion was evaluated by a cross-cut tape method in accordance with JIS K-5400.

Synthesis example 1
In a 300 mL flask purged with nitrogen, 11 g of trimethylsilyl chloride was dissolved in 30 mL of well-dried tetrahydrofuran. This solution was cooled to −78 ° C., and 100 mL of a cyclopentadienyl sodium tetrahydrofuran solution (2.0 mol / L) was added dropwise over 1 hour under a nitrogen stream. Thereafter, stirring was continued at −78 ° C. for 1 hour, and then returned to room temperature over 6 hours. After removing the precipitate in the reaction mixture by filtration under a nitrogen atmosphere, 8 g of trimethylsilylcyclopentadiene was obtained by distillation purification.
Next, 0.5 g of metallic sodium and 30 mL of well-dried tetrahydrofuran were charged into a 100 mL flask purged with nitrogen, and cooled to -78 ° C. Under a nitrogen stream, a solution of 2.5 g of trimethylsilylcyclopentadiene synthesized above in 30 mL of tetrahydrofuran was added dropwise over 1 hour, then the temperature was raised to room temperature over 3 hours, and trimethylsilylcyclopentadienyl sodium A tetrahydrofuran solution (concentration 0.30 mol / L) was obtained.
Furthermore, 5 g of dichloro (cyclooctadienyl) ruthenium was dissolved in 200 mL of well-dried tetrahydrofuran in a nitrogen-substituted 500 mL flask. The solution was cooled to −78 ° C., and 70 mL of the trimethylsilylcyclopentadienyl sodium tetrahydrofuran solution synthesized above was added dropwise over 1 hour under a nitrogen stream. Thereafter, stirring was continued at −78 ° C. for 3 hours, and then returned to room temperature over 12 hours. The reaction mixture was purified once by passing through a neutral alumina column in argon gas, concentrated and then purified again by a neutral alumina column to obtain 0.9 g of bis (trimethylsilylcyclopentadienyl) ruthenium (yield 13). %).

Synthesis example 2
2.1 g of triruthenium dodecacarbonyl (Ru ₃ (CO) ₁₂ ) was placed in a 200 mL flask purged with nitrogen, and placed under reduced pressure at 50 ° C. for 30 minutes. The flask was filled with dry nitrogen after returning to room temperature. 100 mL of well-dried toluene and 60 mL of 1,5-cyclooctadiene purified by distillation were added under a nitrogen atmosphere. The solution was heated to 100 ° C. and stirred for 9 hours. Thereafter, the solvent and unreacted cyclooctadiene were removed under reduced pressure, and the remaining viscous liquid was passed through a silica gel column in nitrogen using hexane as a developing solvent, and a dark brown part was collected. After removing the solvent under reduced pressure, sublimation purification was performed at 133 Pa and 80 ° C. to obtain 0.8 g of cyclooctadienyltricarbonylruthenium as a yellow needle crystal (yield = 31%).

Synthesis example 3
In a 500 mL flask purged with nitrogen, 14.47 g of a 28% methanol solution of sodium methoxide was taken, and 110 ml of methanol was added. A solution obtained by dissolving 9.76 g of ethyl acetoacetate in 100 ml of methanol was added dropwise over 15 minutes under a nitrogen stream. Thereafter, stirring was continued for 1 hour. At this time, the reaction solution, which was colorless over time, turned yellow. Next, a solution prepared by dissolving 5.19 g of anhydrous ruthenium trichloride in 200 ml of methanol was added dropwise over 30 minutes under a nitrogen stream. Then, after returning for 5 hours, it was allowed to stand at room temperature for 24 hours under a nitrogen stream. Precipitates in the reaction mixture were removed with a membrane filter having a pore size of 0.45 μm, and then methanol was removed with an evaporator. The residue was dissolved in 100 mL of ethanol and allowed to stand for 1 hour, and then the precipitated salt was removed with a membrane filter having a pore size of 0.45 μm. Next, the solvent was removed with an evaporator, and the residue was further dried at 60 ° C. under reduced pressure to obtain 9.1 g of tris (1-ethoxybutane-1,3-diketo) ruthenium (yield = 74%).

Synthesis example 4
After replacing the inside of the 2 L four-necked flask with nitrogen gas, 1.5 L of dried tetrahydrofuran and 27.4 g of lithium were charged and bubbled with nitrogen. The contents were cooled to 0 ° C., and 500 g of diphenyldichlorosilane was added dropwise over 1 hour under a nitrogen stream. Stirring was continued until lithium completely disappeared, and the mixture was further heated and stirred at 50 ° C. for 1 hour. After returning to room temperature, the reaction mixture was poured into 5 L of ice water. The precipitate was collected by filtration, washed with water, and then washed with cyclohexane. The crude product thus obtained was recrystallized with ethyl acetate to obtain 180 g of decaphenylcyclopentasilane.
Next, 100 g of decaphenylcyclopentasilane obtained above and 1000 mL of toluene were charged into a 2 L flask purged with nitrogen, 50 g of aluminum chloride was added, and the mixture was stirred in a nitrogen stream at room temperature for 5 hours. Thereafter, hydrogen chloride gas was bubbled for 3 hours.
On the other hand, 42 g of lithium aluminum hydride was suspended in 500 mL of diethyl ether in another 3 L flask and cooled to −20 ° C. The above reaction mixture was added thereto over 1 hour under a nitrogen stream, and stirring was continued at −20 ° C. for 12 hours. Subsequently, after filtering this, 30 g of colorless and transparent cyclopentasilane was obtained by distilling at 2.66 kPa and 70 degreeC (yield = 11%).

Synthesis example 5
After replacing the inside of the 2 L four-necked flask with nitrogen gas, 1.5 L of dried tetrahydrofuran and 27.4 g of lithium were charged and bubbled with nitrogen. The contents were cooled to 0 ° C., and 500 g of diphenyldichlorosilane was added dropwise over 1 hour under a nitrogen stream. Stirring was continued until lithium disappeared completely, and then the reaction mixture was poured into 5 L of ice water. The precipitate was collected by filtration, washed with water, and then washed with cyclohexane to obtain 216 g of dodecaphenylcyclohexasilane.
Next, 100 g of dodecaphenylcyclohexasilane obtained above and 1000 mL of toluene were charged into a 2 L flask purged with nitrogen, and 50 g of aluminum chloride was added, followed by stirring in a nitrogen stream at room temperature for 5 hours. Thereafter, hydrogen chloride gas was bubbled for 3 hours.
On the other hand, 42 g of lithium aluminum hydride was suspended in 500 mL of diethyl ether in another 3 L flask and cooled to −20 ° C. The above reaction mixture was added thereto over 1 hour under a nitrogen stream, and stirring was continued at −20 ° C. for 12 hours. Subsequently, after filtering this, it distilled at 6.65 kPa and 115 degreeC, and obtained 20 g of colorless and transparent silylcyclopentasilanes (yield = 7.1%).

Preparation of silicon substrate having low dielectric constant insulating film layer In a quartz separable flask, 471 g of ethanol, 237 g of ion-exchanged water and 17.2 g of a 25% aqueous solution of tetramethylammonium hydroxide were placed and stirred uniformly. To this solution was added a mixture of 44.9 g of methyltrimethoxysilane and 68.6 g of tetraethoxysilane. The solution was heated to 55 ° C. and stirring was continued at that temperature for 2 hours. Subsequently, 28 g of a 20% aqueous solution of maleic acid and 440 g of propylene glycol monopropyl ether were added, and then the solution was concentrated to 50% at 50 ° C. in terms of complete hydrolysis condensate using an evaporator. This solution was transferred to a separatory funnel, and 300 g of ethyl acetate and 300 g of ion-exchanged water were added and shaken well. The upper layer was taken out, and the solution was concentrated using an evaporator at 50 ° C. until it was 10% in terms of complete hydrolysis condensate. This solution was filtered through a Teflon (registered trademark) filter having a pore diameter of 0.2 μm to obtain an insulating film forming composition having a low dielectric constant.
The obtained composition was applied onto a silicon wafer by a spin coating method, heated in air at 80 ° C. for 5 minutes and then at 200 ° C. for 5 minutes in nitrogen, and further in vacuum at 340 ° C., 360 ° C., and 380 ° C. By heating each in turn for 30 minutes and further heating at 425 ° C. for 1 hour under vacuum, a colorless and transparent low dielectric constant insulating film with a film thickness of 10,000 mm, a relative dielectric constant of 2.2, and an elastic modulus of 5.8 GPa A silicon substrate having a layer was prepared.

Plasma Enhanced Chemical Vapor Deposition Method In the following examples, the night titanium nitride film was formed by the plasma enhanced chemical vapor deposition method according to the following method.
That is, after the sample substrate was mounted in the chamber, the pressure in the chamber was reduced to 0.13 Pa. Next, the substrate temperature is maintained at 550 ° C., and titanium tetrachloride gas, nitrogen gas, and hydrogen gas are allowed to flow into the chamber at a flow rate of 10 mL / min, 350 mL / min, and 50 mL / min, respectively, and plasma in the chamber has a frequency of 2.45 GHz. In an atmosphere, a titanium nitride film was formed on the substrate over 1 hour.

Example 1
0.05 g of bis (trimethylsilylcyclopentadienyl) ruthenium synthesized in Synthesis Example 1 and 0.05 g of cyclopentasilane synthesized in Synthesis Example 4 were weighed and mixed in a quartz boat container under nitrogen (Si / Ru ratio corresponds to 2.5 in molar ratio). This quartz boat-type container and a silicon substrate (hereinafter referred to as “insulating film substrate”) having a low dielectric constant insulating film layer prepared in advance by the above-described method of “creating a silicon substrate having a low dielectric constant insulating film layer”. Were set in a quartz reaction vessel in a nitrogen stream. At this time, the insulating film substrate was placed near the downstream side of the air flow in the reaction vessel with respect to the quartz boat. After flowing nitrogen gas into the reaction vessel at a flow rate of 250 mL / min for 30 minutes at room temperature, a hydrogen / nitrogen mixed gas (hydrogen content: 3 vol%) is caused to flow into the reaction vessel at a flow rate of 100 mL / min, and the inside of the system is further 1300 Pa. And the reaction vessel was heated to 120 ° C. for 30 minutes. Mist was generated from the boat-type container, and deposits were seen on the insulating film substrate. After the generation of mist was completed, a hydrogen / nitrogen mixed gas (hydrogen 3 vol%) was flowed at a flow rate of 500 mL / min at 101.3 kPa, and the reaction vessel was raised to 350 ° C. and held for 1 hour. A film with a metallic luster was obtained on top. The film thickness was 500 mm. When the ESCA spectrum of this film was measured, peaks attributed to Ru _3d orbitals were observed at 280 eV and 284 eV, peaks attributed to Si _2p orbitals were observed at 99.0 eV, and peaks derived from other elements were completely absent. It was not observed and was found to be a mixed film of ruthenium and silicon.
Next, a titanium nitride film having a thickness of 1000 mm is formed by plasma enhanced chemical vapor deposition on the insulating film substrate having a mixed film of ruthenium and silicon formed on the surface, and a low dielectric constant is formed on the silicon substrate. A laminated film in which an insulating film, a mixed film of ruthenium and silicon, and a titanium nitride film were sequentially formed was obtained.
When the adhesion of the silicon substrate on which this multilayer film was formed was evaluated according to the cross-cut tape method, none of the 100 cross-cuts were peeled off, indicating good adhesion.

Example 2
0.05 g of cyclopentasilane synthesized in Synthesis Example 4 was placed in a quartz boat container under nitrogen. The quartz boat type container and the insulating film substrate were set in a quartz reaction container in a nitrogen stream. At this time, the insulating film substrate was placed near the downstream side of the air flow in the reaction vessel with respect to the quartz boat. Nitrogen gas was flowed into the reaction vessel at 50 ° C. at a flow rate of 50 mL / min for 30 minutes. Mist was generated from the boat-type container, and deposits were seen on the insulating film substrate. Thereafter, while flowing nitrogen gas at the same flow rate, the reaction vessel was heated to 120 ° C. and nitrogen gas was further flowed for 30 minutes. Subsequently, when the temperature of the reaction vessel was raised to 300 ° C. and held for 1 hour under a nitrogen stream, a film having a metallic luster was obtained on the substrate. Here, when the insulating film substrate was taken out and the thickness of the formed film was measured, it was 300 mm.
Subsequently, 0.05 g of bis (trimethylsilylcyclopentadienyl) ruthenium synthesized in Synthesis Example 1 was placed in a quartz boat-type vessel under nitrogen, and a metallic luster was formed on the surface of the quartz boat-type vessel and obtained above. An insulating film substrate having a certain film was set in a quartz reaction vessel in nitrogen. Also at this time, the insulating film substrate was placed near the downstream side of the air flow in the reaction vessel with respect to the quartz boat. Nitrogen gas was allowed to flow into the reaction vessel at a flow rate of 250 mL / min for 30 minutes at room temperature. Next, a hydrogen / nitrogen mixed gas (hydrogen content: 3 vol%) was allowed to flow into the reaction vessel at a flow rate of 100 mL / min, the system was further set to 1300 Pa, and the reaction vessel was heated to 120 ° C. for 30 minutes. Mist was generated from the boat-type container, and further deposits were seen on the insulating film substrate. After the generation of mist was completed, the inside of the reaction vessel was filled with a hydrogen / nitrogen mixed gas (hydrogen 3%), and the pressure was adjusted to 101.3 kPa. While maintaining this pressure, the reaction vessel was heated to 350 ° C. while flowing a hydrogen / nitrogen mixed gas (hydrogen 3%) at a flow rate of 500 mL / min and kept at that temperature for 1 hour. Became a metallic glossy film. The thickness of the newly formed film was measured and found to be 250 mm.
When the ESCA spectrum of the laminated film thus formed was measured, peaks 280 eV and 284 eV attributed to the Ru _3d orbit were observed at a depth of 100 mm from the top of the film, except for the top layer of the film. No peaks derived from other elements were observed, and this part was found to be a metal ruthenium film. Further, in the portion having a depth from the top of the film of 100 to 400 mm, in addition to the peak derived from metal ruthenium, a peak attributed to the Si _2p orbit starts to be observed at 99.0 eV, and as the depth of the film progresses, ruthenium The peak intensity derived from the source decreased, and the peak intensity derived from the silicon increased. Therefore, it was found that ruthenium and silicon were mixed in this part. Further, only a peak attributed to silicon was observed at a portion deeper than 400 mm from the uppermost portion of the film, and no peak derived from other elements was observed at all, indicating that this portion was a silicon film.
Next, a 1000-nm thick titanium nitride film is formed by plasma enhanced chemical vapor deposition on the insulating film substrate on which the silicon film, the ruthenium-silicon mixed film, and the ruthenium film are sequentially formed on the surface. As a result, an insulating film having a low dielectric constant, a silicon film, a film in which ruthenium and silicon are mixed, a ruthenium film, and a titanium nitride film are sequentially formed on a silicon substrate.
When the adhesion of the silicon substrate on which this multilayer film was formed was evaluated according to the cross-cut tape method, none of the 100 cross-cuts were peeled off, indicating good adhesion.

Example 3
0.03 g of 1,5-cyclooctadienyl ruthenium tricarbonyl synthesized in Synthesis Example 2 and 0.05 g of cyclopentasilane synthesized in Synthesis Example 4 were weighed and mixed in a quartz boat container under nitrogen. (The Si / Ru ratio corresponds to 3.0 in molar ratio). The quartz boat container and the insulating film substrate were set in a quartz reaction container in a nitrogen stream. At this time, the insulating film substrate was placed near the downstream side of the air flow in the reaction vessel with respect to the quartz boat. After flowing nitrogen gas into the reaction vessel at a flow rate of 250 mL / min for 30 minutes at room temperature, a hydrogen / nitrogen mixed gas (hydrogen content 3 vol%) was flowed at a flow rate of 100 mL / min, and the system was further set to 665 Pa. Was heated to 120 ° C. for 30 minutes. Mist was generated from the boat-type container, and deposits were seen on the insulating film substrate. After the generation of mist was completed, a hydrogen / nitrogen mixed gas (hydrogen 3 vol%) was flowed at a flow rate of 500 mL / min at 101.3 kPa, and the reaction vessel was raised to 350 ° C. and held for 1 hour. A film with a metallic luster was obtained on top. The film thickness was 450 mm. When the ESCA spectrum of this film was measured, peaks attributed to Ru _3d orbitals were observed at 280 eV and 284 eV, peaks attributed to Si _2p orbitals were observed at 99.0 eV, and peaks derived from other elements were completely absent. It was not observed and was found to be a mixed film of ruthenium and silicon.
Next, a titanium nitride film having a thickness of 1000 mm is formed by plasma enhanced chemical vapor deposition on the insulating film substrate having a mixed film of ruthenium and silicon formed on the surface, and a low dielectric constant is formed on the silicon substrate. A laminated film in which an insulating film, a mixed film of ruthenium and silicon, and a titanium nitride film were sequentially formed was obtained.
When the adhesion of the silicon substrate on which this multilayer film was formed was evaluated according to the cross-cut tape method, none of the 100 cross-cuts were peeled off, indicating good adhesion.

Example 4
0.05 g of cyclopentasilane synthesized in Synthesis Example 4 was placed in a quartz boat container under nitrogen. The quartz boat container and the insulating film substrate were set in a quartz reaction container in a nitrogen stream. At this time, the insulating film substrate was placed near the downstream side of the air flow in the reaction vessel with respect to the quartz boat. Nitrogen gas was flowed into the reaction vessel at 50 ° C. at a flow rate of 50 mL / min for 30 minutes. Mist was generated from the boat-type container, and deposits were seen on the insulating film substrate. Thereafter, while flowing nitrogen gas at the same flow rate, the reaction vessel was heated to 120 ° C. and nitrogen gas was further flowed for 30 minutes. Subsequently, when the temperature of the reaction vessel was raised to 300 ° C. and held for 1 hour under a nitrogen stream, a film having a metallic luster was obtained on the substrate. Here, when the insulating film substrate was taken out and the thickness of the formed film was measured, it was 300 mm.
Subsequently, 0.03 g of 1,5-cyclooctadienyl ruthenium tricarbonyl synthesized in Synthesis Example 2 was taken in a quartz boat-type vessel under nitrogen, and the quartz boat-type vessel and the surface obtained above were placed on the surface. An insulating film substrate having a metallic glossy film was set in a quartz reaction vessel in nitrogen. Also at this time, the insulating film substrate was placed near the downstream side of the air flow in the reaction vessel with respect to the quartz boat. Nitrogen gas was allowed to flow into the reaction vessel at a flow rate of 250 mL / min for 30 minutes at room temperature. Next, a hydrogen / nitrogen mixed gas (hydrogen content: 3 vol%) was allowed to flow into the reaction vessel at a flow rate of 100 mL / min, the system was further set to 133 Pa, and the reaction vessel was heated to 180 ° C. for 30 minutes. Mist was generated from the boat-type container, and further deposits were seen on the insulating film substrate. After the generation of mist was completed, the inside of the reaction vessel was filled with a hydrogen / nitrogen mixed gas (hydrogen 3%), and the pressure was adjusted to 101.3 kPa. While maintaining this pressure, the reaction vessel was heated to 350 ° C. while flowing a hydrogen / nitrogen mixed gas (hydrogen 3%) at a flow rate of 500 mL / min and kept at that temperature for 1 hour. Became a metallic glossy film. The film thickness of the newly formed film was measured and found to be 230 mm.
When the ESCA spectrum was measured for the laminated film thus formed, peaks 280 eV and 284 eV attributed to the Ru _3d orbit were observed at a depth of 90 mm from the top of the film, except for the top layer of the film. No peaks derived from other elements were observed, and this part was found to be a metal ruthenium film. Further, in the portion where the depth from the top of the film is 90 to 360 mm, in addition to the peak derived from metal ruthenium, a peak attributed to the Si _2p orbit starts to be observed at 99.0 eV, and as the depth of the film progresses, ruthenium The peak intensity derived from the source decreased, and the peak intensity derived from the silicon increased. Therefore, it was found that ruthenium and silicon were mixed in this part. Furthermore, in the part deeper than 360 mm from the top of the film, only the peak attributed to silicon was observed, and no peak derived from other elements was observed at all, and this part was found to be a silicon film.
Next, a 1000-nm thick titanium nitride film is formed by plasma enhanced chemical vapor deposition on the insulating film substrate on which the silicon film, the ruthenium-silicon mixed film, and the ruthenium film are sequentially formed on the surface. As a result, an insulating film having a low dielectric constant, a silicon film, a film in which ruthenium and silicon are mixed, a ruthenium film, and a titanium nitride film are sequentially formed on a silicon substrate.
When the adhesion of the silicon substrate on which this multilayer film was formed was evaluated according to the cross-cut tape method, none of the 100 cross-cuts were peeled off, indicating good adhesion.

Example 5
Under nitrogen, 1 g of tris (1-ethoxybutane-1,3-diketo) ruthenium synthesized in Synthesis Example 3 and 0.7 g of silylcyclopentasilane synthesized in Synthesis Example 5 were dissolved in 78.4 g of toluene. (The Si / Ru ratio corresponds to 2.0 in molar ratio). This solution was filtered through a Teflon (registered trademark) filter having a pore diameter of 0.2 μm, and then applied to the insulating film substrate by a spin coating method (3,500 rpm) in a nitrogen atmosphere. The coated substrate was evaporated in a nitrogen atmosphere and then heated in a nitrogen atmosphere at 300 ° C. for 30 minutes and then at 400 ° C. for 30 minutes. A metallic gloss film was obtained on the insulating film substrate. The film thickness was 350 mm. When the ESCA spectrum of this film was measured, peaks attributed to Ru _3d orbitals were observed at 280 eV and 284 eV, peaks attributed to Si _2p orbitals were observed at 99.0 eV, and peaks derived from other elements were completely absent. It was not observed and was found to be a mixed film of metal ruthenium and silicon.
Next, a titanium nitride film having a thickness of 1000 mm is formed by plasma enhanced chemical vapor deposition on the insulating film substrate having a mixed film of ruthenium and silicon formed on the surface, and a low dielectric constant is formed on the silicon substrate. A laminated film in which an insulating film, a mixed film of ruthenium and silicon, and a titanium nitride film were sequentially formed was obtained.
When the adhesion of the silicon substrate on which this multilayer film was formed was evaluated according to the cross-cut tape method, none of the 100 cross-cuts were peeled off, indicating good adhesion.

Example 6
After 0.2 g of silylcyclopentasilane synthesized in Synthesis Example 5 is dissolved in 9.8 g of toluene under nitrogen, and foreign matter is removed with a Teflon (registered trademark) filter having a pore size of 0.2 μm, an insulating film substrate is obtained. It was coated on the top by a spin coating method (3,500 rpm) under a nitrogen atmosphere. The coated substrate was placed in a nitrogen atmosphere to evaporate the solvent, and then heated in a nitrogen atmosphere at 400 ° C. for 60 minutes. A metallic glossy film was obtained on the insulating film substrate. The film thickness was 600 mm.
Next, 0.2 g of tris (1-ethoxybutane-1,3-diketo) ruthenium synthesized in Synthesis Example 3 above was dissolved in 9.8 g of toluene under nitrogen, and the pore diameter was 0.2 μm made of Teflon (registered trademark). After filtering with a filter, it was applied on the insulating film substrate having a metallic gloss film on the surface obtained above by a spin coating method (rotation speed is 3500 rpm) in a nitrogen atmosphere. The coated substrate was placed in a nitrogen atmosphere to evaporate the solvent, and then heated at 500 ° C. for 30 minutes in a nitrogen atmosphere. Here, the thickness of the newly formed film was measured and found to be 210 mm.
When the ESCA spectrum was measured for the laminated film thus formed, peaks 280 eV and 284 eV attributed to the Ru _3d orbit were observed at a depth of 90 mm from the top of the film, except for the top layer of the film. No peaks derived from other elements were observed, and this part was found to be a metal ruthenium film. Further, in the portion having a depth of 90 to 330 mm from the top of the film, in addition to the peak derived from metal ruthenium, a peak attributed to the Si _2p orbit starts to be observed at 99.0 eV, and as the depth of the film progresses, ruthenium The peak intensity derived from the source decreased, and the peak intensity derived from the silicon increased. Therefore, it was found that ruthenium and silicon were mixed in this part. Furthermore, only a peak attributed to silicon was observed at a portion deeper than 330 mm from the top of the film, and no peak derived from other elements was observed at all, indicating that this portion was a silicon film.
Next, a 1000-nm thick titanium nitride film is formed by plasma enhanced chemical vapor deposition on the insulating film substrate on which the silicon film, the ruthenium-silicon mixed film, and the ruthenium film are sequentially formed on the surface. As a result, an insulating film having a low dielectric constant, a silicon film, a film in which ruthenium and silicon are mixed, a ruthenium film, and a titanium nitride film are sequentially formed on a silicon substrate.
When the adhesion of the silicon substrate on which this multilayer film was formed was evaluated according to the cross-cut tape method, none of the 100 cross-cuts were peeled off, indicating good adhesion.

Comparative Example 1
0.06 g of commercially available bis (trimethylsilylcyclopentadienyl) ruthenium was placed in a quartz boat container under nitrogen. The quartz boat container and the insulating film substrate were set in a quartz reaction container in a nitrogen stream. At this time, the insulating film substrate was placed near the downstream side of the air flow in the reaction vessel with respect to the quartz boat. Nitrogen gas was allowed to flow into the reaction vessel at a flow rate of 250 mL / min for 30 minutes at room temperature. Thereafter, a hydrogen / nitrogen mixed gas (hydrogen content: 3 vol%) was allowed to flow into the reaction vessel at a flow rate of 100 mL / min, the system was further set to 1300 Pa, and the reaction vessel was heated at 120 ° C. for 30 minutes. Mist was generated from the boat-type container, and deposits were observed on the insulating film substrate installed in the vicinity. After the generation of mist was completed, the reaction vessel was filled with hydrogen / nitrogen mixed gas (hydrogen 3%). Further, while flowing a hydrogen / nitrogen mixed gas (hydrogen 3%) at a flow rate of 500 mL / min at 101.3 kPa, the reaction vessel was raised to 350 ° C. and held there for 1 hour. A film with a metallic luster was obtained on the substrate. The film thickness was 300 mm. When the ESCA spectrum of this film was measured, peaks attributed to the Ru _3d orbital were observed at 280 eV and 284 eV, and no peaks derived from other elements were observed, indicating that the film was a metal ruthenium film.
Next, a 1000-nm-thick titanium nitride film is formed by plasma enhanced chemical vapor deposition on the insulating film substrate on which the metal ruthenium film is formed, and a low dielectric constant insulating film, ruthenium film, and A laminated film in which titanium nitride films were sequentially formed was obtained.
The silicon substrate on which this laminated film was formed was evaluated for adhesion in accordance with the cross-cut tape method, and 50 of the 100 cross-cuts were peeled off.

Comparative Example 2
A 1000-nm thick titanium nitride film was formed on the insulating film substrate by plasma enhanced chemical vapor deposition, and a laminated film in which a low dielectric constant insulating film and a titanium nitride film were sequentially formed on a silicon substrate was obtained.
The silicon substrate on which this multilayer film was formed was evaluated for adhesion in accordance with the cross-cut tape method, and 70 of the 100 cross-cuts were peeled off.

Claims (6)

(A) using at least one ruthenium compound selected from the compounds represented by the following general formula (1), (3), (7) or (9), and (B) a cyclic silane compound as a raw material. A method for forming a ruthenium-silicon mixed film.
(Cp ′) ₂ Ru (1)
Here, Cp ′ is a ligand represented by the following formula (2), and two Cp ′ may be the same or different from each other.

Here, R ¹ is a C 1-6 alkyl group or fluorinated alkyl group, a trimethylsilyl group, or a fluorine atom, a is an integer of 0 to 5, and when a plurality of R ¹ are present, May be different.
(D) Ru (CO) ₃ (3)
Here, D is one selected from ligands represented by the following formulas (4) to (6).

(ACAC ') ₃ Ru (7)
Here, ACAC ′ is a ligand represented by the following formula (8), and the three ACAC ′ may be the same or different from each other.

Here, R ² is a hydrogen atom, a C 1 -C 6 alkyl group or fluorinated alkyl group, or a C 1 -C 6 alkoxyl group, and the two R ² may be the same or different from each other. Good. Moreover, the broken line in Formula (8) represents a resonance structure.
(R ³ COO) ₃ Ru (9)
Here, R3 is an alkyl group of one prime number 1-6, a fluorinated alkyl group or a hydroxyalkyl group, there are three R ³ may be identical or different from each other.   2. The method according to claim 1, wherein the chemical vapor deposition method uses a raw material in which the (A) ruthenium compound and the (B) cyclic silane compound are previously mixed.   The method according to claim 1, wherein the gas of the (A) ruthenium compound and the gas of the (B) cyclic silane compound are obtained by chemical vapor deposition supplied from separate vaporizers.   The method according to claim 1, wherein a raw material in which the (A) ruthenium compound and (B) the cyclic silane compound are mixed in advance is applied on a substrate and then heat-treated.   A coating film of the (B) cyclic silane compound is formed on a substrate, and then a coating film of the (A) ruthenium compound is formed on a film formed by heat treatment, followed by heat treatment. Item 2. The method according to Item 1. The method according to claim 1, wherein the substrate is an insulating film having a relative dielectric constant of 4.0 or less.