WO2019146512A1 - Method for manufacturing thin film battery element - Google Patents

Method for manufacturing thin film battery element Download PDF

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Publication number
WO2019146512A1
WO2019146512A1 PCT/JP2019/001399 JP2019001399W WO2019146512A1 WO 2019146512 A1 WO2019146512 A1 WO 2019146512A1 JP 2019001399 W JP2019001399 W JP 2019001399W WO 2019146512 A1 WO2019146512 A1 WO 2019146512A1
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layer
laser
active material
material layer
absorption layer
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PCT/JP2019/001399
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French (fr)
Japanese (ja)
Inventor
崇 藤林
雄介 久保田
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東京エレクトロン株式会社
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Publication of WO2019146512A1 publication Critical patent/WO2019146512A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K26/00—Working by laser beam, e.g. welding, cutting or boring
    • B23K26/18—Working by laser beam, e.g. welding, cutting or boring using absorbing layers on the workpiece, e.g. for marking or protecting purposes
    • 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
    • H01M4/04—Processes of manufacture in general
    • 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
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • Various aspects and embodiments of the present disclosure relate to methods of manufacturing a thin film battery element.
  • the thin film type all solid battery is formed by laminating elements such as electrodes and electrolyte layers constituting the all solid battery using a shadow mask for each element. For example, physical vapor deposition (PVD) is used to form the element.
  • PVD physical vapor deposition
  • PVD using a shadow mask is difficult to mass-produce because it takes time and effort to manage, align and clean the shadow mask.
  • patterning elements such as an electrode and an electrolyte layer, by laser ablation (for example, refer following patent document 1).
  • lithium transition metal complex oxide is often used as a material used as an active material. Therefore, when processing is performed to increase the surface area of the active material layer using reactive ion etching used in the manufacture of semiconductors, transition metal reactants with low vapor pressure are formed, and microprocessing is difficult. .
  • Lithium ion is an unstable material and easily reacts with moisture. Therefore, when wet etching using pure water, development, peeling, and cleaning processes are performed, lithium in the active material is eluted and the performance as the electrode layer is degraded. In addition, in the case of processing an active material layer having a thickness of several ⁇ m or more, the etching rate is very small in the ion milling method, and the productivity is low. Furthermore, in the ion milling method, the active material is amorphized by ion bombardment, causing a decrease in power and energy density.
  • the processing width of the second harmonic laser beam is about several tens of ⁇ m, so that fine processing is difficult.
  • the laser beam of the third harmonic is used for laser ablation, although the processing width can be miniaturized to about several ⁇ m, the spot diameter of the laser beam becomes smaller, so the range which can be removed at one time by the laser beam is small. And productivity is significantly reduced.
  • One aspect of the present disclosure is a method of manufacturing a thin film battery element, and includes a pattern forming step, a laminate forming step, and an opening forming step.
  • a pattern formation step a laser absorption layer of a predetermined pattern is formed on the collector electrode layer.
  • the laminate formation step the active material layer is laminated on the collecting electrode layer and the laser absorption layer to form a laminate.
  • the opening forming step the laminated body is irradiated with laser light to evaporate the laser absorption layer, thereby forming an opening corresponding to a predetermined pattern in the active material layer.
  • productivity of the thin film battery element can be improved.
  • FIG. 1 is a flowchart showing an example of the manufacturing procedure of the thin film battery element in the first embodiment.
  • FIG. 2 is a cross-sectional view showing an example of the laminate.
  • FIG. 3 is a cross-sectional view showing an example of the laminate.
  • FIG. 4 is a cross-sectional view showing an example of the laminate.
  • FIG. 5 is a diagram showing an example of a laser irradiation apparatus.
  • FIG. 6 is a cross-sectional view showing an example of the laminate.
  • FIG. 7 is a cross-sectional view showing an example of the laminate.
  • FIG. 8 is a cross-sectional view showing an example of a laminate.
  • FIG. 9 is a cross-sectional view showing an example of a laminate.
  • FIG. 1 is a flowchart showing an example of the manufacturing procedure of the thin film battery element in the first embodiment.
  • FIG. 2 is a cross-sectional view showing an example of the laminate.
  • FIG. 3 is a cross-sectional view
  • FIG. 10 is a cross-sectional view showing an example of a laminate.
  • FIG. 11 is a flowchart showing an example of a manufacturing procedure of the thin film battery element in the second embodiment.
  • FIG. 12 is a cross-sectional view showing an example of the laminate.
  • FIG. 13 is a cross-sectional view showing an example of a laminate.
  • FIG. 14 is a cross-sectional view showing an example of a laminate.
  • FIG. 15 is a cross-sectional view showing an example of a laminate.
  • FIG. 16 is a cross-sectional view showing an example of a laminate.
  • FIG. 17 is a cross-sectional view showing an example of a laminate.
  • FIG. 18 is a view showing another example of the laser light irradiation method.
  • FIG. 19 is a view showing another example of the laser light irradiation method.
  • FIG. 20 is a diagram showing another example of the laser light irradiation method.
  • FIG. 1 is a flowchart showing an example of the manufacturing procedure of the thin film battery element in the first embodiment.
  • 2 to 4 and 6 to 10 are cross-sectional views showing an example of the laminate 10.
  • the lower collector electrode layer 12 is stacked on the substrate 11 (S100).
  • the substrate 11 is made of, for example, a material having silicon, glass, or stainless steel as a main component
  • the lower collector electrode layer 12 is made of, for example, a material having titanium, platinum, gold, copper, aluminum, or nickel as a main component.
  • the substrate 11 is made of, for example, a material containing silicon as a main component
  • the lower collector electrode layer 12 is made of, for example, an alloy containing titanium and platinum.
  • the lower collector electrode layer 12 is laminated on the substrate 11 by vapor deposition, sputtering or the like.
  • the laser absorption layer 13 is stacked on the lower collector electrode layer 12 (S101).
  • the laser absorption layer 13 is made of, for example, a material mainly composed of amorphous silicon or amorphous germanium.
  • the laser absorption layer 13 is made of, for example, a material mainly composed of amorphous silicon.
  • the laser absorption layer 13 is stacked on the lower collector electrode layer 12 by chemical vapor deposition (CVD), sputtering or the like. As a result, for example, as shown in FIG. 2, a stacked body 10 in which the lower collector electrode layer 12 and the laser absorption layer 13 are stacked on the substrate 11 is formed.
  • the laser absorption layer 13 is patterned into a predetermined pattern, for example, as shown in FIG. 3 (S102).
  • the patterning of the laser absorption layer 13 is performed by, for example, photolithography, imprint lithography, wet etching, dry etching, or lift-off.
  • Step S102 is an example of a pattern formation process.
  • the laser absorption layer 13 is patterned so that the linear laser absorption layer 13 having a predetermined width (for example, about 1 ⁇ m) is disposed on the lower collector electrode layer 12 at a predetermined interval (for example, about 1 ⁇ m).
  • the patterning of the laser absorption layer 13 is not limited to a linear shape, and may be a zigzag shape, a meander shape, a lattice shape, a dot shape, or the like.
  • the active material layer 14 is stacked on the lower collector electrode layer 12 and the laser absorption layer 13 so as to cover the patterned laser absorption layer 13 (S103). Thereby, for example, a laminate 10 as shown in FIG. 4 is formed.
  • the active material layer 14 functions as a cathode electrode
  • the active material layer 14 is made of, for example, a material containing lithium cobaltate (LCO) or lithium manganate (LMO) as a main component.
  • the active material layer 14 functions as an anode electrode
  • the active material layer 14 is made of, for example, a material containing lithium titanate (LTO) or silicon as a main component.
  • the active material layer 14 is made of, for example, a material containing LCO as a main component, and functions as a cathode electrode.
  • the active material layer 14 is stacked on the lower collector electrode layer 12 and the laser absorption layer 13 by CVD or sputtering. Note that, after the stacked body 10 is formed in step S103, an annealing step may be performed for the purpose of improving the film quality of the stacked body 10. Since the active material layer 14 immediately after film formation is amorphous and unstable, it is desirable to improve film quality by annealing and crystallizing within a predetermined time after film formation of the active material layer 14.
  • the laminate 10 be annealed, for example, within one hour after the active material layer 14 is laminated.
  • the annealing temperature is preferably a temperature within a range of 400 ° C. to 700 ° C., for example.
  • Step S103 is an example of a layered product formation process.
  • FIG. 5 is a view showing an example of the laser irradiation apparatus 100.
  • the laser irradiation apparatus 100 used in the present embodiment includes, for example, a laser oscillator 101, a light guiding unit 102, an emission head 103, a stage 104, and a moving table 105, as shown in FIG.
  • the laser oscillator 101 generates a laser beam.
  • the laser absorption layer 13 and the active material layer 14 are irradiated with laser light to cause laser ablation selectively to the laser absorption layer 13.
  • the wavelength of the laser beam irradiated to the laminate 10 lambda (nm) is E the optical band gap of the laser absorbing layer 13 g, LA (eV), the optical band gap of the active material layer 14 E g, In the case of CE (eV), it is necessary to satisfy the following relational expression (1).
  • the laser oscillator 101 generates laser light of wavelength ⁇ (nm) which satisfies the following relational expression (1).
  • “1240” in the above equation (1) is the value of the product of the Planck constant h (eV ⁇ s) and the speed of light c (m / s) when the unit of the light wavelength ⁇ is expressed in nm. It is.
  • the laser absorption layer 13 is formed of a material containing amorphous silicon as a main component
  • the optical band gaps E g and LA of the laser absorption layer 13 are approximately 1.7 (eV).
  • the active material layer 14 is made of a material having LCO as a main component
  • the optical band gaps E g and CE of the active material layer 14 are about 2.4 (eV). Therefore, in the present embodiment, as the laser light of wavelength ⁇ (nm) satisfying 516 (nm) ⁇ ⁇ 729 (nm), for example, the second harmonic ( ⁇ ) of YAG (Yttrium Aluminum Garnet) laser is used. A laser beam of 532 (nm) is generated.
  • the optical band gaps E g and LA of the laser absorption layer 13 are about 1.0 (eV).
  • the light guiding unit 102 propagates the laser beam generated by the laser oscillator 101 to the emission head 103.
  • the emission head 103 condenses the laser light propagated through the light guide portion 102 and irradiates the laminated body 10 with the laser light.
  • the emission head 103 condenses laser light having a Gaussian distribution in intensity and irradiates the laminated body 10 with spot light of a predetermined size.
  • the stack 10 is placed on the stage 104.
  • the moving table 105 moves the stack 10 on the stage 104 in the X-axis direction and the Y-axis direction by moving the stage 104 in the X-axis direction and the Y-axis direction.
  • the laser beam irradiated onto the stack 10 from the emission head 103 is scanned on the stack 10.
  • the laser beam emitted onto the laminate 10 may be scanned on the laminate 10 by moving the radiation head 103 relative to the laminate 10.
  • the wavelength ⁇ (nm) of the laser beam irradiated onto the stack 10 from the emission head 103 satisfies ⁇ ⁇ 1240 / Eg, LA (nm) as described above. Therefore, the energy of the laser beam irradiated from the emission head 103 onto the stack 10 is E g, LA ⁇ 1240 / ⁇ (eV), and is absorbed by the laser absorption layer 13.
  • E g, LA ⁇ 1240 / ⁇ (eV) the energy of the laser beam irradiated from the emission head 103 onto the stack 10 is E g, LA ⁇ 1240 / ⁇ (eV), and is absorbed by the laser absorption layer 13.
  • laser ablation occurs in which the portion of the laser absorption layer 13 irradiated with the laser light is transpirationally explosively dissipated.
  • the active material layer 14 stacked on the laser absorption layer 13 is blown upward by the impact of explosive transpiration of the laser absorption layer 13.
  • a hole according to the pattern of the laser absorption layer 13 is formed in the active material layer 14 by scanning the laser light on the laminate 10. Ru. That is, when the laser beam is scanned on the laminate 10, an opening corresponding to the pattern of the laser absorption layer 13 is formed in the active material layer 14.
  • the irradiation range of the laser beam from the emission head 103 is scanned on the laminate 10 in the direction of the arrow in FIG. Material layer 14 is removed. Thereby, a plurality of grooves 140 are formed in the active material layer 14.
  • the emission head 103 condenses the laser light, but the focal plane 110 of the laser light is formed at a position away from the laser absorption layer 13 (above the laser absorption layer 13 in the example of FIG. 6). Be done.
  • the laser beam output from the emission head 103 is irradiated below the focal plane 110 in a range wider than the irradiation range of the laser beam formed at the position of the focal plane 110.
  • the width of the laser light irradiation area in the direction perpendicular to the scanning direction on the surface of the laser absorption layer 13 is wider than the width of the groove 140.
  • the width of the irradiation area of the laser light in the direction perpendicular to the scanning direction on the surface of the laser absorption layer 13 corresponds to the pattern of the laser absorption layer 13. It is wider than the diameter of the formed hole.
  • the laser beam output from the emission head 103 can evaporate the laser absorption layer 13 in a wider area, and the plurality of grooves 140 can be formed in the active material layer 14 more efficiently.
  • the focal plane 110 of the laser light may be formed on the opposite side of the emission head 103 with respect to the laser absorption layer 13 (below the laser absorption layer 13 in the example of FIG. 6).
  • step S104 When step S104 is finished, the laminate 10 is in a state as shown in FIG. 7, for example. Note that after step S104, before the next step S105 is performed, a process of removing so-called burrs formed on the active material layer 14 by laser ablation is performed by air knife or solvent ultrasonic cleaning or the like. It is also good.
  • the solid electrolyte layer 15 is stacked on the active material layer 14 so as to cover the plurality of grooves 140 formed in the active material layer 14 in step S104 (S105).
  • a laminate 10 as shown in FIG. 8 is formed.
  • the solid electrolyte layer 15 is made of, for example, a material having lithium phosphate oxynitride (LiPON) as a main component.
  • the solid electrolyte layer 15 is formed by a film forming method having good step coverage such as CVD or ALD (Atomic Layer Deposition).
  • the temperature of the laminate 10 is in the range of 250 to 700 ° C., preferably in the range of 400 to 600 ° C.
  • the pressure in the chamber is in the range of 10 to 2000 Pa, preferably in the range of 10 to 500 Pa.
  • lithium tertiary butoxide Li (t-OBu)
  • Li (TMHD) lithium 2,2,6,6-tetramethyl-3,5-heptanedionate
  • HMDS hexamer Methyldisilazane lithium
  • the temperature of the supply bottle is, for example, 70 to 230 ° C. in the case of Li (t-OBu), for example 200 to 310 ° C. in the case of Li (TMHD), and for example 90 to 180 ° C. in the case of Li (HMDS) .
  • TMP trimethyl phosphate
  • TMOP trimethyl phosphate
  • TEOP triethyl phosphate
  • TEP triethyl phosphate
  • TDMAP triethyl phosphate
  • TDMAPO tris (dimethylamino) phosphine oxide
  • the temperature of the supply bottle is, for example, 25 to 60 ° C. in the case of TMP, 25 to 70 ° C. in the case of TMOP, for example 25 to 120 ° C. in the case of TEOP, for example 25 to 150 ° C.
  • the temperature is, eg, 80 to 160 ° C.
  • the active material layer 16 is stacked on the solid electrolyte layer 15 stacked in step S105 (S106). Thereby, for example, a laminate 10 as shown in FIG. 9 is formed.
  • the active material layer 16 functions as a cathode electrode
  • the active material layer 16 is made of, for example, a material containing LCO or LMO as a main component.
  • the active material layer 16 functions as an anode electrode
  • the active material layer 16 is made of, for example, a material containing LTO or silicon as a main component.
  • the active material layer 16 is made of, for example, a material containing silicon as a main component, and functions as an anode electrode.
  • the active material layer 16 is stacked on the solid electrolyte layer 15 by CVD or sputtering.
  • an annealing process may be performed for the purpose of improving the film quality of the stacked body 10. Since the active material layer 16 immediately after film formation is amorphous and unstable, it is desirable to improve film quality by annealing and crystallizing within a predetermined time after film formation of the active material layer 16. Therefore, it is preferable that the laminate 10 be annealed, for example, within one hour after the active material layer 16 is laminated.
  • the annealing temperature is preferably a temperature within a range of 400 ° C. to 700 ° C., for example.
  • the upper collector electrode layer 17 is stacked on the active material layer 16 (S107). Thereby, for example, a laminate 10 as shown in FIG. 10 is formed.
  • the upper collector electrode layer 17 is made of, for example, a material containing titanium, platinum, gold, copper, aluminum, nickel, or the like as a main component.
  • the upper collector electrode layer 17 is made of, for example, a material containing copper as a main component.
  • the upper collector electrode layer 17 is laminated on the active material layer 16 by vapor deposition, sputtering or the like.
  • the laminate 10 shown in FIG. 10 functions as a thin film battery element.
  • the active material layer 14 at the position corresponding to the pattern of the laser absorption layer 13 is removed by scanning the irradiation range of the laser light on the laminate 10.
  • the plurality of grooves 140 can be formed efficiently. Therefore, the productivity of the thin film battery element can be improved.
  • the laser absorption layer 13 is irradiated with the laser light from the active material layer 14 side.
  • the laser absorption layer is irradiated with the laser light from the substrate side.
  • the laser absorption layer irradiated with the laser light evaporates explosively, and the portion of the active material layer corresponding to the position of the laser absorption layer is blown away in the direction opposite to the emission head 103 side across the substrate. This can suppress adhesion of the blown laser absorbing layer, the active material layer, and the like to the emission head 103. Therefore, the cleaning cycle of the emission head 103 can be made long, and the productivity of the thin film battery element can be further improved.
  • FIG. 11 is a flowchart showing an example of a manufacturing procedure of the thin film battery element in the second embodiment.
  • 12 to 17 are cross-sectional views showing an example of the laminated body 20.
  • FIG. 11 is a flowchart showing an example of a manufacturing procedure of the thin film battery element in the second embodiment.
  • 12 to 17 are cross-sectional views showing an example of the laminated body 20.
  • the lower collector electrode layer 22 is stacked on the substrate 21 (S200).
  • the substrate 21 is made of, for example, glass, quartz, or sapphire, and the lower collector electrode layer 22 is made of, for example, zinc oxide (ZnO), tin oxide (SnO 2), or indium tin oxide (ITO).
  • the substrate 21 is made of, for example, glass, and the lower collector electrode layer 22 is made of, for example, ZnO.
  • the lower collector electrode layer 22 is stacked on the substrate 21 by sputtering or CVD.
  • the laser absorption layer 23 is stacked on the lower collector electrode layer 22 (S201).
  • the laser absorption layer 23 is made of, for example, the same material as the laser absorption layer 13 of the first embodiment. As a result, for example, as shown in FIG. 12, a laminate 20 in which the lower collector electrode layer 22 and the laser absorption layer 23 are laminated on the substrate 21 is formed.
  • the laser absorption layer 23 is patterned into a predetermined pattern by, for example, photolithography (S202).
  • the shape of the patterning of the laser absorption layer 23 is the same as that of the first embodiment.
  • Step S202 is an example of a pattern formation process.
  • the blocking layer 24 is laminated on the lower collector electrode layer 22 and the laser absorption layer 23 so as to cover the patterned laser absorption layer 23 (S203). Thereby, for example, a laminate 20 as shown in FIG. 13 is formed.
  • the blocking layer 24 is made of, for example, a material containing platinum or gold as a main component.
  • the blocking layer 24 is made of, for example, a material containing platinum as a main component.
  • the thickness of the blocking layer 24 is, for example, several nm.
  • Step S203 is an example of a blocking layer formation process.
  • the active material layer 25 is stacked on the blocking layer 24 (S204). Thereby, for example, a laminate 20 as shown in FIG. 14 is formed.
  • the active material layer 25 is made of, for example, the same material as the active material layer 14 of the first embodiment.
  • the blocking layer 24 is provided between the lower collector electrode layer 22 and the active material layer 25
  • lithium ions contained in the active material layer 25 are diffused into the lower collector electrode layer 22. Can be prevented.
  • the active material layer 25 is stacked on the blocking layer 24 by CVD or sputtering. Note that, after the stacked body 10 is formed in step S204, an annealing step may be performed for the purpose of improving the film quality of the stacked body 10.
  • the active material layer 25 immediately after film formation is amorphous and unstable, it is desirable to improve film quality by annealing and crystallizing within a predetermined time after film formation of the active material layer 25. Therefore, it is preferable that the laminate 10 be annealed, for example, within one hour after the active material layer 25 is laminated.
  • the annealing temperature is preferably in the range of 400 ° C. to 700 ° C., for example.
  • Step S204 is an example of a layered product formation process.
  • a plurality of grooves 250 are formed in the active material layer 25 (S205).
  • the irradiation range of the laser light irradiated to the laser absorption layer 23 from the substrate 21 side is scanned in the direction of the arrow in FIG.
  • the laser absorption layer 23 irradiated with the laser light evaporates explosively.
  • the active material layer 25 in a portion corresponding to the laser absorption layer 23 is blown away, and a plurality of grooves 250 corresponding to the pattern of the laser absorption layer 23 are formed in the active material layer 25.
  • the thickness of the blocking layer 24 is several nm, the blocking layer 24 of the part corresponding to the laser absorption layer 23 is also blown away with the active material layer 25 by explosive evaporation of the laser absorption layer 23.
  • the wavelength ⁇ (nm) of the laser light irradiated to the stacked body 20 is a laser
  • the optical band gap of the absorption layer 23 is E g, LA (eV)
  • the optical band gap of the lower collector electrode layer 22 is E g, BC (eV)
  • the following relational expression (2) needs to be satisfied.
  • the laser absorption layer 23 is irradiated with the laser light of wavelength ⁇ (nm) satisfying the following relational expression (2) from the substrate 21 side. (1240 / E g, BC ) (nm) ⁇ ⁇ (1240 / E g, LA ) (nm) (2)
  • the blocking layer 24 is provided between the lower collector electrode layer 22 and the active material layer 25, most of the laser light transmitted through the lower collector electrode layer 22 is reflected by the blocking layer 24. Ru. Therefore, the laser beam transmitted through the lower collector electrode layer 22 hardly reaches the active material layer 25. Therefore, the absorption by the active material layer 25 may not be considered in the required range of the wavelength ⁇ (nm) of the laser light.
  • the optical band gaps E g and LA of the laser absorption layer 23 are approximately 1.0 (eV).
  • the range of the wavelength ⁇ (nm) required for the laser light irradiated to the stacked body 20 is 365 (nm) ⁇ ⁇ 1240 (nm).
  • the focal plane 110 of the laser light is formed at a position distant from the laser absorption layer 23 (below the laser absorption layer 23 in the example of FIG. 15). Therefore, the laser beam output from the emission head 103 is irradiated above the focal plane 110 in a range wider than the irradiation range of the laser beam formed at the position of the focal plane 110. Therefore, the laser beam output from the emission head 103 can evaporate the laser absorption layer 23 in a wider area, and the plurality of grooves 250 can be formed in the active material layer 25 more efficiently.
  • the focal plane 110 of the laser light may be formed on the opposite side of the emission head 103 (above the laser absorption layer 23 in the example of FIG. 15) with the laser absorption layer 23 interposed therebetween.
  • the solid electrolyte layer 26 is stacked on the active material layer 25 so as to cover the plurality of grooves 250 formed in the active material layer 25 in step S205 (S206). Thereby, for example, a laminate 20 as shown in FIG. 16 is formed.
  • the solid electrolyte layer 26 is made of, for example, the same material as the solid electrolyte layer 15 of the first embodiment.
  • the solid electrolyte layer 26 is formed by a film forming method having good step coverage such as CVD or ALD, for example.
  • CVD chemical vapor deposition
  • ALD atomic layer deposition
  • the active material layer 27 is stacked on the solid electrolyte layer 26 stacked in step S206 (S207).
  • the active material layer 27 is made of, for example, the same material as the active material layer 16 of the first embodiment.
  • the active material layer 27 is stacked on the solid electrolyte layer 26 by CVD or sputtering.
  • an annealing step may be performed for the purpose of improving the film quality of the stacked body 10. Since the active material layer 27 immediately after film formation is amorphous and unstable, it is desirable to improve film quality by annealing and crystallizing within a predetermined time after film formation of the active material layer 27. Therefore, it is preferable that the laminate 10 be annealed, for example, within one hour after the active material layer 27 is laminated.
  • the annealing temperature is preferably in the range of 400 ° C. to 700 ° C., for example.
  • the upper collector electrode layer 28 is stacked on the active material layer 27 (S208). Thereby, for example, a laminate 20 as shown in FIG. 17 is formed.
  • the upper collector electrode layer 28 is made of, for example, the same material as that of the upper collector electrode layer 17 of the first embodiment (for example, a material containing copper as a main component).
  • the upper collector electrode layer 28 is laminated on the active material layer 27 by evaporation, sputtering or the like.
  • the laminate 20 shown in FIG. 17 functions as a thin film battery element.
  • the plurality of grooves 250 are formed in the active material layer 25 by laser ablation by the laser beam irradiated to the laser absorption layer 23 from the substrate 21 side.
  • the active material layer 25 or the like blown off by the laser ablation can be prevented from adhering to the laser beam emission head 103. Therefore, the cleaning cycle of the emission head 103 can be made long, and the productivity of the thin film battery element can be further improved.
  • FIG. 18 to FIG. 20 show another example of the laser light irradiation method.
  • the emission head 103 condenses laser light whose intensity has a Gaussian distribution, and irradiates the laminate 10 with spot light of a predetermined size.
  • the laser light irradiation method is not limited to this.
  • the laminated body 10 may be irradiated with laser light using an emission head 103 a that outputs a flat top beam that is laser light having a substantially uniform intensity distribution in a predetermined range.
  • the laser beam is applied to the laminated body 10 using the emission head 103 b that outputs a line beam that is a laser beam of substantially uniform intensity distribution in the irradiation region having the major axis and the minor axis. You may irradiate.
  • a line beam is used as the laser beam, by scanning the line beam in the direction of the minor axis, the entire stack 10 can be irradiated with the laser beam with a smaller number of scans, which further improves the productivity of the thin film battery It can be done.
  • the laser beam is stacked using an emission unit 106 having a plurality of emission heads 103 for condensing a laser beam having a Gaussian distribution and forming a spot beam of a predetermined size.
  • the body 10 may be irradiated.
  • the emission unit 106 or the stacked body 10 moves in a direction orthogonal to the arrangement direction of the plurality of emission heads 103.
  • the entire stack 10 can be irradiated with laser light with a small number of scans, and the productivity of the thin film battery element can be further improved.
  • the entire stack 10 may be included in the irradiation area by the plurality of emission heads 103 using the emission unit 106 in which the plurality of emission heads 103 are two-dimensionally arranged on the surface facing the stack 10. .
  • the productivity of the thin film battery element can be further improved.
  • the other example of the irradiation method of the laser beam demonstrated using FIGS. 18-20 is applicable also to 2nd Embodiment.
  • the lower collector electrode layer is stacked on the substrate, but the disclosed technology is not limited thereto.
  • the substrate is made of a conductive material such as titanium, the lower collector electrode layer may not be provided.

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Abstract

This method for manufacturing a thin film battery element comprises a pattern forming step, a laminate forming step, and an opening forming step. In the pattern forming step, a laser absorbing layer of a predetermined pattern is formed on a collector electrode layer. In the laminate forming step, a laminate is formed by laminating an active material layer on the collector electrode layer and the laser absorbing layer. In the opening forming step, an opening corresponding to a predetermined pattern is formed in the active material layer by irradiating the laminate with a laser and evaporating and dispersing the laser absorbing layer.

Description

薄膜電池素子の製造方法Method of manufacturing thin film battery element
　本開示の種々の側面および実施形態は、薄膜電池素子の製造方法に関する。 Various aspects and embodiments of the present disclosure relate to methods of manufacturing a thin film battery element.
　ウェアラブル、メディカル、ＩｏＴデバイス用のマイクロバッテリーや、電気自動車などの駆動電源および家庭用蓄電池などに用いられる大型のリチウムイオン電池の開発が進められている。なかでも、電極および電解質が全て固体からなる全固体電池は、安全性、高エネルギー密度、および長寿命の点で、近年注目されている。全固体電池には、薄膜型とバルク型がある。薄膜型の全固体電池は、全固体電池を構成する電極や電解質層等の素子が、素子毎のシャドーマスクを用いて積層されることにより形成される。素子の形成には、例えばＰＶＤ（Physical　Vapor　Deposition）が用いられる。 Development of large-sized lithium ion batteries used for wearables, medicals, micro batteries for IoT devices, driving power sources for electric vehicles and storage batteries for home use, etc. is being promoted. Among them, all solid batteries in which the electrode and the electrolyte are all solid are recently attracting attention in terms of safety, high energy density and long life. There are thin film type and bulk type in all solid state batteries. The thin film type all solid battery is formed by laminating elements such as electrodes and electrolyte layers constituting the all solid battery using a shadow mask for each element. For example, physical vapor deposition (PVD) is used to form the element.
　しかし、シャドーマスクを用いたＰＶＤでは、シャドーマスクの管理や位置合わせ、洗浄等の手間がかかるため、大量生産が難しい。そこで、電極や電解質層等の素子をレーザーアブレーションによりパターニングすることにより、薄膜型の全固体電池を製造する技術が知られている（例えば、下記特許文献１参照）。 However, PVD using a shadow mask is difficult to mass-produce because it takes time and effort to manage, align and clean the shadow mask. Then, the technique which manufactures a thin film type all-solid-state battery is known by patterning elements, such as an electrode and an electrolyte layer, by laser ablation (for example, refer following patent document 1).
特開２０１４－５２０３６９号公報JP, 2014-520369, A
　ところで、全固体電池において、高出力密度および高エネルギー密度を両立させるためには、正極または負極を構成する活物質層の表面積を増加させる必要がある。しかし、活物質として利用される材料としては、リチウム遷移金属複合酸化物が用いられることが多い。そのため、半導体の製造において用いられる反応性イオンエッチングを用いて、活物質層の表面積を増加させるための加工を行った場合、低蒸気圧の遷移金属反応物が形成されてしまい、微細加工が難しい。 By the way, in an all solid state battery, in order to make high power density and high energy density compatible, it is necessary to increase the surface area of the active material layer which constitutes a positive electrode or a negative electrode. However, lithium transition metal complex oxide is often used as a material used as an active material. Therefore, when processing is performed to increase the surface area of the active material layer using reactive ion etching used in the manufacture of semiconductors, transition metal reactants with low vapor pressure are formed, and microprocessing is difficult. .
　また、リチウムイオンは、不安定な材料であり、水分と反応しやすい。そのため、純水を使用したウエットエッチングや現像、剥離、洗浄プロセスを行った場合には、活物質中のリチウムが溶出し、電極層としての性能が劣化する。また、数μｍ以上の膜厚の活物質層を加工する場合、イオンミリング法ではエッチングレートが非常に小さく、生産性が低い。さらに、イオンミリング法では、イオン衝撃によって、活物質が非晶質化してしまい、出力およびエネルギー密度の低下を引き起こす。 Lithium ion is an unstable material and easily reacts with moisture. Therefore, when wet etching using pure water, development, peeling, and cleaning processes are performed, lithium in the active material is eluted and the performance as the electrode layer is degraded. In addition, in the case of processing an active material layer having a thickness of several μm or more, the etching rate is very small in the ion milling method, and the productivity is low. Furthermore, in the ion milling method, the active material is amorphized by ion bombardment, causing a decrease in power and energy density.
　また、活物質層をレーザーアブレーションにより加工する場合、第２高調波のレーザー光の加工幅は数十μｍ程度であるため、微細加工が難しい。また、レーザーアブレーションに第３高調波のレーザー光を用いた場合、加工幅を数μｍ程度まで微細化できるものの、レーザー光のスポット径が小さくなった分、レーザー光により一度に除去できる範囲が小さくなり、生産性が著しく低下する。 In addition, when the active material layer is processed by laser ablation, the processing width of the second harmonic laser beam is about several tens of μm, so that fine processing is difficult. When the laser beam of the third harmonic is used for laser ablation, although the processing width can be miniaturized to about several μm, the spot diameter of the laser beam becomes smaller, so the range which can be removed at one time by the laser beam is small. And productivity is significantly reduced.
　本開示の一側面は、薄膜電池素子の製造方法であって、パターン形成工程と、積層体形成工程と、開口形成工程とを含む。パターン形成工程は、集電極層上に所定パターンのレーザー吸収層を形成する。積層体形成工程は、集電極層およびレーザー吸収層上に活物質層を積層することにより、積層体を形成する。開口形成工程は、積層体にレーザー光を照射してレーザー吸収層を蒸散させることにより、活物質層に所定パターンに応じた開口を形成する。 One aspect of the present disclosure is a method of manufacturing a thin film battery element, and includes a pattern forming step, a laminate forming step, and an opening forming step. In the pattern formation step, a laser absorption layer of a predetermined pattern is formed on the collector electrode layer. In the laminate formation step, the active material layer is laminated on the collecting electrode layer and the laser absorption layer to form a laminate. In the opening forming step, the laminated body is irradiated with laser light to evaporate the laser absorption layer, thereby forming an opening corresponding to a predetermined pattern in the active material layer.
　本開示の種々の側面および実施形態によれば、薄膜電池素子の生産性を向上させることができる。 According to various aspects and embodiments of the present disclosure, productivity of the thin film battery element can be improved.
図１は、第１の実施形態における薄膜電池素子の製造手順の一例を示すフローチャートである。FIG. 1 is a flowchart showing an example of the manufacturing procedure of the thin film battery element in the first embodiment. 図２は、積層体の一例を示す断面図である。FIG. 2 is a cross-sectional view showing an example of the laminate. 図３は、積層体の一例を示す断面図である。FIG. 3 is a cross-sectional view showing an example of the laminate. 図４は、積層体の一例を示す断面図である。FIG. 4 is a cross-sectional view showing an example of the laminate. 図５は、レーザー照射装置の一例を示す図である。FIG. 5 is a diagram showing an example of a laser irradiation apparatus. 図６は、積層体の一例を示す断面図である。FIG. 6 is a cross-sectional view showing an example of the laminate. 図７は、積層体の一例を示す断面図である。FIG. 7 is a cross-sectional view showing an example of the laminate. 図８は、積層体の一例を示す断面図である。FIG. 8 is a cross-sectional view showing an example of a laminate. 図９は、積層体の一例を示す断面図である。FIG. 9 is a cross-sectional view showing an example of a laminate. 図１０は、積層体の一例を示す断面図である。FIG. 10 is a cross-sectional view showing an example of a laminate. 図１１は、第２の実施形態における薄膜電池素子の製造手順の一例を示すフローチャートである。FIG. 11 is a flowchart showing an example of a manufacturing procedure of the thin film battery element in the second embodiment. 図１２は、積層体の一例を示す断面図である。FIG. 12 is a cross-sectional view showing an example of the laminate. 図１３は、積層体の一例を示す断面図である。FIG. 13 is a cross-sectional view showing an example of a laminate. 図１４は、積層体の一例を示す断面図である。FIG. 14 is a cross-sectional view showing an example of a laminate. 図１５は、積層体の一例を示す断面図である。FIG. 15 is a cross-sectional view showing an example of a laminate. 図１６は、積層体の一例を示す断面図である。FIG. 16 is a cross-sectional view showing an example of a laminate. 図１７は、積層体の一例を示す断面図である。FIG. 17 is a cross-sectional view showing an example of a laminate. 図１８は、レーザー光の照射方法の他の例を示す図である。FIG. 18 is a view showing another example of the laser light irradiation method. 図１９は、レーザー光の照射方法の他の例を示す図である。FIG. 19 is a view showing another example of the laser light irradiation method. 図２０は、レーザー光の照射方法の他の例を示す図である。FIG. 20 is a diagram showing another example of the laser light irradiation method.
　以下に、開示する薄膜電池素子の製造方法の実施形態について、図面に基づいて詳細に説明する。なお、以下の実施形態により、開示される薄膜電池素子の製造方法が限定されるものではない。 Hereinafter, an embodiment of a method of manufacturing a thin film battery element to be disclosed will be described in detail based on the drawings. In addition, the manufacturing method of the thin film battery element disclosed is not limited by the following embodiment.
（第１の実施形態）
［薄膜電池素子の製造手順］
　図１は、第１の実施形態における薄膜電池素子の製造手順の一例を示すフローチャートである。図２～図４および図６～図１０は、積層体１０の一例を示す断面図である。 First Embodiment
[Production procedure of thin film battery element]
FIG. 1 is a flowchart showing an example of the manufacturing procedure of the thin film battery element in the first embodiment. 2 to 4 and 6 to 10 are cross-sectional views showing an example of the laminate 10.
　まず、基板１１上に下部集電極層１２が積層される（Ｓ１００）。基板１１は、例えばシリコン、ガラス、またはステンレス等を主成分とする材料により構成され、下部集電極層１２は、例えばチタン、白金、金、銅、アルミニウム、またはニッケル等を主成分とする材料により構成される。本実施形態において、基板１１は、例えばシリコンを主成分とする材料により構成され、下部集電極層１２は、例えばチタンおよび白金を含む合金により構成される。下部集電極層１２は、蒸着またはスパッタリング等により基板１１上に積層される。 First, the lower collector electrode layer 12 is stacked on the substrate 11 (S100). The substrate 11 is made of, for example, a material having silicon, glass, or stainless steel as a main component, and the lower collector electrode layer 12 is made of, for example, a material having titanium, platinum, gold, copper, aluminum, or nickel as a main component. Configured In the present embodiment, the substrate 11 is made of, for example, a material containing silicon as a main component, and the lower collector electrode layer 12 is made of, for example, an alloy containing titanium and platinum. The lower collector electrode layer 12 is laminated on the substrate 11 by vapor deposition, sputtering or the like.
　次に、下部集電極層１２上にレーザー吸収層１３が積層される（Ｓ１０１）。レーザー吸収層１３は、例えばアモルファスシリコンまたはアモルファスゲルマニウム等を主成分とする材料により構成される。本実施形態において、レーザー吸収層１３は、例えばアモルファスシリコンを主成分とする材料により構成される。レーザー吸収層１３は、ＣＶＤ（Chemical　Vapor　Deposition）またはスパッタリング等により下部集電極層１２上に積層される。これにより、例えば図２に示されるように、基板１１上に下部集電極層１２およびレーザー吸収層１３が積層された積層体１０が形成される。 Next, the laser absorption layer 13 is stacked on the lower collector electrode layer 12 (S101). The laser absorption layer 13 is made of, for example, a material mainly composed of amorphous silicon or amorphous germanium. In the present embodiment, the laser absorption layer 13 is made of, for example, a material mainly composed of amorphous silicon. The laser absorption layer 13 is stacked on the lower collector electrode layer 12 by chemical vapor deposition (CVD), sputtering or the like. As a result, for example, as shown in FIG. 2, a stacked body 10 in which the lower collector electrode layer 12 and the laser absorption layer 13 are stacked on the substrate 11 is formed.
　次に、レーザー吸収層１３が、例えば図３に示されるように、所定のパターンにパターニングされる（Ｓ１０２）。レーザー吸収層１３のパターニングは、例えばフォトリソグラフィー、インプリントリソグラフィー、ウエットエッチング、ドライエッチング、またはリフトオフ等により行われる。ステップＳ１０２は、パターン形成工程の一例である。 Next, the laser absorption layer 13 is patterned into a predetermined pattern, for example, as shown in FIG. 3 (S102). The patterning of the laser absorption layer 13 is performed by, for example, photolithography, imprint lithography, wet etching, dry etching, or lift-off. Step S102 is an example of a pattern formation process.
　本実施形態では、所定幅（例えば１μｍ程度）の直線状のレーザー吸収層１３が所定間隔（例えば１μｍ程度）で下部集電極層１２上に配置されるようにレーザー吸収層１３がパターニングされる。なお、レーザー吸収層１３のパターニングは、直線状に限られず、ジグザグ状、ミアンダ状、格子状、またはドット状等であってもよい。 In the present embodiment, the laser absorption layer 13 is patterned so that the linear laser absorption layer 13 having a predetermined width (for example, about 1 μm) is disposed on the lower collector electrode layer 12 at a predetermined interval (for example, about 1 μm). The patterning of the laser absorption layer 13 is not limited to a linear shape, and may be a zigzag shape, a meander shape, a lattice shape, a dot shape, or the like.
　次に、パターニングされたレーザー吸収層１３を覆うように、下部集電極層１２およびレーザー吸収層１３上に活物質層１４が積層される（Ｓ１０３）。これにより、例えば図４に示されるような積層体１０が形成される。活物質層１４がカソード電極として機能する場合、活物質層１４は、例えばコバルト酸リチウム（ＬＣＯ）またはマンガン酸リチウム（ＬＭＯ）等を主成分とする材料により構成される。また、活物質層１４がアノード電極として機能する場合、活物質層１４は、例えばチタン酸リチウム（ＬＴＯ）またはシリコン等を主成分とする材料により構成される。本実施形態において、活物質層１４は、例えばＬＣＯを主成分とする材料により構成され、カソード電極として機能する。活物質層１４は、ＣＶＤまたはスパッタリングにより下部集電極層１２およびレーザー吸収層１３上に積層される。なお、ステップＳ１０３において積層体１０が形成された後に、積層体１０の膜質の改善を目的としたアニール工程が行われてもよい。成膜直後の活物質層１４はアモルファスであり不安定なため、活物質層１４の成膜後は所定時間以内にアニールして結晶化させることにより膜質を改善させることが望ましい。従って、活物質層１４が積層された後、例えば１時間以内に積層体１０がアニールされることが好ましい。また、アニール温度は、例えば４００℃から７００℃の範囲内の温度であることが好ましい。ステップＳ１０３は、積層体形成工程の一例である。 Next, the active material layer 14 is stacked on the lower collector electrode layer 12 and the laser absorption layer 13 so as to cover the patterned laser absorption layer 13 (S103). Thereby, for example, a laminate 10 as shown in FIG. 4 is formed. When the active material layer 14 functions as a cathode electrode, the active material layer 14 is made of, for example, a material containing lithium cobaltate (LCO) or lithium manganate (LMO) as a main component. When the active material layer 14 functions as an anode electrode, the active material layer 14 is made of, for example, a material containing lithium titanate (LTO) or silicon as a main component. In the present embodiment, the active material layer 14 is made of, for example, a material containing LCO as a main component, and functions as a cathode electrode. The active material layer 14 is stacked on the lower collector electrode layer 12 and the laser absorption layer 13 by CVD or sputtering. Note that, after the stacked body 10 is formed in step S103, an annealing step may be performed for the purpose of improving the film quality of the stacked body 10. Since the active material layer 14 immediately after film formation is amorphous and unstable, it is desirable to improve film quality by annealing and crystallizing within a predetermined time after film formation of the active material layer 14. Therefore, it is preferable that the laminate 10 be annealed, for example, within one hour after the active material layer 14 is laminated. The annealing temperature is preferably a temperature within a range of 400 ° C. to 700 ° C., for example. Step S103 is an example of a layered product formation process.
　次に、活物質層１４に複数の溝が形成される（Ｓ１０４）。本実施形態では、レーザーアブレーションにより活物質層１４に溝が形成される。ステップＳ１０４は、開口形成工程の一例である。図５は、レーザー照射装置１００の一例を示す図である。本実施形態において用いられるレーザー照射装置１００は、例えば図５に示されるように、レーザー発振器１０１、導光部１０２、出射ヘッド１０３、ステージ１０４、および移動台１０５を備える。レーザー発振器１０１は、レーザー光を発生させる。 Next, a plurality of grooves are formed in the active material layer 14 (S104). In the present embodiment, the grooves are formed in the active material layer 14 by laser ablation. Step S104 is an example of an opening formation process. FIG. 5 is a view showing an example of the laser irradiation apparatus 100. As shown in FIG. The laser irradiation apparatus 100 used in the present embodiment includes, for example, a laser oscillator 101, a light guiding unit 102, an emission head 103, a stage 104, and a moving table 105, as shown in FIG. The laser oscillator 101 generates a laser beam.
　本実施形態では、レーザー吸収層１３および活物質層１４にレーザー光を照射し、レーザー吸収層１３に対して選択的にレーザーアブレーションを発生させる。そのためには、積層体１０に照射されるレーザー光の波長λ（ｎｍ）は、レーザー吸収層１３の光学バンドギャップをＥg,LA（ｅＶ）、活物質層１４の光学バンドギャップをＥg,CE（ｅＶ）とした場合、以下の関係式（１）を満たす必要がある。レーザー発振器１０１は、下記の関係式（１）を満たす波長λ（ｎｍ）のレーザー光を発生させる。
　（１２４０／Ｅg,CE）（ｎｍ）＜λ＜（１２４０／Ｅg,LA）（ｎｍ）　・・・（１）
　ここで、光の波長λ（ｎｍ）は、プランク定数ｈ（ｅＶ・ｓ）、光の速度ｃ（ｍ／ｓ）、および光のバンドギャップＥg（ｅＶ）を用いて、λ＝ｈｃ／Ｅg（ｎｍ）と表される。また、上記の式（１）における「１２４０」は、光の波長λの単位をｎｍで表した場合のプランク定数ｈ（ｅＶ・ｓ）と光の速度ｃ（ｍ／ｓ）との積の値である。 In the present embodiment, the laser absorption layer 13 and the active material layer 14 are irradiated with laser light to cause laser ablation selectively to the laser absorption layer 13. For this purpose, the wavelength of the laser beam irradiated to the laminate 10 lambda (nm) is E the optical band gap of the laser absorbing layer 13 g, LA (eV), the optical band gap of the active material layer 14 E g, In the case of CE (eV), it is necessary to satisfy the following relational expression (1). The laser oscillator 101 generates laser light of wavelength λ (nm) which satisfies the following relational expression (1).
(1240 / E g, CE ) (nm) <λ <(1240 / E g, LA ) (nm) (1)
Here, the wavelength λ (nm) of light is λ = hc / E, using Planck's constant h (eV · s), speed of light c (m / s), and band gap E g (eV) of light. It is expressed as g (nm). Further, “1240” in the above equation (1) is the value of the product of the Planck constant h (eV · s) and the speed of light c (m / s) when the unit of the light wavelength λ is expressed in nm. It is.
　本実施形態において、レーザー吸収層１３はアモルファスシリコンを主成分とする材料により構成されるため、レーザー吸収層１３の光学バンドギャップＥg,LAは、約１．７（ｅＶ）である。また、本実施形態において、活物質層１４はＬＣＯを主成分とする材料により構成されるため、活物質層１４の光学バンドギャップＥg,CEは、約２．４（ｅＶ）である。そのため、本実施形態において、レーザー発振器１０１は、５１６（ｎｍ）＜λ＜７２９（ｎｍ）を満たす波長λ（ｎｍ）のレーザー光として、例えばＹＡＧ（Yttrium　Aluminum　Garnet）レーザーの第２高調波（λ＝５３２（ｎｍ））のレーザー光を発生させる。 In the present embodiment, since the laser absorption layer 13 is formed of a material containing amorphous silicon as a main component, the optical band gaps E g and LA of the laser absorption layer 13 are approximately 1.7 (eV). Further, in the present embodiment, since the active material layer 14 is made of a material having LCO as a main component, the optical band gaps E g and CE of the active material layer 14 are about 2.4 (eV). Therefore, in the present embodiment, as the laser light of wavelength λ (nm) satisfying 516 (nm) <λ <729 (nm), for example, the second harmonic (λ) of YAG (Yttrium Aluminum Garnet) laser is used. A laser beam of 532 (nm) is generated.
　なお、レーザー吸収層１３が例えばアモルファスゲルマニウムを主成分とする材料により構成される場合、レーザー吸収層１３の光学バンドギャップＥg,LAは、約１．０（ｅＶ）である。その場合、レーザー発振器１０１は、５１６（ｎｍ）＜λ＜１２４０（ｎｍ）を満たす波長λ（ｎｍ）のレーザー光として、例えばＹＡＧレーザーの基本波（λ＝１０６４（ｎｍ））のレーザー光を発生させてもよい。 When the laser absorption layer 13 is made of, for example, a material containing amorphous germanium as a main component, the optical band gaps E g and LA of the laser absorption layer 13 are about 1.0 (eV). In that case, the laser oscillator 101 generates, for example, a laser beam of a fundamental wave (λ = 1064 (nm)) of a YAG laser as a laser beam of a wavelength λ (nm) satisfying 516 (nm) <λ <1240 (nm) You may
　導光部１０２は、レーザー発振器１０１で発生したレーザー光を出射ヘッド１０３へ伝搬させる。出射ヘッド１０３は、導光部１０２を伝搬したレーザー光を集光して積層体１０へ照射する。本実施形態において、出射ヘッド１０３は、強度がガウシアン分布となるレーザー光を集光して所定の大きさのスポット光として積層体１０に照射する。ステージ１０４上には、積層体１０が載置される。移動台１０５は、ステージ１０４をＸ軸方向およびＹ軸方向に移動させることにより、ステージ１０４上の積層体１０をＸ軸方向およびＹ軸方向に移動させる。これにより、出射ヘッド１０３から積層体１０上に照射されたレーザー光が、積層体１０上で走査される。なお、積層体１０に対して出射ヘッド１０３の方を移動させることにより、積層体１０上に照射されたレーザー光が積層体１０上で走査されてもよい。 The light guiding unit 102 propagates the laser beam generated by the laser oscillator 101 to the emission head 103. The emission head 103 condenses the laser light propagated through the light guide portion 102 and irradiates the laminated body 10 with the laser light. In the present embodiment, the emission head 103 condenses laser light having a Gaussian distribution in intensity and irradiates the laminated body 10 with spot light of a predetermined size. The stack 10 is placed on the stage 104. The moving table 105 moves the stack 10 on the stage 104 in the X-axis direction and the Y-axis direction by moving the stage 104 in the X-axis direction and the Y-axis direction. Thereby, the laser beam irradiated onto the stack 10 from the emission head 103 is scanned on the stack 10. The laser beam emitted onto the laminate 10 may be scanned on the laminate 10 by moving the radiation head 103 relative to the laminate 10.
　ここで、出射ヘッド１０３から積層体１０上に照射されるレーザー光の波長λ（ｎｍ）は、前述のようにλ＜１２４０／Ｅg,LA（ｎｍ）を満たす。そのため、出射ヘッド１０３から積層体１０上に照射されるレーザー光のエネルギーは、Ｅg,LA＜１２４０／λ（ｅＶ）となり、レーザー吸収層１３において吸収される。これにより、レーザー光が照射されたレーザー吸収層１３の部分が爆発的に蒸散するレーザーアブレーションが発生する。この時、レーザー吸収層１３の上に積層された活物質層１４がレーザー吸収層１３の爆発的な蒸散の衝撃で上方に吹き飛ばされる。これにより、活物質層１４にレーザー吸収層１３のパターンに応じた溝が形成される。また、本実施形態では、１以上の高いアスペクト比の溝を活物質層１４に形成することが可能である。 Here, the wavelength λ (nm) of the laser beam irradiated onto the stack 10 from the emission head 103 satisfies λ <1240 / Eg, LA (nm) as described above. Therefore, the energy of the laser beam irradiated from the emission head 103 onto the stack 10 is E g, LA <1240 / λ (eV), and is absorbed by the laser absorption layer 13. As a result, laser ablation occurs in which the portion of the laser absorption layer 13 irradiated with the laser light is transpirationally explosively dissipated. At this time, the active material layer 14 stacked on the laser absorption layer 13 is blown upward by the impact of explosive transpiration of the laser absorption layer 13. Thereby, a groove corresponding to the pattern of the laser absorption layer 13 is formed in the active material layer 14. Moreover, in the present embodiment, it is possible to form a groove with one or more high aspect ratios in the active material layer 14.
　なお、レーザー吸収層１３がドット状にパターニングされている場合には、レーザー光が積層体１０上で走査されることにより、活物質層１４にレーザー吸収層１３のパターンに応じた穴が形成される。即ち、レーザー光が積層体１０上で走査されることにより、活物質層１４には、レーザー吸収層１３のパターンに応じた開口が形成される。 In addition, when the laser absorption layer 13 is patterned in the shape of a dot, a hole according to the pattern of the laser absorption layer 13 is formed in the active material layer 14 by scanning the laser light on the laminate 10. Ru. That is, when the laser beam is scanned on the laminate 10, an opening corresponding to the pattern of the laser absorption layer 13 is formed in the active material layer 14.
　例えば図６に示されるように、出射ヘッド１０３からのレーザー光の照射範囲が積層体１０上で図６の矢印の方向に走査されることにより、レーザー吸収層１３のパターンに応じた位置の活物質層１４が除去される。これにより、活物質層１４に複数の溝１４０が形成される。本実施形態において、出射ヘッド１０３は、レーザー光を集光するが、レーザー光の焦点面１１０は、レーザー吸収層１３から離れた位置（図６の例では、レーザー吸収層１３の上方）に形成される。 For example, as shown in FIG. 6, the irradiation range of the laser beam from the emission head 103 is scanned on the laminate 10 in the direction of the arrow in FIG. Material layer 14 is removed. Thereby, a plurality of grooves 140 are formed in the active material layer 14. In the present embodiment, the emission head 103 condenses the laser light, but the focal plane 110 of the laser light is formed at a position away from the laser absorption layer 13 (above the laser absorption layer 13 in the example of FIG. 6). Be done.
　そのため、出射ヘッド１０３から出力されたレーザー光は、焦点面１１０の下方において、焦点面１１０の位置に形成されるレーザー光の照射範囲よりも広い範囲に照射される。例えば、レーザー吸収層１３の表面において走査方向と垂直な方向におけるレーザー光の照射領域の幅は、溝１４０の幅よりも広い。また、レーザー吸収層１３がドット状にパターニングされている場合には、レーザー吸収層１３の表面において走査方向と垂直な方向におけるレーザー光の照射領域の幅は、レーザー吸収層１３のパターンに応じて形成される穴の直径よりも広い。そのため、出射ヘッド１０３から出力されたレーザー光は、より広い領域のレーザー吸収層１３を蒸散させることができ、より効率よく活物質層１４に複数の溝１４０を形成することができる。なお、レーザー光の焦点面１１０は、レーザー吸収層１３を挟んで出射ヘッド１０３と反対側（図６の例では、レーザー吸収層１３の下方）に形成されてもよい。 Therefore, the laser beam output from the emission head 103 is irradiated below the focal plane 110 in a range wider than the irradiation range of the laser beam formed at the position of the focal plane 110. For example, the width of the laser light irradiation area in the direction perpendicular to the scanning direction on the surface of the laser absorption layer 13 is wider than the width of the groove 140. When the laser absorption layer 13 is patterned in a dot shape, the width of the irradiation area of the laser light in the direction perpendicular to the scanning direction on the surface of the laser absorption layer 13 corresponds to the pattern of the laser absorption layer 13. It is wider than the diameter of the formed hole. Therefore, the laser beam output from the emission head 103 can evaporate the laser absorption layer 13 in a wider area, and the plurality of grooves 140 can be formed in the active material layer 14 more efficiently. The focal plane 110 of the laser light may be formed on the opposite side of the emission head 103 with respect to the laser absorption layer 13 (below the laser absorption layer 13 in the example of FIG. 6).
　ステップＳ１０４が終了すると、積層体１０は、例えば図７に示されるような状態となる。なお、ステップＳ１０４の後、次のステップＳ１０５が実行される前に、エアーナイフまたは溶媒超音波洗浄等により、レーザーアブレーションにより活物質層１４に形成された、いわゆるバリを除去する工程が実行されてもよい。 When step S104 is finished, the laminate 10 is in a state as shown in FIG. 7, for example. Note that after step S104, before the next step S105 is performed, a process of removing so-called burrs formed on the active material layer 14 by laser ablation is performed by air knife or solvent ultrasonic cleaning or the like. It is also good.
　図１に戻って説明を続ける。次に、ステップＳ１０４によって活物質層１４に形成された複数の溝１４０を覆うように、活物質層１４上に固体電解質層１５が積層される（Ｓ１０５）。これにより、例えば図８に示されるような積層体１０が形成される。本実施形態において、固体電解質層１５は、例えばリン酸リチウムオキシナイトライド（ＬｉＰＯＮ）を主成分とする材料により構成される。また、固体電解質層１５は、例えばＣＶＤまたはＡＬＤ（Atomic　Layer　Deposition）等のステップカバレッジが良好な成膜方法により形成される。 Returning to FIG. 1, the description will be continued. Next, the solid electrolyte layer 15 is stacked on the active material layer 14 so as to cover the plurality of grooves 140 formed in the active material layer 14 in step S104 (S105). Thereby, for example, a laminate 10 as shown in FIG. 8 is formed. In the present embodiment, the solid electrolyte layer 15 is made of, for example, a material having lithium phosphate oxynitride (LiPON) as a main component. In addition, the solid electrolyte layer 15 is formed by a film forming method having good step coverage such as CVD or ALD (Atomic Layer Deposition).
　固体電解質層１５がＣＶＤにより形成される場合のＣＶＤの主な処理条件の一例を挙げるならば、例えば以下の通りである。積層体１０の温度は、２５０～７００℃の範囲内であり、好ましくは４００～６００℃の範囲内である。また、チャンバ内の圧力は、１０～２０００Ｐａの範囲内であり、好ましくは１０～５００Ｐａの範囲内である。 The following is an example of main processing conditions of CVD in the case where the solid electrolyte layer 15 is formed by CVD. The temperature of the laminate 10 is in the range of 250 to 700 ° C., preferably in the range of 400 to 600 ° C. Also, the pressure in the chamber is in the range of 10 to 2000 Pa, preferably in the range of 10 to 500 Pa.
　リチウムの原料としては、例えば、リチウムターシャリーブトキシド（Ｌｉ（ｔ－ＯＢｕ））、リチウム２，２，６，６－テトラメチル－３，５－ヘプタンジオナート（Ｌｉ（ＴＭＨＤ））、または、ヘキサメチルジシラザンリチウム（Ｌｉ（ＨＭＤＳ））等が用いられる。また、供給ボトルの温度は、Ｌｉ（ｔ－ＯＢｕ）の場合、例えば７０～２３０℃、Ｌｉ（ＴＭＨＤ）の場合、例えば２００～３１０℃、Ｌｉ（ＨＭＤＳ）の場合、例えば９０～１８０℃である。 As a raw material of lithium, for example, lithium tertiary butoxide (Li (t-OBu)), lithium 2,2,6,6-tetramethyl-3,5-heptanedionate (Li (TMHD)), or hexamer Methyldisilazane lithium (Li (HMDS)) or the like is used. Further, the temperature of the supply bottle is, for example, 70 to 230 ° C. in the case of Li (t-OBu), for example 200 to 310 ° C. in the case of Li (TMHD), and for example 90 to 180 ° C. in the case of Li (HMDS) .
　また、リンの原料としては、例えば、リン酸トリメチル（ＴＭＰ）、トリメチルホスフェート（ＴＭＯＰ）、トリエチルホスフェート（ＴＥＯＰ）、リン酸トリエチル（ＴＥＰ）、トリス（ジメチルアミノ）ホスフィン（ＴＤＭＡＰ）、または、トリス（ジメチルアミノ）ホスフィンオキシド（ＴＤＭＡＰＯ）等が用いられる。また、供給ボトルの温度は、ＴＭＰの場合、例えば２５～６０℃、ＴＭＯＰの場合、例えば２５～７０℃、ＴＥＯＰの場合、例えば２５～１２０℃、ＴＥＰの場合、例えば２５～１５０℃、ＴＤＭＡＰの場合、例えば３０～１１０℃、ＴＤＭＡＰＯの場合、例えば８０～１６０℃である。 Moreover, as a raw material of phosphorus, for example, trimethyl phosphate (TMP), trimethyl phosphate (TMOP), triethyl phosphate (TEOP), triethyl phosphate (TEP), tris (dimethylamino) phosphine (TDMAP), or tris ( Dimethylamino) phosphine oxide (TDMAPO) or the like is used. Also, the temperature of the supply bottle is, for example, 25 to 60 ° C. in the case of TMP, 25 to 70 ° C. in the case of TMOP, for example 25 to 120 ° C. in the case of TEOP, for example 25 to 150 ° C. In the case of, eg, 30 to 110 ° C., in the case of TDMAPO, the temperature is, eg, 80 to 160 ° C.
　次に、ステップＳ１０５によって積層された固体電解質層１５の上に活物質層１６が積層される（Ｓ１０６）。これにより、例えば図９に示されるような積層体１０が形成される。活物質層１６がカソード電極として機能する場合、活物質層１６は、例えばＬＣＯまたはＬＭＯ等を主成分とする材料により構成される。また、活物質層１６がアノード電極として機能する場合、活物質層１６は、例えばＬＴＯまたはシリコン等を主成分とする材料により構成される。本実施形態において、活物質層１６は、例えばシリコンを主成分とする材料により構成され、アノード電極として機能する。活物質層１６は、ＣＶＤまたはスパッタリングにより固体電解質層１５上に積層される。なお、ステップＳ１０６において積層体１０が形成された後に、積層体１０の膜質の改善を目的としたアニール工程が行われてもよい。成膜直後の活物質層１６はアモルファスであり不安定なため、活物質層１６の成膜後は所定時間以内にアニールして結晶化させることにより膜質を改善させることが望ましい。従って、活物質層１６が積層された後、例えば１時間以内に積層体１０がアニールされることが好ましい。また、アニール温度は、例えば４００℃から７００℃の範囲内の温度であることが好ましい。 Next, the active material layer 16 is stacked on the solid electrolyte layer 15 stacked in step S105 (S106). Thereby, for example, a laminate 10 as shown in FIG. 9 is formed. When the active material layer 16 functions as a cathode electrode, the active material layer 16 is made of, for example, a material containing LCO or LMO as a main component. When the active material layer 16 functions as an anode electrode, the active material layer 16 is made of, for example, a material containing LTO or silicon as a main component. In the present embodiment, the active material layer 16 is made of, for example, a material containing silicon as a main component, and functions as an anode electrode. The active material layer 16 is stacked on the solid electrolyte layer 15 by CVD or sputtering. In addition, after the stacked body 10 is formed in step S106, an annealing process may be performed for the purpose of improving the film quality of the stacked body 10. Since the active material layer 16 immediately after film formation is amorphous and unstable, it is desirable to improve film quality by annealing and crystallizing within a predetermined time after film formation of the active material layer 16. Therefore, it is preferable that the laminate 10 be annealed, for example, within one hour after the active material layer 16 is laminated. The annealing temperature is preferably a temperature within a range of 400 ° C. to 700 ° C., for example.
　次に、活物質層１６上に上部集電極層１７が積層される（Ｓ１０７）。これにより、例えば図１０に示されるような積層体１０が形成される。上部集電極層１７は、例えばチタン、白金、金、銅、アルミニウム、またはニッケル等を主成分とする材料により構成される。本実施形態において、上部集電極層１７は、例えば銅を主成分とする材料により構成される。上部集電極層１７は、蒸着またはスパッタリング等により活物質層１６上に積層される。図１０に示された積層体１０は、薄膜電池素子として機能する。 Next, the upper collector electrode layer 17 is stacked on the active material layer 16 (S107). Thereby, for example, a laminate 10 as shown in FIG. 10 is formed. The upper collector electrode layer 17 is made of, for example, a material containing titanium, platinum, gold, copper, aluminum, nickel, or the like as a main component. In the present embodiment, the upper collector electrode layer 17 is made of, for example, a material containing copper as a main component. The upper collector electrode layer 17 is laminated on the active material layer 16 by vapor deposition, sputtering or the like. The laminate 10 shown in FIG. 10 functions as a thin film battery element.
　以上、第１の実施形態について説明した。上記説明から明らかなように、本実施形態によれば、レーザー光の照射範囲を積層体１０上で走査させることにより、レーザー吸収層１３のパターンに応じた位置の活物質層１４を除去することができ、複数の溝１４０を効率よく形成することができる。そのため、薄膜電池素子の生産性を向上させることができる。 The first embodiment has been described above. As apparent from the above description, according to the present embodiment, the active material layer 14 at the position corresponding to the pattern of the laser absorption layer 13 is removed by scanning the irradiation range of the laser light on the laminate 10. The plurality of grooves 140 can be formed efficiently. Therefore, the productivity of the thin film battery element can be improved.
（第２の実施形態）
　第１の実施形態では、活物質層１４に複数の溝１４０を形成する場合、例えば図６に示されたように、活物質層１４側からレーザー吸収層１３にレーザー光が照射される。これに対し、本実施形態では、基板側からレーザー吸収層にレーザー光が照射される。そして、レーザー光が照射されたレーザー吸収層は爆発的に蒸散し、レーザー吸収層の位置に対応する活物質層の部分が、基板を挟んで出射ヘッド１０３側と反対側の方向へ吹き飛ばされる。これにより、吹き飛ばされたレーザー吸収層および活物質層等が出射ヘッド１０３に付着することを抑制できる。そのため、出射ヘッド１０３のクリーニング周期を長くとることができ、薄膜電池素子の生産性をさらに向上させることができる。 Second Embodiment
In the first embodiment, when the plurality of grooves 140 are formed in the active material layer 14, for example, as shown in FIG. 6, the laser absorption layer 13 is irradiated with the laser light from the active material layer 14 side. On the other hand, in the present embodiment, the laser absorption layer is irradiated with the laser light from the substrate side. Then, the laser absorption layer irradiated with the laser light evaporates explosively, and the portion of the active material layer corresponding to the position of the laser absorption layer is blown away in the direction opposite to the emission head 103 side across the substrate. This can suppress adhesion of the blown laser absorbing layer, the active material layer, and the like to the emission head 103. Therefore, the cleaning cycle of the emission head 103 can be made long, and the productivity of the thin film battery element can be further improved.
［薄膜電池素子の製造手順］
　図１１は、第２の実施形態における薄膜電池素子の製造手順の一例を示すフローチャートである。図１２から図１７は、積層体２０の一例を示す断面図である。 [Production procedure of thin film battery element]
FIG. 11 is a flowchart showing an example of a manufacturing procedure of the thin film battery element in the second embodiment. 12 to 17 are cross-sectional views showing an example of the laminated body 20. FIG.
　まず、基板２１上に下部集電極層２２が積層される（Ｓ２００）。基板２１は、例えばガラス、石英、またはサファイア等により構成され、下部集電極層２２は、例えば酸化亜鉛（ＺｎＯ）、酸化スズ（ＳｎＯ２）、または酸化インジウムスズ（ＩＴＯ）等により構成される。本実施形態において、基板２１は、例えばガラスにより構成され、下部集電極層２２は、例えばＺｎＯにより構成される。下部集電極層２２は、スパッタリングまたはＣＶＤ等により基板２１上に積層される。 First, the lower collector electrode layer 22 is stacked on the substrate 21 (S200). The substrate 21 is made of, for example, glass, quartz, or sapphire, and the lower collector electrode layer 22 is made of, for example, zinc oxide (ZnO), tin oxide (SnO 2), or indium tin oxide (ITO). In the present embodiment, the substrate 21 is made of, for example, glass, and the lower collector electrode layer 22 is made of, for example, ZnO. The lower collector electrode layer 22 is stacked on the substrate 21 by sputtering or CVD.
　次に、下部集電極層２２上にレーザー吸収層２３が積層される（Ｓ２０１）。レーザー吸収層２３は、例えば第１の実施形態のレーザー吸収層１３と同様の材料で構成される。これにより、例えば図１２に示されるように、基板２１上に下部集電極層２２およびレーザー吸収層２３が積層された積層体２０が形成される。 Next, the laser absorption layer 23 is stacked on the lower collector electrode layer 22 (S201). The laser absorption layer 23 is made of, for example, the same material as the laser absorption layer 13 of the first embodiment. As a result, for example, as shown in FIG. 12, a laminate 20 in which the lower collector electrode layer 22 and the laser absorption layer 23 are laminated on the substrate 21 is formed.
　次に、レーザー吸収層２３が、例えばフォトリソグラフィー等により、所定のパターンにパターニングされる（Ｓ２０２）。レーザー吸収層２３のパターニングの形状は、第１の実施形態と同様である。ステップＳ２０２は、パターン形成工程の一例である。 Next, the laser absorption layer 23 is patterned into a predetermined pattern by, for example, photolithography (S202). The shape of the patterning of the laser absorption layer 23 is the same as that of the first embodiment. Step S202 is an example of a pattern formation process.
　次に、パターニングされたレーザー吸収層２３を覆うように、下部集電極層２２およびレーザー吸収層２３上にブロッキング層２４が積層される（Ｓ２０３）。これにより、例えば図１３に示されるような積層体２０が形成される。ブロッキング層２４は、例えば白金または金等を主成分とする材料により構成される。本実施形態において、ブロッキング層２４は、例えば白金を主成分とする材料により構成される。ブロッキング層２４の厚さは、例えば数ｎｍである。ステップＳ２０３は、ブロッキング層形成工程の一例である。 Next, the blocking layer 24 is laminated on the lower collector electrode layer 22 and the laser absorption layer 23 so as to cover the patterned laser absorption layer 23 (S203). Thereby, for example, a laminate 20 as shown in FIG. 13 is formed. The blocking layer 24 is made of, for example, a material containing platinum or gold as a main component. In the present embodiment, the blocking layer 24 is made of, for example, a material containing platinum as a main component. The thickness of the blocking layer 24 is, for example, several nm. Step S203 is an example of a blocking layer formation process.
　次に、ブロッキング層２４上に活物質層２５が積層される（Ｓ２０４）。これにより、例えば図１４に示されるような積層体２０が形成される。活物質層２５は、例えば第１の実施形態の活物質層１４と同様の材料で構成される。本実施形態では、下部集電極層２２と活物質層２５との間にブロッキング層２４が設けられているため、活物質層２５に含まれるリチウムイオンが下部集電極層２２内に拡散してしまうことを防止することができる。活物質層２５は、ＣＶＤまたはスパッタリングによりブロッキング層２４上に積層される。なお、ステップＳ２０４において積層体１０が形成された後に、積層体１０の膜質の改善を目的としたアニール工程が行われてもよい。成膜直後の活物質層２５はアモルファスであり不安定なため、活物質層２５の成膜後は所定時間以内にアニールして結晶化させることにより膜質を改善させることが望ましい。従って、活物質層２５が積層された後、例えば１時間以内に積層体１０がアニールされることが好ましい。また、アニール温度は、例えば４００℃から７００℃の範囲であることが好ましい。ステップＳ２０４は、積層体形成工程の一例である。 Next, the active material layer 25 is stacked on the blocking layer 24 (S204). Thereby, for example, a laminate 20 as shown in FIG. 14 is formed. The active material layer 25 is made of, for example, the same material as the active material layer 14 of the first embodiment. In the present embodiment, since the blocking layer 24 is provided between the lower collector electrode layer 22 and the active material layer 25, lithium ions contained in the active material layer 25 are diffused into the lower collector electrode layer 22. Can be prevented. The active material layer 25 is stacked on the blocking layer 24 by CVD or sputtering. Note that, after the stacked body 10 is formed in step S204, an annealing step may be performed for the purpose of improving the film quality of the stacked body 10. Since the active material layer 25 immediately after film formation is amorphous and unstable, it is desirable to improve film quality by annealing and crystallizing within a predetermined time after film formation of the active material layer 25. Therefore, it is preferable that the laminate 10 be annealed, for example, within one hour after the active material layer 25 is laminated. The annealing temperature is preferably in the range of 400 ° C. to 700 ° C., for example. Step S204 is an example of a layered product formation process.
　次に、活物質層２５に複数の溝２５０が形成される（Ｓ２０５）。本実施形態では、例えば図１５に示されるように、基板２１側からレーザー吸収層２３に照射されたレーザー光の照射範囲が積層体２０の基板２１上で図１５の矢印の方向に走査され、レーザー光が照射されたレーザー吸収層２３が爆発的に蒸散する。これにより、レーザー吸収層２３に対応する部分の活物質層２５が吹き飛ばされ、活物質層２５にレーザー吸収層２３のパターンに対応する複数の溝２５０が形成される。なお、ブロッキング層２４の厚さは数ｎｍであるため、レーザー吸収層２３の爆発的な蒸散により、レーザー吸収層２３に対応する部分のブロッキング層２４も活物質層２５と共に吹き飛ばされる。 Next, a plurality of grooves 250 are formed in the active material layer 25 (S205). In the present embodiment, for example, as shown in FIG. 15, the irradiation range of the laser light irradiated to the laser absorption layer 23 from the substrate 21 side is scanned in the direction of the arrow in FIG. The laser absorption layer 23 irradiated with the laser light evaporates explosively. Thereby, the active material layer 25 in a portion corresponding to the laser absorption layer 23 is blown away, and a plurality of grooves 250 corresponding to the pattern of the laser absorption layer 23 are formed in the active material layer 25. In addition, since the thickness of the blocking layer 24 is several nm, the blocking layer 24 of the part corresponding to the laser absorption layer 23 is also blown away with the active material layer 25 by explosive evaporation of the laser absorption layer 23.
　下部集電極層２２およびレーザー吸収層２３のうち、レーザー吸収層２３に対して選択的にレーザーアブレーションを発生させるためには、積層体２０に照射されるレーザー光の波長λ（ｎｍ）は、レーザー吸収層２３の光学バンドギャップをＥg,LA（ｅＶ）、下部集電極層２２の光学バンドギャップをＥg,BC（ｅＶ）とした場合、以下の関係式（２）を満たす必要がある。基板２１側からレーザー吸収層２３へは、以下の関係式（２）を満たす波長λ（ｎｍ）のレーザー光が照射される。
　（１２４０／Ｅg,BC）（ｎｍ）＜λ＜（１２４０／Ｅg,LA）（ｎｍ）　・・・（２） Of the lower collector electrode layer 22 and the laser absorption layer 23, in order to cause laser ablation selectively to the laser absorption layer 23, the wavelength λ (nm) of the laser light irradiated to the stacked body 20 is a laser Assuming that the optical band gap of the absorption layer 23 is E g, LA (eV) and the optical band gap of the lower collector electrode layer 22 is E g, BC (eV), the following relational expression (2) needs to be satisfied. The laser absorption layer 23 is irradiated with the laser light of wavelength λ (nm) satisfying the following relational expression (2) from the substrate 21 side.
(1240 / E g, BC ) (nm) <λ <(1240 / E g, LA ) (nm) (2)
　なお、本実施形態では、下部集電極層２２と活物質層２５との間にブロッキング層２４が設けられているため、下部集電極層２２を透過したレーザー光の大半がブロッキング層２４で反射される。そのため、下部集電極層２２を透過したレーザー光は活物質層２５にほとんど届かない。従って、レーザー光の波長λ（ｎｍ）の要求範囲において、活物質層２５による吸収を考慮しなくてもよい。 In the present embodiment, since the blocking layer 24 is provided between the lower collector electrode layer 22 and the active material layer 25, most of the laser light transmitted through the lower collector electrode layer 22 is reflected by the blocking layer 24. Ru. Therefore, the laser beam transmitted through the lower collector electrode layer 22 hardly reaches the active material layer 25. Therefore, the absorption by the active material layer 25 may not be considered in the required range of the wavelength λ (nm) of the laser light.
　また、本実施形態において、レーザー吸収層２３はアモルファスシリコンを主成分とする材料により構成されるため、レーザー吸収層２３の光学バンドギャップＥg,LAは、約１．７（ｅＶ）である。また、本実施形態において、下部集電極層２２はＺｎＯにより構成されるため、下部集電極層２２の光学バンドギャップＥg,BCは、約３．４（ｅＶ）である。そのため、本実施形態において、積層体２０に照射されるレーザー光に要求される波長λの範囲は、３６５（ｎｍ）＜λ＜７２９（ｎｍ）である。このようなレーザー光としては、例えばＹＡＧレーザーの第２高調波（λ＝５３２（ｎｍ））を用いることができる。 Further, in the present embodiment, since the laser absorption layer 23 is made of a material having amorphous silicon as a main component, the optical band gaps E g and LA of the laser absorption layer 23 are approximately 1.7 (eV). Further, in the present embodiment, since the lower collector electrode layer 22 is made of ZnO, the optical band gaps Eg and BC of the lower collector electrode layer 22 are about 3.4 (eV). Therefore, in the present embodiment, the range of the wavelength λ required for the laser light irradiated to the stacked body 20 is 365 (nm) <λ <729 (nm). As such a laser beam, for example, the second harmonic (λ = 532 (nm)) of a YAG laser can be used.
　なお、レーザー吸収層２３が例えばアモルファスゲルマニウムを主成分とする材料により構成される場合、レーザー吸収層２３の光学バンドギャップＥg,LAは、約１．０（ｅＶ）である。その場合、積層体２０に照射されるレーザー光に要求される波長λ（ｎｍ）の範囲は、３６５（ｎｍ）＜λ＜１２４０（ｎｍ）である。このようなレーザー光としては、例えばＹＡＧレーザーの基本波（λ＝１０６４（ｎｍ））を用いることもできる。 When the laser absorption layer 23 is made of, for example, a material containing amorphous germanium as a main component, the optical band gaps E g and LA of the laser absorption layer 23 are approximately 1.0 (eV). In that case, the range of the wavelength λ (nm) required for the laser light irradiated to the stacked body 20 is 365 (nm) <λ <1240 (nm). As such a laser beam, for example, a fundamental wave (λ = 1064 (nm)) of a YAG laser can also be used.
　本実施形態においても、レーザー光の焦点面１１０は、レーザー吸収層２３から離れた位置（図１５の例では、レーザー吸収層２３の下方）に形成される。そのため、出射ヘッド１０３から出力されたレーザー光は、焦点面１１０の上方において、焦点面１１０の位置に形成されるレーザー光の照射範囲よりも広い範囲に照射される。そのため、出射ヘッド１０３から出力されたレーザー光は、より広い領域のレーザー吸収層２３を蒸散させることができ、より効率よく活物質層２５に複数の溝２５０を形成することができる。なお、レーザー光の焦点面１１０は、レーザー吸収層２３を挟んで出射ヘッド１０３と反対側（図１５の例では、レーザー吸収層２３の上方）に形成されてもよい。 Also in the present embodiment, the focal plane 110 of the laser light is formed at a position distant from the laser absorption layer 23 (below the laser absorption layer 23 in the example of FIG. 15). Therefore, the laser beam output from the emission head 103 is irradiated above the focal plane 110 in a range wider than the irradiation range of the laser beam formed at the position of the focal plane 110. Therefore, the laser beam output from the emission head 103 can evaporate the laser absorption layer 23 in a wider area, and the plurality of grooves 250 can be formed in the active material layer 25 more efficiently. The focal plane 110 of the laser light may be formed on the opposite side of the emission head 103 (above the laser absorption layer 23 in the example of FIG. 15) with the laser absorption layer 23 interposed therebetween.
　図１１に戻って説明を続ける。次に、ステップＳ２０５によって活物質層２５に形成された複数の溝２５０を覆うように、活物質層２５上に固体電解質層２６が積層される（Ｓ２０６）。これにより、例えば図１６に示されるような積層体２０が形成される。固体電解質層２６は、例えば第１の実施形態の固体電解質層１５と同様の材料で構成される。また、固体電解質層２６は、例えばＣＶＤまたはＡＬＤ等のステップカバレッジが良好な成膜方法により形成される。固体電解質層２６がＣＶＤにより形成される場合のＣＶＤの主な処理条件の一例は、第１の実施形態と同様である。 Returning to FIG. 11, the description will be continued. Next, the solid electrolyte layer 26 is stacked on the active material layer 25 so as to cover the plurality of grooves 250 formed in the active material layer 25 in step S205 (S206). Thereby, for example, a laminate 20 as shown in FIG. 16 is formed. The solid electrolyte layer 26 is made of, for example, the same material as the solid electrolyte layer 15 of the first embodiment. In addition, the solid electrolyte layer 26 is formed by a film forming method having good step coverage such as CVD or ALD, for example. One example of the main processing conditions of CVD when the solid electrolyte layer 26 is formed by CVD is the same as in the first embodiment.
　次に、ステップＳ２０６によって積層された固体電解質層２６の上に活物質層２７が積層される（Ｓ２０７）。活物質層２７は、例えば第１の実施形態の活物質層１６と同様の材料で構成される。活物質層２７は、ＣＶＤまたはスパッタリングにより固体電解質層２６上に積層される。なお、ステップＳ２０７において積層体１０が形成された後に、積層体１０の膜質の改善を目的としたアニール工程が行われてもよい。成膜直後の活物質層２７はアモルファスであり不安定なため、活物質層２７の成膜後は所定時間以内にアニールして結晶化させることにより膜質を改善させることが望ましい。従って、活物質層２７が積層された後、例えば１時間以内に積層体１０がアニールされることが好ましい。また、アニール温度は、例えば４００℃から７００℃の範囲であることが好ましい。 Next, the active material layer 27 is stacked on the solid electrolyte layer 26 stacked in step S206 (S207). The active material layer 27 is made of, for example, the same material as the active material layer 16 of the first embodiment. The active material layer 27 is stacked on the solid electrolyte layer 26 by CVD or sputtering. Note that, after the stacked body 10 is formed in step S207, an annealing step may be performed for the purpose of improving the film quality of the stacked body 10. Since the active material layer 27 immediately after film formation is amorphous and unstable, it is desirable to improve film quality by annealing and crystallizing within a predetermined time after film formation of the active material layer 27. Therefore, it is preferable that the laminate 10 be annealed, for example, within one hour after the active material layer 27 is laminated. The annealing temperature is preferably in the range of 400 ° C. to 700 ° C., for example.
　次に、活物質層２７上に上部集電極層２８が積層される（Ｓ２０８）。これにより、例えば図１７に示されるような積層体２０が形成される。上部集電極層２８は、例えば第１の実施形態の上部集電極層１７と同様の材料（例えば銅を主成分とする材料）で構成される。上部集電極層２８は、蒸着またはスパッタリング等により活物質層２７上に積層される。図１７に示された積層体２０は、薄膜電池素子として機能する。 Next, the upper collector electrode layer 28 is stacked on the active material layer 27 (S208). Thereby, for example, a laminate 20 as shown in FIG. 17 is formed. The upper collector electrode layer 28 is made of, for example, the same material as that of the upper collector electrode layer 17 of the first embodiment (for example, a material containing copper as a main component). The upper collector electrode layer 28 is laminated on the active material layer 27 by evaporation, sputtering or the like. The laminate 20 shown in FIG. 17 functions as a thin film battery element.
　以上、第２の実施形態について説明した。上記説明から明らかなように、本実施形態によれば、基板２１側からレーザー吸収層２３に照射されたレーザー光によるレーザーアブレーションによって、活物質層２５に複数の溝２５０が形成される。これにより、レーザーアブレーションにより吹き飛ばされた活物質層２５等がレーザー光の出射ヘッド１０３に付着することを抑制できる。そのため、出射ヘッド１０３のクリーニング周期を長くとることができ、薄膜電池素子の生産性をさらに向上させることができる。 The second embodiment has been described above. As apparent from the above description, according to the present embodiment, the plurality of grooves 250 are formed in the active material layer 25 by laser ablation by the laser beam irradiated to the laser absorption layer 23 from the substrate 21 side. Thus, the active material layer 25 or the like blown off by the laser ablation can be prevented from adhering to the laser beam emission head 103. Therefore, the cleaning cycle of the emission head 103 can be made long, and the productivity of the thin film battery element can be further improved.
［その他］
　なお、本明細書に開示された技術は、上記した実施形態に限定されるものではなく、その要旨の範囲内で数々の変形が可能である。 [Others]
Note that the technology disclosed in the present specification is not limited to the above-described embodiment, and various modifications are possible within the scope of the present invention.
　図１８～図２０は、レーザー光の照射方法の他の例を示す図である。例えば、上記した第１の実施形態において、出射ヘッド１０３は、強度がガウシアン分布となるレーザー光を集光して所定の大きさのスポット光として積層体１０に照射する。しかし、レーザー光の照射方法は、これに限られない。例えば図１８に示されるように、所定範囲において略均一な強度分布のレーザー光であるフラットトップビームを出力する出射ヘッド１０３ａを用いて、積層体１０にレーザー光を照射してもよい。 FIG. 18 to FIG. 20 show another example of the laser light irradiation method. For example, in the above-described first embodiment, the emission head 103 condenses laser light whose intensity has a Gaussian distribution, and irradiates the laminate 10 with spot light of a predetermined size. However, the laser light irradiation method is not limited to this. For example, as shown in FIG. 18, the laminated body 10 may be irradiated with laser light using an emission head 103 a that outputs a flat top beam that is laser light having a substantially uniform intensity distribution in a predetermined range.
　また、例えば図１９に示されるように、長軸と短軸とを有する照射領域において略均一な強度分布のレーザー光であるラインビームを出力する出射ヘッド１０３ｂを用いて、積層体１０にレーザー光を照射してもよい。レーザー光としてラインビームが用いられる場合、短軸の方向にラインビームを走査することにより、少ない走査回数で積層体１０全体にレーザー光を照射することができ、薄膜電池素子の生産性をさらに向上させることができる。 For example, as shown in FIG. 19, the laser beam is applied to the laminated body 10 using the emission head 103 b that outputs a line beam that is a laser beam of substantially uniform intensity distribution in the irradiation region having the major axis and the minor axis. You may irradiate. When a line beam is used as the laser beam, by scanning the line beam in the direction of the minor axis, the entire stack 10 can be irradiated with the laser beam with a smaller number of scans, which further improves the productivity of the thin film battery It can be done.
　また、例えば図２０に示されるように、強度がガウシアン分布となるレーザー光を集光して所定の大きさのスポット光とする出射ヘッド１０３を複数有する出射ユニット１０６を用いて、レーザー光を積層体１０に照射してもよい。図２０の例では、出射ユニット１０６または積層体１０は、複数の出射ヘッド１０３の配列方向に直交する方向へ移動する。これにより、少ない走査回数で積層体１０全体にレーザー光を照射することができ、薄膜電池素子の生産性をさらに向上させることができる。 For example, as shown in FIG. 20, the laser beam is stacked using an emission unit 106 having a plurality of emission heads 103 for condensing a laser beam having a Gaussian distribution and forming a spot beam of a predetermined size. The body 10 may be irradiated. In the example of FIG. 20, the emission unit 106 or the stacked body 10 moves in a direction orthogonal to the arrangement direction of the plurality of emission heads 103. As a result, the entire stack 10 can be irradiated with laser light with a small number of scans, and the productivity of the thin film battery element can be further improved.
　また、積層体１０に対向する面に複数の出射ヘッド１０３が２次元に配列された出射ユニット１０６を用いて、複数の出射ヘッド１０３によって積層体１０全体が照射領域に含まれるようにしてもよい。この場合、出射ユニット１０６を走査させる必要がなくなるため、薄膜電池素子の生産性をさらに向上させることができる。なお、図１８から図２０を用いて説明したレーザー光の照射方法の他の例は、第２の実施形態に対しても適用可能である。 Alternatively, the entire stack 10 may be included in the irradiation area by the plurality of emission heads 103 using the emission unit 106 in which the plurality of emission heads 103 are two-dimensionally arranged on the surface facing the stack 10. . In this case, since it is not necessary to scan the emitting unit 106, the productivity of the thin film battery element can be further improved. In addition, the other example of the irradiation method of the laser beam demonstrated using FIGS. 18-20 is applicable also to 2nd Embodiment.
　また、上記した各実施形態では、基板上に下部集電極層が積層されたが、開示の技術はこれに限られない。例えば、基板がチタン等の導電性の材料により構成される場合、下部集電極層は設けられなくてもよい。 In each of the above-described embodiments, the lower collector electrode layer is stacked on the substrate, but the disclosed technology is not limited thereto. For example, when the substrate is made of a conductive material such as titanium, the lower collector electrode layer may not be provided.
１０　積層体
１１　基板
１２　下部集電極層
１３　レーザー吸収層
１４　活物質層
１４０　溝
１５　固体電解質層
１６　活物質層
１７　上部集電極層
２０　積層体
２１　基板
２２　下部集電極層
２３　レーザー吸収層
２４　ブロッキング層
２５　活物質層
２５０　溝
２６　固体電解質層
２７　活物質層
２８　上部集電極層
１００　レーザー照射装置
１０１　レーザー発振器
１０２　導光部
１０３　出射ヘッド
１０４　ステージ
１０５　移動台
１０６　出射ユニット
１１０　焦点面 DESCRIPTION OF SYMBOLS 10 stacked body 11 substrate 12 lower collecting electrode layer 13 laser absorption layer 14 active material layer 140 groove 15 solid electrolyte layer 16 active material layer 17 upper collecting electrode layer 20 laminated body 21 substrate 22 lower collecting electrode layer 23 laser absorption layer 24 blocking layer Reference Signs List 25 active material layer 250 groove 26 solid electrolyte layer 27 active material layer 28 upper collector electrode layer 100 laser irradiation device 101 laser oscillator 102 light guiding unit 103 emission head 104 stage 105 moving table 106 emission unit 110 focal plane

Claims (10)

  1. 　集電極層上に所定パターンのレーザー吸収層を形成するパターン形成工程と、
    　前記集電極層および前記レーザー吸収層上に活物質層を積層することにより、積層体を形成する積層体形成工程と、
    　前記積層体にレーザー光を照射して前記レーザー吸収層を蒸散させることにより、前記活物質層に前記所定パターンに応じた開口を形成する開口形成工程と
    を含む薄膜電池素子の製造方法。     Forming a laser absorption layer of a predetermined pattern on the collecting electrode layer;
    A laminate forming step of forming a laminate by laminating an active material layer on the collecting electrode layer and the laser absorption layer;
    And a step of forming an opening corresponding to the predetermined pattern in the active material layer by irradiating the laminated body with laser light to evaporate the laser absorption layer.
  2. 　前記開口形成工程では、前記活物質層側から前記積層体に前記レーザー光が照射され、　前記レーザー光の波長λ（ｎｍ）は、
    　前記レーザー吸収層の光学バンドギャップをＥg,LA（ｅＶ）、前記活物質層の光学バンドギャップをＥg,CE（ｅＶ）とした場合、（１２４０／Ｅg,CE）（ｎｍ）＜λ＜（１２４０／Ｅg,LA）（ｎｍ）を満たす請求項１に記載の薄膜電池素子の製造方法。     In the opening forming step, the laminated body is irradiated with the laser light from the side of the active material layer, and the wavelength λ (nm) of the laser light is
    Assuming that the optical band gap of the laser absorption layer is E g, LA (eV) and the optical band gap of the active material layer is E g, CE (eV), (1240 / E g, CE ) (nm) <λ The manufacturing method of the thin film battery element of Claim 1 which satisfy | fills <(1240 / Eg, LA ) (nm).
  3. 　前記集電極層は、基板上に積層され、
    　前記集電極層と前記基板とは、レーザー光を透過する材料により形成され、
    　前記パターン形成工程の後に、前記集電極層および前記レーザー吸収層の上に、ブロッキング層を形成するブロッキング層形成工程をさらに含み、
    　前記積層体形成工程では、前記ブロッキング層の上に前記活物質層が積層されることにより、前記積層体が形成され、
    　前記開口形成工程では、前記基板側から前記積層体にレーザー光が照射される請求項１に記載の薄膜電池素子の製造方法。     The collecting electrode layer is laminated on a substrate,
    The collector electrode layer and the substrate are formed of a material that transmits laser light,
    And forming a blocking layer on the collecting electrode layer and the laser absorption layer after the patterning step.
    In the laminate forming step, the active material layer is laminated on the blocking layer to form the laminate.
    The method for manufacturing a thin film battery element according to claim 1, wherein the laminated body is irradiated with a laser beam from the substrate side in the opening forming step.
  4. 　前記レーザー光の波長λ（ｎｍ）は、
    　前記レーザー吸収層の光学バンドギャップをＥg,LA（ｅＶ）、前記集電極層の光学バンドギャップをＥg,BE（ｅＶ）とした場合、（１２４０／Ｅg,BE）（ｎｍ）＜λ＜（１２４０／Ｅg,LA）（ｎｍ）を満たす請求項１に記載の薄膜電池素子の製造方法。     The wavelength λ (nm) of the laser light is
    Assuming that the optical band gap of the laser absorption layer is E g, LA (eV) and the optical band gap of the collecting electrode layer is E g, BE (eV), (1240 / E g, BE ) (nm) <λ The manufacturing method of the thin film battery element of Claim 1 which satisfy | fills <(1240 / Eg, LA ) (nm).
  5. 　前記レーザー吸収層は、アモルファスシリコンまたはアモルファスゲルマニウムを含む請求項１に記載の薄膜電池素子の製造方法。 The method of claim 1, wherein the laser absorption layer comprises amorphous silicon or amorphous germanium.
  6. 　前記活物質層は、コバルト酸リチウム、マンガン酸リチウム、チタン酸リチウム、シリコン、またはリチウムの少なくともいずれかを含む請求項１に記載の薄膜電池素子の製造方法。 The method for manufacturing a thin film battery element according to claim 1, wherein the active material layer contains at least one of lithium cobaltate, lithium manganate, lithium titanate, silicon, or lithium.
  7. 　前記集電極層は、チタン、白金、金、銅、アルミニウム、またはニッケルの少なくともいずれかを含む請求項１に記載の薄膜電池素子の製造方法。 The method for manufacturing a thin film battery element according to claim 1, wherein the collecting electrode layer contains at least one of titanium, platinum, gold, copper, aluminum, or nickel.
  8. 　前記開口形成工程において、前記レーザー光を集光させる光学系は、前記レーザー吸収層から離れた位置が焦点となるように前記レーザー光を集光させる請求項１に記載の薄膜電池素子の製造方法。 The method for manufacturing a thin film battery element according to claim 1, wherein in the opening forming step, an optical system for condensing the laser light condenses the laser light such that a position away from the laser absorption layer is a focal point. .
  9. 　前記パターン形成工程では、前記集電極層上に前記所定パターンの前記レーザー吸収層が複数配置され、
    　前記開口形成工程では、前記積層体に照射される前記レーザー光が、前記積層体上で走査されることにより、前記レーザー吸収層が配置されたそれぞれの位置において前記活物質層に前記所定パターンに応じた開口が形成される請求項１に記載の薄膜電池素子の製造方法。     In the pattern forming step, a plurality of the laser absorbing layers of the predetermined pattern are disposed on the collecting electrode layer,
    In the opening forming step, the laser light irradiated to the laminated body is scanned on the laminated body to form the predetermined pattern on the active material layer at each position where the laser absorbing layer is disposed. The method for manufacturing a thin film battery element according to claim 1, wherein a corresponding opening is formed.
  10. 　前記開口形成工程では、前記レーザー吸収層を蒸散させることにより、前記所定パターンに応じた溝が前記活物質層に形成され、
    　前記レーザー吸収層の表面において前記レーザー光の走査方向と垂直な方向における前記レーザー光の照射領域の幅は、前記溝の幅よりも広い請求項９に記載の薄膜電池素子の製造方法。      In the opening forming step, a groove corresponding to the predetermined pattern is formed in the active material layer by evaporating the laser absorption layer.
    The method of manufacturing a thin film battery element according to claim 9, wherein a width of an irradiation area of the laser light in a direction perpendicular to a scanning direction of the laser light on the surface of the laser absorption layer is wider than a width of the groove.
PCT/JP2019/001399 2018-01-25 2019-01-18 Method for manufacturing thin film battery element WO2019146512A1 (en)

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JPH02303696A (en) * 1989-05-17 1990-12-17 Matsushita Electric Works Ltd Machining method utilizing laser beam
US20070092637A1 (en) * 2005-09-15 2007-04-26 Plastic Logic Limited Forming holes using laser energy
JP2014520369A (en) * 2011-06-17 2014-08-21 アプライド マテリアルズ インコーポレイテッド Maskless manufacturing of thin film batteries
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JP2021012840A (en) * 2019-07-09 2021-02-04 ローム株式会社 Thin-film all-solid-state battery, electronic device, and manufacturing method of thin-film all-solid-state battery
JP7319114B2 (en) 2019-07-09 2023-08-01 ローム株式会社 Thin-film type all-solid-state battery, electronic device, and method for manufacturing thin-film type all-solid-state battery

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