US20110232573A1 - Catalytic Chemical Vapor Deposition Apparatus - Google Patents

Catalytic Chemical Vapor Deposition Apparatus Download PDF

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US20110232573A1
US20110232573A1 US13/133,230 US200813133230A US2011232573A1 US 20110232573 A1 US20110232573 A1 US 20110232573A1 US 200813133230 A US200813133230 A US 200813133230A US 2011232573 A1 US2011232573 A1 US 2011232573A1
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wire
catalyst
tantalum
catalyst wire
vapor deposition
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Shuji Osono
Masanori Hashimoto
Shin Asari
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Ulvac Inc
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Ulvac Inc
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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
    • C23C16/44—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
    • 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
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
    • C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • 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
    • 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
    • C23C16/22—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 inorganic material, other than metallic material
    • C23C16/24—Deposition of silicon only
    • 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
    • C23C16/22—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 inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/34—Nitrides
    • C23C16/345—Silicon nitride
    • 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
    • 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
    • C23C16/46—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 heating the substrate
    • 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
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02612—Formation types
    • H01L21/02617—Deposition types
    • H01L21/0262—Reduction or decomposition of gaseous compounds, e.g. CVD

Definitions

  • the present invention relates to a catalytic chemical vapor deposition apparatus that supplies a source gas to a heated catalyst wire installed in a reaction chamber and deposits generated decomposition species on a base material to be film-formed in the reaction chamber, to thereby perform film formation.
  • Catalytic-chemical vapor deposition is a film formation method of supplying a reactive gas (source gas) to a catalyst wire heated to, for example, 1,500 to 2,000° C. and depositing decomposition species (deposited species) generated using catalysis or thermal decomposition reaction of the reactive gas on a base material to be film-formed.
  • the catalytic-chemical vapor deposition is similar to plasma CVD in that decomposition species of a reactive gas are deposited on a base material to thereby perform film formation.
  • decomposition species are generated using catalysis or thermal decomposition reaction of the reactive gas on a catalyst wire having a high temperature. Therefore, the catalytic-chemical vapor deposition has an advantage that surface damage due to plasma is not caused and a use efficiency of a source gas is high, as compared to the plasma CVD in which plasma is formed to generate decomposition species of a reactive gas.
  • the catalytic-chemical vapor deposition is used when a silicon (Si)-based film is formed.
  • a tungsten (W) wire is widely used (see, for example, Patent Document 1).
  • tungsten is prone to undergo an alloying reaction with silicon (silicidation).
  • silicon silicon
  • examples of a material having a lower silicidation speed than that of tungsten include tantalum (Ta).
  • Ta tantalum
  • tantalum has lower mechanical strength than that of tungsten, and particularly has low creep strength when used in high temperature. Therefore, in the case where metal tantalum is used for a catalyst wire, there arise problems that thermal expansion is caused at a time of heating, and accordingly a wire diameter is made small and wire resistance is made large, a wire temperature is raised, and blowout is prone to occur. Therefore, it is impossible to improve productivity.
  • Patent Document 2 discloses a catalyst wire obtained by coating a surface of a tantalum wire with boron nitride (BN).
  • BN boron nitride
  • the present invention has been made in view of the problems described above and has an object to provide a catalytic chemical vapor deposition apparatus capable of prolonging the service life of a catalyst wire.
  • a catalytic chemical vapor deposition apparatus including a reaction chamber, a gas introduction source, a catalyst wire, and a heat source.
  • the gas introduction source introduces a source gas to the reaction chamber.
  • the catalyst wire includes a tantalum wire and a boride layer formed on a surface of the tantalum wire and is arranged to be opposed to a substrate to be processed that is installed in the reaction chamber.
  • the heat source heats the catalyst wire.
  • a catalytic chemical vapor deposition apparatus including a reaction chamber, a gas introduction source, a catalyst wire, and a heat source.
  • the gas introduction source introduces a source gas to the reaction chamber.
  • the catalyst wire includes a tantalum wire and a boride layer formed on a surface of the tantalum wire and is arranged to be opposed to a substrate to be processed that is installed in the reaction chamber.
  • the heat source heats the catalyst wire.
  • the boride of the metal tantalum is harder than the metal tantalum. Therefore, by using the tantalum wire having the boride layer formed on the surface thereof as a catalyst wire, it is possible to reduce thermal expansion of the catalyst wire, improve the mechanical strength, and prolong the service life. Further, according to the structure described above, the service life can be prolonged as compared to a catalyst wire obtained by coating the surface of the tantalum wire with boron nitride or carbon.
  • a tantalum wire is installed in a reaction chamber and is subjected to energization heating while a diborane (B 2 H 6 ) gas is introduced in the reaction chamber.
  • a film thickness of a boride layer is not particularly limited and can be adjusted as appropriate based on a heating temperature of the tantalum wire, a gas concentration of the diborane gas, a reaction time, or the like.
  • the catalytic chemical vapor deposition apparatus may further include a control means for performing energization heating of the catalyst wire with the heat source by continuous energization.
  • the tantalum wire having the boride layer formed on the surface thereof is used as a catalyst wire and subjected to energization heating to perform film formation.
  • the control means for performing energization heating of the catalyst wire by continuous energization is installed and the energization heating of the catalyst wire is successively performed during film formation, with the result that a heat shock given to the catalyst wire can be relieved, the generation of cracks on the boride layer can be suppressed, and the service life of the catalyst wire can be prolonged.
  • FIG. 1 is a schematic structural view of a catalytic chemical vapor deposition apparatus according to an embodiment of the present invention.
  • a catalytic chemical vapor deposition apparatus 1 includes a vacuum chamber 3 in which a reaction chamber 2 is formed. To the vacuum chamber 3 , a vacuum pump 4 is connected so that the reaction chamber 2 can be evacuated to a predetermined degree of vacuum. The reaction chamber 2 is formed inside an anti-adhesive plate 5 installed in the vacuum chamber 3 .
  • the catalyst wires 6 are each constituted of a tantalum (Ta) wire.
  • the plurality of catalyst wires 6 are set parallel to each other so as to cross the inside of the reaction chamber 2 in a vertical direction. It should be noted that the installation form of the catalyst wires 6 is not limited to the above-mentioned vertical direction, and the catalyst wires 6 may be installed in a form of crossing the reaction chamber 2 in a horizontal direction.
  • the respective catalyst wires 6 are installed so as to pass through through-holes 5 a and 5 b formed on a top surface and a bottom surface of the anti-adhesive plate 5 , and both end portions thereof are connected to a control unit 8 (control means) set outside the vacuum chamber 3 .
  • the control unit 8 includes a heat source to perform energization heating on the catalyst wires 6 .
  • the control unit 8 is for performing energization heating of the catalyst wires 6 by continuous energization, and is constituted of a computer or the like that adjusts a current supply source and supply current.
  • a substrate S serving as a base material to be film-formed is set inside the reaction chamber 2 .
  • the substrate S for example, a rectangular glass substrate is used.
  • two substrates S are opposed to each other so as to sandwich the catalyst wires 6 therebetween.
  • the substrates S are installed in the reaction chamber 2 such that a long side direction of the substrates S is orthogonal to an extending direction of the catalyst wires 6 .
  • the substrates S are supported by a substrate support means (not shown).
  • the substrate support means has a structure incorporating a heat source to heat the substrates S to a predetermined temperature.
  • the anti-adhesive plate 5 has a substantially rectangular solid shape, and gas introduction pipes 7 are installed at four side portions of the anti-adhesive plate 5 .
  • the gas introduction pipes 7 are for introducing a source gas or a diborane (B 2 H 6 ) gas to the reaction chamber 2 , and are connected to a source gas supply unit 9 a and a diborane gas supply unit 9 b installed outside the vacuum chamber 3 via a gas supply line.
  • the source gas or diborane gas ejected from the gas introduction pipes 7 is mainly introduced between the two substrates S.
  • a gas introduction source is constituted of the source gas supply unit 9 a , the gas introduction pipes 7 , and the like.
  • the catalytic chemical vapor deposition apparatus 1 is constituted as described above. Next, the catalytic-chemical vapor deposition of this embodiment using the catalytic chemical vapor deposition apparatus 1 will be described.
  • the vacuum pump 4 is operated to evacuate the vacuum chamber 3 and reduce a pressure of the reaction chamber 2 to a predetermined degree of vacuum (for example, 1 Pa).
  • a diborane gas is introduced from the diborane gas supply unit 9 b to the reaction chamber 2 and the catalyst wires 6 are energized by the control unit 8 to be heated to a predetermined temperature (for example, 1,700° C.) or more.
  • a predetermined temperature for example, 1,700° C.
  • a film thickness of the boride layer is not particularly limited and can be adjusted as appropriate based on a heating temperature of the tantalum wire, a gas concentration of the diborane gas, a reaction time, or the like.
  • the step of forming a boride layer on the surface of the tantalum wire may be performed after the substrates S are installed in the vacuum chamber 3 , or may be performed before the substrates S are installed therein. Further, in a chamber to which a diborane gas supply line cannot be provided, a catalyst wire of tantalum boride whose boride layer is formed in advance somewhere else may be relocated.
  • a source gas is introduced from the source gas supply unit 9 a to the reaction chamber 2 .
  • a mixed gas of a silane (SiH 4 ) gas and hydrogen (H 2 ) is used as a source gas to form a silicon (Si) film on the surface of the substrate S.
  • a film to be formed on the surface of the substrate S may be a silicon nitride film (SiN) formed using silane, hydrogen, and ammonia (NH 3 ), a silicon nitride film formed using trisilylamine ((SiH 3 ) 3 N), ammonia, and hydrogen, a silicon nitride film formed using hexamethyldisilazane ((CH 3 ) 3 SiNHSi(CH 3 ) 3 , abbreviated to HMDS), a silicon oxide film (SiO) formed using silane, hydrogen, and oxygen (O2) or dinitrogen monoxide (N 2 O), a silicon oxide film formed using silane and tetraethoxysilane (Si(OC 2 H 5 ) 4 , abbreviated to TEOS), a phosphorus-doped silicon film (n+Si film) or a boron-doped silicon (p+Si film) formed using silane, hydrogen, and
  • SiN
  • a DC voltage is applied to the catalyst wires 6 by the by the control unit 8 , and the catalyst wires 6 are heated to high temperature of, for example, 1,700° C. or more. Further, at this time, the substrates S are heated to a predetermined temperature (for example, about 300° C.).
  • the source gas is introduced between the two substrates S opposed to each other from the gas introduction pipes 7 . Then, the source gas comes into contact with the catalyst wires 6 heated to high temperature, and decomposition species of a reactive gas generated by catalysis or thermal decomposition reaction are deposited on the substrate S so that a film is formed.
  • a heating temperature of the catalyst wires 6 is controlled while the energization heating of the catalyst wires 6 is successively performed by the control unit 8 at a time of film formation of the substrate S so that the heat shock given to the catalyst wires 6 is reduced.
  • a method of increasing/decreasing temperature of the catalyst wires 6 in a plurality of steps is included in addition to a method of continuously controlling a current amount and keeping the catalyst wires 6 to be heated to a predetermined temperature.
  • the tantalum wire having the boride layer formed on the surface thereof as the catalyst wire 6 it is possible to reduce the thermal expansion of the catalyst wire 6 , improve the mechanical strength, prolong the service life, and improve the productivity. Further, since the catalyst wire is formed of a material mainly composed of tantalum, it is possible to suppress an alloying reaction with the source gas (silicidation) and realize stable film formation.
  • FIGS. 3A and 3B are SEM pictures each showing a side surface of a catalyst wire having a boride layer formed on a surface thereof.
  • FIG. 3A shows an example in which energization heating is intermittently performed (by on/off operation), and it is apparent that surface cracks are generated.
  • FIG. 3B shows an example in which energization heating is successively performed, and the generation of surface cracks is not found.
  • the substrates S and tantalum wires serving as the catalyst wires 6 are installed in the reaction chamber 2 .
  • the vacuum pump 4 is operated to evacuate the vacuum chamber 3 , and the pressure of the reaction chamber 2 is reduced to a predetermined degree of vacuum (for example, 1 Pa).
  • a source gas and a diborane gas are introduced to the reaction chamber 2 from the source gas supply unit 9 a and the diborane gas supply unit 9 b via the gas introduction pipes 7 , and the respective catalyst wires 6 are energized by the control unit 8 and heated to a predetermined temperature (for example, 1,700° C.) or more.
  • the diborane gas introduced to the reaction chamber 2 comes into contact with the catalyst wires 6 and is decomposed so that a boride (tantalum boride) layer is formed on the surface of each catalyst wire 6 . Accordingly, the surface of the catalyst wire 6 is cured, with the result that the thermal expansion is reduced, the mechanical strength is improved, and the service life is prolonged.
  • a boride tantalum boride
  • the source gas introduced to the reaction chamber 2 comes into contact with the catalyst wires 6 and is decomposed so that reaction products thereof (decomposition species) are deposited on the surface of the substrate S. Accordingly, a silicon film is formed on the surface of the substrate S.
  • silicon as decomposition species of the source gas has a lower vapor pressure than that of boron (B), and does not adhere to the catalyst wire 6 or adheres thereto and then evaporates immediately under a reduced-pressure atmosphere of 1 Pa and a high temperature state of 1,700° C. or more. Therefore, a silicon film is not deposited on the surface of the catalyst wire 6 and the boride layer formed on the surface of the catalyst wire 6 is not affected.
  • the energization heating of the catalyst wire 6 by the control unit 8 is successively performed. Accordingly, it is possible to suppress the generation of surface cracks of the catalyst wire 6 in the step of forming a boride layer of the catalyst wire 6 and the film formation step, and improve the mechanical strength and durability of the catalyst wire 6 to improve the productivity.
  • the same effect as that of the first embodiment described above can be obtained.
  • FIG. 4 shows a relationship between expansion of the catalyst wire and a time.
  • the catalyst wires used in the experiment were a Ta catalyst wire (Sample 1) formed of a metal tantalum wire (99.5% pure) that is formed into a U shape and has a diameter of 1 mm and a length of 3,000 mm, a B—Ta catalyst wire (Sample 2) obtained by boriding a surface of the tantalum wire described above, and a BN—Ta catalyst wire (Sample 3) obtained by coating the surface of the tantalum wire described above with boron nitride.
  • a Ta catalyst wire (Sample 1) formed of a metal tantalum wire (99.5% pure) that is formed into a U shape and has a diameter of 1 mm and a length of 3,000 mm
  • a B—Ta catalyst wire (Sample 2) obtained by boriding a surface of the tantalum wire described above
  • a BN—Ta catalyst wire (Sample 3) obtained by coating the surface of the tantalum wire described above with boron nitride.
  • the Sample 1 (Ta catalyst wire) was expanded abruptly from the start of film formation and leaded to rupture.
  • the expansion amount exceeded 20%.
  • the durability was largely improved as compared to the Sample 1.
  • deformation was hardly found from the start of film formation.
  • expansion was gradually caused from the start of film formation, which leaded to rupture eventually. This may be caused because cracks were generated on the surface due to a heat shock at the time of turning current ON/OFF.
  • the expansion at the time of rupture exceeded 10%, but the durability was improved five times or more as compared to the Sample 1.
  • the catalyst wire (Sample 2) having the boride layer formed on the surface of the tantalum wire has a largely improved durability compared to the solid tantalum wire (Sample 1) and the tantalum wire (Sample 3) having the boron nitride formed on the surface thereof. Further, it was confirmed that by performing the energization heating of the catalyst wire by the continuous energization, the generation of surface cracks is suppressed and the service life of the catalyst wire can be prolonged.
  • the mixed gas of silane and hydrogen is used as a source gas, but the source gas is not limited thereto and can be changed as appropriate in accordance with types of film-formation materials.
  • the example has been described in which two substrates S are opposed to each other in the reaction chamber 2 and the plurality of catalyst wires 6 are installed between the two substrates in the vertical direction, but the structure of the reaction chamber 2 is not limited to the above example.
  • a solar battery is manufactured by, first, forming a metal electrode formed of a Mo film or the like on a substrate of glass, aluminum, or the like by sputtering or thermal CVD, then forming a p-type layer (for example, CuInSe 2 film) and an n-type layer (for example, CdS film), and forming a transparent electrode formed of ZnO or the like thereon.
  • a p-type layer for example, CuInSe 2 film
  • an n-type layer for example, CdS film
  • FIG. 1 A schematic structural view of a catalytic chemical vapor deposition apparatus according to an embodiment of the present invention.
  • FIG. 2 A schematic perspective view of a reaction chamber of the apparatus shown in FIG. 1 .
  • FIG. 3 Pictures of a side view (SEM) each showing a surface condition of a catalyst wire installed in the reaction chamber, in which A shows a state where surface cracks are generated and B shows a state where surface cracks are not generated.
  • FIG. 4 A diagram showing durability of various samples of catalyst wires described in Examples of the present invention.

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JP2012227380A (ja) * 2011-04-20 2012-11-15 Ulvac Japan Ltd 通電加熱線、通電加熱線の製造方法および真空処理装置
CN108048815A (zh) * 2017-12-08 2018-05-18 中国科学技术大学 用于确定临近催化化学气相沉积中催化剂的热形变的装置和方法
CN113755787A (zh) * 2020-06-01 2021-12-07 株式会社爱发科 通电加热丝的制造方法以及制造装置

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CN103339286A (zh) * 2011-01-04 2013-10-02 易捷康技术有限公司 用于热丝化学气相沉积的丝
JP5919482B2 (ja) * 2011-03-03 2016-05-18 パナソニックＩｐマネジメント株式会社 触媒化学気相成膜装置、それを用いた成膜方法及び触媒体の表面処理方法
JP2020164932A (ja) * 2019-03-29 2020-10-08 株式会社アルバック 通電加熱線、通電加熱線の製造方法および真空処理装置

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CN113755787A (zh) * 2020-06-01 2021-12-07 株式会社爱发科 通电加热丝的制造方法以及制造装置

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RU2011128436A (ru) 2013-01-20
RU2486283C2 (ru) 2013-06-27
US10000850B2 (en) 2018-06-19
WO2010067424A1 (fr) 2010-06-17
EP2374915A4 (fr) 2012-07-18
KR20110084520A (ko) 2011-07-25
EP2374915A1 (fr) 2011-10-12
EP2374915B1 (fr) 2014-01-22

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