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WO2012118200A1 - Procédé de formation de couche mince métallique, couche mince métallique, et dispositif de formation de couche mince métallique - Google Patents

Procédé de formation de couche mince métallique, couche mince métallique, et dispositif de formation de couche mince métallique Download PDF

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Publication number
WO2012118200A1
WO2012118200A1 PCT/JP2012/055448 JP2012055448W WO2012118200A1 WO 2012118200 A1 WO2012118200 A1 WO 2012118200A1 JP 2012055448 W JP2012055448 W JP 2012055448W WO 2012118200 A1 WO2012118200 A1 WO 2012118200A1
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Prior art keywords
thin film
raw material
metal thin
reactive gas
organometallic compound
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English (en)
Japanese (ja)
Inventor
幸浩 霜垣
秀治 清水
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University of Tokyo NUC
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University of Tokyo NUC
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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
    • 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
    • C23C16/44—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 method of coating
    • C23C16/448—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 method of coating characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials
    • C23C16/4488—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 method of coating characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials by in situ generation of reactive gas by chemical or electrochemical reaction
    • 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
    • C23C16/44—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 method of coating
    • C23C16/455—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 method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45523—Pulsed gas flow or change of composition over time
    • 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 potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table 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 Table
    • 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 Table by chemical means, e.g. CVD, LPCVD, PECVD, laser CVD

Definitions

  • the present invention relates to a method for forming a metal thin film, a metal thin film, and a metal thin film forming apparatus.
  • transition elements are often used as the material for such a metal thin film, and techniques such as PVD (Physical Vapor Deposition) and CVD (Chemical Vapor Deposition) are known as film forming methods.
  • PVD Physical Vapor Deposition
  • CVD Chemical Vapor Deposition
  • the PVD method is a film forming method called a physical vapor deposition method, and is characterized in that a thin film is formed by evaporating a substance by physical means, and sputtering and vapor deposition are classified into this method.
  • the PVD method has the merit that a high-purity film can be produced.
  • a vacuum higher than a high vacuum is required as a film forming condition, a large capital investment is required for the exhaust system, and a film is formed. There is a drawback that the step coverage of the film is poor.
  • the CVD method is a film forming method called a chemical vapor deposition method, in which a metal raw material is supplied in a gaseous state onto a substrate, and a desired film is formed by dissociation / reaction by a chemical reaction on the gas phase or the substrate surface.
  • a metal raw material is supplied in a gaseous state onto a substrate
  • a desired film is formed by dissociation / reaction by a chemical reaction on the gas phase or the substrate surface.
  • Methods classified into CVD methods include, for example, thermal CVD method, PECVD method (Plasma-Enhanced Chemical Vapor Deposition), HWCVD method (Hot Wire Chemical Vapor Deposition), ALD method (Atomic Layer film method). .
  • the thermal CVD method is a method in which a metal raw material is transported in a gaseous state to the substrate surface, and a film is formed using thermal decomposition or surface reaction on the heated substrate. Although it depends on the type of surface reaction, it is generally excellent in step coverage because of its low sticking probability.
  • the PECVD method is a method in which a metal raw material is appropriately decomposed in a gas phase using plasma energy and then transported to the substrate surface to form a film.
  • a volatile raw material is used as the metal raw material, it is often possible to form a film.
  • the HWCVD method is also called a Cat-CVD method, which is a method in which a metal raw material is dissociated by contacting a hot wire functioning as a catalyst, and transported to the substrate surface in that state to form a film.
  • a catalyst a mesh-like metal may be used instead of a wire.
  • the HWCVD method has not only the advantage that the exhaust system is inexpensive, but also the advantage that the area can be increased simply by stretching the wire.
  • the ALD method is a film forming method also called an atomic layer deposition method, in which a metal raw material is transported until it is saturated and adsorbed on the substrate surface, and then a residual gas is exhausted and then a reaction gas is transported to the substrate surface to perform surface reaction.
  • This is a method of forming a film by depositing one atomic layer or several atomic layers at a time.
  • Patent Document 1 discloses a method of dissociating a metal raw material by bringing it into contact with a hot wire. (Hereinafter referred to as “HWARD method”).
  • Non-Patent Document 1 discloses a technique for forming a metal thin film by thermal CVD under atmospheric pressure using biscyclopentadienyl cobalt (cobaltcene) as a metal raw material.
  • the thermal CVD method often includes reaction by-products in the film, which makes it difficult to obtain a high-purity film and has a disadvantage that the resistance is higher than that of bulk metal.
  • metal raw materials that can be used for thermal CVD film formation and film formation conditions are limited, and it is difficult to obtain a metal thin film with high purity and good step coverage.
  • many of the metal raw materials used in the thermal CVD method contain oxygen and halogen, which has the disadvantage of adversely affecting the film quality of the metal thin film formed.
  • the PECVD method also includes ionized reactive species in addition to the radical reactive species, and thus has a disadvantage that the adhesion rate is high and the step coverage is inferior to that of the thermal CVD method. In addition, there are inconveniences that the base is damaged by plasma and that impurities are more easily contained than in the thermal CVD method.
  • the HWCVD method does not damage the underlayer, but if a metal raw material is used, a metal species is deposited on the wire or on the insulator portion of the wire, causing a short circuit. There was a disadvantage that it was not suitable for the membrane.
  • the ALD method is basically the same as the thermal CVD method, there is a disadvantage that the metal raw materials and film forming conditions that can be used are limited.
  • the method described in Patent Document 1 uses a tungsten material containing oxygen or halogen as the metal material, and there is a disadvantage that the metal material that can be used is limited.
  • the metal raw material contains oxygen and halogen, there is a disadvantage that these adversely affect the film quality of the formed metal thin film.
  • the thermal CVD method described in Non-Patent Document 1 is performed under atmospheric pressure, there is a disadvantage that the step coverage of the formed metal thin film is poor.
  • the present invention employs the following configuration. (1) That is, in the first aspect of the present invention, a raw material transporting step for transporting an organometallic compound raw material onto a film forming object placed in a vacuum chamber, and a reactive gas is heated to a metal contact. And a reactive gas transporting step of transporting onto the film-forming object placed in the vacuum chamber after contacting the medium.
  • the organometallic compound raw material and / or the reactive gas is selected from the group consisting of a carbon atom, a nitrogen atom, a hydrogen atom, a silicon atom, a phosphorus atom, a boron atom, and a metal atom. Preferably, it consists of only one or two or more atoms.
  • the said organometallic compound raw material contains the organometallic compound shown by following Chemical formula (1) in the film forming method of said (1) and (2).
  • M 1 is any one of cobalt, nickel, iron, manganese, ruthenium and chromium
  • R 1 to R 5 are hydrogen or carbonized represented by C n H 2n + 1 where n is 1 or more. Hydrogen.
  • the said organometallic compound raw material contains the organometallic compound shown by following Chemical formula (2) in the film forming method of said (1) and (2).
  • M 2 is tungsten, molybdenum, or titanium
  • R 6 to R 10 are hydrogen or a hydrocarbon represented by C n H 2n + 1 where n is 1 or more.
  • the said organometallic compound raw material contains the organometallic compound shown by following Chemical formula (3) in the film forming method of said (1) and (2).
  • M 3 is platinum, niobium, zirconium or titanium
  • R 11 to R 15 are hydrogen or a hydrocarbon represented by C n H 2n + 1 where n is 1 or more
  • R 16 to R 18 is a hydrocarbon represented by C n H 2n + 1 where n is 1 or more.
  • the reactive gas contains at least one of ammonia, dimethylhydrazine, methylamine, dimethylamine, silane, disilane, and hydrogen. It is preferable.
  • the metal catalyst body contains at least one of tungsten, platinum, rhodium and ruthenium.
  • the metal catalyst body is heated by energization only during the reactive gas transfer step.
  • the raw material transfer step and the reactive gas transfer step are alternately repeated, and the residual gas in the vacuum chamber is removed between the steps. It is preferable to have a purge step.
  • the pressure in the vacuum chamber is 1.33 ⁇ 10 2 Pa or less in the reactive gas transfer step.
  • a second aspect of the present invention is a metal thin film characterized by being formed by the method for forming a metal thin film according to any one of (1) to (11) above.
  • a vacuum chamber in which a film forming object can be freely placed, and an organometallic compound raw material on the film forming object placed in the vacuum chamber.
  • a raw material transporting means capable of transporting, and a reactive gas transporting means capable of transporting a reactive gas after contacting a heated metal catalyst body on a film-forming target placed in the vacuum chamber. It is a metal thin film forming apparatus characterized by having.
  • n is an integer that can be arbitrarily selected and is preferably 1 to 15 It is more preferably 1 to 10, more preferably 1 to 5, and particularly preferably 1 to 3.
  • C n H 2n + 1 include methyl, ethyl and butyl.
  • R 1 to R 5 may be the same as or different from each other.
  • R 6 to R 10 may be the same as or different from each other.
  • R 11 to R 18 may be the same as or different from each other.
  • all of R contained in the organometallic compound may be hydrogen, or all R, 1 to 8 or 2 to 4 R may be hydrocarbons arbitrarily selected.
  • a metal thin film can be formed without using a high vacuum with low impurities and good step coverage.
  • FIG. 1 is a schematic configuration diagram showing a metal thin film forming apparatus according to an embodiment of the present invention.
  • FIG. 2A is a diagram showing the energy required for the release of cyclopentadienyl from cobaltene.
  • FIG. 2B is a diagram showing the energy required for the release of cyclopentadienyl from cobaltocene in which H is bound to cobalt.
  • FIG. 2C shows the energy required for the release of cyclopentadienyl from cobaltocene in which NH 2 is bonded to cobalt.
  • FIG. 3 is a diagram showing a metal thin film deposition cycle in one embodiment of the present invention.
  • FIG. 4 is a diagram showing a metal thin film deposition cycle in one embodiment of the present invention.
  • the metal thin film deposition apparatus of the present embodiment is an apparatus capable of depositing a metal thin film by the HWALD method.
  • a film forming apparatus 1 includes a vacuum chamber 2 that can be depressurized, a raw material transport unit 3 that can transport an organometallic compound raw material, and a reactive gas that can transport a reactive gas. And conveying means 4.
  • a mounting table 5 is provided in the vacuum chamber 2, and the substrate 6 (film forming object) can be freely mounted on the mounting table 5.
  • a heater (not shown) is provided inside the mounting table 5 so that the substrate 6 can be heated.
  • the composition, shape, and size of the film-forming target may be arbitrarily selected unless there is a particular problem.
  • an exhaust pump 7 is connected to the vacuum chamber 2 via an exhaust pipe (not shown) and an on-off valve (not shown) so that the exhaust can be performed.
  • a pressure gauge (not shown) is provided in the vacuum chamber 2 so that the pressure can be measured.
  • a metal catalyst body 8 that is in contact with a reactive gas described later is provided.
  • the metal catalyst body 8 a well-known one used in the HWCVD method or the like may be used. It may be a metal composed of a single element or various alloys. In particular, it is preferably substantially made of tungsten, platinum, rhodium or ruthenium.
  • the film forming temperature can be lowered, so that the progress of side reactions and the diffusion of substances in the substrate can be suppressed, and the step coverage can be improved. it can.
  • the film forming temperature can be selected according to need.
  • the film forming temperature is in the range of 100 to 650 ° C., for example. Further, as a preferred example, it may be in the range of 100 to 400 ° C., more preferably in the range of 250 to 350 ° C.
  • the metal catalyst body 8 is connected to a power source 9 and is configured to be heated by energization.
  • the reactive gas is activated into active species by contacting the metallic color medium 8 heated by this energization.
  • the metal catalyst body 8 may be disposed in the vacuum chamber 2 or may be installed in another upstream chamber (not shown) separated from the vacuum chamber 2 by a shutter (not shown). Good.
  • the vacuum chamber 2 is provided with a gas ejection part 10, and the raw material conveying means 3 and the reactive gas conveying means 4 are connected to the gas ejection part 10.
  • the raw material transport means 3 is generally composed of a raw material supply source 11, a pipe 12 connected to the raw material supply source 11, and a valve 13 attached to the pipe 12.
  • the pipe 12 is connected to the gas ejection unit 10. ing.
  • the pipe 12 is branched upstream of the valve 13 (on the raw material supply source 11 side), and the branched pipe 14 is connected to the pipe 16 via the valve 15.
  • the raw material supply source 11 may have any configuration as long as an organometallic compound raw material can be supplied.
  • the raw material storage tank 17 in which the organometallic compound is stored, the pipe 18 connected to the liquid phase part of the raw material storage tank 17, and the pipe connected to the gas phase part of the raw material storage tank 17 12 is comprised.
  • an inert gas such as helium
  • the organometallic compound raw material can be accompanied and led out from the pipe 12.
  • the organic metal compound raw material is liquid at room temperature, and a configuration capable of vaporization by bubbling is adopted.
  • a configuration capable of vaporization by bubbling is not necessarily required.
  • an organic metal compound raw material that is gaseous at normal temperature may be used as a raw material, and when a liquid material is used, it may be gasified by vaporization by a vaporizer or by vaporization by heating.
  • the gasified organometallic compound raw material taken out from the gas phase portion of the raw material reservoir 17 is introduced into the vacuum chamber 2 through the gas jetting part 10 by the raw material transport means 3 configured as described above. , Transported onto the substrate 6.
  • the reactive gas conveying means 4 is generally configured by a reactive gas supply source 21, a pipe 22 connected to the reactive gas supply source 21, and a valve 23 attached to the pipe 22. It is connected to the gas ejection part 10.
  • the reactive gas supply source 21 may have any configuration as long as it can supply reactive gas.
  • the pipe 22 is branched upstream of the valve 23 (reactive gas supply source 21 side), and the branched pipe 24 is connected to the pipe 16 via the valve 25.
  • the reactive gas derived from the reactive gas supply source 21 is introduced into the vacuum chamber 2 through the gas jetting part 10 by the reactive gas conveying means 4 configured as described above, and comes into contact with the metal catalyst body 8. Above, it is transferred onto the substrate 6.
  • the method for forming a metal thin film according to this embodiment includes a raw material transfer step and a reactive gas transfer step, which will be described first.
  • the raw material conveyance process is a process of transporting the organometallic compound raw material onto the substrate 6 placed in the vacuum chamber 2.
  • the substrate may be arbitrarily selected as long as there is no problem.
  • Various materials can be used as the organic metal compound raw material. However, it preferably comprises only one or two or more atoms selected from the group consisting of carbon atoms, nitrogen atoms, hydrogen atoms, silicon atoms, phosphorus atoms, boron atoms, and metal atoms.
  • the said metal atom can be selected as needed, atoms, such as cobalt, manganese, nickel, ruthenium, tungsten, molybdenum, platinum, titanium, are mentioned, for example. By selecting such a material, it is possible to prevent halogen and oxygen from being contained in the formed metal thin film, and to prevent deterioration in film quality.
  • the organometallic compound raw material may contain an organometallic compound represented by the chemical formula (1), an organometallic compound represented by the chemical formula (2), or an organometallic compound represented by the chemical formula (3).
  • the organometallic compound raw material preferably contains 0 to 100% by weight of these organometallic compounds, more preferably 50 to 100% by weight, even more preferably 75 to 100% by weight, and more preferably 90 to 100% by weight. Is particularly preferred.
  • the organometallic compound raw material may be composed of any one of these organometallic compounds (1) to (3).
  • M 1 is any one of cobalt, nickel, iron, manganese, ruthenium and chromium, and R 1 to R 5 are hydrogen or carbonized represented by C n H 2n + 1 where n is 1 or more. Hydrogen.
  • M 2 is tungsten, molybdenum, or titanium, and R 6 to R 10 are hydrogen or a hydrocarbon represented by C n H 2n + 1 where n is 1 or more.
  • M 3 is platinum, niobium, zirconium or titanium
  • R 11 to R 15 are hydrogen or a hydrocarbon represented by C n H 2n + 1 where n is 1 or more
  • R 16 to R 18 is a hydrocarbon represented by C n H 2n + 1 where n is 1 or more.
  • the organometallic raw material represented by the chemical formula (1) or the chemical formula (2) is a biscyclopentadienyl compound (common name: metallocene), and its synthesis has been reported with various metals. By selecting such a material, a metal thin film with fewer impurities can be formed. In addition, when metallocene is used, it is possible to form a film even under reduced pressure by adopting the HWARD method, so that a metal thin film with good step coverage can be obtained.
  • the organometallic compound raw material can be used as it is if it is gaseous at room temperature, and if it is liquid, it can be vaporized by bubbling using an inert gas such as helium, vaporized by a vaporizer, or heated. What is necessary is just to use gasified by vaporization. Further, helium or the like may be used as a carrier gas in combination with the organometallic compound raw material.
  • the vaporized organometallic compound material is introduced into the gas ejection portion 10 via the pipe 12 and then introduced into the vacuum chamber 2. At this time, the valve 15 is closed and the valve 13 is open. Then, the organometallic compound material introduced into the vacuum chamber 2 is transferred to the substrate 6. As described above, the organometallic compound raw material is transferred onto the substrate 6 placed in the vacuum chamber 2.
  • the metal catalyst body 8 disposed in the vacuum chamber 2 is not energized and kept in an unheated state. Thereby, in addition to suppressing the temperature rise of the substrate surface, the effects of preventing the metal catalyst body from being deteriorated and reducing the power consumption can be obtained.
  • the organometallic compound raw material need not be one type, and may be two or more types. When two or more types are used, they may be transferred onto the substrate 6 simultaneously or sequentially.
  • the reactive gas transporting step is a step of transporting the reactive gas onto the substrate 6 placed in the vacuum chamber 2 after contacting the heated metal catalyst body 8.
  • the reactive gas consists of one or more atoms selected from carbon atoms, nitrogen atoms, hydrogen atoms, silicon atoms, phosphorus atoms, boron atoms, and metal atoms. Is preferred.
  • the said metal atom can be selected as needed, atoms, such as cobalt, manganese, ruthenium, tungsten, molybdenum, platinum, titanium, aluminum, gallium, tin, are mentioned, for example. By selecting such a material, it is possible to prevent halogen and oxygen from being contained in the formed metal thin film, and to prevent deterioration in film quality.
  • the reactive gas contains at least one of ammonia, dimethylhydrazine, methylamine, dimethylamine, silane, disilane and hydrogen.
  • the gas may be composed of only one of them.
  • the reactive gas is preferably a gas containing nitrogen atoms.
  • H or NH 2 is not bonded to the metal atom contained in the metallocene, a lot of energy is required to dissociate the metal atom.
  • H is bonded to a metal atom, not much energy is required to dissociate the metal atom.
  • the metal atom is dissociated. The energy required for this is small.
  • the reactive gas contains nitrogen atoms when it is necessary to form a film under a reduced pressure of 1 Pa to 133 Pa or when it is necessary to form a film under a temperature condition of 400 ° C. or lower. Those that do are preferred.
  • cobaltene M 1 in the above chemical formula (1) is cobalt
  • FIG. 2A when H or NH 2 is not bonded to cobalt, cyclopentadiene is released from cobaltcene. Requires 50.5 kcal / mol.
  • FIG. 2B when H is bonded to cobalt, only 29.1 kcal / mol is required to release cyclopentadiene from cobaltene, and as shown in FIG.
  • NH 2 is bonded to cobalt, only about 15.2 kcal / mol is required.
  • the reactive gas can also be diluted with other inert gas.
  • the reactive gas supplied from the reactive gas supply source 21 is introduced into the gas ejection unit 10 via the pipe 22 and then introduced into the vacuum chamber 2. At this time, the valve 25 is closed and the valve 23 is open. Further, when the reactive gas is introduced into the vacuum chamber 2, the reactive gas may be introduced through a shower head 26 provided in the gas ejection unit 10.
  • the reactive gas introduced into the vacuum chamber 2 comes into contact with the metal catalyst body 8 heated by energization or the like, and is then transferred onto the substrate 6.
  • the reactive gas is selected from NX n radical, SiX n radical, BXn radical (X is hydrogen or hydrocarbon, n is an integer of 1 to 3) and H radical. It is preferably activated to at least one active species. As described above, the reactive gas is brought into contact with the heated metal catalyst body 8 and then conveyed onto the substrate 6 placed in the vacuum chamber 2.
  • the metal thin film forming method of this embodiment is basically a film forming method by the HWALD method. However, it differs from the conventional method in that the reactive gas is brought into contact with the heated metal catalyst body. Therefore, specifically, the organometallic compound raw material is transported onto the substrate 6, the supply of the organometallic compound raw material is stopped in a state where the organometallic compound raw material is saturatedly adsorbed on the substrate 6, and then the reaction is performed on the substrate 6 By supplying the property gas, the organometallic compound raw material is formed on the substrate 6.
  • This process is defined as one cycle, and the cycle is repeated a plurality of times until a metal thin film having a desired film thickness is formed on the substrate 6.
  • the number of cycles may be arbitrarily selected, and examples include 50 to 1000 times, more preferably 70 to 700 times, still more preferably 80 to 500 times, and particularly preferably 100 to 400 times. You may select the flow volume, supply time, etc. of a reactive gas or an organometallic compound raw material as needed.
  • the metal thin film is not formed on the substrate 6 only by transporting the organometallic compound raw material, but is formed only after the reactive gas is transported. Since only the organometallic compound raw material that is saturated and adsorbed on the substrate 6 is formed, a thin film is formed in units of one atom or several atoms.
  • the raw material transport process and the reactive gas transport process are alternately repeated.
  • Switching between the raw material transfer process and the reactive gas transfer process may be controlled by opening and closing the valves 13 and 23. Further, during the raw material transfer process, the reactive gas derived from the reactive gas supply source 21 may be discharged out of the system through the pipes 24 and 16 by closing the valve 23 and opening the valve 25. Conversely, during the reactive gas transfer process, the valve 13 is closed and the valve 15 is opened, so that the organometallic compound raw material may be discharged out of the system via the pipes 14 and 16. As described above, a metal thin film is formed on the substrate 6 by alternately performing the raw material transport process and the reactive gas transport process.
  • the lower limit of the pressure in the vacuum chamber 2 in all steps of the film forming process is arbitrarily selected, but is preferably 0.013 Pa or more. By forming the film under such reduced pressure, the step coverage of the formed metal thin film is improved.
  • the method for forming a metal thin film according to this embodiment includes a raw material transfer step and a reactive gas transfer step, a metal thin film with low impurities and good step coverage can be formed. Moreover, since a high vacuum is not required in the film forming process, the manufacturing apparatus is not expensive. In addition, since the raw material transfer step and the reactive gas transfer step are performed alternately, it is possible to prevent the metal thin film from being deposited on the metal catalyst body.
  • the organometallic compound raw material or / and the reactive gas consists of only one or more atoms selected from the group consisting of carbon atoms, nitrogen atoms, hydrogen atoms, silicon atoms, phosphorus atoms, boron atoms and metal atoms. Therefore, it is possible to prevent halogen and oxygen from being mixed into the formed metal thin film, and to form a metal thin film with good film quality.
  • API automatic pressure controller
  • a raw material bottle containing cobaltcene is first heated to 50 ° C., and supplied with a raw material vapor by helium at a flow rate of 30 sccm for 3 seconds.
  • purging with helium at a flow rate of 30 sccm is performed for 2 seconds.
  • ammonia at a flow rate of 30 sccm is supplied into the vacuum chamber for 9 seconds.
  • a current of 3 A is applied to the tungsten wire to heat it up red.
  • purging with helium at a flow rate of 30 sccm is performed for 2 seconds.
  • the above steps were set as one cycle, and the material supply, purge, ammonia supply, energization, and purge were repeated 400 times.
  • Example 1 As a result, in Example 1, as shown in Table 2, the film forming speed was 0.04 nm / cycle, and the resistivity of the obtained film was 20 ⁇ cm. Further, after the film formation, the composition of the metal thin film obtained by X-ray photoelectron spectroscopy (XPS) was examined, and all of carbon, oxygen and nitrogen in the film were 1% or less, which is the detection lower limit.
  • XPS X-ray photoelectron spectroscopy
  • Example 2 In Example 2, helium was not circulated in the purge process, but vacuuming was performed. As shown in Table 1, a metal thin film was formed under the same conditions as in Example 1. In Example 2, as shown in Table 2, the film formation rate was 0.05 nm / cycle, and the resistivity was 20 ⁇ cm. Moreover, after the film formation, the composition of the metal thin film obtained by X-ray photoelectron spectroscopy (XPS) was examined.
  • XPS X-ray photoelectron spectroscopy
  • Examples 3 to 5 In Examples 3 to 5, the nickel metallocene, manganocene, or ferrocene was used in place of cobalt sen as the organometallic compound raw material, respectively, and the other conditions were the same as in Example 1; A simulation was performed on the composition of The results are shown in Table 3. In Table 3, the results of Example 1 (Co), Example 2 (Ni), Example 3 (Mn), and Example 4 (Fe) are shown in order from the top row.
  • APC automatic pressure controller
  • As the organic metal compound raw material two kinds of biscyclopentadienyl cobalt (cobaltene) and biscyclopentadienyl tungsten stainless hydride were used, ammonia was used as a reactive gas, and tungsten wire was used as a metal catalyst.
  • a method of simultaneously supplying two kinds of organometallic compound raw materials was adopted. Specifically, first, a raw material bottle containing cobaltcene was heated to 50 ° C., and a raw material bottle containing biscyclopentadienyl tungsten stainless hydride was heated to 100 ° C. Thereafter, helium at a flow rate of 30 sccm is bubbled through each bottle to entrain the raw material vapor, and cobalt cene and biscyclopentadienyl tungsten stent hydride are simultaneously supplied into the vacuum chamber for 3 seconds. Next, purging with helium at a flow rate of 30 sccm is performed for 2 seconds.
  • ammonia at a flow rate of 30 sccm is supplied into the vacuum chamber for 9 seconds.
  • a current of 3 A is applied to the tungsten wire to heat it up red.
  • purging with helium at a flow rate of 30 sccm is performed for 2 seconds. The above steps were taken as one cycle, and as shown in FIG. 3, the supply of raw material, purge, supply of ammonia, energization, and purge were repeated 400 times.
  • Example 6 the film forming speed was 0.04 nm / cycle, and the resistivity was 25 ⁇ cm. Further, after the film formation, the composition of the metal thin film obtained by X-ray photoelectron spectroscopy (XPS) was examined. As a result, the cobalt composition was 95% and the tungsten composition was 5%. 1% or less.
  • XPS X-ray photoelectron spectroscopy
  • APC automatic pressure controller
  • As the organic metal compound raw material two kinds of biscyclopentadienyl cobalt (cobaltene) and biscyclopentadienyl tungsten stainless hydride were used, ammonia was used as a reactive gas, and tungsten wire was used as a metal catalyst.
  • a method of sequentially supplying two kinds of organometallic compound raw materials was adopted. Specifically, first, a raw material bottle containing cobaltcene was heated to 50 ° C., and a raw material bottle containing biscyclopentadienyl tungsten stainless hydride was heated to 100 ° C. Thereafter, helium at a flow rate of 30 sccm was passed through each bottle to entrain the raw material vapor, and were sequentially transported onto the substrate.
  • cobaltsen is first supplied into the vacuum chamber for 3 seconds.
  • purging with helium at a flow rate of 30 sccm is performed for 2 seconds.
  • ammonia at a flow rate of 30 sccm is supplied into the vacuum chamber for 9 seconds.
  • a current of 3 A is applied to the tungsten wire to heat it up red.
  • purging with helium at a flow rate of 30 sccm is performed for 2 seconds.
  • Example 7 the film forming speed was 0.04 nm / cycle, and the resistivity was 25 ⁇ cm. Further, after the film formation, the composition of the metal thin film obtained by X-ray photoelectron spectroscopy (XPS) was examined. As a result, the cobalt composition was 90%, the tungsten composition was 10%, and carbon, oxygen, and nitrogen were both lower detection limits. % Or less.
  • XPS X-ray photoelectron spectroscopy
  • Comparative Example 1 In Comparative Example 1, an experiment by a thermal CVD method was performed.
  • the apparatus used for the thermal CVD method is the same apparatus as that used in Example 1, except that the tungsten filament is removed.
  • the raw material bottle containing cobaltcene was heated to 50 ° C., and the raw material vapor was entrained by helium at a flow rate of 30 sccm and supplied into the vacuum chamber.
  • hydrogen gas was supplied into the vacuum chamber at a flow rate of 30 sccm.
  • the metal thin film was not formed even when supplied for 60 minutes.
  • Comparative Example 2 As shown in Table 4, an experiment was performed under the same conditions as in Comparative Example 1 except that ammonia was used instead of hydrogen gas. As a result, as shown in Table 5, the metal thin film was not formed even when supplied for 60 minutes.
  • Comparative Example 3 In Comparative Example 3, an experiment by PECVD was performed.
  • the apparatus used for the PECVD method is the same as that used in Example 1, except that the tungsten filament is removed and an electrode is provided on the substrate side so that capacitively coupled plasma can be generated between the substrate and the showerhead. It is an attached device.
  • the raw material bottle containing cobaltcene was heated to 50 ° C., and the raw material vapor was entrained by helium at a flow rate of 30 sccm and supplied into the vacuum chamber.
  • hydrogen gas was supplied into the vacuum chamber at a flow rate of 30 sccm.
  • 150 W RF was applied using the shower head and the substrate stage (mounting table) as electrodes to generate capacitively coupled plasma.
  • the film formation rate was 2 nm / min, and the resistivity of the obtained film was 250 ⁇ cm.
  • the composition of the metal thin film obtained by X-ray photoelectron spectroscopy (XPS) was examined. As a result, both oxygen and nitrogen were 1% or less, which is the lower detection limit, but 35% carbon was contained. It was.
  • Comparative Example 4 In Comparative Example 4, an experiment by the PEALD method was performed.
  • the apparatus used in the PEALD method is the same as that used in Example 1, except that the tungsten filament is removed and a 10 cm glass tube is provided at the ammonia introduction port, where inductively coupled plasma can be generated. Thus, it is the apparatus which provided the coil of 100 turns on the glass tube outer side.
  • APC automatic pressure controller
  • the raw material bottle containing cobaltcene is heated to 50 ° C., and the raw material vapor is accompanied by helium at a flow rate of 30 sccm and supplied into the vacuum chamber for 3 seconds.
  • purging with helium at a flow rate of 30 sccm is performed for 2 seconds.
  • ammonia at a flow rate of 30 sccm is supplied into the vacuum chamber for 6 seconds.
  • inductively coupled plasma was generated at the ammonia supply port.
  • purging with helium at a flow rate of 30 sccm is performed for 2 seconds.
  • the above process was set as one cycle, and the combination of material supply, purge, ammonia supply, plasma generation, and purge was repeated 400 times.
  • the film formation rate was 0.01 nm / cycle, and the resistivity of the obtained film was 50 ⁇ cm.
  • the composition of the metal thin film obtained by X-ray photoelectron spectroscopy (XPS) was examined. As a result, oxygen was 1% or less, which is the lower limit of detection, but carbon was 4% and nitrogen was 10%. It was included.
  • the present invention can be widely used in manufacturing industries that manufacture products using metal thin films. It is possible to provide a method for forming a metal thin film that has low impurities, good step coverage, and does not use high vacuum.

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Abstract

L'invention concerne un procédé de formation de couche mince métallique, caractérisé en ce qu'il comprend une étape de transfert de matériau brut pour transférer le matériau brut sous forme d'un composé métallique organique sur une cible de formation de couche mince chargée dans une chambre à vide, et une étape de transfert de gaz réactif destinée à amener le gaz réactif en contact avec un corps de catalyseur métallique chauffé, puis à transférer le gaz réactif sur la cible de formation de couche mince qui a été chargée dans la chambre à vide.
PCT/JP2012/055448 2011-03-03 2012-03-02 Procédé de formation de couche mince métallique, couche mince métallique, et dispositif de formation de couche mince métallique Ceased WO2012118200A1 (fr)

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US10361118B2 (en) 2016-10-07 2019-07-23 Samsung Electronics Co., Ltd. Organometallic precursors, methods of forming a layer using the same and methods of manufacturing semiconductor devices using the same

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KR102341229B1 (ko) 2017-07-18 2021-12-17 가부시키가이샤 고준도가가쿠 겐큐쇼 금속 박막의 원자층 퇴적 방법
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KR102713324B1 (ko) * 2022-05-04 2024-10-07 (주)원익머트리얼즈 코발트 박막 형성용 전구체 화합물, 및 이를 이용한 고순도 코발트 박막을 형성하는 방법, 및 코발트 박막

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