KR101760968B1 - Material for forming ruthenium film and method for forming ruthenium film - Google Patents
Material for forming ruthenium film and method for forming ruthenium film Download PDFInfo
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- KR101760968B1 KR101760968B1 KR1020127021010A KR20127021010A KR101760968B1 KR 101760968 B1 KR101760968 B1 KR 101760968B1 KR 1020127021010 A KR1020127021010 A KR 1020127021010A KR 20127021010 A KR20127021010 A KR 20127021010A KR 101760968 B1 KR101760968 B1 KR 101760968B1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
- H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
- H01L21/285—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation
- H01L21/28506—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers
- H01L21/28512—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic System
- H01L21/28556—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic System by chemical means, e.g. CVD, LPCVD, PECVD, laser CVD
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/06—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material
- C23C16/18—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material from metallo-organic compounds
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
- H01L21/76841—Barrier, adhesion or liner layers
- H01L21/76843—Barrier, adhesion or liner layers formed in openings in a dielectric
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
- H01L21/76841—Barrier, adhesion or liner layers
- H01L21/76871—Layers specifically deposited to enhance or enable the nucleation of further layers, i.e. seed layers
- H01L21/76873—Layers specifically deposited to enhance or enable the nucleation of further layers, i.e. seed layers for electroplating
Abstract
The object of the present invention is to provide a material for forming a ruthenium film which is easily decomposed even in the absence of an oxidizing agent such as oxygen.
The solution of the present invention is a ruthenium film-forming material containing a compound represented by the following formula (1).
≪ Formula 1 >
(Wherein 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, L 2 is at least M is an integer of 0 to 4, n is an integer of 0 to 2, provided that 1 + m + 2n = 1, 5 or 6)
Description
The present invention relates to a ruthenium film forming material and a ruthenium film forming method.
BACKGROUND ART [0002] Semiconductor devices represented by dynamic random access memories (DRAMs) are required to change materials of respective metal films and metal oxide films constituting devices in accordance with their high integration and miniaturization.
Among them, the improvement of the conductive metal film in the use of the multilayer wiring in the semiconductor device is required, and the conversion into the copper wiring with high conductivity is progressing. For the purpose of enhancing the conductivity of the copper wiring, a low dielectric constant material (low-k material) is used as an interlayer insulating film material of the multilayer wiring. However, there is a problem that the oxygen atoms contained in the low-dielectric-constant material are easily attracted to the copper wiring and the conductivity thereof is lowered. Therefore, for the purpose of preventing the movement of oxygen from the low dielectric constant material, a technique of forming a barrier film between the low dielectric constant material and the copper wiring has been studied. A metal ruthenium film has been attracting attention as a material which is used for the use of this barrier film, in which oxygen from the dielectric layer is difficult to be taken in, and as a material which can be easily processed by dry etching. Furthermore, metal ruthenium has been attracting attention for the purpose of satisfying both the role of both the barrier film and the plating growth film in the damascene film formation method of embedding the copper wiring by a plating method.
Also in the capacitor of a semiconductor device, a metal ruthenium film has attracted attention due to its high oxidation resistance and high conductivity as an electrode material of a high dielectric constant material such as alumina, tantalum pentoxide, hafnium oxide, barium titanate and strontium (BST).
Conventional sputtering has been widely used to form the above-mentioned metal ruthenium film. However, a chemical vapor deposition method has been studied as a response to miniaturization of the structure, thin film formation, and improvement in mass productivity.
However, in general, the metal film formed by the chemical vapor deposition method has a problem in that the surface morphology is deteriorated, such as the aggregation state of the minute crystals being erratic. As a means for solving the problem of such a morphology, tris (dipivaloylmetagnato) ruthenium It has been studied to use ruthenocene, bis (alkylcyclopentadienyl) ruthenium, (cyclohexadienyl) ruthenium tricarbonyl or the like as a chemical vapor phase growth material (see Patent Documents 1 to 5).
In addition, when these chemical vapor deposition materials are used in the production process, good storage stability of the materials is required from the viewpoint of preventing the deterioration of the material adjacent to the metal ruthenium film in the film forming process and stabilizing the production conditions thereof. However, conventional ruthenocene, bis (alkylcyclopentadienyl) ruthenium, and the like have a problem in that oxidation of adjoining materials in a short time due to the influence of oxygen mixing in the film forming process and deterioration of performance thereof occurs. Further, when oxygen is not mixed in the film forming step, there is a problem that it is difficult to form a ruthenium film.
On the other hand, a ruthenium film is required to have high purity and excellent performance as a barrier film and a plating growth film, and excellent adhesion to a substrate.
The object of the present invention is to provide a ruthenium film forming material which is easily decomposed even in the absence of an oxidizing agent such as oxygen and can form a ruthenium film having high purity and high adhesion to a substrate in a short time, And a method for forming a ruthenium film using the above material.
Means for Solving the Problems In order to achieve the above object, the inventors of the present invention conducted extensive research and discovered that the above object can be achieved by using a compound represented by the following formula (1), thereby completing the present invention.
That is, the present invention provides the following [1] to [6].
[1] A ruthenium film-forming material comprising a compound represented by the following formula (1).
(Wherein 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, L 2 is at least M is an integer of 0 to 4, n is an integer of 0 to 2, provided that 1 + m + 2n = 1, 5 or 6)
[2] A material for forming a ruthenium film for chemical vapor deposition according to [1] above.
[3] A method for forming a ruthenium film using the ruthenium film forming material according to the above [1] or [2].
[4] A process for producing a ruthenium film-forming material, comprising the steps of: supplying a ruthenium film-forming material for supplying the ruthenium film-forming material described in [2] above to a substrate; Forming a ruthenium film on a substrate;
[5] The method for forming a ruthenium film according to the above [4], wherein the temperature of the thermal decomposition in the film forming step is 100 ° C to 800 ° C.
[6] The method for forming a ruthenium film according to [4] or [5], wherein the thermal decomposition in the film forming step is performed in an inert gas or a reducing gas.
The ruthenium film forming material of the present invention can be easily decomposed even in the absence of an oxidizing agent such as oxygen to form a ruthenium film. Therefore, oxidation of adjacent materials and deterioration of performance thereof are less likely to occur.
Further, according to the ruthenium film forming material of the present invention, a ruthenium film of high purity with a small amount of residual impurities can be easily obtained in a short time. This ruthenium film has excellent performance as a barrier film and a plating growth film, and has excellent adhesion to a substrate.
Hereinafter, the present invention will be described in detail.
The ruthenium film forming material of the present invention comprises a compound represented by the following formula (1).
≪ Formula 1 >
Wherein 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, a halogen atom, a hydrocarbon group having 1 to 4 carbon atoms or a hydrocarbon group having 1 to 4 carbon atoms Of the halogenated hydrocarbon group, and more preferably a halogen atom.
As the halogen atom for R 1 , a fluorine atom, a chlorine atom, a bromine atom and an iodine atom are exemplified, and a fluorine atom and a chlorine atom are preferable, and a fluorine atom is more preferable.
Examples of the hydrocarbon group having 1 to 4 carbon atoms for R 1 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group and a t- A propyl group, an isopropyl group, and a t-butyl group, more preferably a methyl group or an ethyl group.
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 a chloromethyl group, a dichloromethyl group, a trichloromethyl group, a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a pentafluoroethyl group, a perfluoro- Butyl group, a perfluoro isopropyl group, a perfluoro-n-butyl group, a perfluoroisobutyl group and a perfluoro-t-butyl group, and examples thereof include a fluoromethyl group, a difluoromethyl group, , Perfluoro-n-propyl group, perfluoroisopropyl group and perfluoro-t-butyl group are preferable, and fluoromethyl group, di More preferably a fluoromethyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, or a pentafluoroethyl group.
In formula (1), L 1 is a hydrogen atom or a halogen atom, preferably a hydrogen atom.
When L 1 is a halogen atom, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom and a chlorine atom are preferable, and a fluorine atom is more preferable.
In the formula (1), L 2 is an unsaturated hydrocarbon compound having 4 to 10 carbon atoms and at least two double bonds.
The number of double bonds is preferably 2 from the viewpoint of availability of the compound. In this case, the unsaturated hydrocarbon compound may be a conjugated diene compound or a nonconjugated diene compound.
The number of carbon atoms of the unsaturated hydrocarbon compound is 4 to 10, preferably 5 to 8.
Specific examples include 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,5-hexadiene, 1,4-hexadiene, 1-pentadiene, 1,6-heptadiene, 1,5-heptadiene, 1,4-heptadiene, 1-hexadiene, , 7-octadiene, 1,6-octadiene, 1,5-octadiene and 1,4-octadiene, cyclic dienes such as cyclopentadiene, 1,5-cyclooctadiene, 1,3-cyclooctadiene , 1,4-cyclohexadiene, 1,3-cyclohexadiene, and 2,5-norbornadiene.
In the general formula (1), l is an integer of 1 to 5, and preferably an integer of 3 to 5 in view of high vapor pressure of the compound.
M is preferably an integer of 0 to 4, more preferably an integer of 0 to 3, and more preferably an integer of 0 to 2, from the viewpoint that the melting point of the compound is low.
In the general formula (1), n is an integer of 0 to 2, preferably 0 or 1, and more preferably 0, from the viewpoint of forming a high-purity ruthenium film of good quality.
Further, l + m + 2n = 5 or 6.
The method of synthesizing the compound represented by the above formula (1) includes, for example, a process comprising a step of reacting ruthenium trichloride with a compound represented by the formula PR 1 3 in the above formula (1). Further, in the process, at least two kinds of compound selected from hydrogen, fluorine, chlorine, bromine and iodine, as needed, and unsaturated having 4 to 10 carbon atoms having at least two double bonds represented by L 2 in the formula (1) And at least one compound selected from a hydrocarbon compound may be reacted.
The reaction is preferably carried out in the presence of a catalyst, and examples of the catalyst include copper and zinc.
The reaction temperature is not particularly limited, but is preferably 50 to 400 ° C, more preferably 100 to 350 ° C, and further preferably 120 to 300 ° C.
The pressure at the time of the reaction is not particularly limited. In the case of reacting a gaseous compound under standard conditions such as trifluorophosphine, hydrogen, fluorine, and chlorine, the pressure is usually 10 to 1000 atm , Preferably 50 to 800 atm, and more preferably 100 to 600 atm.
Specific examples of the compound represented by the formula (1) include, for example,
(pentafluorophenyl) ruthenium (0), pentakis (trichlorophosphine) ruthenium (0), pentakis (trimethylphosphine) ruthenium (0), pentakis (triethylphosphine) ruthenium (0), and the like;
(η-1,4-cyclohexadiene) tris (trifluorophosphine) ruthenium (0), (η-1,4-cyclohexadiene) Tris (trimethylphosphine) ruthenium (0), (1,5-cyclooctadiene) tris (trifluorophosphine) ruthenium (0), (1,5- (Η-1,6-heptadiene) tris (trimethylphosphine) ruthenium (0), (η-1,6-heptadiene) A ruthenium compound having a valence of 0 of ruthenium such as 1,7-octadiene) tris (trifluorophosphine) ruthenium (0), (eta-1,7-octadiene) tris (trimethylphosphine) ruthenium ;
(II) dihydride, (difluoro) tetrakis (trifluorophosphine) ruthenium (II), and tetrakis (triphenylphosphine) ruthenium Tetrakis (trimethylphosphine) ruthenium (II), tetrakis (trimethylphosphine) ruthenium (II) dihydride, (difluoro) tetrakis (trimethylphosphine) ruthenium (Dichloro) tetrakis (trimethylphosphine) ruthenium (II); a ruthenium compound having a valence of 2;
(trifluorophosphine) ruthenium (III) trihydride and (trifluoro) tris (trifluorophosphine) ruthenium (III) A ruthenium compound having a valence of ruthenium of 3;
(tetrafluoro) bis (trifluorophosphine) ruthenium (IV), (tetrafluorophosphine) ruthenium (IV) tetra hydride, (Trifluoro) tetrakis (triphenylphosphine) ruthenium (IV), tetrakis (triphenylphosphine) ruthenium (IV) hydride, (difluoro) tetrakis ) Ruthenium (IV) dihydride, (dibromo) tetrakis (trifluorophosphine) ruthenium (IV) dihydride, (fluoro) tetrakis (trifluorophosphine) ruthenium Ruthenium compounds having a valence of 3 of ruthenium such as rhodium (iodine) tetrakis (trifluorophosphine) ruthenium (IV) trihydride,
And the like.
These compounds may be used alone or as a mixture of two or more of them to form a ruthenium film-forming material. It is preferable to use one kind of compound alone as a material for forming a ruthenium film.
The ruthenium film forming method of the present invention uses the above ruthenium film forming material.
The ruthenium film forming method of the present invention may be a known method other than the use of the ruthenium film forming material described above. For example, the following chemical vapor deposition method (the following processes (1) and (Including step (2)).
The ruthenium film forming material of the present invention is supplied on a substrate (for example, a substrate), and then the ruthenium film forming material supplied on the substrate is heated and decomposed to form a ruthenium film on the substrate. Specifically, (1) vaporizing or evaporating the ruthenium film forming material of the present invention under reduced pressure and heating to deposit the vaporized or vaporized material thereof on a substrate (for example, a substrate), and then (2) Is thermally decomposed to form a ruthenium film on the substrate. Even if the ruthenium film forming material of the present invention is decomposed in the step (1), the effect of the present invention is not weakened, and the step (1) and the step (2) may be performed at the same time.
Suitable materials such as glass, silicon semiconductor, quartz, metal, metal oxide, and synthetic resin can be used as the material of the base which can be used here, but it is a material that can withstand the temperature of the step of thermally decomposing the ruthenium compound desirable.
In the above step (1), the temperature for vaporizing or evaporating the ruthenium compound is preferably -100 to 350 ° C, more preferably -80 to 200 ° C, and particularly preferably -60 to 150 ° C.
In the step (1), the decompression condition for vaporizing or evaporating the ruthenium compound is preferably 1000 Pa or less, more preferably 100 Pa or less, particularly preferably 50 Pa or less. The lower limit value of the decompression condition is not particularly limited, but is usually 1 Pa in view of the performance of the decompression apparatus.
In the above step (2), the temperature at which the ruthenium compound is heated and decomposed is preferably 100 to 800 ° C, more preferably 100 to 600 ° C, further preferably 180 to 450 ° C, , And particularly preferably 250 to 410 ° C.
The chemical vapor phase growth method of the present invention can be carried out under any condition in the presence or absence of an inert gas and also under any condition in the presence or absence of a reducing gas. It is preferable that either or both of an inert gas and a reducing gas are present.
Examples of the inert gas include nitrogen gas, argon gas, and helium gas. Examples of the reducing gas include hydrogen gas and ammonia gas. The chemical vapor deposition method of the present invention can also be carried out in the coexistence of an oxidizing gas. Examples of the oxidizing gas include oxygen, carbon monoxide, nitrous oxide and the like.
Particularly, for the purpose of reducing the amount of impurities in the formed ruthenium film, it is preferable that these reducing gases coexist. When the reducing gas is coexisted, the ratio of the reducing gas in the atmosphere is preferably 1 to 100 mol%, more preferably 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 particularly preferably 0.1 mol% or less.
The step (2) in the chemical vapor phase growth method of the present invention can be carried out under any conditions under pressure, normal pressure and reduced pressure. Among these, it is preferable to carry out under atmospheric pressure or reduced pressure, more preferably under a pressure of 15,000 Pa or less.
The ruthenium film forming material of the present invention is preferably stored under an atmosphere of an inert gas. Examples of the inert gas include nitrogen gas, argon gas, and helium gas.
The ruthenium film obtained as described above has high purity and electrical conductivity and can be suitably used for, for example, a barrier film of a wiring electrode, a plated growth film, a capacitor electrode and the like.
[Example]
Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to these Examples.
[Synthesis Example 1] Synthesis of pentakis (trifluorophosphine) ruthenium (0)
5.03 g of ruthenium trichloride and 10.08 g of copper were put in a vacuum, and trifluorophosphine was introduced until the temperature reached 500 atm. The mixture was heated at 250 ° C for 15 hours. After the completion of the reaction, the solution was cooled to room temperature and then dried under reduced pressure to remove the trifluorophosphine. The obtained solid was sublimated and purified at 30 DEG C and 0.013 atm (10 Torr) to obtain 7.80 g of pentakis (trifluorophosphine) ruthenium (0) as a white solid. The yield was 60% by weight.
Synthesis Example 2 Synthesis of pentakis (triethylphosphine) ruthenium (0)
5.03 g of ruthenium trichloride, 10.08 g of copper and 10 mL of triethylphosphine was placed in a sealed tube and heated at 220 캜 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 obtain 3.67 g of pentakis (triethylphosphine) ruthenium (0) as a white solid. The yield was 22 wt%.
Synthesis Example 3 Synthesis of (1,5-cyclooctadiene) tris (trifluorophosphine) ruthenium (0)
5.03 g of ruthenium trichloride, 10.08 g of copper and 50 mL of 1,5-cyclooctadiene was cooled to -78 ° C., and the reactor was evacuated and the trifluorophosphine was introduced until the temperature reached 400 atm. At 180 ° C. Lt; / RTI > 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 alumina column chromatography (developing solvent: diethyl ether) in a nitrogen atmosphere. The obtained solution was concentrated to obtain (1,5-cyclooctadiene) tris (trifluorophosphine) ruthenium 0) (1.71 g) as a pale yellow liquid. The yield was 15% by weight.
[Synthesis Example 4] Synthesis of (1,5-cyclooctadiene) tris (trimethylphosphine) ruthenium (0)
5.03 g of ruthenium trichloride, 10.08 g of copper, 20 mL of 1,5-cyclooctadiene and 10 mL of trimethylphosphine, and the mixture was heated at 160 DEG C for 90 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 alumina column chromatography (developing solvent: diethyl ether) in a nitrogen atmosphere. The obtained solution was concentrated to obtain (1,5-cyclooctadiene) tris (trimethylphosphine) ruthenium (0) 0.63 g as a pale yellow liquid. The yield was 6% by weight.
[Synthesis Example 5] Synthesis of tetrakis (trifluorophosphine) ruthenium (II) dihydride
5.03 g of ruthenium trichloride, and 10.08 g of copper were put in a vacuum, and 300 atm of trifluorophosphine and 100 atm of hydrogen were introduced, followed by heating at 270 캜 for 15 hours. After completion of the reaction, the solution was cooled to room temperature and then dried under reduced pressure to remove trifluorophosphine and hydrogen. The obtained liquid was filtered under a nitrogen atmosphere and distilled under reduced pressure at 0.013 atm (10 Torr) at room temperature to obtain 7.68 g of tetrakis (trifluorophosphine) ruthenium (II) dihydride as a colorless transparent liquid. The yield was 70% by weight.
[Synthesis Example 6] Synthesis of (1,5-octadiene) tris (trifluorophosphine) ruthenium (0)
5.03 g of ruthenium trichloride, 10.08 g of copper and 50 mL of 1,5-octadiene was cooled to -78 ° C., and the reactor was evacuated. The trifluorophosphine was introduced until the temperature reached 400 atm. At 120 ° C. And heated for 100 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 alumina column chromatography (developing solvent: diethyl ether) in a nitrogen atmosphere. The obtained solution was concentrated to obtain (1,5-octadiene) tris (trifluorophosphine) ruthenium ) As a pale yellow liquid. The yield was 10% by weight.
[Synthesis Example 7] Synthesis of (dichloro) tetrakis (trifluorophosphine) ruthenium (II)
5.03 g of ruthenium trichloride, and 10.08 g of copper were put in a vacuum, and 300 ml of trifluorophosphine and 100 atm of chlorine were introduced, followed by heating at 250 ° C for 15 hours. After completion of the reaction, the solution was cooled to room temperature and then 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 4.83 g of (dichloro) tetrakis (trifluorophosphine) ruthenium (II) as a pale yellow liquid. The yield was 41% by weight.
In the following examples, the resistivity was measured by a probe resistivity meter (model: RT-80 / RG-80) manufactured by NAPSON. The film thickness was measured by an X-ray analyzer (model: X'Pert MRD) manufactured by Philips Corporation. The ESCA spectrum was measured with a measuring machine (type: JPS80) manufactured by Nihon Denshi Co., The adhesion was evaluated by the lattice tape method in accordance with JIS K-5400. When the peeling between the substrate and the ruthenium film was not observed at all, the peeling was observed between the substrate and the ruthenium film Quot; x ".
[Example 1]
(1) Formation of ruthenium film
0.05 g of pentakis (trifluorophosphine) ruthenium (0) obtained in Synthesis Example 1 was weighed into a quartz boat vessel in nitrogen gas, and set in a quartz reaction vessel. A silicon wafer with a thermally oxidized film was placed in the vicinity of the downstream side of the gas flow in the reaction vessel, and hydrogen gas was flowed at a flow rate of 300 mL / min for 20 minutes in the reaction vessel at room temperature. Thereafter, hydrogen gas was flowed into the reaction vessel at a flow rate of 100 mL / min, the pressure in the system was reduced to 13 Pa, and the reaction vessel was heated at 80 DEG C for 5 minutes. Mist was generated from the boat type vessel, and sediments were observed on the quartz substrate installed in the vicinity. After completion of the generation of the mist, the decompression was stopped and nitrogen gas was returned to the system to return the pressure. Subsequently, nitrogen gas (hydrogen gas content: 3 vol%) was flown at 101.3 kPa at a flow rate of 200 mL / The temperature of the container was raised to 350 캜 and maintained as it was for 1 hour, and a film having metallic luster was obtained on the substrate. The film thickness of this film was 0.05 mu m.
The ESCA spectrum of this film was measured. As a result, peaks attributed to the Ru 3d orbit were observed at 280 eV and 284 eV, and no peaks derived from other elements were observed, indicating that the film was metal ruthenium. Table 1 shows the results of evaluating the resistivity of the ruthenium film by the four-terminal method.
The adhesion of the formed ruthenium film to the substrate was evaluated by a lattice tape method, and no peeling between the substrate and the ruthenium film was observed at all.
(2) Test of storage stability
As a confirmation of storage stability, thermal degradation to heat was examined. 1 g of pentacyl (trifluorophosphine) ruthenium (0) was placed in a 100-mL pressure-resistant stainless steel pressure-tight sealed container, and the container was sealed under a nitrogen atmosphere. The pressure in the system was reduced to 13 Pa, Respectively. There was no apparent change in pentakis (trifluorophosphine) ruthenium (0) even after one month.
Thereafter, the container was returned to room temperature, and the inside of the container was replaced with dry nitrogen. Then, the film formation was carried out in the same manner as in the above (1), and a film having metallic luster was obtained on the substrate. Various physical properties of the obtained metal ruthenium film were evaluated in the same manner as in (1) above. The results are shown in Table 1.
(3) Test of vaporization characteristics
As a confirmation of the vaporization characteristics, the vaporization amount was measured by the following test method. In a glove box under a dry nitrogen atmosphere at room temperature, 1 g of pentakis (trifluorophosphine) ruthenium (0) was placed in a 100-mL capacity container with pressure-resistant stainless steel and tightened. Thereafter, the container was placed on a hot plate, the valve was opened, and the inside of the container was subjected to pressure reduction at 13 Pa for 5 minutes while heating at 80 占 폚. Thereafter, after the valve was closed, the container was cooled to room temperature for 3 hours, and the valve was slowly opened in the glove box to return the pressure in the container to normal pressure. Thereafter, the vessel was opened to measure the amount of the remaining sample, and the amount of vaporization during the decompression treatment was calculated. As a result, the vaporization amount was 0.85 g.
The vaporization rate of 1 g of pentakis (trifluorophosphine) ruthenium (0) stored for one month in the same manner as in Example 1 (2) was also calculated in the same manner as in Example 1, Was 0.84 g. The results are shown in Table 1.
[Example 2]
(1) Formation of ruthenium film
Except that 0.05 g of pentakis (triethylphosphine) ruthenium (0) obtained in Synthesis Example 2 was used instead of 0.05 g of pentakis (trifluorophosphine) ruthenium (0) A film having metallic luster was obtained. Various physical properties of the obtained metal ruthenium film were evaluated in the same manner as in Example 1. [ The results are shown in Table 1.
(2) Test of storage stability
(Triethylphosphine) ruthenium (0) obtained in Synthesis Example 2 was used instead of 1 g of pentakis (trifluorophosphine) ruthenium (0) as a confirmation of storage stability, . The results are shown in Table 1.
(3) Test of vaporization characteristics
(Triethylphosphine) ruthenium (0) obtained in Synthesis Example 2 was used instead of 1 g of pentakis (trifluorophosphine) ruthenium (0) as identification of the vaporization characteristics, The amount of vaporization was measured. The results are shown in Table 1.
[Example 3]
(1) Formation of ruthenium film
Except that 0.05 g of (1,5-cyclooctadiene) tris (trifluorophosphine) ruthenium (0) obtained in Synthesis Example 3 was used instead of 0.05 g of pentakis (trifluorophosphine) ruthenium (0) A film having metallic luster was obtained on the substrate in the same manner as in Example 1. Various physical properties of the obtained metal ruthenium film were evaluated in the same manner as in Example 1. [ The results are shown in Table 1.
(2) Test of storage stability
(1,5-cyclooctadiene) tris (trifluorophosphine) ruthenium (0) 1 (1) obtained in Synthesis Example 3 was used instead of 1 g of pentakis (trifluorophosphine) ruthenium g was used in place of the polyimide precursor. The results are shown in Table 1.
(3) Test of vaporization characteristics
(1,5-cyclooctadiene) tris (trifluorophosphine) ruthenium (0) 1 (1) obtained in Synthesis Example 3 was used instead of 1 g of pentakis (trifluorophosphine) ruthenium g, the vaporization amount was measured in the same manner as in Example 1. < tb > < TABLE > The results are shown in Table 1.
[Example 4]
(1) Formation of ruthenium film
Except that 0.05 g of (1,5-cyclooctadiene) tris (trimethylphosphine) ruthenium (0) obtained in Synthesis Example 4 was used instead of 0.05 g of pentakis (trifluorophosphine) ruthenium (0) 1, a film having metallic luster was obtained on the substrate. Various physical properties of the obtained metal ruthenium film were evaluated in the same manner as in Example 1. [ The results are shown in Table 1.
(2) Test of storage stability
1 g of (1,5-cyclooctadiene) tris (trimethylphosphine) ruthenium (0) obtained in Synthesis Example 4 was used instead of 1 g of pentakis (trifluorophosphine) ruthenium (0) The evaluation was carried out in the same manner as in Example 1, except that it was used. The results are shown in Table 1.
(3) Test of vaporization characteristics
1 g of (1,5-cyclooctadiene) tris (trimethylphosphine) ruthenium (0) obtained in Synthesis Example 4 was used instead of 1 g of pentakis (trifluorophosphine) ruthenium (0) The amount of vaporization was measured in the same manner as in Example 1, except that it was used. The results are shown in Table 1.
[Example 5]
(1) Formation of ruthenium film
(Trifluorophosphine) ruthenium (II) dihydride 0.05 g obtained in Synthesis Example 5 was used instead of 0.05 g of pentakis (trifluorophosphine) ruthenium (0) g was used and the reaction vessel was set at -50 캜, a film having metallic luster was obtained on the substrate in the same manner as in Example 1. Various physical properties of the obtained metal ruthenium film were evaluated in the same manner as in Example 1. [ The results are shown in Table 1.
(2) Test of storage stability
As a confirmation of storage stability, the thermal degradability was examined. 1 g of tetrakis (trifluorophosphine) ruthenium (II) dihydride was placed in a 100-mL pressure-resistant stainless steel pressure-tight sealed container, and the container was sealed under a nitrogen atmosphere. The pressure in the system was reduced to 13 Pa, ≪ / RTI > There was no apparent change in the tetrakis (trifluorophosphine) ruthenium (II) dihydride after one month.
Thereafter, the container was returned to room temperature, and the inside of the container was replaced with dry nitrogen. Then, the film formation was carried out in the same manner as in the above (1), and a film having metallic luster was obtained on the substrate. Various physical properties of the obtained metal ruthenium film were evaluated in the same manner as in Example 1, and no change was observed. The results are shown in Table 1.
(3) Test of vaporization characteristics
As a confirmation of the vaporization characteristics, the vaporization amount was measured by the following test method. In a glove box under a dry nitrogen atmosphere at room temperature, 1 g of tetrakis (trifluorophosphine) ruthenium (II) dihydride was charged into a 100-mL capacity pressure-resistant stainless steel vessel equipped with a valve and tightly closed. Thereafter, the container was placed on a hot plate, the valve was opened, and the inside of the container was subjected to pressure reduction at 13 Pa for 5 minutes while being cooled to -50 占 폚. Thereafter, after the valve was closed, the vessel was returned to room temperature over 3 hours, and the valve was slowly opened in the glove box to return the pressure in the vessel to normal pressure. Thereafter, the vessel was opened to measure the amount of the remaining sample, and the amount of vaporization during the decompression treatment was calculated. As a result, the vaporization amount was 0.98 g.
The vaporization characteristics of 1 g of tetrakis (trifluorophosphine) ruthenium (II) dihydride stored for one month in the same manner as in Example 5 (2) above were also calculated in the same manner as in , And the amount of vaporization was 1.00 g. The results are shown in Table 1.
[Example 6]
(1) Formation of ruthenium film
Except that 0.05 g of (1,5-octadiene) tris (trifluorophosphine) ruthenium (0) obtained in Synthesis Example 6 was used instead of 0.05 g of pentakis (trifluorophosphine) ruthenium (0) A film having metallic luster was obtained on the substrate in the same manner as in Example 1. Various physical properties of the obtained metal ruthenium film were evaluated in the same manner as in Example 1. [ The results are shown in Table 1.
(2) Test of storage stability
As a confirmation of the storage stability, 1 g of (1,5-octadiene) tris (trifluorophosphine) ruthenium (0) obtained in Synthesis Example 6 was used instead of 1 g of pentakis (trifluorophosphine) ruthenium Was used in place of the polyimide precursor. The results are shown in Table 1.
(3) Test of vaporization characteristics
As a confirmation of the vaporization characteristics, 1 g of (1,5-octadiene) tris (trifluorophosphine) ruthenium (0) obtained in Synthesis Example 6 was used instead of 1 g of pentakis (trifluorophosphine) ruthenium , The vaporization amount was measured in the same manner as in Example 1. [ The results are shown in Table 1.
[Example 7]
(1) Formation of ruthenium film
Except that 0.05 g of (dichloro) tetrakis (trifluorophosphine) ruthenium (II) obtained in Synthesis Example 7 was used instead of 0.05 g of tetrakis (trifluorophosphine) ruthenium (II) dihydride, A film having metallic luster was obtained on the substrate in the same manner as in Example 5. Various physical properties of the obtained metal ruthenium film were evaluated in the same manner as in Example 5. [ The results are shown in Table 1.
(2) Test of storage stability
1 g of (dichloro) tetrakis (trifluorophosphine) ruthenium (II) obtained in Synthesis Example 7 was used instead of 1 g of tetrakis (trifluorophosphine) ruthenium (II) dihydride as a confirmation of storage stability The evaluation was carried out in the same manner as in Example 5 except that it was used. The results are shown in Table 1.
(3) Test of vaporization characteristics
1 g of (dichloro) tetrakis (trifluorophosphine) ruthenium (II) obtained in Synthesis Example 7 was used instead of 1 g of tetrakis (trifluorophosphine) ruthenium (II) dihydride as a confirmation of the vaporization characteristics. The amount of vaporization was measured in the same manner as in Example 5, except that it was used. The results are shown in Table 1.
Claims (6)
≪ Formula 1 >
(Wherein 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, L 2 is at least M is an integer of 0 to 4, n is an integer of 0 to 2, provided that 1 + m + 2n = 1, 5 or 6)
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