Patent Grant
10526698
The present invention relates to a chemical deposition raw material including a heterogeneous polynuclear complex, which is used for producing a composite metal thin film or a composite metal compound thin film including different kinds of metals by a chemical deposition method such as a CVD method or an ALD method. Specifically, the present invention relates to a chemical deposition raw material which is capable of forming a thin film including a composite metal in one-time film formation and which is capable of forming a film at a low temperature (about 200° C.) while having moderate thermal stability.
In various kinds of devices such as semiconductors, various kinds of metal thin films are used for satisfying the required properties of the devices. As a method for forming these metal thin films, a chemical deposition method such as a CVD method, which is capable of forming a uniform and homogeneous film at a high film formation rate and in conformity with even a three-dimensional shape etc. of a device, is used.
As a metal complex that is a raw material in formation of a metal thin film by the chemical deposition method, a complex including a plurality of ligands such as cyclopentadienyl with one metal as a central metal (nucleus) (hereinafter, referred to as a mononuclear complex) as shown in the following chemical formula 1 is known. A complex including a plurality of metals of the same kind as central metals (hereinafter, referred to as a homogeneous polynuclear complex) as shown in the following chemical formula 2 is also known.
In formation of a metal thin film for use in a device such as a semiconductor by use of the above-mentioned mononuclear complex or homogeneous polynuclear complex as a chemical deposition raw material, a thin film including a plurality of kinds of metals is often applied. In a device having a reduced size and weight, such as a semiconductor, a plurality of metal thin films are applied, and deposited for imparting various kinds of required properties, so that the device is densified and highly integrated while attaining required properties. For example, when copper is used as a wiring material of a semiconductor, a structure is used in which a thin film of MnO, MnSiO or the like as a barrier layer for preventing diffusion of copper, and a thin film of ruthenium and the like as a base for introducing the barrier layer are deposited together.
As an example of forming a thin film including a plurality of metals as described above, mention is made of Patent Document 1, Patent Document 2 and so on. Patent Document 1 suggests that a plurality of mononuclear complexes etc. are provided, and metal thin films are sequentially deposited from the complexes to form a plurality of metal layers each including a single metal. Patent Document 2 suggests that a plurality of mononuclear complexes are mixed beforehand, and dissolved or emulsified to obtain an inert liquid, and from the inert liquid, a composite metal thin film containing a plurality of metals is formed.
However, when a plurality of thin films are sequentially formed by use of a plurality of complexes as in Patent Document 1, a large number of steps are required for film formation, condition setting is complicated, much time and labor is needed for quality control of raw materials, and use of a plurality of raw materials causes an increase in cost. When a plurality of metal complexes are mixed beforehand as in Patent Document 2, the complexes have different vaporization properties, and therefore the ratio of metals in the thin film easily varies, so that formation of a homogeneous film becomes difficult. Before film formation, raw materials may react with each other, leading to degeneration.
The present invention has been made in view of the background described above, and provides a chemical deposition raw material which is capable of forming a plurality of kinds of metal thin films in a simple process, and capable of forming a homogeneous thin film, and is easily quality-controlled.
As a solution to the problems described above, the present inventors conducted the following studies for synthesizing a complex including a plurality of kinds of metals as central metals in one complex (hereinafter, referred to as a heterogeneous polynuclear complex), and applying the complex as a chemical deposition raw material instead of applying a plurality of complexes having different metal species as in a conventional art.
When a heterogeneous polynuclear complex is applied as a chemical deposition raw material, first a plurality of kinds of metals as central metals should be all deposited in formation of a metal thin film by a chemical deposition method as a required property of the chemical deposition raw material. Preferably, the deposition ratios of a plurality of metals are almost the same. The chemical deposition raw material should also have such a general required property of a chemical deposition raw material that in formation of a thin film by a chemical deposition method, the chemical deposition raw material has thermal stability sufficient to prevent thermal decomposition in a vaporization stage while having a decomposition property which ensures that a film can be formed at a low temperature. The present inventors extensively conducted studies on a complex having all the above-mentioned properties, and resultantly arrived at a chemical deposition raw material of the present invention which includes a heterogeneous polynuclear complex having a configuration as described below.
The present invention relates to a chemical deposition raw material for producing a composite metal thin film or a composite metal compound thin film by a chemical deposition method, including a heterogeneous polynuclear complex in which a cyclopentadienyl (L) and a carbonyl are coordinated to a first transition metal (M1) and a second transition metal (M2) as central metals, the heterogeneous polynuclear complex being represented by the following formula:
wherein M1 and M2 are mutually different transition metals; x is an integer of 1 or more and 2 or less, and y is an integer of 1 or more and 9 or less; and R1 to R5 are each one of a hydrogen atom and an alkyl group with a carbon number of 1 or more and 5 or less.
As described above, the complex in the present invention is a heterogeneous polynuclear complex including a plurality of kinds of transition metals: a first transition metal (M1) and a second transition metal (M2) as central metals of the complex, and to these central metals are coordinated a cyclopentadienyl (L) and a carbonyl (—CO) as ligands. When a thin film is formed from the complex by a chemical deposition method, a plurality of metals as central metals are all deposited.
The complex of the present invention has moderate thermal stability because the cyclopentadienyl as a ligand has a relatively strong bonding force with a transition metal, and the carbonyl as a ligand has a relatively weak bonding force with a transition metal. With the carbon number of the alkyl group as each of substituents R1 to R5 arbitrarily designed, the vapor pressure and the melting point are adjustable.
Hereinafter, the heterogeneous polynuclear complex included in the chemical deposition raw material according to the present invention will be described in detail.
First, x and y representing the numbers of cyclopentadienyls (L) and carbonyls (—CO), respectively, in the raw material of the present invention will be described. x is an integer of 1 or more and 2 or less, and y is an integer of 1 or more and 9 or less; and Preferably, x is 1 or more and 2 or less, and y is 2 or more and 7 or less.
Preferred ranges of the integers that can be selected as x and y depend on the kind (valence) of the transition metal and the correlation associated with the value of x. For example, regarding x and y, preferably y is 5 to 7 when x is 1, and y is 2 to 4 when x is 2. Preferably y is 3 to 7 when at least one of M1 and M2 is Mn or Re, and preferably y is 2 to 6 when at least one of M1 and M2 is Co, Rh or Ir.
It is especially preferable that x is 1 and y is n+2 as a combination of x and y, and mention is made of a chemical deposition raw material including a heterogeneous polynuclear complex represented by the following formula:
wherein M1 is one of Ru, Mn and Fe, M2 is one of V, Cr, Mn, Fe, Co and Ni, and M1 and M2 are different; n is 3 or more and 5 or less; and R1 to R5 are each one of a hydrogen atom and an alkyl group with a carbon number of 1 or more and 5 or less.
M1 and M2 are mutually different transition metals. What can be named as examples of the transition metal are titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), niobium (Nb), molybdenum (Mo), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), tantalum (Ta), tungsten (W), rhenium (Re), osmium (Os), iridium (Ir), platinum (Pt) and gold (Au). As the transition metal, Mn, Fe, Co, Ni, Cu, Nb, Mo, Ru, Rh, Ta, W, Ir and Pt are preferable, and Mn, Fe, Co, Ni, Cu, Mo, Ru, W and Pt are especially preferable. As the transition metal as M1, Ru, Mn and Fe are especially preferable, and as the transition metal as M2, Mn, Fe, Co and Ni are especially preferable.
Ligands to be coordinated to central metals will now be described. In the raw material of the present invention, a cyclopentadienyl (L) and a carbonyl are coordinated to central metals including two transition metals. The present inventors conceived the raw material based on the following grounds regarding the configurations of the central metals and the ligands coordinated to the central metals.
When coordinated to a transition metal together with a carbonyl, the “cyclopentadienyl (L)” as a ligand forms a compound which has a small molecular weight, and is easily vaporized as a chemical deposition raw material, and also the cyclopentadienyl (L) is hardly thermally decomposed in a vaporization stage before film formation, so that stable vaporization is easily attained.
Here, comparison between the ligands for ease of separation from the central metal shows that the carbonyl (—CO) tends to be more easily separated from the central metal than the cyclopentadienyl (L). Thus, when a composite metal thin film is formed by a chemical deposition method, the amount of each transition metal deposited in the thin film is likely to depend on the kind of a ligand coordinated to each transition metal. Of two transition metals, a transition metal having a larger amount of the carbonyl and a smaller amount of the cyclopentadienyl in terms of a ligand tends to be deposited in a larger amount in the formed composite metal thin film. For example, in the case of the following compound that is mentioned as a preferred example in the present invention, the second transition metal M2 to which only the carbonyl is coordinated is apt to be deposited in a larger amount in the composite metal thin film than the first transition metal M1 to which the cyclopentadienyl is coordinated.
wherein M1 is one of Ru, Mn and Fe, M2 is one of V, Cr, Mn, Fe, Co and Ni, and M1 and M2 are different; n is 3 or more and 5 or less; and each of R1 to R5 is a hydrogen atom, or an alkyl group with a carbon number of 1 or more and 5 or less.
Each of substituents R1 to R5 of the cyclopentadienyl is a hydrogen atom or an alkyl group with a carbon number of 1 or more and 5 or less, preferably one of a hydrogen atom, a methyl group, an ethyl group, a propyl group and a butyl group. When the carbon chain is excessively long, the vapor pressure of the complex tends to decrease, and in the case of a long-chain alkyl group with a carbon number of more than 5, the complex is difficult to vaporize. The total carbon number of all the substituents R1 to R5 is preferably 1 or more and 4 or less. By limiting not only the carbon number of one substituent but also the total carbon number of all the substituents, thermal stability of the complex is more easily maintained. Either a linear or branched alkyl group can be applied as each of substituents R1 to R5. For example, when a propyl group or a butyl group is applied, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, a sec-butyl group, a tert-butyl group or the like can be applied.
In the complex in the present invention, the total number of carbonyls (CO) is 1 or more and 9 or less, and preferably the ligand of the first transition metal (M1) has two or three carbonyls. The coordination number (n) of carbonyls as the ligand of the second transition metal (M2) is preferably 3 or more and 5 or less, especially preferably 4 or 5. The coordination number (n) is especially preferably 5 when M2 is Mn or Re, and the coordination number (n) is especially preferably 4 when M2 is Co, Rh or Ir.
Specific kinds of heterogeneous polynuclear complexes that are preferred for the chemical deposition raw material of the present invention are listed below as examples.
The chemical deposition raw material of the present invention described above can be produced in the following manner: a starting raw material that is a cyclopentadienyl derivative with the first transition metal (M1) as a central metal is reacted with a complex to which a plurality of carbonyls are coordinated with the second transition metal (M2) as a central metal.
The chemical deposition raw material according to the present invention is useful for formation of a composite metal thin film by a CVD method. This thin film formation method includes preparing a reaction gas by vaporizing a raw material including a heterogeneous polynuclear complex, introducing the reaction gas to a substrate surface, and decomposing the complex to deposit a plurality of metals. In this method, the heterogeneous polynuclear complex according to the present invention is used as a raw material.
The reaction atmosphere during formation of the thin film is preferably a reducing atmosphere, and therefore preferably hydrogen or ammonia is introduced as a reaction gas. The heating temperature during film formation is preferably 150° C. to 350° C. When the heating temperature is lower than 150° C., the film formation hardly proceeds, and thus a required thickness is hard to obtain. When the heating temperature is higher than 350° C., formation of a uniform thin film is difficult.
With the chemical deposition raw material according to the present invention, a composite metal thin film or a composite metal compound thin film containing a plurality of metals can be formed from a single raw material as described above. The raw material of the present invention has a high vapor pressure, is capable of producing a thin film at a low temperature, has moderate thermal stability, and is thus suitable for film formation by a chemical deposition method.
Hereinafter, the best embodiments in the present invention will be described.
In the embodiments, the following five kinds of complexes were synthesized. Synthesized complexes were each evaluated for physical properties, and subjected to a film formation test as a chemical deposition raw material.
A heterogeneous polynuclear complex (pentacarbonyl[dicarbonyl(η5-cyclopentadienyl)ruthenium]manganese (Mn—Ru)) having ruthenium as a first transition metal and manganese as a second transition metal was produced. The synthesis reaction formula is as described below. Hereinafter, the production process will be described in detail.
1.95 g (5 mmol) of decacarbonyldimanganese and 0.23 g (10 mmol) of metal sodium were added in a flask containing 250 ml of tetrahydrofuran. The solution was stirred at room temperature for 24 hours, a solution obtained by dissolving 3.49 g (10 mmol) of dicarbonyl(η5-cyclopentadienyl)iodoruthenium in 250 ml of tetrahydrofuran was then added, and the mixture was heated at 55° C. and stirred for 18 hours. After completion of the reaction, the reaction product was cooled to room temperature, and concentrated to obtain a muddy reaction mixture. The reaction mixture was extracted with hexane, and purified by column chromatography with silica gel as a carrier and a mixed solvent of hexane and dichloromethane as an eluent. Sublimation purification was performed to obtain 2.94 g (7.0 mmol) of pentacarbonyl[dicarbonyl(η5-cyclopentadienyl)ruthenium]manganese (Mn—Ru) as a specified substance (yield: 70%).
A heterogeneous polynuclear complex (pentacarbonyl[dicarbonyl(η5-cyclopentadienyl)iron]manganese (Fe—Mn)) having iron as a first transition metal and manganese as a second transition metal was produced. The synthesis reaction formula is as described below. Hereinafter, the production process will be described in detail.
1.95 g (5 mmol) of decacarbonyldimanganese and 0.23 g (10 mmol) of metal sodium were added in a flask containing 250 ml of tetrahydrofuran. The solution was stirred at room temperature for 24 hours, a solution obtained by dissolving 3.04 g (10 mmol) of dicarbonyl(η5-cyclopentadienyl)iodoiron in 250 ml of tetrahydrofuran was then added, and the mixture was stirred at room temperature for 2 days. After completion of the reaction, the reaction product was cooled to room temperature, and concentrated to obtain a muddy reaction mixture. The reaction mixture was extracted with hexane, and purified by column chromatography with silica gel as a carrier and hexane as an eluent. Sublimation purification was performed to obtain 1.86 g (5.0 mmol) of pentacarbonyl[dicarbonyl(η5-cyclopentadienyl)iron]manganese (Fe—Mn) as a specified substance (yield: 50%).
A heterogeneous polynuclear complex (dicarbonyl(η5-cyclopentadienyl)(tetracarbonylcobalt)ruthenium (Co—Ru)) having ruthenium as a first transition metal and cobalt as a second transition metal was produced. The synthesis reaction formula is as described below. Hereinafter, the production process will be described in detail.
1.71 g (5 mmol) of octacarbonyldicobalt and 0.23 g (10 mmol) of metal sodium were added in a flask containing 250 ml of tetrahydrofuran. The solution was stirred at room temperature for 24 hours, a solution obtained by dissolving 3.49 g (10 mmol) of dicarbonyl(η5-cyclopentadienyl)iodoruthenium in 250 ml of tetrahydrofuran was then added, and the mixture was stirred at room temperature for 18 hours. After completion of the reaction, the reaction product was cooled to room temperature, and concentrated to obtain a muddy reaction mixture. The reaction mixture was extracted with hexane, and purified by column chromatography with alumina as a carrier and a mixed solvent of hexane and dichloromethane as an eluent. Sublimation purification was performed to obtain 2.56 g (6.5 mmol) of pentacarbonyldicarbonyl(η5-cyclopentadienyl)(tetracarbonylcobalt)ruthenium (Co—Ru) as a specified substance (yield: 65%).
A heterogeneous polynuclear complex (dicarbonyl(η5-cyclopentadienyl)(tetracarbonylcobalt)iron (Co—Fe)) having iron as a first transition metal and cobalt as a second transition metal was produced. The synthesis reaction formula is as described below. Hereinafter, the production process will be described in detail.
1.71 g (5 mmol) of octacarbonyldicobalt and 0.23 g (10 mmol) of metal sodium were added in a flask containing 250 ml of tetrahydrofuran. The solution was stirred at room temperature for 24 hours, a solution obtained by dissolving 3.04 g (10 mmol) of dicarbonyl(η5-cyclopentadienyl)iodoiron in 250 ml of tetrahydrofuran was then added, and the mixture was stirred at room temperature for 2 days. After completion of the reaction, the reaction product was cooled to room temperature, and concentrated to obtain a muddy reaction mixture. The reaction mixture was extracted with hexane, and purified by column chromatography with silica gel as a carrier and hexane as an eluent. Sublimation purification was performed to obtain 2.44 g (7.0 mmol) of dicarbonyl(η5-cyclopentadienyl)(tetracarbonylcobalt)iron (Co—Fe) as a specified substance (yield: 70%).
A heterogeneous polynuclear complex (pentacarbonyl[dicarbonyl(η5-methylcyclopentadienyl)ruthenium]manganese (Mn—Ru)) in which a cyclopentadienyl derivative having one methyl group as a substituent was coordinated was produced. The synthesis reaction formula is as described below. Hereinafter, the production process will be described in detail.
1.95 g (5 mmol) of decacarbonyldimanganese and 0.23 g (10 mmol) of metal sodium were added in a flask containing 250 ml of tetrahydrofuran. The solution was stirred at room temperature for 24 hours, a solution obtained by dissolving 3.65 g (10 mmol) of dicarbonyl(η5-methylcyclopentadienyl)iodoruthenium in 250 ml of tetrahydrofuran was then added, and the mixture was heated at 55° C. and stirred for 18 hours. After completion of the reaction, the reaction product was cooled to room temperature, and concentrated to obtain a muddy reaction mixture. The reaction mixture was extracted with hexane, and purified by column chromatography with silica gel as a carrier and a mixed solvent of hexane and dichloromethane as an eluent. Sublimation purification was performed to obtain 2.59 g (6.0 mmol) of pentacarbonyl[dicarbonyl(η5-methylcyclopentadienyl)ruthenium]manganese (Mn—Ru) as a specified substance (yield: 60%).
Evaluation of physical properties of heterogeneous polynuclear complex: Physical properties were evaluated by TG for the heterogeneous polynuclear complexes produced in Examples 1 and 5. Analysis was performed by observing a change in weight of a complex sample (5 mg) in heating of the sample at a temperature elevation rate of 5° C./min over a measurement temperature range, i.e. from room temperature to 450° C., under a nitrogen atmosphere in TG-DTA2000SA manufactured by BRUKER Corporation. The results are shown in
The results of TG in
Film formation test: Next, a film formation test was conducted in which a composite metal thin film was formed by a CVD method with the complex produced in Example 5 as a raw material compound.
The metal thin film was formed on a substrate (15 mm×15 mm) with a silicon oxide film deposited on a silicon substrate by use of tetraethoxysilane (TEOS). As a film formation apparatus, a hot wall type thermal CVD apparatus was used. A reaction gas (hydrogen) was fed at a constant flow rate by use of a mass flow controller. Film formation conditions are as described below. The result of observing a cross-section of the metal thin film with a SEM is shown in
Substrate: SiO2
Film formation temperature: 250° C.
Sample temperature: 70° C.
Film formation pressure: 5 torr
Reaction gas (hydrogen) flow rate: 10 sccm
Film formation time: 20 minutes
The metal thin film formed in this way was shiny silvery-white, and had a thickness of 74.9 nm.
M1/M2 ratio: the Ru/Mn ratio was analyzed as an abundance of metal elements by an X-ray photoelectron spectroscopy (XPS) method for the metal thin film formed as described above. As a measurement apparatus, KRATOS Axis Nova manufactured by Shimadzu Corporation was used. In this measurement, the thin film (thickness: 74.9 nm) was analyzed in a depth direction from the vicinity of the surface to the upper side of the vicinity of the interface with the SiO2 film. In the vicinity of the interface with the SiO2 film, influences of Si and O made it difficult to correctly analyze the Ru/Mn ratio, and the analysis was performed over a range where these influences were small. The results are shown in
The present invention is capable of forming a composite metal thin film from a single raw material by a chemical deposition method, and it is easy to make the thin film homogeneous and control quality of raw materials. Thus, the present invention can be applied to uses which employ a structure in which a plurality of metal layers are deposited, such as copper diffusion layers in semiconductor devices.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2015-096981 | May 2015 | JP | national |
This application is a divisional of U.S. patent application Ser. No. 15/564,819, which was filed on Oct. 6, 2017, which is a national phase of PCT application no. PCT/JP2016/063695, which was filed on May 9, 2016, and which claims priority to Japanese Application No. 2015-096981, filed on May 12, 2015, the disclosures of which are incorporated by reference herein in their entireties and for all purposes.
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| Number | Date | Country | |
|---|---|---|---|
| 20190177837 A1 | Jun 2019 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | 15564819 | US | |
| Child | 16277789 | US |
