WO2013080503A1 - Procédé de fabrication de film mince, et matériau de silicium permettant la mise en œuvre de celui-ci - Google Patents

Procédé de fabrication de film mince, et matériau de silicium permettant la mise en œuvre de celui-ci Download PDF

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Publication number
WO2013080503A1
WO2013080503A1 PCT/JP2012/007510 JP2012007510W WO2013080503A1 WO 2013080503 A1 WO2013080503 A1 WO 2013080503A1 JP 2012007510 W JP2012007510 W JP 2012007510W WO 2013080503 A1 WO2013080503 A1 WO 2013080503A1
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Prior art keywords
silicon
silicon material
rod
thin film
fitting portion
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PCT/JP2012/007510
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English (en)
Japanese (ja)
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遊馬 神山
本田　和義
末次　大輔
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パナソニック株式会社
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/02—Silicon
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/24—Vacuum evaporation
    • C23C14/246—Replenishment of source 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/24—Vacuum evaporation
    • C23C14/28—Vacuum evaporation by wave energy or particle radiation
    • C23C14/30—Vacuum evaporation by wave energy or particle radiation by electron bombardment
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/56—Apparatus specially adapted for continuous coating; Arrangements for maintaining the vacuum, e.g. vacuum locks
    • C23C14/562—Apparatus specially adapted for continuous coating; Arrangements for maintaining the vacuum, e.g. vacuum locks for coating elongated substrates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a thin film manufacturing method and a silicon material that can be used in the method.
  • Thin film technology is widely deployed to improve the performance and miniaturization of devices. Device thinning not only brings direct benefits to users, but also plays an important role in environmental aspects such as protecting earth resources and reducing power consumption. Progress in thin film technology needs to meet the demands for high efficiency, stabilization, high productivity, and low cost in thin film manufacturing. For example, in order to increase the productivity of thin films, long-time film formation techniques are essential. In thin film manufacturing using a vacuum deposition method, material supply to an evaporation source is effective for long-time film formation.
  • Patent Document 1 discloses a technique in which a material is once dissolved above a crucible and then the dissolved material is supplied to the crucible.
  • Patent Document 2 describes a technique for improving the utilization efficiency of raw materials by providing irregularities at the ends of the raw material rods so that a certain raw material rod can be held by another raw material rod.
  • Patent Document 3 describes a rod-shaped silicon material having controlled crystal grains as a material for supplying silicon to an evaporation source.
  • JP-A-62-177174 JP 2002-155354 A Japanese Patent No. 4657385
  • Patent Document 3 The silicon material described in Patent Document 3 is effective in suppressing cracks caused by rapid heating and splash associated with the cracks. However, it may be difficult to obtain a sufficient effect under specific conditions such as the initial dissolution of the silicon material. Therefore, a technique that can more sufficiently suppress the occurrence of splash is desired.
  • An object of the present invention is to provide a technique for suppressing the occurrence of splash at the initial stage of dissolution of a silicon material.
  • this disclosure Depositing particles flying from the evaporation source on the substrate at a predetermined deposition position in a vacuum so that a thin film is formed on the substrate; Dissolving the rod-shaped material containing the raw material of the thin film above the evaporation source, and supplying the dissolved material to the evaporation source,
  • the rod-shaped material has (i) a rod-shaped first silicon material having a first fitting portion at the rear end in the axial direction, and (ii) a second fitting portion at the front end in the axial direction.
  • the second silicon material is made of polycrystalline silicon including a plurality of crystal grains having a long axis facing a specific direction, and the second fitting portion is in a state where the rod-shaped material is held horizontally.
  • the major axis of the plurality of crystal grains appears on the upper surface of
  • the rod-shaped material is transported horizontally to melt the first silicon material and the second silicon material in this order, the second silicon material is removed from the upper surface of the second fitting portion.
  • a thin film manufacturing method is provided in which dissolution of the second silicon material is started by heating.
  • Schematic of a thin film manufacturing apparatus Schematic top view of the evaporation source Schematic showing the outline of a silicon rod produced by the casting method Partial enlarged sectional view perpendicular to the axial direction of the silicon rod shown in FIG. 3A
  • Schematic showing the production method of silicon rod by the first casting method 3A and 3B is a bird's-eye view of a silicon material made from the silicon rod shown in FIG.
  • Three views of the silicon material shown in FIG. 4A A bird's-eye view of a silicon material made from a silicon rod made by unidirectional solidification
  • Three views of the silicon material shown in FIG. 5A Overhead view of another silicon material made from a silicon rod made by unidirectional solidification Three views of the silicon material shown in FIG.
  • FIG. 6A An overhead view of yet another silicon material made from a silicon rod made by unidirectional solidification Three views of the silicon material shown in FIG. 7A
  • Patent Document 3 The silicon material described in Patent Document 3 is effective in suppressing cracks caused by rapid heating and splash associated with the cracks. However, immediately after starting to irradiate the electron beam to dissolve the silicon material, the situation is slightly different from that at the time of stabilization. That is, although large cracks do not occur, fine chipping occurs, which can cause splash.
  • the first aspect of the present disclosure is: Depositing particles flying from the evaporation source on the substrate at a predetermined deposition position in a vacuum so that a thin film is formed on the substrate; Dissolving the rod-shaped material containing the raw material of the thin film above the evaporation source, and supplying the dissolved material to the evaporation source,
  • the rod-shaped material has (i) a rod-shaped first silicon material having a first fitting portion at the rear end in the axial direction, and (ii) a second fitting portion at the front end in the axial direction.
  • the second silicon material is made of polycrystalline silicon including a plurality of crystal grains having a long axis facing a specific direction, and the second fitting portion is in a state where the rod-shaped material is held horizontally.
  • the major axis of the plurality of crystal grains appears on the upper surface of
  • the rod-shaped material is transported horizontally to melt the first silicon material and the second silicon material in this order, the second silicon material is removed from the upper surface of the second fitting portion.
  • a thin film manufacturing method is provided in which dissolution of the second silicon material is started by heating.
  • the second silicon material is combined with the first silicon material by fitting the second fitting portion to the first fitting portion. Therefore, the second silicon material can be preheated while melting the first silicon material through the fitting portion. Furthermore, the second silicon material is produced so that the major axis of the crystal grain appears on the upper surface of the second fitting portion in a state where the rod-shaped material is held horizontally.
  • the second silicon material is started to melt by heating the second silicon material from the upper surface of the second fitting portion. By doing so, it is possible to reduce the number of crystal grain boundaries that are the starting points of cracking due to thermal shock in the initial stage of dissolution of the second silicon material. Therefore, chipping of minute crystal grains can be suppressed, and splash at the initial stage of dissolution of the second silicon material can be suppressed.
  • the second aspect of the present disclosure provides a thin film manufacturing method in which, in the supply step, the upper surface of the second fitting portion is irradiated with an electron beam or a laser in addition to the first aspect. According to the electron beam or laser, the dissolution rate can be adjusted relatively easily and the heating range can be easily controlled.
  • the first fitting portion has a concave shape or a convex shape
  • the second fitting portion has a convex shape or a concave shape.
  • the fourth aspect of the present disclosure provides a thin film manufacturing method in which, in addition to the first or second aspect, the first fitting portion has a concave shape, and the second fitting portion has a convex shape.
  • the second silicon material is preheated mainly by radiant heat from the first silicon material.
  • the second fitting portion is a convex portion having a surface parallel to the axial direction as the upper surface.
  • the silicon material has a surface perpendicular to the axial direction as a surface adjacent to the convex portion, and the long axis of the plurality of crystal grains appears on the surface perpendicular to the axial direction.
  • the second silicon material is made of a silicon rod made by a casting method or a unidirectional solidification method
  • the silicon A thin film manufacturing method is provided in which the second fitting portion of the second silicon material is formed by cutting a part of a rod.
  • the grains can be formed radially from the center of the silicon rod.
  • the major axis of the crystal grains can be parallel to the radial direction. Accordingly, when the first fitting portion and the second fitting portion are formed by cutting, the long axis of the crystal grains is likely to appear on the cut surface.
  • the silicon rod produced by the unidirectional solidification method the long axes of silicon crystal grains are arranged in one direction. That is, the direction of the major axis of the crystal grains can be constant regardless of the cutting position.
  • the substrate is a long substrate
  • the deposition step is configured such that the long substrate unwound from an unwinding roll is the predetermined substrate.
  • a thin film manufacturing method is provided in which the supply step is performed while the deposition step is performed, including transporting to a take-up roll via the film formation position. According to such a method, continuous film formation for a long time is possible.
  • silicon as a negative electrode active material capable of inserting and extracting lithium is deposited on the substrate as a negative electrode current collector by the thin film manufacturing method according to any one of the first to seventh aspects.
  • a method for producing a negative electrode for a lithium ion secondary battery is provided.
  • a high quality negative electrode for lithium ion secondary batteries can be manufactured.
  • the ninth aspect of the present disclosure is: A rod-shaped silicon material, A columnar body, A convex portion located at one end of the main body portion; A recess located at the other end of the main body, With
  • the silicon material is composed of polycrystalline silicon containing crystal grains having a major axis facing a specific direction,
  • the convex portion includes a surface parallel to the axial direction of the silicon material, A silicon material in which the major axis of the crystal grain appears on the surface is provided.
  • the ninth aspect it is possible to reduce the number of crystal grain boundaries that are the starting points of cracking due to thermal shock in the initial stage of dissolution of the silicon material. Therefore, chipping of minute crystal grains can be suppressed, and splash at the initial stage of dissolution of the silicon material can be suppressed.
  • the silicon material is made of a silicon rod made by a casting method or a unidirectional solidification method, and the silicon rod is cut by partially cutting the silicon rod.
  • a silicon material is provided in which a recess or protrusion is formed. According to the tenth aspect, the same effect as in the sixth aspect is obtained.
  • an eleventh aspect of the present disclosure provides a silicon material that can be used in combination with a plurality of the silicon materials by fitting the convex part into the concave part. According to the fitting of the concave portion and the convex portion, a heating effect by radiant heat can be sufficiently obtained.
  • particles flying from an evaporation source are placed at a predetermined film formation position in a vacuum so that a thin film is formed on the substrate.
  • a thin film manufacturing method including a step of depositing on the substrate, and a step of dissolving a rod-shaped material containing the raw material of the thin film above the evaporation source and supplying the dissolved material to the evaporation source.
  • a silicon material is provided as the rod-shaped material.
  • the thirteenth aspect of the present disclosure includes Disposing the cylindrical mold around the heater so that the mold is positioned between the heater disposed in the furnace and the inner wall of the furnace; Pouring silicon melt into the mold; Using the heater, the temperature in the furnace is maintained at a temperature at which the solidification of silicon gradually proceeds, and a temperature gradient is formed from the heater toward the inner wall to solidify the silicon in the mold.
  • a process of A method of manufacturing a silicon rod is provided.
  • a silicon rod having the same structural characteristics as a silicon rod obtained by a unidirectional solidification method can be obtained regardless of the casting method. That is, a silicon rod in which major axes of silicon crystal grains are arranged in one direction can be obtained.
  • FIG. 4A only abstractly show the direction of the major axis of the crystal grains contained in the silicon material, and the crystal grains of the size shown in these drawings are included in the silicon material. Note that this is not the case.
  • the thin film manufacturing apparatus 20 includes a vacuum container 22, a substrate transport unit 50, a shielding plate 29, an evaporation source 9, and a material supply unit 52.
  • the substrate transfer unit 50, the shielding plate 29, the evaporation source 9, and the material supply unit 52 are disposed inside the vacuum container 22.
  • a vacuum pump 34 is connected to the vacuum vessel 22.
  • An electron gun 15 and a source gas introduction tube 30 are provided on the side wall of the vacuum vessel 22.
  • the space inside the vacuum vessel 22 is divided into a first side space (lower space) in which the evaporation source 9 is disposed and a second side space (upper space) in which the substrate transport unit 50 is disposed by the shielding plate 29. It is divided.
  • An opening 31 is provided in the shielding plate 29, and evaporated particles from the evaporation source 9 advance from the first side space to the second side space through the opening 31.
  • the substrate transport unit 50 has a function of supplying the substrate 21 to a predetermined film formation position 33 facing the evaporation source 9 and a function of retracting the substrate 21 after film formation from the film formation position 33.
  • the film forming position 33 is a position on the transport path of the substrate 21 and means a position defined by the opening 31 of the shielding plate 29.
  • the substrate transport unit 50 is constituted by an unwinding roll 23, a transporting roller 24, a cooling can 25 and a winding roll 27.
  • a substrate 21 before film formation is prepared on the unwinding roll 23.
  • the transport rollers 24 are disposed on the upstream side and the downstream side in the transport direction of the substrate 21.
  • the upstream transport roller 24 guides the substrate 21 fed from the unwinding roll 23 to the cooling can 25.
  • the cooling can 25 guides the substrate 21 to the film forming position 33 while supporting the substrate 21, and guides the substrate 21 after the film formation to the transport roller 24 on the downstream side.
  • the cooling can 25 has a cylindrical shape and is cooled by a coolant such as cooling water.
  • the substrate 21 travels along the peripheral surface of the cooling can 25 and is cooled by the cooling can 25 from the side opposite to the side facing the evaporation source 9.
  • the downstream transport roller 24 guides the substrate 21 after film formation to the take-up roll 27.
  • the take-up roll 27 is driven by a motor (not shown) and takes up and stores the substrate 21 on which the thin film is formed.
  • the thin film manufacturing apparatus 20 is a so-called winding type thin film manufacturing apparatus that forms a thin film on the substrate 21 being conveyed from the unwinding roll 23 to the winding roll 27.
  • a driving motor may be disposed outside the vacuum container 22. In this case, the driving force of the motor can be transmitted to various rolls in the vacuum vessel 22 through the rotation introduction terminal.
  • the substrate transport unit 50 may be configured such that the substrate 21 travels linearly at the film formation position 33.
  • a thin film can be formed on the substrate 21 on the transport path from the first transport roller to the second transport roller.
  • the substrate 21 is a long substrate having flexibility.
  • the material of the substrate 21 is not particularly limited, and a polymer film and a metal foil can be used.
  • the polymer film are a polyethylene terephthalate film, a polyethylene naphthalate film, a polyamide film, and a polyimide film.
  • the metal foil are aluminum foil, copper foil, nickel foil, titanium foil, and stainless steel foil. A composite material of a polymer film and a metal foil can also be used for the substrate 21.
  • the dimensions of the substrate 21 are not particularly limited because they are determined according to the type and production quantity of the thin film to be manufactured.
  • the width of the substrate 21 is, for example, 50 to 1000 mm, and the thickness of the substrate 21 is, for example, 3 to 150 ⁇ m.
  • the substrate 21 is transported at a constant speed.
  • the conveyance speed varies depending on the type of thin film to be manufactured and the film formation conditions, but is, for example, 0.1 to 500 m / min.
  • the film formation rate is, for example, 1 to 50 ⁇ m / min.
  • An appropriate tensile force is applied to the substrate 21 being transferred in accordance with the material of the substrate 21, the dimensions of the substrate 21, the film forming conditions, and the like.
  • the substrate 21 may be intermittently transferred.
  • the evaporation source 9 is configured to heat the material 9b in the crucible 9a with the electron beam 18 from the electron gun 15. That is, the thin film manufacturing apparatus 20 of this embodiment is configured as a vacuum vapor deposition apparatus. The evaporation source 9 is disposed below the vacuum vessel 22 so that the evaporated material proceeds vertically upward. Instead of the electron beam, the material 9b in the crucible 9a may be heated by other methods such as resistance heating and induction heating.
  • the shape of the opening of the crucible 9a is, for example, circular, oval, rectangular, or donut shape. In continuous vacuum deposition, it is effective for the film thickness uniformity in the width direction to use a crucible 9a having a rectangular opening wider than the film forming width.
  • a metal, an oxide, a refractory, or the like can be used as a material for the crucible 9a.
  • metals are copper, molybdenum, tantalum, tungsten and alloys containing these.
  • oxides are alumina, silica, magnesia and calcia.
  • refractories are boron nitride and carbon.
  • the crucible 9a may be water-cooled.
  • the source gas introduction pipe 30 extends from the outside to the inside of the vacuum vessel 22. One end of the source gas introduction pipe 30 is directed to the space between the evaporation source 9 and the substrate 21. The other end of the source gas introduction pipe 30 is connected to a source gas supply source such as a gas cylinder or a gas generator outside the vacuum vessel 22 (not shown). If at least one selected from oxygen gas and nitrogen gas is supplied into the vacuum vessel 22 through the source gas introduction pipe 30, a thin film containing oxide, nitride or oxynitride of the material 9b in the crucible 9a can be formed. .
  • the inside of the vacuum vessel 22 is maintained at a pressure suitable for forming a thin film by the vacuum pump 34, for example, 1.0 ⁇ 10 ⁇ 1 to 1.0 ⁇ 10 ⁇ 3 Pa.
  • Various vacuum pumps such as a rotary pump, an oil diffusion pump, a cryopump, and a turbo molecular pump can be used as the vacuum pump 34.
  • the material supply unit 52 is used for dissolving the rod-shaped material 32 containing the raw material of the thin film to be formed above the evaporation source 9 and supplying the dissolved material to the evaporation source 9 in the form of droplets 14. .
  • a silicon material 32 is used as the rod-shaped material 32.
  • silicon is continuously supplied to the evaporation source 9 according to consumption of the material 9b (silicon melt) in the crucible 9a without purging the inside of the vacuum vessel 22 with a gas such as air. Can supply.
  • silicon can be supplied to the evaporation source 9 while silicon particles flying from the evaporation source 9 are deposited on the substrate 21. Thereby, continuous film formation for a long time becomes possible.
  • the material supply unit 52 includes the conveyor 10, the electron gun 15, and the material standby unit 11.
  • the conveyor 10 plays a role of holding the silicon material 32 horizontally and transporting the silicon material 32 above the crucible 9a.
  • the electron gun 15 plays a role of heating the silicon material 32 conveyed above the crucible 9a.
  • the electron gun 15 is also used for heating and evaporating the material 9b in the crucible 9a.
  • a spare silicon material 32 or an additional silicon material 32 is prepared in the material standby unit 11.
  • “horizontal” does not necessarily mean that the axial direction (longitudinal direction) of the silicon material 32 completely coincides with the horizontal direction.
  • the axial direction of the silicon material 32 may be inclined from the horizontal direction by, for example, 2 to 3 degrees.
  • the silicon material 32 is conveyed above the crucible 9a by the conveyor 10, heated by the electron beam 16, and melted.
  • the silicon melt generated by melting falls in the form of droplets 14 into the crucible 9a.
  • silicon as a raw material for the thin film is supplied to the crucible 9a.
  • An electron gun for heating the silicon material 32 may be provided separately from the electron gun for heating the material 9b in the crucible 9a.
  • a laser irradiation apparatus can be used instead of the electron gun or together with the electron gun.
  • the crucible 9 a has a rectangular opening that is wider than the opening width 35 of the opening 31 of the shielding plate 29.
  • the position of the tip of the silicon material 32 is determined so as not to overlap the opening 31 of the shielding plate 29 in plan view.
  • the electron beam 18 is irradiated to a scanning range 36 that is set wider than the opening width 35 of the shielding plate 29 in the longitudinal direction (width direction) of the crucible 9a. This improves the film thickness uniformity of the thin film in the width direction.
  • the electron beam 18 is irradiated to both ends of the scanning range 36 for a longer time than the other positions in the width direction, there is a further effect in improving the film thickness uniformity in the width direction.
  • the irradiation position of the electron beam 16 for dissolving the silicon material 32 is set outside the scanning range 36 of the electron beam 18.
  • the drop position of the silicon droplet 14 is set outside the scanning range 36. If the irradiation position of the electron beam 16 and the drop position of the droplet 14 are set outside the scanning range 36 of the electron beam 18, the temperature change of the material 9b (silicon melt) due to the supply of the droplet 14 and the material 9b. The influence of the vibration of the liquid level on film formation can be reduced.
  • the silicon material described in Patent Document 3 is effective in suppressing cracks caused by rapid heating and splash associated with the cracks.
  • fine chipping may occur, which may cause splash.
  • the reason for this is that (i) silicon is held near room temperature and rapid heating is likely to occur, and (ii) silicon is a semiconductor, so the electrical and thermal conductivity of silicon is low near room temperature, and electrons It is mentioned that the irradiated part of the line is easily heated locally.
  • the silicon material of Patent Document 3 has a structure in which fine crystal grains on the surface absorb thermal shock and prevent cracks from propagating to the inside. In the initial stage of heating, since there is no silicon melt around the heated portion, even if fine crystal grains on the surface are cracked by thermal shock, they are not absorbed by the melt and are likely to splash from the silicon material and cause splash.
  • the silicon material 32 used in this embodiment includes a rod-shaped first silicon material 32a and a rod-shaped second silicon material 32b.
  • the first silicon material 32a has a first fitting portion 41 (concave portion 41) at the rear end in the axial direction (longitudinal direction).
  • the 2nd silicon material 32b has the 2nd fitting part 43 (convex part 43) in the front end of an axial direction (longitudinal direction).
  • the second silicon material 32b is composed of polycrystalline silicon including a plurality of crystal grains 42 having a major axis facing a specific direction, and is a rod-shaped silicon material.
  • the long axes of the plurality of crystal grains 42 are formed on the upper surface 43 p of the second fitting portion 43 in a state where 32 is held horizontally.
  • the second fitting portion 43 has a second surface. The silicon material 32b is heated to start the dissolution of the second silicon material 32b.
  • the second silicon is melted while the first silicon material 32a is melted through the first fitting portion 41 of the first silicon material 32a and the second fitting portion 43 of the second silicon material 32b.
  • the material 32b can be preheated. Furthermore, the number of crystal grain boundaries that are the starting points of cracking due to thermal shock can be reduced in the initial stage of melting of the second silicon material 32b. Therefore, chipping of microcrystals can be suppressed, and splash at the initial stage of dissolution of the second silicon material 32b can be suppressed.
  • the upper surface 43p of the second fitting portion 43 is irradiated with an electron beam or a laser.
  • the upper surface 43p is a surface to be irradiated with an electron beam or a laser first. According to the electron beam or laser, the dissolution rate can be adjusted relatively easily and the heating range can be easily controlled. However, it is not impossible to melt the silicon material 32 by other heating methods such as induction heating.
  • the silicon material 32 may be formed by combining three or more silicon materials.
  • the structure, dimensions, composition, and the like of the first silicon material 32a may be different from those of the second silicon material 32b.
  • the first silicon material 32a has a mass of, for example, 0.5 kg or more, in other words, a sufficient heat capacity. According to such a first silicon material 32a, when the tip is rapidly heated, the tip of the first silicon material 32a is selectively dissolved, so that it is easy to maintain a certain dropping position. That is, the droplet 14 does not fall out of the crucible 9a, and a stable material supply to the crucible 9a is possible. Although there is no upper limit in particular in the mass of the 1st silicon material 32a, when the magnitude
  • a rod-shaped first silicon material 32a and a rod-shaped second silicon material 32b are used. If the surface area is made as small as possible, the water content on the surface can be reduced.
  • the first silicon material 32a and the second silicon material 32b are typically in the form of rods having a circular cross section.
  • the diameters of the first silicon material 32a and the second silicon material 32b are not particularly limited, but are, for example, in the range of 50 to 100 mm.
  • the structure of the first fitting portion 41 and the second fitting portion 43 is not particularly limited.
  • the first fitting portion 41 of the first silicon material 32a has, for example, a concave shape or a convex shape.
  • the second fitting portion 43 of the second silicon material 32b has a shape that fits the first fitting portion 41, that is, a convex shape or a concave shape. That is, the first fitting portion 41 may be a concave portion or a convex portion.
  • the second fitting portion 43 may be a convex portion or a concave portion. According to the fitting of the concave portion and the convex portion, a heating effect by radiant heat can be sufficiently obtained.
  • the first fitting portion 41 of the first silicon material 32a has a concave shape
  • the second fitting portion 43 of the second silicon material 32b has a convex shape.
  • the second silicon material 32b is preheated mainly by radiant heat from the first silicon material 32a.
  • the second silicon material 32b further includes a columnar main body 40.
  • the first fitting part 41 (concave part 41) or the second fitting part 43 (convex part 43) is located at one end of the main body part 40.
  • a concave portion 41 is provided at one end (rear end) of the main body portion 40
  • a convex portion 43 is provided at the other end (front end) of the main body portion 40.
  • the second silicon material 32b is made of, for example, a silicon rod 132 having a prismatic or cylindrical shape manufactured by a casting method.
  • a silicon rod 132 in which crystal grains are arranged substantially radially from the center in a cross section perpendicular to the axial direction can be used as the second silicon material 32b.
  • the silicon rod 132 is obtained by sequentially solidifying silicon from the outer peripheral portion by a casting method.
  • the silicon rod 132 can be manufactured by the following method. As shown in FIG. 3C, a mold 62 is placed in a furnace 60.
  • the mold 62 is a cylindrical mold having a bottom.
  • the temperature in the furnace 60 can be adjusted by a heater 61 disposed on the inner wall of the furnace 60 so as to surround the mold 62.
  • the temperature in the furnace 60 is raised to an appropriate temperature (for example, a temperature in the range of 600 to 1000 ° C.) using the heater 61 while the mold 62 is empty. Thereby, the mold 62 is preheated.
  • the silicon melt is poured into the mold 62 while maintaining the temperature in the furnace 60 at an appropriate temperature (for example, a temperature in the range of 600 to 1000 ° C.).
  • silicon starts to solidify in a short time (for example, about 1 minute), and fine crystal grains as shown in FIG. 3B are formed.
  • the temperature in the furnace 60 is maintained at the above temperature (a temperature in the range of 600 to 1000 ° C.) for several hours (for example, 4 to 24 hours).
  • the silicon gradually solidifies from the inner peripheral surface of the mold 62 toward the center.
  • a silicon rod 132 having the structure shown in FIG. 3B is obtained.
  • the heater 61 is turned off and the temperature in the furnace 60 is gradually cooled to near room temperature.
  • rod by a casting method is described in detail also in patent document 3, for example.
  • the first fitting portion 41 (concave portion 41) and the second fitting portion 43 (convex portion 43) of the second silicon material 32b are cut by cutting a part of the silicon rod 132. Can be formed.
  • the crystal grains can be formed radially from the center of the silicon rod 132.
  • the major axis of the crystal grains can be parallel to the radial direction. Therefore, when forming the 1st fitting part 41 and the 2nd fitting part 43 by cutting, it is easy to make the long axis of a crystal grain appear on a cut surface.
  • the method of forming the first fitting portion 41 and the second fitting portion 43 is not limited to cutting. For example, when the mold has an uneven shape in advance, the unevenness of the mold is transferred to the silicon rod by pouring a silicon melt into the mold.
  • the end of the silicon rod 132 is processed so that two cut surfaces 43p parallel to the axial direction and two cut surfaces 40q perpendicular to the axial direction are formed. .
  • the convex part 43 as the 2nd fitting part 43 is formed.
  • the two cut surfaces 43p (upper surface and lower surface) of the convex portion 43 are parallel to each other, and are approximately parallel to the major axis of the silicon crystal grain 42, respectively. That is, the major axis of the silicon crystal grain 42 appears on the cut surface 43p.
  • the two cut surfaces 40q may be parallel to the major axis of the crystal grain 42.
  • the crystal grains 42 are formed substantially radially.
  • the distance L from the center of the silicon rod 132 to the cut surface 43p is preferably within 20% of the radius of the silicon rod 132.
  • the distance L is preferably 5% or more of the radius of the silicon rod 132.
  • the convex portion 43 has a length equal to or longer than the irradiation width of the electron beam 16. According to such a configuration, it is possible to prevent the main body portion 40 from being irradiated with the electron beam 16 before the entire convex portion 43 is melted, and the main body portion 40 from starting to melt. Thereby, the possibility that the undissolved convex part 43 falls to the evaporation source 9 can be reduced.
  • the silicon material 32 obtained by inserting the convex portion 43 of the second silicon material 32b into the concave portion 41 of the first silicon material 32a is used.
  • Silicon can be supplied to the evaporation source 9.
  • silicon exhibits a behavior different from that of a metal material. That is, in addition to thermal expansion, a phase change of the crystal system occurs at 1100 ° C. to 1200 ° C. With the phase change, silicon contracts by about 10% in terms of volume expansion. Silicon is a brittle material.
  • the convex portion 43 of the second silicon material 32b is inserted into the concave portion 41 of the first silicon material 32a, the convex portion 43 and the concave portion 41 are twisted due to complicated thermal expansion and contraction behavior during heating, and brittleness is caused. Destruction can occur. Therefore, it is desirable that the size of the concave portion 41 is larger than the size of the convex portion 43.
  • the concave portion 41 is set so that the volume ratio (V1 / V2) satisfies the relationship of 0.8 ⁇ (V1 / V2) ⁇ 0.95.
  • the shape and dimension of the convex part 43 can be set. This is desirable because the convex portion 43 is hardly pressed by the concave portion 41 when contraction due to phase change occurs.
  • the second silicon material 32b may be made of a silicon rod having a prismatic or cylindrical shape made by a unidirectional solidification method.
  • the first fitting part 41 (concave part 41) and the second fitting part 43 (convex part 43) of the second silicon material 32b can be formed.
  • the first silicon material 32a In the silicon rod produced by the unidirectional solidification method, the crystal grains are relatively large. For this reason, the silicon rod produced by the unidirectional solidification method may break due to thermal shock during melting. Accordingly, when using a silicon rod produced by the unidirectional solidification method as the first silicon material 32a and the second silicon material 32b, a silicon rod having a sufficient cross-sectional area to ensure high fracture strength. It is desirable to use
  • the convex portion 43 includes a surface 43p (upper surface) parallel to the axial direction of the second silicon material 32b.
  • the major axis of the crystal grain 42 appears on the surface 43p.
  • the silicon rod produced by the unidirectional solidification method has long axes of silicon crystal grains arranged in one direction. That is, the direction of the major axis of the crystal grains can be constant regardless of the cutting position. Therefore, as long as the strength of the concave portion 41 and the convex portion 43 can be ensured, the cutting position is not particularly restricted.
  • the convex portion 43 has a length equal to or longer than the irradiation width of the electron beam 16 in a direction parallel to the axial direction. According to such a configuration, it is possible to prevent the main body portion 40 from being irradiated with the electron beam 16 before the entire convex portion 43 is melted, and the main body portion 40 from starting to melt. Thereby, the possibility that the undissolved convex part 43 falls to the evaporation source 9 can be reduced.
  • the long axis of the crystal grain 42 may be perpendicular to the axial direction (longitudinal direction) of the second silicon material 32b (and the first silicon material 32a).
  • the major axis of the crystal grain 42 may be parallel to the axial direction (longitudinal direction) of the second silicon material 32b (and the first silicon material 32a). According to the unidirectional solidification method, the control of the direction of the major axis of the crystal grains 42 is relatively easy.
  • the second silicon material 32 b includes a plurality of convex portions 43 provided at one end of the main body portion 40. That is, the shape, the number, and the like of the concave portion 41 (first fitting portion) and the convex portion 43 (second fitting portion) are not particularly limited.
  • the concave portion 41 and the convex portion 43 may each have a plurality of steps.
  • the second silicon material 32b may have a stepped portion at one end or both ends thereof.
  • the fitting structure of the first silicon material 32a and the second silicon material 32b may be formed by overlapping the concave portion 41 on the convex portion 43.
  • the first silicon material 32a is dissolved so that the rear end portion (first fitting portion) of the first silicon material 32a is covered from the top end portion (second fitting portion) of the second silicon material 32b from above.
  • the postures of the material 32a and the second silicon material 32b are determined. In this way, the front end portion of the second silicon material 32b is likely to be preheated by receiving radiant heat from the rear end portion of the first silicon material 32a before melting.
  • the long axes of the silicon crystal grains can be arranged in one direction as in the one-way solidification method. That is, according to the second casting method, it is possible to simultaneously receive both the profit obtained by the first casting method described with reference to FIG. 3C and the profit obtained by the unidirectional solidification method.
  • FIG. 13 is a schematic view showing a method for producing a silicon material by the second casting method.
  • a furnace 70 provided with a cooler 71 on the inner wall is prepared.
  • the cooler 71 serves to form a temperature gradient described later in the furnace 70.
  • the heater 61 is disposed in the furnace 70, and the mold 62 is disposed around the heater 61.
  • the mold 62 is a cylindrical mold having a bottom.
  • the heater 61 is disposed in the center of the furnace 70, and a plurality of molds 62 are disposed around the heater 61 so as to surround the heater 61. That is, the mold 62 is arranged around the heater 61 so that the mold 62 is positioned between the heater 61 arranged in the furnace 70 and the inner wall of the furnace 70.
  • the temperature in the furnace 70 can be adjusted by the heater 61.
  • the mold 62 is preheated by raising the temperature in the furnace 70 to an appropriate temperature (for example, a temperature in the range of 600 to 1000 ° C.) using the heater 61 while the mold 62 is empty.
  • the inner wall of the furnace 70 is cooled using the cooler 71.
  • a temperature gradient is formed in the furnace 70 from the heater 61 toward the inner wall of the furnace 70.
  • the silicon melt is poured into the mold 62 while maintaining the temperature in the furnace 60 at an appropriate temperature (for example, a temperature in the range of 600 to 1000 ° C.). Near the inner peripheral surface of the mold 62, silicon starts to solidify in a short time (for example, about 1 minute), and fine crystal grains are formed. This is the same as the first casting method described with reference to FIG. 3C.
  • the heater 61 After pouring the silicon melt into the mold 62, the heater 61 is used for several hours (for example, 4 to 24 hours) to set the temperature in the furnace 70 to a predetermined temperature (600 to Temperature within a range of 1000 ° C.). Further, cooling of the inner wall of the furnace 70 by the cooler 71 is continued so that a state in which a temperature gradient is formed from the heater 61 toward the wall portion of the furnace 70 is maintained. In this way, silicon is solidified in the mold 62. Specifically, as indicated by arrows in FIG. 13, the silicon in the mold 62 gradually solidifies along a temperature gradient. After the silicon is solidified in the mold 62, the heater 61 is turned off and the temperature in the furnace 70 is gradually cooled to near room temperature.
  • a predetermined temperature 600 to Temperature within a range of 1000 ° C.
  • the silicon rod 80 having the structure shown in FIG. 14A is obtained. That is, in the silicon rod 80 shown in FIG. 14A, the major axes of the silicon crystal grains are arranged substantially in one direction.
  • a virtual boundary line at a position advanced several millimeters (for example, 3 to 5 mm) from the outer peripheral surface of the silicon rod 80 toward the center is defined as the first boundary line, the outer peripheral surface of the silicon rod 80 and the first boundary line
  • the second silicon material 32b (and the first silicon material 32a) shown in FIG. 14B can be produced.
  • the second silicon material 32 b (and the first silicon material 32 a) has the convex portion 43 as the second fitting portion 43.
  • the convex portion 43 has two surfaces 43p (cut surfaces) parallel to the axial direction as an upper surface and a lower surface.
  • the second silicon material 32b (and the first silicon material 32a) further includes two surfaces 40q (cut surfaces) perpendicular to the axial direction as surfaces adjacent to the second fitting portion 43 (convex portion 43). Long axes of a plurality of crystal grains 42 also appear on the surface 40q.
  • the occurrence of splash can be suppressed even when the surface 40q is irradiated with an electron beam or a laser in a state where the preheating of the second silicon material 32b is insufficient.
  • the cutting process for forming the second fitting portion 43 is not essential.
  • silicon is solidified very slowly at a temperature close to the melting point of silicon in order to prevent the silicon ingot from cracking due to the volume expansion of silicon.
  • the silicon melt is poured into the crucible, and the temperature around the crucible is lowered from 1410 ° C. to 1380 ° C. at a rate of 1 ° C./h over 30 hours.
  • a cooler for forming a temperature gradient is arranged at a position facing the bottom of the crucible so that the silicon gradually solidifies along the vertical direction.
  • the productivity of the unidirectional solidification method is not very good, and the price of the silicon rod obtained by the unidirectional solidification method is also high.
  • the casting method described with reference to FIG. 13 requires much shorter time and much less power consumption than the unidirectional solidification method. Nevertheless, according to the casting method described with reference to FIG. 13, it is possible to obtain a silicon rod 80 (FIG. 14A) having the same structural characteristics as a silicon rod obtained by the unidirectional solidification method. Further, since the cylindrical silicon rod 80 can be obtained without performing the cutting process, there is a possibility that waste of material can be omitted.
  • the second silicon material 32b (and the first silicon material 32a) made of the silicon material 80 not only has a cylindrical shape, but also surrounds the entire surface region filled with fine crystal grains. (FIG. 14B). Therefore, no matter how the fitting portions 41 and 43 are formed at the end portion of the silicon rod 80, the main body portion 40 of the second silicon material 32b extends over the entire surface layer region filled with fine crystal grains. Have. When the second silicon material 32b is stably melted, the fine crystal grains absorb the thermal shock, prevent the crack from propagating to the inside, and thereby suppress the occurrence of splash.
  • the area for heat transfer by radiant heat is expanded, and the major axis of the crystal grain appears on the first surface to be heated.
  • the fitting structure of the first fitting portion and the second fitting portion is not particularly limited.
  • heating means such as an infrared lamp
  • the first silicon material 32a and the second silicon material 32b are joined by a casting method in which a small amount of silicon melt is placed on the portion to be joined, and thereby, the first silicon material 32a to the second silicon material 32b are joined. Heat transfer may be promoted.
  • Example 1 Using the thin film manufacturing apparatus described with reference to FIG. 1, a silicon thin film was formed on a substrate while supplying materials from a silicon material obtained by combining two silicon materials to a crucible.
  • the conveyance speed of the substrate was 2 m / min.
  • a copper foil having a width of 30 cm and a thickness of 35 ⁇ m was used as the substrate.
  • the pressure inside the vacuum vessel was 3 ⁇ 10 ⁇ 2 Pa.
  • the silicon material was irradiated with an electron beam to drop the silicon melt on the crucible, the silicon melt in the crucible was irradiated with the electron beam to evaporate the silicon, thereby depositing silicon on the substrate.
  • the conveyance speed of the silicon material was adjusted so that the silicon melt was supplied to the crucible at a rate of 1 g / min.
  • the intensity of the electron beam was 1 kW / cm 2 .
  • the conveyance speed of the substrate was 2 m / min.
  • the two silicon materials are the same ones produced by the casting method described with reference to FIG. 3C, and each has the shape of a cylinder having a diameter of 55 mm and a length of 200 mm.
  • a convex portion was formed at the front end of each silicon material, and a concave portion was formed at the rear end.
  • the major axis of the crystal grain appeared on the upper surface of the convex portion.
  • the convex portion of the second silicon material was inserted into the concave portion of the first silicon material to form a rod-shaped silicon material. Dissolution of the rod-shaped silicon material started from the convex portion of the first silicon material.
  • the posture of the rod-shaped silicon material was adjusted so that the electron beam was irradiated on the upper surface of the convex portion.
  • the number of splashes having a particle size of 100 ⁇ m or more adhered to the substrate during the period from the start of irradiation of the electron beam to the first silicon material to 30 seconds was counted by photography and image processing. Further, the number of splashes having a particle diameter of 100 ⁇ m or more adhered to the substrate during the period from the start of irradiation of the electron beam to the second silicon material to 30 seconds later was also counted by the same method. The start point of irradiation of the second silicon material with the electron beam was visually confirmed from the view port of the vacuum vessel.
  • Example 2 Two silicon materials having the structure shown in FIGS. 5A and 5B were prepared, and these were combined to obtain a rod-like silicon material. A thin film was formed under the same conditions as in Example 1 except that this rod-shaped silicon material was used, and the number of splashes was counted.
  • the two silicon materials were the same ones produced by the unidirectional solidification method, and each had the shape of a regular quadrangular prism having a side of 60 mm and a length of 200 mm. Long axes of crystal grains appeared on the front and top surfaces of the protrusions.
  • Example 3 Two silicon materials having the structure shown in FIGS. 6A and 6B were prepared, and these were combined to obtain a rod-like silicon material. A thin film was formed under the same conditions as in Example 1 except that this rod-shaped silicon material was used, and the number of splashes was counted.
  • the two silicon materials were the same ones produced by the unidirectional solidification method, and each had the shape of a regular quadrangular prism having a side of 60 mm and a length of 200 mm.
  • the major axis of crystal grains appeared on the upper surface of the convex portion.
  • the minor axis of crystal grains appeared in front of the silicon material.
  • Example 1 Two silicon materials CE1 having the structure shown in FIGS. 10A and 10B were prepared. These were the same as the silicon material of Example 1 except that they did not have recesses and protrusions. A thin film was formed under the same conditions as in Example 1 except that the first silicon material and the second silicon material were brought into contact with each other, and the number of splashes was counted.
  • Example 2 Two silicon materials CE2 having the structure shown in FIGS. 11A and 11B were prepared. These were the same as the silicon material of Example 2 except that they did not have recesses and protrusions. A thin film was formed under the same conditions as in Example 1 except that the first silicon material and the second silicon material were brought into contact with each other, and the number of splashes was counted.
  • Table 1 shows the splash count results.
  • “first” represents the number of splashes generated in the initial stage of dissolution of the first silicon material.
  • “Second” represents the number of splashes generated in the initial stage of dissolution of the second silicon material.
  • Example 1 the number of splashes derived from the first silicon material in Example 1 was slightly smaller than the number of splashes derived from the first silicon material in Comparative Example 1. The reason for this may be that fine crystal grains in the outer peripheral portion are removed from the silicon material of Example 1 in order to form the concave and convex portions. Also, in Example 1, the number of splash deposits derived from the second silicon material could be reduced to 1/7 of the number of splash deposits derived from the first silicon material. On the other hand, in Comparative Example 1, the second silicon material was not sufficiently preheated, so that there was no significant difference in the number of deposited splashes between the first silicon material and the second silicon material.
  • the preheating of the second silicon material and the exposure of the long axis of the crystal grains on the upper surface of the fitting portion produced a synergistic effect, and the number of splash deposits could be greatly reduced.
  • the present invention can be applied to the production of a long electrode plate for an electricity storage device.
  • a metal foil such as a copper foil or a copper alloy foil is used as the substrate 21.
  • the material 9b (silicon) in the crucible 9a is evaporated by the electron beam 18 to form a silicon thin film on the substrate 21 as a negative electrode current collector.
  • a silicon thin film containing silicon and silicon oxide can be formed on the substrate 21 by introducing a small amount of oxygen gas into the vacuum vessel 22. Since silicon can occlude and release lithium, the substrate 21 on which the silicon thin film is formed can be used as a negative electrode of a lithium ion secondary battery.
  • capacitors, sensors, solar cells, optical films, moisture-proof films, conductive films, etc. are mainly composed of at least one of silicon and silicon oxide.
  • the present invention can be applied to the manufacture of thin films included as In particular, the present invention is particularly effective when forming an electrode plate for an electricity storage device that requires long-time film formation and formation of a relatively thick film.
  • the silicon material of the present invention is effective when melted and supplied to a crucible, it is necessary to continuously generate a silicon melt such as a continuous CZ method (Czochralski method) or a continuous casting method. It can also be used for processes.

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Abstract

Le procédé de l'invention contient : une étape au cours de laquelle un matériau est déposé sur un substrat (21); et une étape au cours de laquelle une source d'évaporation (9) est alimentée en matériau. Le matériau (32) sous forme de barre est dissous au-dessus de la source d'évaporation (9). Le matériau (32) sous forme de barre contient un premier matériau de silicium (32a), et un second matériau de silicium (32b). Une seconde partie ajustement (43) du second matériau de silicium (32b), s'ajuste sur une première partie ajustement (41) du premier matériau de silicium (32a). Le second matériau de silicium (32b) est configuré par un silicium polycristallin qui contient des particules cristallines (42) possédant un axe longitudinal orienté dans une direction spécifique. L'axe longitudinal des particules cristallines (42) apparaît sur une face supérieure (43p) de la seconde partie ajustement (43) dans un état dans lequel le matériau (32) sous forme de barre est maintenu horizontalement. Le premier matériau de silicium (32a) et le second matériau de silicium (32b) sont dissous dans cet ordre, et le second matériau de silicium (32b) est chauffé à partir de la face supérieure (43p) de la seconde partie ajustement (43).
PCT/JP2012/007510 2011-11-28 2012-11-21 Procédé de fabrication de film mince, et matériau de silicium permettant la mise en œuvre de celui-ci WO2013080503A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0578827A (ja) * 1991-09-20 1993-03-30 Mitsubishi Heavy Ind Ltd 原料供給装置
JPH05339729A (ja) * 1992-06-09 1993-12-21 Kobe Steel Ltd 真空蒸着めっき方法
JP2002212706A (ja) * 2001-01-10 2002-07-31 Sony Corp 真空蒸着方法及び真空蒸着装置
WO2011001689A1 (fr) * 2009-07-02 2011-01-06 パナソニック株式会社 Procédé de fabrication de film mince et matériau en silicium qui peut être utilisé dans le procédé

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0578827A (ja) * 1991-09-20 1993-03-30 Mitsubishi Heavy Ind Ltd 原料供給装置
JPH05339729A (ja) * 1992-06-09 1993-12-21 Kobe Steel Ltd 真空蒸着めっき方法
JP2002212706A (ja) * 2001-01-10 2002-07-31 Sony Corp 真空蒸着方法及び真空蒸着装置
WO2011001689A1 (fr) * 2009-07-02 2011-01-06 パナソニック株式会社 Procédé de fabrication de film mince et matériau en silicium qui peut être utilisé dans le procédé

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