TWI512130B - A method for forming a ruthenium film material and a ruthenium film - Google Patents

Description

Method for forming ruthenium film and method for forming ruthenium film

The present invention relates to a material for forming a ruthenium film and a method for forming a ruthenium film.

A semiconductor device represented by a DRAM (Dynamic Random Access Memory) is required to change the material of each metal film and metal oxide film constituting the device as it is highly integrated and miniaturized.

In particular, in the use of multilayer wiring in a semiconductor device, improvement of a conductive metal film is required, and progress is made to convert into a new copper wiring having high conductivity. In order to improve the conductivity of the copper wiring, a low dielectric material (low-k material) is used in the interlayer insulating film material of the multilayer wiring. However, the oxygen atoms contained in the low dielectric material easily enter the copper wiring, causing a problem that the conductivity thereof is lowered. Therefore, in order to prevent the movement of oxygen from a low dielectric material, a technique of forming a barrier film between a low dielectric material and a copper wiring is reviewed. As for the material for use in the barrier film which is difficult to obtain oxygen from the dielectric layer and the material which can be easily processed by dry etching, the metal ruthenium film is attracting attention. Further, in the damascene film formation method in which the copper wiring is buried by the plating method, the role of both the barrier film and the plated growth film is satisfied, and the metal is attracting attention. Further, in the capacitance of the semiconductor device, as an electrode material of a high dielectric material such as alumina, ruthenium pentoxide, ruthenium oxide, or barium strontium titanate (BST), the metal ruthenium film has high oxidation resistance and High electrical conductivity is also attracting attention.

In the formation of the above-mentioned metal tantalum film, a sputtering method has been conventionally used. However, in recent years, a chemical vapor deposition method has been reviewed as a measure for miniaturization, thinning, and mass productivity of the structure.

However, in general, the state of the microcrystals of the metal film formed by the chemical vapor deposition method is sparse, and the surface morphology is deteriorated. Therefore, it is reviewed to use ginseng (di-p-amyl phthalate) ruthenium in the chemical vapor deposition material. Tris (dipivaloylmethanato) ruthenium) or ruthenium (Ruthenocene), bis(alkylcyclopentadienyl) fluorene, (dicyclohexadienyl) fluorene tricarbonyl, etc. as means for solving this morphological problem (refer to patent Literature 1~5).

Further, when these chemical vapor deposition materials are used in the production step, in order to prevent deterioration of the material adjacent to the metal ruthenium film in the film formation step, the production conditions are stabilized, and good storage stability of the material is required. However, the conventional problem of ferrocene or bis(alkylcyclopentadienyl) ruthenium or the like is the effect of mixed oxygen in the film formation step, and the adjacent material is oxidized in a short time and the performance is deteriorated. Further, when oxygen is not mixed in the film formation step, there is a problem that the ruthenium film is difficult to form a film.

On the other hand, the ruthenium film is required to have high purity, excellent performance as a barrier film and a plated growth film, and excellent adhesion to a substrate.

[Previous Technical Literature]

[Patent Literature]

[Patent Document 1] JP-A-6-283438

[Patent Document 2] Japanese Patent Publication No. 11-35589

[Patent Document 3] JP-A-2002-114795

[Patent Document 4] JP-A-2002-212112

[Patent Document 5] JP-A-2006-241557

The present invention has been made in view of the above problems, and an object thereof is to provide a ruthenium film which can be easily decomposed even in the absence of an oxidizing agent such as oxygen, and can form a ruthenium film having high purity and excellent adhesion to a substrate in a short time. A material for forming, and a method for forming a tantalum film using the material.

In order to achieve the above object, the present inventors have conducted active research and found that the above object can be attained by using a compound represented by the following formula (1), and thus the present invention has been completed.

That is, the present invention provides the following [1] to [6].

[1] A material for forming a ruthenium film, which contains a compound represented by the following formula (1),

Ru(PR ¹ ₃ ) _l (L ¹ ) _m (L ² ) _n (1)

(In the above formula (1), R ^{1 is} each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 4 carbon atoms, or a halogenated hydrocarbon group having 1 to 4 carbon atoms, and L ¹ is a hydrogen atom or a halogen atom, and L ² is An unsaturated hydrocarbon compound having 4 to 10 carbon atoms having at least two double bonds, l is an integer from 1 to 5, m is an integer from 0 to 4, and n is an integer from 0 to 2, but l+m+2n= 5 or 6).

[2] The material for forming a ruthenium film according to the above [1], which is used for a chemical vapor deposition method.

[3] A method for forming a ruthenium film, which comprises the material for forming a ruthenium film according to the above [1] or [2].

[4] A method for forming a ruthenium film, comprising the step of supplying a ruthenium film forming material to a substrate obtained by supplying the ruthenium film forming material according to the above [2], and thermally decomposing the ruthenium film forming material. A film forming step of forming a ruthenium film on the above substrate.

[5] The method for forming a ruthenium film according to the above [4], wherein the heat decomposition temperature in the film formation step is from 100 ° C to 800 ° C.

[6] The method for forming a ruthenium film according to the above [4] or [5] wherein the thermal decomposition in the film formation step is carried out in an inert gas or a reducing gas.

The material for forming a ruthenium film of the present invention can be easily decomposed to form a ruthenium film even in the absence of an oxidizing agent such as oxygen. Therefore, the oxidation of the adjacent material and the performance degradation associated therewith are small.

Moreover, according to the material for forming a ruthenium film of the present invention, a high-purity good quality ruthenium film having a small amount of residual impurities can be easily obtained in a short time. The ruthenium film is excellent in performance as a barrier film and a plated growth film, and is excellent in adhesion to a substrate.

Hereinafter, the present invention will be described in detail.

The material for forming a ruthenium film of the present invention contains a compound represented by the following formula (1).

Ru(PR ¹ ₃ ) _l (L ¹ ) _m (L ² ) _n (1)

In the above formula (1), R ^{1 is} each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 4 carbon atoms, or a halogenated hydrocarbon group having 1 to 4 carbon atoms, preferably a halogen atom or a hydrocarbon group having 1 to 4 carbon atoms. Or a halogenated hydrocarbon group having 1 to 4 carbon atoms, more preferably a halogen atom.

The halogen atom in R ¹ is exemplified by a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, preferably a fluorine atom or a chlorine atom, more preferably a fluorine atom.

Further, the hydrocarbon group having 1 to 4 carbon atoms in R ¹ may, for example, be a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group or a t-butyl group, preferably a methyl group or a ethyl group. Base, n-propyl, isopropyl, tert-butyl, more preferably methyl or ethyl.

Further, the halogenated hydrocarbon group having 1 to 4 carbon atoms in R ¹ is preferably a fluorinated hydrocarbon group, a chlorinated hydrocarbon group or a brominated hydrocarbon group, more preferably a fluorinated hydrocarbon group.

Specific examples thereof include chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, Perfluoro-n-propyl, perfluoroisopropyl, perfluoro-n-butyl, perfluoroisobutyl, perfluoro-tert-butyl, preferably fluoromethyl, difluoromethyl, trifluoromethyl, 2, 2,2-trifluoroethyl, pentafluoroethyl, perfluoro-n-propyl, perfluoroisopropyl, perfluoro-tert-butyl, more preferably fluoromethyl, difluoromethyl, trifluoromethyl, 2,2,2-Trifluoroethyl, pentafluoroethyl.

In the formula (1), L ¹ is a hydrogen atom or a halogen atom, preferably a hydrogen atom.

When L ¹ is a halogen atom, the halogen atom is exemplified by a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, preferably a fluorine atom or a chlorine atom, more preferably a fluorine atom.

Further, in the formula (1), L ² is an unsaturated hydrocarbon compound having 4 to 10 carbon atoms and having at least two double bonds.

Specific examples thereof include 1,3-pentadiene, 1,5-hexadiene, 1,4-hexadiene, 1,3-hexadiene, 2,4-hexadiene, and 3-methyl group. -1,3-pentadiene, 2-methyl-1,4-pentadiene, 1,6-heptadiene, 1,5-heptadiene, 1,4-heptadiene, 1,7- Chain diene such as octadiene, 1,6-octadiene, 1,5-octadiene, 1,4-octadiene, 1,5-cyclooctadiene, 1,3-cyclooctadiene a cyclic diene such as 1,4-cyclohexadiene or 1,3-cyclohexadiene.

Further, in the formula (1), l is an integer of from 1 to 5, and from the viewpoint of increasing the vapor pressure of the compound, it is preferably an integer of from 3 to 5.

Further, in the formula (1), m is an integer of 0 to 4, and from the viewpoint of lowering the melting point of the compound, it is preferably an integer of 0 to 3, more preferably an integer of 0 to 2.

Further, in the formula (1), n is an integer of 0 to 2, and from the viewpoint of forming a good quality ruthenium film, it is preferably 0 or 1, more preferably 0.

Furthermore, l+m+2n=5 or 6

The method for synthesizing the compound represented by the above formula (1) is exemplified by a method comprising, for example, a step of reacting ruthenium trichloride with a compound represented by PR ¹ ₃ in the above formula (1).

Further, in the above step, at least one compound selected from hydrogen, fluorine, chlorine, bromine and iodine, and carbon having at least two double bonds represented by L ² in the above formula (1) may be optionally used. The at least one compound selected from the number of unsaturated hydrocarbon compounds of 4 to 10 is reacted.

The above reaction is preferably carried out in the presence of a catalyst, and examples of the catalyst include copper, zinc, and the like.

The reaction temperature is not particularly limited, and is preferably from 50 to 400 ° C, more preferably from 100 to 350 ° C, still more preferably from 120 ° C to 300 ° C.

Further, the pressure at the time of the reaction is not particularly limited, but when trifluorophosphine, hydrogen, fluorine, chlorine or the like is reacted as a gas compound under standard conditions, it is usually 10 to 1000 atmospheres (hereinafter, also referred to as "atm"). Preferably, it is 50 to 800 atmospheres, more preferably 100 to 600 atmospheres.

Specific examples of the compound represented by the above formula (1) include, for example, the following compounds: l = 5, m = 0, n = 0, which is a compound of tris(trifluorophosphine) ruthenium (0), wu (three) Chlorophosphonium) ruthenium (0), ketone (trimethylphosphine) ruthenium (0), wu (triethylphosphine) ruthenium (0), etc. ruthenium valence of 0 钌 compound; l = 3, m = 0, The compound of n=1 is (η-1,4-cyclohexadiene) ginseng (trifluorophosphine) ruthenium (0), (η-1,4-cyclohexadiene) ginseng (trimethylphosphine) ruthenium (0), (1,5-cyclooctadiene) ginseng (trifluorophosphine) ruthenium (0), (1,5-cyclooctadiene) ginseng (trimethylphosphine) ruthenium (0), (η- 1,6-heptadiene) ginseng (trifluorophosphine) ruthenium (0), (η-1,6-heptadiene) ginseng (trimethylphosphine) ruthenium (0), (η-1, 7-octyl) a diene) ruthenium (trifluorophosphine) ruthenium (0), (η-1,7-octadiene) ginseng (trimethylphosphine) ruthenium (0), etc. The valence of ruthenium is 0 ; compound; l=4 , m=2, n=0 compounds, are indane (trifluorophosphine) ruthenium (II), (difluoro) ruthenium (trifluorophosphine) ruthenium (II), (dichloro) ruthenium (trifluorophosphine)钌(II), indane (trimethylphosphine) ruthenium (II), (difluoro) ruthenium (trimethylphosphine) ruthenium (II), (dichloro) ruthenium (trimethylphosphine) ruthenium (II) The compound having an valence of 2 is a ruthenium compound; the compound having l=3, m=3, n=0 is a trihydrogenation (trifluorocarbon)钌 (III), (trifluoro) ginseng (trifluorophosphine) ruthenium (III) and the like, the valence of ruthenium is 3 ruthenium compound; l = 2, m = 4, n = 0, the compound is tetrahydro bis ( Trifluorophosphine) ruthenium (IV), (tetrafluoro) bis(trifluorophosphine) ruthenium (IV), (tetrachloro) bis(trifluorophosphine) ruthenium (IV), hydrogenated (trifluoro) ruthenium (trifluorophosphine)钌(IV), dihydro(difluoro)phosphonium (trifluorophosphine) ruthenium (IV), dihydro(dibromo)phosphonium (trifluorophosphine) ruthenium (IV), trihydro(fluoro) ruthenium (trifluorophosphine)钌 (IV), trihydrogen (iodo) ruthenium (trifluorophosphine) ruthenium (IV) and the like, the valence of ruthenium is 3 ruthenium compound;

These compounds may be used singly or in combination of two or more kinds as materials for forming a ruthenium film. It is preferred to use a single compound as a material for forming a ruthenium film.

The method for forming a ruthenium film of the present invention is a method of using the above-mentioned material for forming a ruthenium film.

In the method for forming a ruthenium film of the present invention, in addition to the above-mentioned material for forming a ruthenium film, a conventionally known method can be used, and for example, a chemical vapor deposition method as described below (including the following steps (1) and (2)) can be employed. ) Implementation.

The ruthenium film-forming material of the present invention is supplied onto a substrate (for example, a substrate), and then the ruthenium film-forming material supplied onto the substrate is thermally decomposed to form a ruthenium film on the substrate. Specifically, (1) vaporizing or evaporating the material for forming a ruthenium film of the present invention under reduced pressure and heating, and depositing a vapor or an evaporant on a substrate (for example, a substrate), and then (2) obtaining the resultant The deposit is heated to thermally decompose to form a ruthenium film on the substrate. Further, in the above step (1), even if the material for forming a ruthenium film of the present invention is decomposed, the effects of the present invention are not impaired, and the above step (1) and the above step (2) can be simultaneously performed.

As the base material used herein, a suitable material such as glass, ruthenium semiconductor, quartz, metal, metal oxide, synthetic resin or the like can be used, but a material which can withstand the temperature at which the ruthenium compound is thermally decomposed is preferable.

In the above step (1), the temperature at which the ruthenium compound is vaporized or evaporated is preferably from -100 to 350 ° C, more preferably from -80 to 200 ° C, most preferably from -60 to 150 ° C.

In the above step (1), the pressure-reducing condition at the time of vaporizing or evaporating the ruthenium compound is preferably 1,000 Pa or less, more preferably 100 Pa or less, and most preferably 50 Pa or less. The lower limit of the reduced pressure condition is not particularly limited, but is usually 1 Pa from the viewpoint of the performance of the pressure reducing device.

In the above step (2), the temperature at which the hydrazine compound is thermally decomposed is preferably from 100 to 800 ° C, more preferably from 100 to 600 ° C, still more preferably from 180 to 450 ° C, and even more preferably from 200 to 420 ° C. It is 250~410 °C.

The chemical vapor deposition method of the present invention can be carried out in any of the conditions of an inert gas and in the absence of it, and can be carried out in the presence or absence of a reducing gas. However, it is preferred to have either or both of an inert gas and a reducing gas.

The inert gas is exemplified by, for example, nitrogen gas, argon gas, helium gas or the like. Further, the reducing gas may, for example, be hydrogen gas, ammonia gas or the like. Further, the chemical vapor deposition method of the present invention can also be carried out in the presence of an oxidizing gas. Here, examples of the oxidizing gas include oxygen, carbon monoxide, and nitrogen monoxide.

In particular, in order to reduce the amount of impurities in the film formed film, it is preferable to coexist such reducing gases. When a reducing gas is coexisted, the proportion of the reducing gas in the atmosphere is preferably from 1 to 100 mol%, more preferably from 3 to 100 mol%.

The proportion of the oxidizing gas in the atmosphere is preferably 10 mol% or less, more preferably 1 mol% or less, and most preferably 0.1 mol% or less.

The above step (2) in the chemical vapor deposition method of the present invention can also be carried out under any conditions of pressure, normal pressure and reduced pressure. Among them, it is preferably carried out under normal pressure or under reduced pressure, and more preferably at a pressure of 15,000 Pa or less.

The material for forming a ruthenium film of the present invention is preferably stored in an atmosphere of an inert gas. The inert gas is exemplified by, for example, nitrogen gas, argon gas, helium gas or the like.

The tantalum film obtained as described above has high purity and conductivity, and can be preferably used for, for example, a barrier film of a wiring electrode, a plating growth film, a capacitor electrode, or the like.

[Examples]

The invention is specifically illustrated by the following examples, but the invention is not limited by the examples.

[Synthesis Example 1] Synthesis of uranium (trifluorophosphine) ruthenium (0)

A reactor in which 5.03 g of antimony trichloride and 10.08 g of copper were placed was evacuated, and trifluorophosphine was introduced until it reached 500 atm, and heated at 250 ° C for 15 hours. After completion of the reaction, the solution was cooled to room temperature and dried under reduced pressure to remove trifluorophosphine. The obtained solid was purified by sublimation at 30 ° C, 0.013 atm (10 Torr) to obtain a white solid of s(trifluorophosphonium) hydrazine (0) 7.80 g. The yield was 60% by weight.

[Synthesis Example 2] Synthesis of Wu (triethylphosphine) ruthenium (0)

An ampule of 5.03 g of antimony trichloride, 10.08 g of copper and 10 mL of triethylphosphine was placed and sealed at 220 ° C for 24 hours. After completion of the reaction, the solution was cooled to room temperature and then filtered under a nitrogen atmosphere. The filtrate was dried under reduced pressure to remove triethylphosphine to give a white solid (3. The yield was 22% by weight.

[Synthesis Example 3] Synthesis of (1,5-cyclooctadiene) ginseng (trifluorophosphine) ruthenium (0)

The reactor in which 5.03 g of antimony trichloride, 10.08 g of copper, and 50 mL of 1,5-cyclooctadiene were placed was cooled to -78 ° C to be vacuumed, and trifluorophosphine was introduced until it reached 400 atm, and heated at 180 ° C for 72 hours. . After completion of the reaction, the solution was cooled to room temperature, and then filtered under a nitrogen atmosphere. The filtrate was dried under reduced pressure, and then subjected to a column chromatography under a nitrogen atmosphere (developing solvent: diethyl ether), and the obtained solution was concentrated to obtain (1, 5-cyclooctadiene) ginseng (trifluorophosphine) hydrazine (0) 1.71 g of a pale yellow liquid. The yield was 15% by weight.

[Synthesis Example 4] Synthesis of (1,5-cyclooctadiene) ginseng (trimethylphosphine) ruthenium (0)

An ampule of 5.03 g of antimony trichloride, 10.08 g of copper, 20 mL of 1,5-cyclooctadiene, and 10 mL of trimethylphosphine was placed, and heated at 160 ° C for 90 hours. After completion of the reaction, the solution was cooled to room temperature and then filtered under a nitrogen atmosphere. After the filtrate was dried under reduced pressure, an alumina column chromatography (developing solvent: diethyl ether) was carried out under a nitrogen atmosphere, and the obtained solution was concentrated to obtain (1,5-cyclooctadiene) gins (trimethylphosphine) ruthenium (0). ) 0.63 g of a pale yellow liquid. The yield was 6% by weight.

[Synthesis Example 5] Synthesis of indane (trifluorophosphine) ruthenium (II)

A reactor in which 5.03 g of antimony trichloride and 10.08 g of copper were placed was evacuated, and 300 atm of trifluorophosphine and 100 atm of hydrogen were introduced, and the mixture was heated at 270 ° C for 15 hours. After completion of the reaction, the solution was cooled to room temperature and dried under reduced pressure to remove trifluorophosphine and hydrogen. The obtained solution was filtered under a nitrogen atmosphere, and distilled under reduced pressure at a temperature of 0.013 atm (10 Torr) at room temperature to obtain 7.68 g of a colorless transparent liquid of indane (trifluorophosphonium) ruthenium (II). The yield was 70% by weight.

[Synthesis Example 6] Synthesis of (1,5-octadiene) ginseng (trifluorophosphine) ruthenium (0)

The reactor in which 5.03 g of antimony trichloride, 10.08 g of copper, and 50 mL of 1,5-cyclooctadiene were placed was cooled to -78 ° C, and then evacuated, and trifluorophosphine was introduced until it reached 400 atm, and heated at 120 ° C for 100 hours. . After the reaction was completed, the solution was cooled to room temperature and filtered under a nitrogen atmosphere. After drying the filtrate under reduced pressure, an alumina column chromatography (developing solvent: diethyl ether) was carried out under a nitrogen atmosphere, and the resulting solution was concentrated to obtain (1,5-cyclooctadiene) gin (trifluorophosphine) ruthenium (0). 1.14g of pale yellow liquid. The yield was 10% by weight.

[Synthesis Example 7] Synthesis of (dichloro)phosphonium (trifluorophosphine) ruthenium (II)

A reactor in which 5.03 g of antimony trichloride and 10.08 g of copper were placed was evacuated, and 300 atm of trifluorophosphine and 100 atm of chlorine were introduced, and the mixture was heated at 250 ° C for 15 hours. After completion of the reaction, the solution was cooled to room temperature and dried under reduced pressure to remove trifluorophosphine and chlorine. The obtained liquid was filtered under a nitrogen atmosphere, and distilled under reduced pressure at 10 Torr at room temperature to obtain a pale yellow liquid of (dichloro)phosphonium (trifluorophosphonium) ruthenium (II) 4.83 g. The yield was 41% by weight.

In the following examples, the specific resistance was measured using a probe resistivity meter (Model: RT-80/RG-80) manufactured by Napson Corporation. The film thickness was measured by an oblique incident X-ray analyzer (Model: X'Pert MRD) manufactured by Philips. The ESCA spectrum was measured using a measuring instrument (Model: JPS80) manufactured by JEOL. In addition, the adhesion was evaluated by the checkerboard tape test method based on JIS K-5400. When the peeling of the substrate and the ruthenium film was not found, it was evaluated as "○", and it was found that the substrate and the ruthenium film were peeled off as "X". "."

[Example 1]

(1) Formation of ruthenium film

The amount of 0.05 g of (trifluorophosphine) ruthenium (0) obtained in Synthesis Example 1 was placed in a quartz ship type container and fixed in a quartz reaction vessel. A crucible wafer to which a thermal oxide film was attached was placed in the vicinity of the downstream side of the gas flow in the reaction vessel, and hydrogen gas was flowed into the reaction vessel at a flow rate of 300 mL/min at room temperature for 20 minutes. Subsequently, hydrogen gas was flowed into the reaction vessel at a flow rate of 100 mL/min, and then the inside of the system was depressurized to 13 Pa, and then the reaction vessel was heated at 80 ° C for 5 minutes. A mist is generated from the ship type container, and deposits are found on the quartz substrate disposed nearby. After the completion of the mist, the pressure was reduced, and nitrogen gas was introduced into the system to restore the pressure. Then, at a flow rate of 200 mL/min, nitrogen gas (hydrogen content: 3% by volume) was passed at 101.3 kPa to raise the temperature of the reaction vessel to 350. After the temperature was maintained for 1 hour, a film having a metallic luster was obtained on the substrate. The film thickness of this film was 0.05 μm.

When the ESCA spectrum of the film was measured, a peak belonging to the Ru _3d orbital region was observed at 280 eV and 284 eV, and no peak derived from other elements was observed at all, and it was found to be a metal ruthenium. The results of evaluating the specific resistance of the tantalum film by the 4-terminal method are shown in Table 1.

After the adhesion to the substrate was evaluated by the checkerboard tape method for the tantalum film formed here, peeling of the substrate and the tantalum film was not observed at all.

(2) Test for storage stability

Conduct a review of the deterioration of heat as a confirmation of storage stability. 1 g of uranium (trifluorophosphine) ruthenium (0) was placed in a 100 mL-capacity stainless steel pressure-resistant sealed container under a nitrogen atmosphere to be sealed, and the inside of the system was depressurized to 13 Pa, and the entire container was heated to 80 ° C and stored. After one month, the (trifluorophosphine) ruthenium (0) remained unchanged in appearance.

Subsequently, the container was returned to room temperature, and after replacing the inside of the container with dry nitrogen, a film having a metallic luster was obtained on the substrate after film formation was carried out in the same manner as in the above (1). The physical properties of the obtained metal ruthenium film were evaluated in the same manner as in the above (1). The results are shown in Table 1.

(3) Test of gasification characteristics

The gasification amount was measured by the following test method as confirmation of gasification characteristics. In a glove box at room temperature under a dry nitrogen atmosphere, 1 g of (trifluorophosphine) ruthenium (0) was placed in a pressure-resistant stainless steel container of a 100 mL capacity device valve and tightened. Subsequently, the container was placed on a hot plate, the valve was opened, and the inside of the container was depressurized to 13 Pa for 5 minutes while heating at 80 °C. After the valve was closed, it was left to cool for 3 hours to return the container to room temperature, and the valve in the glove box was immediately opened to restore the pressure in the container to normal pressure. Subsequently, the container was opened and the amount of the remaining sample was measured, and the amount of gasification at the time of pressure reduction treatment was calculated, and the amount of gasification was 0.85 g.

Further, in the same manner as in (2) of Example 1, the vaporization amount was also calculated for the gasification characteristics of 1 g of trifluorophosphine (0) for one month, and the gasification amount was 0.84 g. The results are shown in Table 1.

[Embodiment 2]

(1) Formation of ruthenium film

Except that 0.05 g of (triethylphosphine) ruthenium (0) obtained in Synthesis Example 2 was used instead of 0.05 g of trifluorophosphine (0), the same as in Example 1, a metallic luster was obtained on the substrate. membrane. Various physical properties of the obtained metal ruthenium film were evaluated as in Example 1. The results are shown in Table 1.

(2) Test for storage stability

The evaluation was carried out as in Example 1 except that 1 g of (triethylphosphine) ruthenium (0) obtained in Synthesis Example 2 was used instead of 1 g of tris(trifluorophosphine) ruthenium (0) as the storage stability. The results are shown in Table 1.

(3) Test of gasification characteristics

A gasification amount was carried out as in Example 1 except that 1 g of tris(triethylphosphine) ruthenium (0) was used instead of 1 g of tris(trifluorophosphine) ruthenium (0) as the gasification characteristics. Determination. The results are shown in Table 1.

[Example 3]

(1) Formation of ruthenium film

Except that 0.05 g of (1,5-bicyclooctadiene) gin (trifluorophosphine) ruthenium (0) obtained in Synthesis Example 3 was used instead of 0.05 g of trifluorophosphine (0), the remainder was as in Example 1. Generally, a film having a metallic luster is obtained on the substrate. Various physical properties of the obtained metal ruthenium film were evaluated as in Example 1. The results are shown in Table 1.

(2) Test for storage stability

In addition to the use of (1,5-bicyclooctadiene) ginseng (trifluorophosphine) ruthenium (0) 1 g obtained in Synthetic Example 3 instead of (trifluorophosphine) ruthenium (0) 1 g as confirmation of storage stability, Evaluation was carried out as in Example 1. The results are shown in Table 1.

(3) Test of gasification characteristics

In addition to the use of (1,5-bicyclooctadiene) ginseng (trifluorophosphine) ruthenium (0) 1 g obtained in Synthetic Example 3 instead of (trifluorophosphine) ruthenium (0) 1 g as confirmation of gasification characteristics, The amount of gasification was measured as in Example 1. The results are shown in Table 1.

[Example 4]

(1) Formation of ruthenium film

Except that 0.05 g of (1,5-bicyclooctadiene) ginseng (trimethylphosphine) ruthenium (0) obtained in Synthesis Example 4 was used instead of 0.05 g of trifluorophosphine ruthenium (0). Generally, a film having a metallic luster is obtained on a substrate. Various physical properties of the obtained metal ruthenium film were evaluated as in Example 1. The results are shown in Table 1.

(2) Test for storage stability

In addition to the use of (1,5-bicyclooctadiene) ginseng (trimethylphosphine) ruthenium (0) 1 g obtained in Synthetic Example 4 instead of (trifluorophosphine) ruthenium (0) 1 g as a confirmation of storage stability, The evaluation was carried out as in Example 1. The results are shown in Table 1.

(3) Test of gasification characteristics

In addition to the use of (1,5-bicyclooctadiene) ginseng (trimethylphosphine) ruthenium (0) 1 g obtained in Synthetic Example 4 instead of (trifluorophosphine) ruthenium (0) 1 g as confirmation of gasification characteristics, The measurement of the amount of gasification was carried out as in Example 1. The results are shown in Table 1.

[Example 5]

(1) Formation of ruthenium film

In addition to 0.05 g of indane (trifluorophosphine) ruthenium (II) obtained in Synthesis Example 5, instead of 0.05 g of trifluorophosphine (0), and the reaction vessel was changed to 80 ° C and the reaction vessel was changed to -50 ° C. As in Example 1, a film having a metallic luster was obtained on the substrate. Various physical properties of the obtained metal ruthenium film were evaluated as in Example 1. The results are shown in Table 1.

(2) Test for storage stability

Review of deterioration is performed as confirmation of storage stability. 1 g of indane (trifluorophosphine) ruthenium (II) was placed in a 100 mL-capacity stainless steel pressure-resistant sealed container under a nitrogen atmosphere, and sealed, and the inside of the system was depressurized to 13 Pa, and then the whole container was cooled to -50 ° C. Store. After one month, the indane (trifluorophosphine) ruthenium (II) did not change in appearance.

Subsequently, the container was returned to room temperature, and after replacing the inside of the container with dry nitrogen, a film having a metallic luster was obtained on the substrate after film formation was carried out in the same manner as in the above (1). Various physical properties of the obtained metal ruthenium film were evaluated as in Example 1, and no change was observed. The results are shown in Table 1.

(3) Test of gasification characteristics

The gasification amount was measured by the following test method as confirmation of gasification characteristics. In a glove box at room temperature under a dry nitrogen atmosphere, 1 g of hydrazine (trifluorophosphine) ruthenium (II) was placed in a pressure-resistant stainless steel container of a 100 mL capacity device valve and tightened. Subsequently, the container was placed on a hot plate, the valve was opened, and the inside of the container was decompressed to 13 Pa for 5 minutes while cooling at -50 °C. After closing the valve, the container was returned to room temperature after 3 hours, and the valve in the glove box was immediately opened to restore the pressure in the container to normal pressure. Subsequently, the vessel was opened and the amount of the remaining sample was measured, and the amount of gasification at the time of pressure reduction treatment was calculated, and the amount of vaporization was 0.98 g.

Further, in the same manner as in the above (2) of the fifth embodiment, the gasification amount of 1 g of hydrazine (trifluorophosphine) ruthenium (II) was stored for one month, and the gasification amount was also calculated, and the gasification amount was 1.00. g. The results are shown in Table 1.

[Embodiment 6]

(1) Formation of ruthenium film

Except that 0.05 g of (1,5-octadiene) gins(trifluorophosphine) ruthenium (0) obtained in Synthesis Example 6 was used instead of 0.05 g of trifluorophosphine (0), the remainder was as in Example 1. A film having a metallic luster is obtained on the substrate. Various physical properties of the obtained metal ruthenium film were evaluated as in Example 1. The results are shown in Table 1.

(2) Test for storage stability

In addition to the use of (1,5-octadiene) ginseng (trifluorophosphine) ruthenium (0) 1 g obtained in Synthetic Example 6 instead of (trifluorophosphine) ruthenium (0) 1 g as confirmation of storage stability, Evaluation was carried out in the same manner as in Example 1. The results are shown in Table 1.

(3) Test of gasification characteristics

In addition to the use of (1,5-octadiene) ginseng (trifluorophosphine) ruthenium (0) 1 g obtained in Synthetic Example 6 instead of (trifluorophosphine) ruthenium (0) 1 g as confirmation of gasification characteristics, The measurement of the amount of gasification was carried out in the same manner as in Example 1. The results are shown in Table 1.

[Embodiment 7]

(1) Formation of ruthenium film

Except that 0.05 g of (dichloro)phosphonium (trifluorophosphine) ruthenium (II) obtained in Synthesis Example 7 was used instead of 0.05 g of indane (trifluorophosphine) ruthenium (II), as in Example 5, on the substrate. A film having a metallic luster is obtained. Various physical properties of the obtained metal ruthenium film were evaluated as in Example 5. The results are shown in Table 1.

(2) Test for storage stability

Except that 1 g of (dichloro)phosphonium (trifluorophosphine) ruthenium (II) obtained in Synthesis Example 7 was used instead of 1 g of indane (trifluorophosphine) ruthenium (II) as the storage stability, the remainder was as in Example 5. Conduct an evaluation. The results are shown in Table 1.

(3) Test of gasification characteristics

Except that 1 g of (dichloro)phosphonium (trifluorophosphine) ruthenium (II) obtained in Synthesis Example 7 was used instead of 1 g of indane (trifluorophosphine) ruthenium (II) as the gasification characteristics, the remainder was as in Example 5. The amount of gasification was measured. The results are shown in Table 1.

Claims (7)

A use of a material obtained by mixing a compound represented by the following formula (1) alone or in combination of two or more, in the formation of a ruthenium film, Ru(PR ¹ ₃ ) _l (L ¹ ) _m (L ² ) _n (1) (In the above formula (1), R ^{1 is} each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 4 carbon atoms, or a halogenated hydrocarbon group having 1 to 4 carbon atoms, and L ¹ is a hydrogen atom or a halogen atom, and L ² is An unsaturated hydrocarbon compound having 4 to 10 carbon atoms having at least two double bonds, l is an integer from 1 to 5, m is an integer from 0 to 4, and n is an integer from 0 to 2, but l+m+2n= 5 or 6). As described in the scope of claim 1, the foregoing materials are used in chemical vapor deposition. A method for forming a ruthenium film, which is a material for forming a ruthenium film obtained by mixing a compound represented by the following formula (1) alone or in combination of two or more, Ru(PR ¹ ₃ ) _l (L ¹ ) _m (L ² ) _n (1) (In the above formula (1), R ^{1 is} each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 4 carbon atoms, or a halogenated hydrocarbon group having 1 to 4 carbon atoms, and L ¹ is a hydrogen atom or a halogen atom. L ² is an unsaturated hydrocarbon compound having 4 to 10 carbon atoms and having at least two double bonds, 1 is an integer of 1 to 5, m is an integer of 0 to 4, and n is an integer of 0 to 2, but l+m +2n=5 or 6). The method for forming a ruthenium film according to claim 3, wherein the ruthenium film is formed Materials are used for chemical vapor deposition. A method for forming a ruthenium film, which comprises forming a ruthenium film for supplying a ruthenium film-forming material obtained by mixing a compound represented by the following formula (1), which is used in a chemical vapor deposition method, or a mixture of two or more kinds thereof, onto a substrate. a material supply step, and a film forming step of forming a ruthenium film on the substrate by thermally decomposing the ruthenium film forming material, Ru(PR ¹ ₃ ) _l (L ¹ ) _m (L ² ) _n (1) (the above formula In (1), each of R ^{1 is} independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 4 carbon atoms, or a halogenated hydrocarbon group having 1 to 4 carbon atoms, L ¹ is a hydrogen atom or a halogen atom, and L ² has at least two. One double bond carbon number 4 to 10 unsaturated hydrocarbon compound, l is an integer from 1 to 5, m is an integer from 0 to 4, n is an integer from 0 to 2, but l+m+2n=5 or 6 ). The method for forming a ruthenium film according to the fifth aspect of the invention, wherein the heat-decomposing temperature in the film forming step is from 100 ° C to 800 ° C. The method of forming a ruthenium film according to claim 5 or 6, wherein the thermal decomposition in the film formation step is carried out in an inert gas or a reducing gas.