WO2010082644A1 - Scribing apparatus and scribing method - Google Patents
Scribing apparatus and scribing method Download PDFInfo
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- WO2010082644A1 WO2010082644A1 PCT/JP2010/050457 JP2010050457W WO2010082644A1 WO 2010082644 A1 WO2010082644 A1 WO 2010082644A1 JP 2010050457 W JP2010050457 W JP 2010050457W WO 2010082644 A1 WO2010082644 A1 WO 2010082644A1
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- WIPO (PCT)
- Prior art keywords
- scribing
- flexible substrate
- film
- photoelectric conversion
- target
- Prior art date
Links
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1876—Particular processes or apparatus for batch treatment of the devices
-
- 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
- B23K26/08—Devices involving relative movement between laser beam and workpiece
- B23K26/083—Devices involving movement of the workpiece in at least one axial direction
- B23K26/0838—Devices involving movement of the workpiece in at least one axial direction by using an endless conveyor belt
- B23K26/0846—Devices involving movement of the workpiece in at least one axial direction by using an endless conveyor belt for moving elongated workpieces longitudinally, e.g. wire or strip material
-
- 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
- B23K26/36—Removing material
- B23K26/362—Laser etching
- B23K26/364—Laser etching for making a groove or trench, e.g. for scribing a break initiation groove
-
- 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
- B23K26/36—Removing material
- B23K26/40—Removing material taking account of the properties of the material involved
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
- H01L21/67005—Apparatus not specifically provided for elsewhere
- H01L21/67011—Apparatus for manufacture or treatment
- H01L21/67092—Apparatus for mechanical treatment
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/77—Manufacture or treatment of devices consisting of a plurality of solid state components or integrated circuits formed in, or on, a common substrate
- H01L21/78—Manufacture or treatment of devices consisting of a plurality of solid state components or integrated circuits formed in, or on, a common substrate with subsequent division of the substrate into plural individual devices
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/042—PV modules or arrays of single PV cells
- H01L31/0445—PV modules or arrays of single PV cells including thin film solar cells, e.g. single thin film a-Si, CIS or CdTe solar cells
- H01L31/046—PV modules composed of a plurality of thin film solar cells deposited on the same substrate
- H01L31/0463—PV modules composed of a plurality of thin film solar cells deposited on the same substrate characterised by special patterning methods to connect the PV cells in a module, e.g. laser cutting of the conductive or active layers
-
- 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
- B23K2103/00—Materials to be soldered, welded or cut
- B23K2103/16—Composite materials, e.g. fibre reinforced
- B23K2103/166—Multilayered materials
- B23K2103/172—Multilayered materials wherein at least one of the layers is non-metallic
-
- 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
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/541—CuInSe2 material PV cells
-
- 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
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T83/00—Cutting
- Y10T83/02—Other than completely through work thickness
- Y10T83/0333—Scoring
- Y10T83/0341—Processes
Definitions
- the present invention relates to a scribing apparatus and a scribing method for performing scribing on a strip-like continuous flexible film on which a scribing target film is formed.
- Photoelectric conversion devices having a photoelectric conversion layer that generates a current by absorbing light and electrodes for drawing out the current generated in the photoelectric conversion layer are used in various applications, such as solar cells and the like.
- Most of the conventional solar cells are Si cells using bulk monocrystalline Si, polycrystalline Si, or thin film amorphous Si.
- compound semiconductor solar cells that do not depend on Si has been carried out.
- compound semiconductor solar cells two types are known, one of which is a bulk system, such as GaAs system and the like, and the other of which is a thin film system, such as CIS
- Cu-In-Se system formed of a group Ib element, a group IHb element, and a group VIb element, CIGS (Cu-In-Ga-Se) , or the like.
- CIS systems or CIGS systems has high light absorption rates and high energy conversion efficiency is reported.
- Flexible substrates for photoelectric conversion devices may include a substrate having a metal base on which an insulation film is formed, and the like.
- integrated devices are monolithically fabricated for high efficiency and low cost.
- One of the key technologies for that purpose is to divide a film into many cells by providing separation grooves in the film.
- Thin film photoelectric conversion device 100 has first separation grooves 161 that run through only lower electrode 120, second separation grooves 162 that run through photoelectric conversion layer 130 and buffer layer 140, and third separation grooves 163 that run through only upper electrode layer 150 in a lateral sectional view and fourth separation grooves 164 that run through photoelectric conversion layer 130, buffer layer 140, and upper electrode layer 150 in a longitudinal sectional view.
- first separation grooves 161 are formed by laser scribing while second to fourth separation grooves 162 to 164 are formed by mechanical scribing using a scriber blade.
- Japanese Unexamined Patent Publication No. 10 (1998) -027918 discloses an apparatus in which, while conveying a web of flexible substrate on which a target scribing film is formed, laser scribing is performed with the flexible substrate being brought into contact with and pressed by a roller-like substrate support means (claim 2, Figure 1, and the like) .
- Japanese Unexamined Patent Publication No. 2001-044471 discloses an apparatus in which, while conveying a web of flexible substrate on which a target scribing film is formed, laser scribing is performed with the flexible substrate being held by a flat plate like substrate position keeping means (claim 3, Figure 3, and the like) .
- 2004-146773 discloses, as a conventional technology, an apparatus in which, while conveying a web of flexible substrate on which a target scribing film is formed, mechanical scribing using a scriber blade is performed with the flexible substrate being held by two guide rolls
- Publication No. 2004-146773 also proposes the use of micro plasma dry etching for separation groove formation (claim 1, Figure 1, and the like) .
- micro plasma dry etching for separation groove formation
- Japanese Unexamined Patent Publication Nos. 10 (1998) -027918, 2001-044471, and 2004-146773, however, do not describe specific conditions at all, such as the tensile strength, pressing force, and the like to be applied to the flexible substrate, so that specific conditions for stably forming an accurate separation groove in a thin film are not clear.
- the present invention has been developed in view of the circumstances described above, and it is an object of the present invention to provide a scribing apparatus and a scribing method capable of, while conveying a substrate web, performing efficient and accurate scribing on a target scribing film with a high yield rate and stably.
- a scribing apparatus of the present invention is an apparatus, including: a conveyance means for conveying a web of strip-like continuous flexible substrate on which a target scribing film is formed by applying a tensile strength to the flexible substrate; a pressing means, having a convex curved surface, for pressing the flexible substrate by bringing the convex curved surface into contact with the flexible substrate from a side on which the target subscribing film is not formed; and a scribing means for performing scribing on the target scribing film formed on the surface of a portion of the flexible substrate pressed by the pressing means, wherein a tensile strength Tn and a pressing force P applied to the flexible substrate per unit cross-sectional area during the scribing satisfy Formulae (1) to (3) below:
- the tensile strength Tn and pressing force P are parameters represented by the following formulae:
- the flexible substrate may be conveyed by continuous conveyance or intermittent conveyance.
- the scribing may be performed when the substrate is in conveyance or stopped.
- the flexible substrate may include any one or more types of films, such as an insulation film, an electrode, and the like, between the surface of the substrate and the target scribing film.
- the cross-sectional area of the flexible substrate is defined as the cross-sectional area including the layer or layers formed under the target scribing film.
- the target scribing film may be a single layer film or a laminated film.
- the conveyance means includes a first roller for paying out the flexible substrate and a second roller for rolling up the flexible substrate after subjected to the scribing
- the pressing means includes a pressing roller for pressing the flexible substrate.
- the pressing roller has a radius of 40 to 300 mm.
- the position of the convex curved surface is changeable with respect to the flexible substrate .
- a scribing means that has a scriber blade and performs mechanical scribing may be cited.
- the material of the scriber blade is diamond.
- an angle ⁇ formed between a face of the scriber blade on the side that moves relative to the flexible substrate and a normal line to the surface of the flexible substrate is -80° ⁇ a ⁇ 35°, and more preferably -70° ⁇ ⁇ ⁇ 0°.
- the angle ⁇ describe above is referred to herein as "rake angle”.
- Figure 8B is a sectional view schematically illustrating a flexible substrate B, a target scribing film M, a scriber blade 31, and a rake angle ⁇ .
- face Sl of scriber blade 31 on the side that moves relative to the flexible substrate is inclined to a side opposite to the relative moving direction D with respect to the normal line V to the surface of the flexible substrate, it is defined herein that oc > 0, and when face Sl is inclined to the same direction as the relative moving direction D with respect to the normal line V to the surface of the flexible substrate, it is defined that ⁇ ⁇ 0.
- an example position of scriber blade 31 when ⁇ > 0 is represented by the solid line and an example position of scriber blade 31 when ⁇ ⁇ 0 is represented by the broken line.
- the scribing means may be a means that has a laser light emission optical system and performs laser scribing.
- the scribing apparatus of the present invention is an apparatus, including a plurality of sets of the pressing means and scribing means to increase the depth and/or width of a separation groove to be formed in the target scribing film in a stepwise manner.
- the scribing apparatus of the present invention is preferably applied to a case where the flexible substrate is a substrate of a metal base on which an insulation film is formed and the target scribing film is a semiconductor film, a conductive film, or a laminated film of these films, or the like.
- the scribing apparatus of the present invention is preferably applied to the manufacture of a photoelectric conversion device.
- the scribing apparatus of the present invention is preferably applied to the manufacture of a photoelectric conversion device having a photoelectric conversion layer that includes a compound semiconductor formed of a group Ib element, a group IHb element, and a group VIb element.
- the scribing apparatus of the present invention is preferably applied to the manufacture of a photoelectric conversion device having a photoelectric conversion layer that includes a compound semiconductor formed of at least one type of group Ib element selected from the group consisting of Cu and Ag, at least one type of IHb element selected from the group consisting of Al, Ga, and In, and at least one type of VIb element selected from the group consisting of S, Se, and Te.
- Element group representation herein is based on the short period periodic table.
- a compound semiconductor formed of a group Ib element, a group IHb element, and a group VIb element is sometimes represented herein as "group I-III-VI semiconductor".
- Each of the group Ib element, group IHb element, and group VI element, which are constituent elements of group I-III-VI semiconductor may be one type or two or more types of elements. Further, the I-III-VI semiconductor included in the photoelectric conversion layer may be one type or two or more types of semiconductors.
- a scribing method of the present invention is a method for performing scribing, while conveying a web of strip-like continuous flexible substrate on which a target scribing film is formed by applying a tensile strength to the flexible substrate, on the target scribing film with the flexible substrate being pressed by a convex curved surface by bringing the convex curved surface into contact with the flexible substrate from a side on which the target subscribing film is not formed, wherein a tensile strength Tn and a pressing force P applied to the flexible substrate per unit cross-sectional area during the scribing satisfy Formulae (1) to (3) below: 1.5 MPa ⁇ Tn ⁇ 25 MPa (1)
- the tensile strength Tn and pressing force P are parameters represented by the following formulae:
- Tn T/Ss (Pa)
- P T/ (W x R) (Pa)
- T represents the tensile strength applied the entire cross-section of the flexible substrate
- S s represents the cross-sectional area of the flexible substrate
- W represents the width of the flexible substrate
- R represents the radius of curvature of the convex curved surface.
- scribing apparatus and scribing method of the present invention while conveying a substrate web, scribing may be performed efficiently and highly accurately on a target scribing film with a high yield rate and stably.
- Figure 1 is a perspective view of a scribing apparatus according to an embodiment of the present invention.
- Figure 2 is a design modification of the apparatus shown in Figure 1.
- Figure 3 is a design modification of the apparatus shown in Figure 1.
- Figure 4 is a design modification of the apparatus shown in Figure 1.
- Figure 5A is a schematic sectional view of a photoelectric conversion device taken along a lateral direction, illustrating an example structure thereof.
- Figure 5B is a schematic sectional view of a photoelectric conversion device taken along a longitudinal direction, illustrating an example structure thereof.
- Figure 6 is a schematic sectional view of a substrate, illustrating the structure thereof.
- Figure 7 is a perspective view of a substrate, illustrating a manufacturing method thereof.
- Figure 8A is a front elevation of a scriber blade and an adjacent portion viewed from a traveling direction of the scriber blade.
- Figure 8B is a sectional view schematically illustrating a flexible substrate, a target scribing film, a scriber blade, and a rake angle.
- Figure 1 is a schematic perspective view of the apparatus.
- Scribing apparatus 1 of the present embodiment includes conveyance means 10 for conveying a web of strip-like continuous flexible substrate B on which a target scribing film M is formed by applying a tensile strength to the flexible substrate, pressing means 20 for pressing the flexible substrate B from a side on which the target scribing film M is not formed, and scribing means 30 for performing scribing on the target scribing film M formed on the surface of a portion of the flexible substrate B pressed by pressing means 20.
- the flexible substrate B There is not any specific restriction on the flexible substrate B, and a metal substrate, a substrate of metal base with an insulation film formed thereon, a resin substrate, and the like are cited. There is not any specific restriction on the target scribing film M, and a semiconductor film, a conductive film, a laminated film of these films, and the like are cited.
- conveyance means 10 is roughly constituted by first turnable roller (payout roller) 11 for paying out the strip-like continuous flexible film B on which the target scribing filmM is formed and second turnable roller (roll-up roller) 12 for rolling up the flexible substrate B after subjected to the scribing.
- First roller 11 may be a conveyance roller that conveys the substrate from a previous process to the scribing process .
- second roller 12 may be a conveyance roller that conveys the substrate from the scribing process to a next process.
- Pressing means 20 is roughly constituted by turanble pressing roller 21 for pressing flexible substrate B and a position adjustment mechanism (not shown) for adjusting the position of the roller 21 in up-down directions.
- Pressing roller 21 has convex curved surface 2IS which is brought into contact with the flexible substrate B from the side on which the target scribing film M is not formed to press the flexible substrate B.
- Pressing roller 21 has a positioning function for the scribing as well as the function for pressing flexible substrate B.
- the position of pressing roller 21 in up-down direction is adjustable by the position adjustment mechanism, and the pressing force and tensile strength applied to the flexible substrate B by pressing roller 21 may be adjusted by adjusting the position of pressing roller 21 (convex curved surface 21S) .
- width W of flexible substrate B there is not any specific restriction on width W of flexible substrate B and, for example, 150 to 2000 mm. There is not any specific restriction on the width of first roller 11, second roller 12, and pressing roller 21, and a width of 1.2 to 1.5 times the width W of flexible substrate B is preferable. There is not any specific restriction on the radius of pressing roller 21, and 40 to 300 mm is preferable. There is not any specific restriction on the conveyance speed of the substrate and is, for example, 1 to 150 m/min. Scribing means 30 is disposed opposite to pressing roller 21 across the flexible substrate B and is roughly constituted by a plurality of scriber blades 31 for mechanically performing scribing. The plurality of scriber blades 31 is arranged in the width direction of flexible substrate B. The position of each scriber blade 31 in the width direction of the substrate and up-down direction is adjustable. In Figure 1, the reference symbol H represents a separation groove formed by the scribing.
- Apparatus 1 of the present embodiment also includes meandering correction means 40, each constituted bymeandering detection sensor 41 and a plurality of meandering correction rollers 42.
- the position of each scriber blade 31 in the width direction of the substrate and the clearance between each scriber blade 31 and pressing roller 21 are set to specific values according to the scribing section of the target scribing film M and the depth of the separation groove H to be formed, and while a tensile strength and a pressing force are applied to the flexible substrate B, a specific load is applied to scriber blade 31 to perform scribing such that the surface of the target scribing film M is scratched.
- the position of scriber blade 31 is adjusted during an off-time of scribing and basically fixed during scribing.
- fine movement control is performed on scriber blade 31 such that the clearance between scriber blade 31 and pressing roller 21 is maintained constant following a vibration of the apparatus and the like. Implementation of such control allows separation grooves H with small variations in the depth and width to be formed.
- the width 31W of the cutting edge of scriber blade refers to a maximum width contacting the target scribing film M in a front elevation of the scriber blade 31 viewed from a traveling direction thereof ( Figure 8A, which is a front elevation of a scriber blade and an adjacent portion viewed from a traveling direction of the scriber blade) .
- the width 31W of the cutting edge of scriber blade 31 is selected, for example, from the range of 10 to 300 urn.
- Apparatus 1 of the present embodiment is adjusted such that the tensile strength Tn and pressing force P applied to the flexible substrate B per unit cross-sectional area at the time of scribing satisfy Formulae (1) to (3) below.
- Tensile strength Tn and pressing force P are parameters represented by the following formulae.
- T represents the tensile strength applied to the entire cross-section of the flexible substrate
- S s represents the cross-sectional area of the flexible substrate
- W represents the width of the flexible substrate
- R represents the radius of curvature of the convex curved surface.
- the position of the pressing roller 21 in up-down directions is adjustable and the pressing force and tensile strength applied to the flexible substrate B by pressing roller 21 is adjustable.
- the position of pressing roller is adjusted such that Formulae (1) to (3) above are satisfied and the adjusted position is maintained during scribing.
- a hard material resistant to breakage and abrasion is preferably used.
- Such materials include diamond, boron nitride, various types of metals, and the like. Among them, diamond is most preferably used since it is durable and allows scribing of stable size and shape.
- angle (rake angle) ⁇ formed between face Sl of scriber blade 31 on the side that moves relative to the flexible substrate B and a normal line to the surface of the flexible substrate for ⁇ and plus/minus thereof, reference is directed to the description under "Disclosure of Invention" and Figure 8B) .
- the inventor of the present invention has confirmed that favorable scribing may be performed with a rake angle ⁇ at least in the range -80° ⁇ ⁇ ⁇ 35° (Examples 15 to 22) .
- scriber blade 31 takes the form of breaking into between the flexible substrate B and an uncut portion of the target scribing film M to be cut now.
- scriber blade 31 takes the form of overhanging on an uncut portion of the target scribing film M to be cut now.
- the inventor of the present invention has found that a so-called picking in which an uncut portion to be cut now is detached irregularly over an excessive range occurs frequently when ⁇ > 0 and less frequently when ⁇ ⁇ 0.
- the picking occurs, accurate scribing is prevented and the yield rate is decreased.
- the rake angle ⁇ is -70° ⁇ a. ⁇ 0, more preferably, -70° ⁇ a ⁇ -5°, and particularly preferable, -60° ⁇ ⁇ ⁇ -35°.
- angle (clearance angle) Y formed between face S2 of scriber blade 31 opposite to the side that moves relative to the flexible substrate B and the surface of the flexible substrate B is preferable to be not smaller than 10°.
- Y is in the range described above, scribing of stable quality may be performed.
- Scribing apparatus 1 of the present embodiment is structured in the manner as described above.
- the tensile strength and pressing force applied to the flexible substrate B at the time of scribing are adjusted in preferable ranges, so that the warpage, undulation, deflection, and the like are favorably reduced. This allows easy control of positioning, cutting depth, and the like of scribing, whereby accurate scribing may be performed. Further, it is not likely that excessive tensile strength or pressing force is applied to the flexible substrate B which may cause small abrasions and cracks around a separation groove H formed or invisible damages .
- scribing apparatus 1 of the present embodiment and a scribing method using the same, efficient and accurate scribing may be performed on the target scribing film M with a high yield rate and stably.
- efficient and accurate scribing may be performed on the target scribing film M with a high yield rate and stably.
- Scribing apparatus 1 of the present embodiment may be used for manufacturing any electronic device that requires scribing.
- Scribing apparatus 1 of the present embodiment may be preferably used for manufacturing a photoelectric conversion device. Scribing apparatus 1 of the present embodiment may be preferably used for manufacturing a photoelectric conversion device having a photoelectric conversion layer that includes a compound semiconductor formed of a group Ib element, a group IHb element, and a group VIb element. Scribing apparatus 1 of the present embodiment may be preferably used for manufacturing a photoelectric conversion device having a photoelectric conversion layer that includes a compound semiconductor formed of at least one type of group Ib element selected from the group consisting of Cu and Ag, at least one type of IHb element selected from the group consisting of Al, Ga, and In, and at least one type of VIb element selected from the group consisting of S, Se, and Te.
- the photoelectric conversion rate of the device is improved. This would be the ability of the apparatus to perform highly accurate scribing and reduced stress incurred on the device during processing, whereby defects or damages are reduced. (Design Changes)
- the present invention is not limited to the embodiment described above, and design changes may be made as appropriate without departing from the sprit of the present invention.
- the form of pressing means 20 is not limited to pressing roller 21, and any form may be employed as long as it has a convex curved surface.
- scriber blade 31 maybe configured to be scannable in width directions of the substrate. Such structure allows scribing in a parallel direction, a vertical direction, and an oblique direction with respect to the conveyance direction of the substrate. For example, a vertical scribing may be performed by conveying the substrate intermittently and scanning scriber blade 31 in width directions of the substrate while the conveyance is stopped.
- the scribing means may be a means which is roughly constituted by laser light emission optical system 50 and performs laser scribing.
- Laser light emission optical system 50 includes laser oscillator 52 which is energized by power source 51 and oscillates laser light, light control/transmission optical systems 53 to 56 for controlling or transmitting the laser light, and laser head 59 for emitting the laser light on the s ⁇ rface of a target scribing film M formed on a flexible substrate B.
- the light control/transmission optical systems include attenuator 53 for controlling the energy of the laser light oscillated in the laser oscillator 56, slit 54 for shaping the optical image of the laser light into a slit-like form, condenser lens 55 for condensing the laser light shaped into the slit-like form, and optical fiber 56 for transmitting the laser light condensed by condenser lens 55.
- Laser head 59 includes variable slit 57 for reshaping the optical image of the laser light transmitted through optical fiber 56 into a slit-like form having a desired size and condenser lens 58.
- Laser head 59 is configured to be scannable in width directions of the substrate.
- the wavelength of the laser light there is not any specific restriction on the wavelength of the laser light and appropriately designed according to the light absorption wavelength of a target scribing film M.
- the target scribing film M is a Mo lower electrode of a photoelectric conversion device
- laser light with a center wavelength of 500 to 1100 nm is preferably used.
- the target scribing film M is a photoelectric conversion layer or an upper electrode of a photoelectric conversion device, laser light with a center wavelength of not greater than 400 nm is preferably used.
- Laser emission conditions such as the wavelength, emission energy, laser output pattern, emission time, and the like, are adjusted according to the light absorption coefficient of the target scribing film M, whereby accurate scribing with a desired depth and width may be performed.
- the absorption coefficient is high and diffraction effect or the like is small, so that the laser emission range may be determined easily without unnecessary power being applied to a surrounding area, whereby the scribing may be performed accurately.
- Optical systems of laser light emission optical system 50 are not limited to those shown in Figure 3 and are appropriately changed in the designs.
- a plurality of sets of pressing means 20 and scribing means 30 may be provided.
- Such structure allows the depth and/or width of a separation groove H to be increased in a stepwise manner.
- Such design change may also be applicable to the apparatus shown in Figure 3.
- the structure for increasing the depth and/or width of a separation groove H to be formed on a target scribing film M in a stepwise manner may reduce an instantaneous load (a mechanical load in mechanical scribing and a thermal load in laser scribing) incurred by a surrounding area of a separation groove H at the time of scribing, whereby the yield rate and device performance may be improved. Further, the load (a mechanical load in mechanical scribing and a thermal load in laser scribing) incurred by pressing roller 21 may also be reduced, whereby the durability of the apparatus may be increased.
- Figure 5A is a schematic sectional view of the photoelectric conversion device in a lateral direction
- Figure 5B is a schematic sectional view of the photoelectric conversion device in a longitudinal direction
- Figure 6 is a schematic sectional view of a substrate, illustrating the structure thereof
- Figure 7 is a perspective view of a substrate, illustrating a manufacturing method thereof.
- each component is not drawn to scale in order to facilitate visual recognition.
- "lateral direction of a photoelectric conversion device” and “longitudinal direction of a photoelectric conversion device” correspond respectively to a width direction and a conveyance direction of a flexible substrate used.
- photoelectric conversion device 100 is a device having flexible substrate 110 on which lower electrode (rear electrode) 120, photoelectric conversion layer 130, buffer layer 140, and upper electrode layer 150 are stacked in this order.
- Photoelectric conversion device 100 has first separation grooves 161 that run through only lower electrode 120, second separation grooves 162 that run through photoelectric conversion layer 130 and buffer layer 140, and third separation grooves 163 that run through onlyupper electrode layer 150 in a lateral sectional view and fourth separation grooves 164 that run through photoelectric conversion layer 130, buffer layer 140, and upper electrode layer 150 in a longitudinal sectional view.
- the above configuration may provide a structure in which the device is divided into many cells C by first to fourth separation grooves 161 to 164. Further, upper electrode 150 is filled in second separation grooves 162, whereby a structure in which upper electrode 150 of a certain cell C is serially connected to lower electrode 120 of adjacent cell C may be obtained.
- flexible substrate 110 is a substrate obtained by anodizing at least one surface side of an Al-based metal base 111.
- Substrate 110 may be a substrate of metal base 111 having anodized film 112 on each side as illustrated on the left of Figure 6 or a substrate of metal base 111 having anodized film 112 on either one of the sides as illustrated on the right of Figure 6.
- anodized film 112 is an AI 2 O 3 based film.
- the thickness of metal base 111 is, for example, 50 to 500 um, and the thickness of anodized film 112 is, for example, 0.5 to 20 um.
- Major component of the metal base herein is defined as a component occupying 50% by mass or more.
- Metal base 111 may be a metal base that includes a minor element, a pure Al substrate, or an alloy of Al with another metal element.
- a pure Al substrate with an Al content of not less than 95% by mass is preferably used as metal base 111 on which anodized film 112 is formed.
- Anodization may be performed by immersing metal base 111, which is cleaned, smoothed by polishing, and the like as required, as an anode with a cathode in an electrolyte, and applying a voltage between the anode and cathode.
- Al based metal base 111 is anodized
- an oxidization reaction proceeds from surface Ills in a direction substantially perpendicular to surface Ills, and Al 2 O 3 based anodized film 112 is formed.
- Anodized film 112 generated by the anodization has a structure in which multiple fine columnar bodies, each having a substantially regular hexagonal shape in plan view, are tightly arranged.
- Each fine columnar body 112a has a fine pore 112b, in substantially the center, extending substantially linearly in a depth direction from surface Ills, and the bottom surface of each fine columnar body 112a has a rounded shape.
- a barrier layer without any fine pore 112b is formed at a bottom area of fine columnar bodies 112a.
- Anodized film 112 without any fine pore 112b may also be formed by appropriately arranging the anodizing conditions.
- Photoelectric conversion layer 130 includes one or more types of compound semiconductors of at least one type of group Ib element, at least one type of group IHb element, and at least one type of group VIb element (group I-III-VI semiconductors) and generates a current by absorbing light.
- photoelectric conversion layer 130 is a layer that includes one or more types of compound semiconductors of at least one type of group Ib element selected from the group consisting of Cu and Ag, at least one type of group IHb element selected from the group consisting of B, Al, Ga, and In, and at least one type of group VIb element selected from the group consisting of O, S, Se, and Te .
- photoelectric conversion layer 130 includes one or more types of compound semiconductors of at least one type of group Ib element selected from the group consisting of Cu and Ag, at least one type of group IHb element selected from the group consisting of Al, Ga, and In, and at least one type of group VIb element selected from the group consisting of S, Se, and Te.
- the compound semiconductors described above may include but not limited to CuAlS 2 , CuGaS 2 , CuInS 2 , CuAlSe 2 , CuGaSe 2 , CuInSe 2 (CIS), AgAlS 2 , AgGaS 2 , AgInS 2 , AgAlSe 2 , AgGaSe 2 , AgInSe 2 , AgAlTe 2 , AgGaTe 2 , AgInTe 2 , Cu(In 1 -XGa x )Se 2 (CIGS), Cu (Ini_ x Al x ) Se 2 , Cu(Ini- x Ga x ) (S, Se) 2 , Ag(Ini_ x Ga x )Se 2 , and Ag(Ini- x Ga x ) (S, Se) 2 .
- photoelectric conversion layer 130 includes CuInSe 2 (CIS) and/or CuInSe 2 solidified with Ga, i.e., Cu(In, Ga)Se 2 (CIGS) .
- CIS and CIGS are semiconductors having a chalcopyrite crystal structure, and high light absorption rates and high energy conversion efficiency are reported. They also have excellent durability and have less deterioration in the efficiency due to light exposure.
- Photoelectric conversion layer 130 includes an impurity for obtaining an intended semiconductor conductivity type .
- the impurity may be included in photoelectric conversion layer 130 by diffusing from an adjacent layer or by active doping.
- Photoelectric conversion layer 130 may have a density distribution of constituent elements of group I-III-VI semiconductors and/or impurities, and may have a plurality of layer regions of different semiconductivities, such as n-type, p-type, i-type, and the like.
- the band gap width/carrier mobility and the like may be controlled by providing a distribution of the amount of Ga in photoelectric conversion layer 130 in the thickness direction, whereby high conversion efficiency may be designed.
- Photoelectric conversion layer 130 may include one or more types of semiconductors other than the group I-III-VI semiconductor.
- Group I-III-VI semiconductor may include but not limited to a semiconductor of group IVb element, such as Si (group IV semiconductor) , a semiconductor of group IIIb element and group Vb element such as GaAs (group IH-V semiconductor) , and a semiconductor of group Hb element and group VIb element, such as CdTe (group H-VI semiconductor) .
- group IVb element such as Si
- group IIIb element and group Vb element such as GaAs
- group Hb element and group VIb element such as CdTe (group H-VI semiconductor)
- Photoelectric conversion layer 130 may include any arbitrary component other than semiconductors and an impurity for causing the semiconductors to become an intended conductivity type within a limit that does not affect the properties. There is not any specific restriction on the content of group I-III-VI semiconductors in photoelectric conversion layer 130, in which not less than 75% by mass is preferable, not less than 95% by mass is more preferable, and not less than 99% by mass is particularly preferable. (Electrodes, Buffer Layer)
- Each of lower electrode 120 and upper electrode 150 is made of a conductive material.
- Upper electrode 50 on the light input side needs to be transparent. In view of effective use of light, it is preferable that lower electrode 120 on the substrate side has light reflectivity.
- a main layer of photoelectrical conversion layer 130 excluding a region adjacent to buffer layer 140 is a p-type semiconductor, lower electrode 120 is used as a positive electrode and upper electrode 150 is used as a negative electrode. If the main layer of photoelectric conversion layer 130 is an n-type semiconductor, the polarity of lower electrode 120 and upper electrode 150 is reversed.
- lower electrode 120 Mo, Cr, W, or a combination thereof is preferably used.
- upper electrode 150 ZnO, ITO (indium tin oxide) , SnO 2 , or a combination thereof is preferably used.
- Lower electrode 120 and/or upper electrode 150 may have a single layer structure or a laminated structure, such as a two-layer structure.
- buffer layer 140 CdS, ZnS, ZnO, ZnMgO, ZnS(O, OH), or a combination thereof is preferably used.
- the major component of the electrodes and buffer layer is defined as a component occupying 50% by mass or more.
- a preferable combination of the compositions is, for example, Mo lower electrode/CdS buffer layer/CIGS photoelectric conversion layer/ZnO upper electrode. (Other Layers)
- Photoelectric conversion device 100 may have any other layer as required in addition to those described above.
- a contact layer buffer layer
- an alkali barrier layer for preventing diffusion of alkali ions may be provided, as required, between substrate 110 and lower electrode 120.
- a reference is directed to Japanese Unexamined Patent Publication No. 8 (1996) -222750 for a preferred embodiment of the alkali barrier layer.
- Photoelectric conversion device 100 of the present embodiment is structured in the manner as described above.
- scribing is performed to form first to fourth separation grooves 161 to 164.
- scribing appropriate for the material and property of each film is performed.
- first separation grooves 161 are formed by laser scribing while second to fourth separation grooves 162 to 164 are formed by mechanical scribing using a scriber blade or laser scribing.
- photoelectric conversion devices 100 having high photoelectric conversion efficiency may be manufactured with a high yield rate and stably, while conveying a substrate web.
- the use of the scribing apparatus of the present invention allows separation grooves 161 to 164 to be formed highly accurately even under the conditions of roll-to-roll processing that requires a faster processing speed than that of a sheet-to-sheet processing.
- Photoelectric conversion device 100 shown here is just an example, and the scribing apparatus of the present invention is applicable to the manufacture of any type of photoelectric conversion device using a flexible substrate, such as metal substrate, substrate of metal base on which an insulation film is formed, resin substrate, or the like. Further, the scribing apparatus of the present invention is applicable to the manufacture of any other device than photoelectric conversion device. [Examples]
- a strip-like continuous Al thin plate with a purity of not less than 99.5% and a width of 300 mm was provided as the metal base.
- the Al plate was anodized in a boric acid solution to obtain a strip-like continuous flexible substrate of a 200 um thick Al base having a 5 um thick anodized film (Al 2 Cb film) on each side.
- the anodized film is has fine pores formed in a regular manner in which the thickness of the barrier layer was about 50 nm, the pitch of fine pores was about 150 nm, and the pore diameter of the fine pores was about 50 nm.
- a Mo lower electrode with a thickness of 0.7 um was formed over the entire surface of the obtained photoelectric conversion layer substrate by Ar sputtering. Thereafter, laser scribing was performed on the Mo lower electrode using the apparatus shown in Figure 3 to form a plurality of first separation grooves with a depth of about 0.7 um and a width of about 130 um.
- the conveyance speed of the substrate was 3 m/min.
- the laser YAG laser with a center wavelength of 1064 nm was used. Viewed in a width direction of the substrate, a plurality of first separation groove was formed with a pitch of 10 mm, whereby the lower electrode was divided into 24 cells.
- a Cu (In 0-7 GaO.3) Se 2 thin film was deposited by multi source simultaneous deposition with a thickness of about 1.7 ⁇ m over the entire surface of the substrate having the lower electrode formed thereon. The deposition of the
- Cu(In o .7Gao.3) Se ⁇ thin film was performed under a vacuumdegree of about lCr 4 Pa (lcr 7 Torr) by providing Cu, In, Ga, and Se deposition sources in a vacuum vessel.
- the temperature of the deposition crucible was controlled appropriately and substrate temperature was 530 0 C.
- a CdS film was deposited by chemical deposition with a thickness of about 50 nm over the entire surface of the substrate having the photoelectric conversion layer formed thereon.
- the chemical deposition was performed by heating a water solution of cadmium nitrate, thiourea, and ammonia to about 80°C and soaking the photoelectric conversion layer in the water solution.
- Al doped ZnO film was formed by Ar sputtering with a thickness of 0.6 ⁇ m.
- mechanical scribing using a scriber blade was performed on the upper electrode using the same apparatus as that used for forming the second separation grooves to form a plurality of third separation grooves with a depth of about 3.2 ⁇ m and a width of about 140 urn, whereby the upper electrode was divided into 24 cells.
- a plurality of second separation grooves was formed with a pitch of 10 mm, whereby the upper electrode was divided into 24 cells.
- the scribing blade used and conditions for brining the scriber blade into contact with the substrate were identical to those for forming the second separation grooves .
- each module has a structure in which three cell units, each having 24 cells connected in series, are connected in parallel.
- the first to fourth separation grooves were formed under the same conditions with respect to the radius of the pressing roller, tensile strength Tn and pressing force P, Tn x P, applied to the flexible substrate per unit cross-sectional area at the time of scribing. These data are shown in Table 1.
- Examples 1 to 11 produced by setting conditions with respect to the radius of the pressing roller, tensile strength Tn and pressing force P, Tn x P, applied to the flexible substrate per unit cross-sectional area at the time of scribing within the ranges of the present invention has higher photoelectric conversion efficiency and yield rate in comparison with Comparative
- Examples 1 to 3 produced by setting the parameters outside of the ranges of the present invention, meaning that photoelectric conversion devices having excellent properties were produced stably.
- the radius of the pressing roller was set within the range from 40 to 300 mm, which provided favorable results . Note that the manufacture of a pressing roller with a radius greater than 300 mm was difficult and evaluation thereof was not conducted. (Example 12)
- Example 12 in which scribing was performed in two steps for one separation groove has favorable results, that is, has higher photoelectric conversion efficiency and yield rate in comparison with Example 5 in which scribing was performed in single step for one separation groove. This shows that it is more preferable to perform scribing in a plurality of steps.
- Example 13 boron nitride sintered body (BN)
- Example 14 WC-TiC-TaC-Co alloy (equivalent to JIS-K-IO material) Manufacturing conditions and evaluation results of Examples 5, 13, and 14 are shown in Table 3. As Table 3 shows, diamond is particularly preferable as the material of the scriber blade. (Examples 15 to 22)
- Example 23 Solar cell modules were obtained and evaluated in the same manner as that for Examples 1 to 11 other than that the second to fourth separation grooves were formed by laser scribing using the apparatus shown in Figure 3. As for the laser, a third harmonic of YAG with a center wavelength of 355 nm was used. Each module showed identical results to those of Examples 1 to 11.
- the scribing apparatus of the present invention may be used for scribing any target scribing film, and may be used for scribing a semiconductor film, a conductive film, a laminated film of these films, and the like of devices such as a photoelectric conversion device and the like.
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Abstract
Performing scribing accurately with a high yield rate. A scribing apparatus (1), including a conveyance means (10) for conveying a web of strip-like continuous flexible substrate (B) on which a target scribing film (M) is formed by applying a tensile strength, a pressing means (20) for pressing the flexible substrate (B) by bringing a convex curved surface (21S) into contact with the flexible substrate (B) from a side on which the target subscribing film (M) is not formed, and a scribing means (30) for performing scribing on the target scribing film (M) in which a tensile strength Tn and a pressing force P applied to the flexible substrate per unit cross-sectional area during the scribing satisfy Formulae (1) to (3) below: 1.5 MPa ≤ Tn ≤ 25 MPa ------------- (1) 4 kPa ≤ P ≤ 50 kPa ------------------- (2) 5 GPa2 ≤ Tn x P ≤ 800 GPa2 ------ (3)
Description
DESCRIPTION
SCRIBING APPARATUS AND SCRIBING METHOD
Technical Field
The present invention relates to a scribing apparatus and a scribing method for performing scribing on a strip-like continuous flexible film on which a scribing target film is formed.
Background Art
Photoelectric conversion devices having a photoelectric conversion layer that generates a current by absorbing light and electrodes for drawing out the current generated in the photoelectric conversion layer are used in various applications, such as solar cells and the like. Most of the conventional solar cells are Si cells using bulk monocrystalline Si, polycrystalline Si, or thin film amorphous Si. Recently, however, research and development of compound semiconductor solar cells that do not depend on Si has been carried out. As compound semiconductor solar cells, two types are known, one of which is a bulk system, such as GaAs system and the like, and the other of which is a thin film system, such as CIS
(Cu-In-Se) system formed of a group Ib element, a group IHb element, and a group VIb element, CIGS (Cu-In-Ga-Se) , or the like. CIS systems or CIGS systems has high light absorption rates and high energy conversion efficiency is reported.
In various fields of electronic devices including thin film photoelectric conversion devices, development of technologies for forming and processing various functional films on a flexible substrate, thereby laminating an entire device into a sheet has been conducted. Such a process may reduce the amount of material used and allows continuous processing (roll-to-roll processing) so that the manufacturing costs may be reduced. Flexible substrates for photoelectric conversion devices may include a substrate having a metal base on which an insulation film is formed, and the like. Heretofore, integrated devices are monolithically fabricated
for high efficiency and low cost. One of the key technologies for that purpose is to divide a film into many cells by providing separation grooves in the film.
For example, as shown in Figures 5A and 5B, Thin film photoelectric conversion device 100 has first separation grooves 161 that run through only lower electrode 120, second separation grooves 162 that run through photoelectric conversion layer 130 and buffer layer 140, and third separation grooves 163 that run through only upper electrode layer 150 in a lateral sectional view and fourth separation grooves 164 that run through photoelectric conversion layer 130, buffer layer 140, and upper electrode layer 150 in a longitudinal sectional view.
In the photoelectric conversion device described above, scribing appropriate for the material and property of each film is performed. For a CIGS device, for example, it is customary that first separation grooves 161 are formed by laser scribing while second to fourth separation grooves 162 to 164 are formed by mechanical scribing using a scriber blade.
When scribing a target film formed on a flexible substrate by roll-to-roll processing, it is necessary to perform the scribing while preventing warpage, undulation, deflection, and the like of the flexible film in order to accurately and efficiently perform the scribing.
Japanese Unexamined Patent Publication No. 10 (1998) -027918 discloses an apparatus in which, while conveying a web of flexible substrate on which a target scribing film is formed, laser scribing is performed with the flexible substrate being brought into contact with and pressed by a roller-like substrate support means (claim 2, Figure 1, and the like) . Japanese Unexamined Patent Publication No. 2001-044471 discloses an apparatus in which, while conveying a web of flexible substrate on which a target scribing film is formed, laser scribing is performed with the flexible substrate being held by a flat plate like substrate position keeping means (claim 3, Figure 3, and the like) .
Japanese Unexamined Patent Publication No. 2004-146773 discloses, as a conventional technology, an apparatus in which, while conveying a web of flexible substrate on which a target scribing film is formed, mechanical scribing using a scriber blade is performed with the flexible substrate being held by two guide rolls
(claim 3, Figure 3, and the like) . Japanese Unexamined Patent
Publication No. 2004-146773 also proposes the use of micro plasma dry etching for separation groove formation (claim 1, Figure 1, and the like) . When performing scribing on a target film formed on a flexible substrate by roll-to-roll processing, it is necessary to highly accurately form a separation groove at a speed faster than that of sheet-to-sheet processing. For example, in a photoelectric conversion device, if a first separation groove that runs through the lower electrode is not clearly formed and a residue of the electrode which should have been removed remains, a short circuit occurs between the electrode and an electrode of an adjacent cell, whereby leakage current flows anddesiredphotoelectrical conversion efficiency can not be obtained. Otherwise, if the lower electrode is cut too deeply and an insulation film on the substrate is also cut, a dielectric breakdown occurs, resulting in a short circuit between the lower electrode and metal base.
Japanese Unexamined Patent Publication Nos. 10 (1998) -027918, 2001-044471, and 2004-146773, however, do not describe specific conditions at all, such as the tensile strength, pressing force, and the like to be applied to the flexible substrate, so that specific conditions for stably forming an accurate separation groove in a thin film are not clear.
If the tensile strength or pressing force is too small, it is difficult to prevent warpage, undulation, and deflection of a flexible substrate, whereby the positioning and cutting depth control of the scribing become difficult. On the other hand, if the tensile strength or pressing force is too large, an excessive stress is applied to the flexible substrate, causing small abrasions and cracks around a separation groove or invisible damages.
The present invention has been developed in view of the circumstances described above, and it is an object of the present invention to provide a scribing apparatus and a scribing method capable of, while conveying a substrate web, performing efficient and accurate scribing on a target scribing film with a high yield rate and stably.
Disclosure of Invention
A scribing apparatus of the present invention is an apparatus, including: a conveyance means for conveying a web of strip-like continuous flexible substrate on which a target scribing film is formed by applying a tensile strength to the flexible substrate; a pressing means, having a convex curved surface, for pressing the flexible substrate by bringing the convex curved surface into contact with the flexible substrate from a side on which the target subscribing film is not formed; and a scribing means for performing scribing on the target scribing film formed on the surface of a portion of the flexible substrate pressed by the pressing means, wherein a tensile strength Tn and a pressing force P applied to the flexible substrate per unit cross-sectional area during the scribing satisfy Formulae (1) to (3) below:
1.5 MPa < Tn < 25 MPa (1) 4 kPa < P < 50 kPa (2)
5 GPa2 < Tn x P < 800 GPa2 (3)
The tensile strength Tn and pressing force P are parameters represented by the following formulae:
Tn = T/Ss (Pa), P = T/ (W x R) (Pa) (where, T represents the tensile strength applied the entire cross-section of the flexible substrate, Ss represents the cross-sectional area of the flexible substrate, W represents the width of the flexible substrate, and R represents the radius of curvature of the convex curved surface.) In the scribing apparatus of the present invention, the
flexible substrate may be conveyed by continuous conveyance or intermittent conveyance. In the case of the intermittent conveyance, the scribing may be performed when the substrate is in conveyance or stopped. There is not any specific restriction on the flexible substrate and a metal substrate, a substrate of metal base on which an insulation film is formed, a resin substrate, and the like may be cited. The flexible substrate may include any one or more types of films, such as an insulation film, an electrode, and the like, between the surface of the substrate and the target scribing film. In this case, the cross-sectional area of the flexible substrate is defined as the cross-sectional area including the layer or layers formed under the target scribing film. The target scribing film may be a single layer film or a laminated film.
In the scribing apparatus of the present invention, it is preferable that the conveyance means includes a first roller for paying out the flexible substrate and a second roller for rolling up the flexible substrate after subjected to the scribing, and the pressing means includes a pressing roller for pressing the flexible substrate. In such a configuration, it is preferable that the pressing roller has a radius of 40 to 300 mm. In the scribing apparatus of the present invention, it is preferable that the position of the convex curved surface is changeable with respect to the flexible substrate .
As for the scribing means, a scribing means that has a scriber blade and performs mechanical scribing may be cited. In this case, it is preferable that the material of the scriber blade is diamond.
When the scribing means is a means that has a scriber blade and performs mechanical scribing, it is preferable that an angle α formed between a face of the scriber blade on the side that moves relative to the flexible substrate and a normal line to the surface of the flexible substrate is -80° ≤ a ≤ 35°, and more preferably -70° ≤ α ≤ 0°. The angle α describe above is referred to herein as "rake angle".
Figure 8B is a sectional view schematically illustrating a flexible substrate B, a target scribing film M, a scriber blade 31,
and a rake angle α. When face Sl of scriber blade 31 on the side that moves relative to the flexible substrate is inclined to a side opposite to the relative moving direction D with respect to the normal line V to the surface of the flexible substrate, it is defined herein that oc > 0, and when face Sl is inclined to the same direction as the relative moving direction D with respect to the normal line V to the surface of the flexible substrate, it is defined that α < 0. In Figure 8B, an example position of scriber blade 31 when α > 0 is represented by the solid line and an example position of scriber blade 31 when α < 0 is represented by the broken line.
The scribing means may be a means that has a laser light emission optical system and performs laser scribing.
Preferably, the scribing apparatus of the present invention is an apparatus, including a plurality of sets of the pressing means and scribing means to increase the depth and/or width of a separation groove to be formed in the target scribing film in a stepwise manner.
The scribing apparatus of the present invention is preferably applied to a case where the flexible substrate is a substrate of a metal base on which an insulation film is formed and the target scribing film is a semiconductor film, a conductive film, or a laminated film of these films, or the like. The scribing apparatus of the present invention is preferably applied to the manufacture of a photoelectric conversion device. The scribing apparatus of the present invention is preferably applied to the manufacture of a photoelectric conversion device having a photoelectric conversion layer that includes a compound semiconductor formed of a group Ib element, a group IHb element, and a group VIb element. The scribing apparatus of the present invention is preferably applied to the manufacture of a photoelectric conversion device having a photoelectric conversion layer that includes a compound semiconductor formed of at least one type of group Ib element selected from the group consisting of Cu and Ag, at least one type of IHb element selected from the group consisting of Al, Ga, and In, and at least one type of VIb element selected from the group consisting of S, Se, and Te.
Element group representation herein is based on the short period periodic table. A compound semiconductor formed of a group Ib element, a group IHb element, and a group VIb element is sometimes represented herein as "group I-III-VI semiconductor". Each of the group Ib element, group IHb element, and group VI element, which are constituent elements of group I-III-VI semiconductor, may be one type or two or more types of elements. Further, the I-III-VI semiconductor included in the photoelectric conversion layer may be one type or two or more types of semiconductors. A scribing method of the present invention is a method for performing scribing, while conveying a web of strip-like continuous flexible substrate on which a target scribing film is formed by applying a tensile strength to the flexible substrate, on the target scribing film with the flexible substrate being pressed by a convex curved surface by bringing the convex curved surface into contact with the flexible substrate from a side on which the target subscribing film is not formed, wherein a tensile strength Tn and a pressing force P applied to the flexible substrate per unit cross-sectional area during the scribing satisfy Formulae (1) to (3) below: 1.5 MPa < Tn < 25 MPa (1)
4 kPa < P < 50 kPa (2)
5 GPa2 < Tn x P < 800 GPa2 (3)
The tensile strength Tn and pressing force P are parameters represented by the following formulae:
Tn = T/Ss (Pa), P = T/ (W x R) (Pa)
(where, T represents the tensile strength applied the entire cross-section of the flexible substrate, Ss represents the cross-sectional area of the flexible substrate, W represents the width of the flexible substrate, and R represents the radius of curvature of the convex curved surface.)
According to the scribing apparatus and scribing method of the present invention, while conveying a substrate web, scribing may be performed efficiently and highly accurately on a target scribing film with a high yield rate and stably.
Brief Description of Drawings
Figure 1 is a perspective view of a scribing apparatus according to an embodiment of the present invention.
Figure 2 is a design modification of the apparatus shown in Figure 1.
Figure 3 is a design modification of the apparatus shown in Figure 1.
Figure 4 is a design modification of the apparatus shown in Figure 1. Figure 5A is a schematic sectional view of a photoelectric conversion device taken along a lateral direction, illustrating an example structure thereof.
Figure 5B is a schematic sectional view of a photoelectric conversion device taken along a longitudinal direction, illustrating an example structure thereof.
Figure 6 is a schematic sectional view of a substrate, illustrating the structure thereof.
Figure 7 is a perspective view of a substrate, illustrating a manufacturing method thereof. Figure 8A is a front elevation of a scriber blade and an adjacent portion viewed from a traveling direction of the scriber blade.
Figure 8B is a sectional view schematically illustrating a flexible substrate, a target scribing film, a scriber blade, and a rake angle.
Best Mode for Carrying Out the Invention [Scribing Apparatus]
A structure of a scribing apparatus according to an embodiment of the present invention will be described with reference to the accompanying drawings. Figure 1 is a schematic perspective view of the apparatus.
Scribing apparatus 1 of the present embodiment includes conveyance means 10 for conveying a web of strip-like continuous flexible substrate B on which a target scribing film M is formed
by applying a tensile strength to the flexible substrate, pressing means 20 for pressing the flexible substrate B from a side on which the target scribing film M is not formed, and scribing means 30 for performing scribing on the target scribing film M formed on the surface of a portion of the flexible substrate B pressed by pressing means 20.
There is not any specific restriction on the flexible substrate B, and a metal substrate, a substrate of metal base with an insulation film formed thereon, a resin substrate, and the like are cited. There is not any specific restriction on the target scribing film M, and a semiconductor film, a conductive film, a laminated film of these films, and the like are cited.
In the present embodiment, conveyance means 10 is roughly constituted by first turnable roller (payout roller) 11 for paying out the strip-like continuous flexible film B on which the target scribing filmM is formed and second turnable roller (roll-up roller) 12 for rolling up the flexible substrate B after subjected to the scribing. First roller 11 may be a conveyance roller that conveys the substrate from a previous process to the scribing process . Likewise, second roller 12 may be a conveyance roller that conveys the substrate from the scribing process to a next process.
Pressing means 20 is roughly constituted by turanble pressing roller 21 for pressing flexible substrate B and a position adjustment mechanism (not shown) for adjusting the position of the roller 21 in up-down directions. Pressing roller 21 has convex curved surface 2IS which is brought into contact with the flexible substrate B from the side on which the target scribing film M is not formed to press the flexible substrate B. Pressing roller 21 has a positioning function for the scribing as well as the function for pressing flexible substrate B.
In the present embodiment, the position of pressing roller 21 in up-down direction is adjustable by the position adjustment mechanism, and the pressing force and tensile strength applied to the flexible substrate B by pressing roller 21 may be adjusted by adjusting the position of pressing roller 21 (convex curved surface
21S) .
There is not any specific restriction on width W of flexible substrate B and, for example, 150 to 2000 mm. There is not any specific restriction on the width of first roller 11, second roller 12, and pressing roller 21, and a width of 1.2 to 1.5 times the width W of flexible substrate B is preferable. There is not any specific restriction on the radius of pressing roller 21, and 40 to 300 mm is preferable. There is not any specific restriction on the conveyance speed of the substrate and is, for example, 1 to 150 m/min. Scribing means 30 is disposed opposite to pressing roller 21 across the flexible substrate B and is roughly constituted by a plurality of scriber blades 31 for mechanically performing scribing. The plurality of scriber blades 31 is arranged in the width direction of flexible substrate B. The position of each scriber blade 31 in the width direction of the substrate and up-down direction is adjustable. In Figure 1, the reference symbol H represents a separation groove formed by the scribing.
Apparatus 1 of the present embodiment also includes meandering correction means 40, each constituted bymeandering detection sensor 41 and a plurality of meandering correction rollers 42.
In the present embodiment, the position of each scriber blade 31 in the width direction of the substrate and the clearance between each scriber blade 31 and pressing roller 21 are set to specific values according to the scribing section of the target scribing film M and the depth of the separation groove H to be formed, and while a tensile strength and a pressing force are applied to the flexible substrate B, a specific load is applied to scriber blade 31 to perform scribing such that the surface of the target scribing film M is scratched. In the present embodiment, the position of scriber blade 31 is adjusted during an off-time of scribing and basically fixed during scribing. It is preferably, however, that fine movement control is performed on scriber blade 31 such that the clearance between scriber blade 31 and pressing roller 21 is maintained constant following a vibration of the apparatus and the like. Implementation of such
control allows separation grooves H with small variations in the depth and width to be formed.
There is not any specific restriction on the width 31W of the cutting edge of scriber blade and is selected according to the width of a separation groove H. The width 31W of the cutting edge refers to a maximum width contacting the target scribing film M in a front elevation of the scriber blade 31 viewed from a traveling direction thereof (Figure 8A, which is a front elevation of a scriber blade and an adjacent portion viewed from a traveling direction of the scriber blade) . The width 31W of the cutting edge of scriber blade 31 is selected, for example, from the range of 10 to 300 urn. There is not any specific restriction on the load applied to scriber blade 31 and selected, for example, from the range of 150 to 40OmN.
In order to stably forming separation grooves H in the target scribing film M by preventing warpage, undulation, and deflection of the flexible substrate B, the tensile strength and pressing force applied to the flexible substrate B are important. Apparatus 1 of the present embodiment is adjusted such that the tensile strength Tn and pressing force P applied to the flexible substrate B per unit cross-sectional area at the time of scribing satisfy Formulae (1) to (3) below.
1.5 MPa < Tn < 25MPa (1)
4kPa < P < 5OkPa (2)
5 GPa2 < Tn x P < 800 GPa2 (3) Tensile strength Tn and pressing force P are parameters represented by the following formulae.
Tn - T/Ss (Pa), P = T/ (W x R) (Pa)
(where, T represents the tensile strength applied to the entire cross-section of the flexible substrate, Ss represents the cross-sectional area of the flexible substrate, W represents the width of the flexible substrate, and R represents the radius of curvature of the convex curved surface.)
As described above, in the present embodiment, the position of the pressing roller 21 in up-down directions is adjustable and the pressing force and tensile strength applied to the flexible
substrate B by pressing roller 21 is adjustable. In the present embodiment, the position of pressing roller is adjusted such that Formulae (1) to (3) above are satisfied and the adjusted position is maintained during scribing. There is not any specific limitation on the material of scriber blade 31, and a hard material resistant to breakage and abrasion is preferably used. Such materials include diamond, boron nitride, various types of metals, and the like. Among them, diamond is most preferably used since it is durable and allows scribing of stable size and shape.
There is not any specific restriction on the angle (rake angle) α formed between face Sl of scriber blade 31 on the side that moves relative to the flexible substrate B and a normal line to the surface of the flexible substrate (for α and plus/minus thereof, reference is directed to the description under "Disclosure of Invention" and Figure 8B) . The inventor of the present invention has confirmed that favorable scribing may be performed with a rake angle α at least in the range -80°< α < 35° (Examples 15 to 22) .
As illustrated in Figure 8B, if a > 0, face Sl of scriber blade 31 on the side that moves relative to the flexible substrate B is inclined opposite to the relative moving direction D with respect to the normal line V to the surface of the flexible substrate. In this case, scriber blade 31 takes the form of breaking into between the flexible substrate B and an uncut portion of the target scribing film M to be cut now.
On the other hand, if α < 0, face Sl of scriber blade 31 on the side that moves relative to the flexible substrate B is inclined to the relative moving direction D with respect to the normal line V to the surface of the flexible substrate. In this case, scriber blade 31 takes the form of overhanging on an uncut portion of the target scribing film M to be cut now.
The inventor of the present invention has found that a so-called picking in which an uncut portion to be cut now is detached irregularly over an excessive range occurs frequently when α > 0 and less frequently when α < 0. When the picking occurs, accurate
scribing is prevented and the yield rate is decreased. Thus, α ≤
0 is preferable and α< 0 is more preferable. Further, when a. < -10°, scriber blade 31 is excessively inclined to a horizontal side which may prevent accurate scribing in the depth direction. Preferably, the rake angle α is -70°≤ a. ≤ 0, more preferably, -70°≤ a ≤ -5°, and particularly preferable, -60°< α < -35°.
There is not any specific restriction on the angle (clearance angle) Y formed between face S2 of scriber blade 31 opposite to the side that moves relative to the flexible substrate B and the surface of the flexible substrate B, and is preferable to be not smaller than 10°. When Y is in the range described above, scribing of stable quality may be performed.
Scribing apparatus 1 of the present embodiment is structured in the manner as described above. In the present embodiment, the tensile strength and pressing force applied to the flexible substrate B at the time of scribing are adjusted in preferable ranges, so that the warpage, undulation, deflection, and the like are favorably reduced. This allows easy control of positioning, cutting depth, and the like of scribing, whereby accurate scribing may be performed. Further, it is not likely that excessive tensile strength or pressing force is applied to the flexible substrate B which may cause small abrasions and cracks around a separation groove H formed or invisible damages .
Thus, according to scribing apparatus 1 of the present embodiment and a scribing method using the same, efficient and accurate scribing may be performed on the target scribing film M with a high yield rate and stably. The use of scribing apparatus
1 of the present embodiment allows separation grooved H to be formed highly accurately even under the conditions of roll-to-roll processing that requires a faster processing speed than that of a sheet-to-sheet processing.
Scribing apparatus 1 of the present embodiment may be used for manufacturing any electronic device that requires scribing.
Scribing apparatus 1 of the present embodiment may be preferably used for manufacturing a photoelectric conversion device. Scribing
apparatus 1 of the present embodiment may be preferably used for manufacturing a photoelectric conversion device having a photoelectric conversion layer that includes a compound semiconductor formed of a group Ib element, a group IHb element, and a group VIb element. Scribing apparatus 1 of the present embodiment may be preferably used for manufacturing a photoelectric conversion device having a photoelectric conversion layer that includes a compound semiconductor formed of at least one type of group Ib element selected from the group consisting of Cu and Ag, at least one type of IHb element selected from the group consisting of Al, Ga, and In, and at least one type of VIb element selected from the group consisting of S, Se, and Te.
When a photoelectric conversion device is manufactured using scribing apparatus 1 of the present embodiment, the photoelectric conversion rate of the device is improved. This would be the ability of the apparatus to perform highly accurate scribing and reduced stress incurred on the device during processing, whereby defects or damages are reduced. (Design Changes) The present invention is not limited to the embodiment described above, and design changes may be made as appropriate without departing from the sprit of the present invention.
The form of pressing means 20 is not limited to pressing roller 21, and any form may be employed as long as it has a convex curved surface.
As scribing apparatus 2 shown in Figure 2, scriber blade 31 maybe configured to be scannable in width directions of the substrate. Such structure allows scribing in a parallel direction, a vertical direction, and an oblique direction with respect to the conveyance direction of the substrate. For example, a vertical scribing may be performed by conveying the substrate intermittently and scanning scriber blade 31 in width directions of the substrate while the conveyance is stopped.
As scribing apparatus 3 shown in Figure 3, the scribing means may be a means which is roughly constituted by laser light emission
optical system 50 and performs laser scribing. Laser light emission optical system 50 includes laser oscillator 52 which is energized by power source 51 and oscillates laser light, light control/transmission optical systems 53 to 56 for controlling or transmitting the laser light, and laser head 59 for emitting the laser light on the sμrface of a target scribing film M formed on a flexible substrate B.
The light control/transmission optical systems include attenuator 53 for controlling the energy of the laser light oscillated in the laser oscillator 56, slit 54 for shaping the optical image of the laser light into a slit-like form, condenser lens 55 for condensing the laser light shaped into the slit-like form, and optical fiber 56 for transmitting the laser light condensed by condenser lens 55. Laser head 59 includes variable slit 57 for reshaping the optical image of the laser light transmitted through optical fiber 56 into a slit-like form having a desired size and condenser lens 58. Laser head 59 is configured to be scannable in width directions of the substrate. There is not any specific restriction on the wavelength of the laser light and appropriately designed according to the light absorption wavelength of a target scribing film M. For example, when the target scribing film M is a Mo lower electrode of a photoelectric conversion device, laser light with a center wavelength of 500 to 1100 nm is preferably used. If the target scribing film M is a photoelectric conversion layer or an upper electrode of a photoelectric conversion device, laser light with a center wavelength of not greater than 400 nm is preferably used. Laser emission conditions, such as the wavelength, emission energy, laser output pattern, emission time, and the like, are adjusted according to the light absorption coefficient of the target scribing film M, whereby accurate scribing with a desired depth and width may be performed. In a short wavelength range, the absorption coefficient is high and diffraction effect or the like is small, so that the laser emission range may be determined easily without unnecessary
power being applied to a surrounding area, whereby the scribing may be performed accurately.
Optical systems of laser light emission optical system 50 are not limited to those shown in Figure 3 and are appropriately changed in the designs.
As scribing apparatus 4 shown in Figure 4, a plurality of sets of pressing means 20 and scribing means 30 may be provided. Such structure allows the depth and/or width of a separation groove H to be increased in a stepwise manner. Such design change may also be applicable to the apparatus shown in Figure 3.
The structure for increasing the depth and/or width of a separation groove H to be formed on a target scribing film M in a stepwise manner may reduce an instantaneous load (a mechanical load in mechanical scribing and a thermal load in laser scribing) incurred by a surrounding area of a separation groove H at the time of scribing, whereby the yield rate and device performance may be improved. Further, the load (a mechanical load in mechanical scribing and a thermal load in laser scribing) incurred by pressing roller 21 may also be reduced, whereby the durability of the apparatus may be increased.
[Photoelectric Conversion Device]
An example structure of a photoelectric conversion device which can be manufactured by a scribing apparatus of the present invention will be described with reference to the accompanying drawings. Figure 5A is a schematic sectional view of the photoelectric conversion device in a lateral direction, and Figure 5B is a schematic sectional view of the photoelectric conversion device in a longitudinal direction. Figure 6 is a schematic sectional view of a substrate, illustrating the structure thereof, and Figure 7 is a perspective view of a substrate, illustrating a manufacturing method thereof. In the drawings, each component is not drawn to scale in order to facilitate visual recognition. Generally, "lateral direction of a photoelectric conversion device" and "longitudinal direction of a photoelectric conversion device" correspond respectively to a width direction and a conveyance direction of a
flexible substrate used.
As illustrated in Figures 5A and 5B, photoelectric conversion device 100 is a device having flexible substrate 110 on which lower electrode (rear electrode) 120, photoelectric conversion layer 130, buffer layer 140, and upper electrode layer 150 are stacked in this order.
Photoelectric conversion device 100 has first separation grooves 161 that run through only lower electrode 120, second separation grooves 162 that run through photoelectric conversion layer 130 and buffer layer 140, and third separation grooves 163 that run through onlyupper electrode layer 150 in a lateral sectional view and fourth separation grooves 164 that run through photoelectric conversion layer 130, buffer layer 140, and upper electrode layer 150 in a longitudinal sectional view. The above configuration may provide a structure in which the device is divided into many cells C by first to fourth separation grooves 161 to 164. Further, upper electrode 150 is filled in second separation grooves 162, whereby a structure in which upper electrode 150 of a certain cell C is serially connected to lower electrode 120 of adjacent cell C may be obtained. Such configuration allows manufacture of an integrated device in which multiple unit devices are connected in series by a very simple process flow of repeating thin film formation and separation groove formation. (Flexible Substrate) In the present embodiment, flexible substrate 110 is a substrate obtained by anodizing at least one surface side of an Al-based metal base 111. Substrate 110 may be a substrate of metal base 111 having anodized film 112 on each side as illustrated on the left of Figure 6 or a substrate of metal base 111 having anodized film 112 on either one of the sides as illustrated on the right of Figure 6. Here, anodized film 112 is an AI2O3 based film. There is not any specific restriction on the thickness of metal base 111 and anodized film 112. The thickness of metal base 111 is, for example, 50 to 500 um, and the thickness of anodized film 112 is, for example, 0.5 to 20 um.
"Major component of the metal base" herein is defined as a component occupying 50% by mass or more. Metal base 111 may be a metal base that includes a minor element, a pure Al substrate, or an alloy of Al with another metal element. As metal base 111 on which anodized film 112 is formed, a pure Al substrate with an Al content of not less than 95% by mass is preferably used.
Anodization may be performed by immersing metal base 111, which is cleaned, smoothed by polishing, and the like as required, as an anode with a cathode in an electrolyte, and applying a voltage between the anode and cathode. As shown in Figure 7, when Al based metal base 111 is anodized, an oxidization reaction proceeds from surface Ills in a direction substantially perpendicular to surface Ills, and Al2O3 based anodized film 112 is formed. Anodized film 112 generated by the anodization has a structure in which multiple fine columnar bodies, each having a substantially regular hexagonal shape in plan view, are tightly arranged. Each fine columnar body 112a has a fine pore 112b, in substantially the center, extending substantially linearly in a depth direction from surface Ills, and the bottom surface of each fine columnar body 112a has a rounded shape. Normally, a barrier layer without any fine pore 112b is formed at a bottom area of fine columnar bodies 112a. Anodized film 112 without any fine pore 112b may also be formed by appropriately arranging the anodizing conditions. (Photoelectric Conversion Layer) Photoelectric conversion layer 130 includes one or more types of compound semiconductors of at least one type of group Ib element, at least one type of group IHb element, and at least one type of group VIb element (group I-III-VI semiconductors) and generates a current by absorbing light. Preferably, photoelectric conversion layer 130 is a layer that includes one or more types of compound semiconductors of at least one type of group Ib element selected from the group consisting of Cu and Ag, at least one type of group IHb element selected from the group consisting of B, Al, Ga, and In, and at least one type of group VIb element selected from the group consisting of O, S,
Se, and Te .
In view of a high light absorption rate and high photoelectric conversion efficiency, it is preferable that photoelectric conversion layer 130 includes one or more types of compound semiconductors of at least one type of group Ib element selected from the group consisting of Cu and Ag, at least one type of group IHb element selected from the group consisting of Al, Ga, and In, and at least one type of group VIb element selected from the group consisting of S, Se, and Te. The compound semiconductors described above may include but not limited to CuAlS2, CuGaS2, CuInS2, CuAlSe2, CuGaSe2, CuInSe2 (CIS), AgAlS2, AgGaS2, AgInS2, AgAlSe2, AgGaSe2, AgInSe2, AgAlTe2, AgGaTe2, AgInTe2, Cu(In1-XGax)Se2 (CIGS), Cu (Ini_xAlx) Se2, Cu(Ini-xGax) (S, Se)2, Ag(Ini_xGax)Se2, and Ag(Ini-xGax) (S, Se)2. It is particularly preferable that photoelectric conversion layer 130 includes CuInSe2 (CIS) and/or CuInSe2 solidified with Ga, i.e., Cu(In, Ga)Se2 (CIGS) . CIS and CIGS are semiconductors having a chalcopyrite crystal structure, and high light absorption rates and high energy conversion efficiency are reported. They also have excellent durability and have less deterioration in the efficiency due to light exposure.
Photoelectric conversion layer 130 includes an impurity for obtaining an intended semiconductor conductivity type . The impurity may be included in photoelectric conversion layer 130 by diffusing from an adjacent layer or by active doping.
Photoelectric conversion layer 130 may have a density distribution of constituent elements of group I-III-VI semiconductors and/or impurities, and may have a plurality of layer regions of different semiconductivities, such as n-type, p-type, i-type, and the like. For example, in the CIGS system, the band gap width/carrier mobility and the like may be controlled by providing a distribution of the amount of Ga in photoelectric conversion layer 130 in the thickness direction, whereby high conversion efficiency may be designed. Photoelectric conversion layer 130 may include one or more
types of semiconductors other than the group I-III-VI semiconductor. Semiconductors other than the group I-III-VI semiconductor may include but not limited to a semiconductor of group IVb element, such as Si (group IV semiconductor) , a semiconductor of group IIIb element and group Vb element such as GaAs (group IH-V semiconductor) , and a semiconductor of group Hb element and group VIb element, such as CdTe (group H-VI semiconductor) .
Photoelectric conversion layer 130 may include any arbitrary component other than semiconductors and an impurity for causing the semiconductors to become an intended conductivity type within a limit that does not affect the properties. There is not any specific restriction on the content of group I-III-VI semiconductors in photoelectric conversion layer 130, in which not less than 75% by mass is preferable, not less than 95% by mass is more preferable, and not less than 99% by mass is particularly preferable. (Electrodes, Buffer Layer)
Each of lower electrode 120 and upper electrode 150 is made of a conductive material. Upper electrode 50 on the light input side needs to be transparent. In view of effective use of light, it is preferable that lower electrode 120 on the substrate side has light reflectivity. When a main layer of photoelectrical conversion layer 130 excluding a region adjacent to buffer layer 140 is a p-type semiconductor, lower electrode 120 is used as a positive electrode and upper electrode 150 is used as a negative electrode. If the main layer of photoelectric conversion layer 130 is an n-type semiconductor, the polarity of lower electrode 120 and upper electrode 150 is reversed.
As for the major component of lower electrode 120, Mo, Cr, W, or a combination thereof is preferably used. As for the major component of upper electrode 150, ZnO, ITO (indium tin oxide) , SnO2, or a combination thereof is preferably used. Lower electrode 120 and/or upper electrode 150 may have a single layer structure or a laminated structure, such as a two-layer structure. As for buffer layer 140, CdS, ZnS, ZnO, ZnMgO, ZnS(O, OH), or a combination thereof is preferably used. The major component of the electrodes and buffer
layer is defined as a component occupying 50% by mass or more. A preferable combination of the compositions is, for example, Mo lower electrode/CdS buffer layer/CIGS photoelectric conversion layer/ZnO upper electrode. (Other Layers)
Photoelectric conversion device 100 may have any other layer as required in addition to those described above. For example, a contact layer (buffer layer) for enhancing the adhesion of layers may be provided, as required, between substrate 110 and lower electrode 120, and/or between lower electrode 120 and photoelectric conversion layer 130. Further, an alkali barrier layer for preventing diffusion of alkali ions may be provided, as required, between substrate 110 and lower electrode 120. A reference is directed to Japanese Unexamined Patent Publication No. 8 (1996) -222750 for a preferred embodiment of the alkali barrier layer.
Photoelectric conversion device 100 of the present embodiment is structured in the manner as described above. In the manufacture of photoelectric conversion device 100, scribing is performed to form first to fourth separation grooves 161 to 164. For the photoelectric conversion device 100, scribing appropriate for the material and property of each film is performed. For a CIGS device, for example, first separation grooves 161 are formed by laser scribing while second to fourth separation grooves 162 to 164 are formed by mechanical scribing using a scriber blade or laser scribing.
By forming separation grooves 161 to 164 using the scribing apparatus of the present invention, photoelectric conversion devices 100 having high photoelectric conversion efficiency may be manufactured with a high yield rate and stably, while conveying a substrate web. The use of the scribing apparatus of the present invention allows separation grooves 161 to 164 to be formed highly accurately even under the conditions of roll-to-roll processing that requires a faster processing speed than that of a sheet-to-sheet processing. Photoelectric conversion device 100 shown here is just an
example, and the scribing apparatus of the present invention is applicable to the manufacture of any type of photoelectric conversion device using a flexible substrate, such as metal substrate, substrate of metal base on which an insulation film is formed, resin substrate, or the like. Further, the scribing apparatus of the present invention is applicable to the manufacture of any other device than photoelectric conversion device. [Examples]
Examples and Comparative Examples will now be described. (Example 1)
<Manufacture of Photoelectric Conversion Layer Substrate>
A strip-like continuous Al thin plate with a purity of not less than 99.5% and a width of 300 mm was provided as the metal base. After polishing the surface, the Al plate was anodized in a boric acid solution to obtain a strip-like continuous flexible substrate of a 200 um thick Al base having a 5 um thick anodized film (Al2Cb film) on each side. The anodized film is has fine pores formed in a regular manner in which the thickness of the barrier layer was about 50 nm, the pitch of fine pores was about 150 nm, and the pore diameter of the fine pores was about 50 nm.
<Manufacture of Photoelectric Conversion Device and Solar Cell Module>
A Mo lower electrode with a thickness of 0.7 um was formed over the entire surface of the obtained photoelectric conversion layer substrate by Ar sputtering. Thereafter, laser scribing was performed on the Mo lower electrode using the apparatus shown in Figure 3 to form a plurality of first separation grooves with a depth of about 0.7 um and a width of about 130 um. The conveyance speed of the substrate was 3 m/min. As for the laser, YAG laser with a center wavelength of 1064 nm was used. Viewed in a width direction of the substrate, a plurality of first separation groove was formed with a pitch of 10 mm, whereby the lower electrode was divided into 24 cells.
Then, as a photoelectric conversion layer, a Cu (In0-7GaO.3) Se2 thin film was deposited by multi source simultaneous deposition with
a thickness of about 1.7 μm over the entire surface of the substrate having the lower electrode formed thereon. The deposition of the
Cu(Ino.7Gao.3) Se∑ thin filmwas performed under a vacuumdegree of about lCr4 Pa (lcr7 Torr) by providing Cu, In, Ga, and Se deposition sources in a vacuum vessel. Here, the temperature of the deposition crucible was controlled appropriately and substrate temperature was 5300C.
Next, as a buffer layer, a CdS film was deposited by chemical deposition with a thickness of about 50 nm over the entire surface of the substrate having the photoelectric conversion layer formed thereon. The chemical deposition was performed by heating a water solution of cadmium nitrate, thiourea, and ammonia to about 80°C and soaking the photoelectric conversion layer in the water solution.
After forming the buffer layer, mechanical scribing was performed on the photoelectric conversion layer and buffer layer using the apparatus shown in Figure 1 to form a plurality of second separation grooves with a depth of about 1.8um and a width of about 140μm. The plurality of second separation grooves was formed simultaneously by arranging scriber blades corresponding to the number of second separation grooves to be formed. The conveyance speed of the substrate was 18 m/min. A flat diamond scriber blade with a cutting edge width of lOOμm was used. Viewed in a width direction of the substrate, a plurality of second separation grooves was formed with a pitch of 10 mm, whereby the stack of photoelectric conversion layer and buffer layer was divided into 24 cells. Conditions for brining the scriber blade into contact with the substrate were as follows. Rake angle α = -35° Cutting edge angle β = 60° Clearance angle Y = 65° Load applied to scriber blade = 280 itiN
Next, as an upper electrode, Al doped ZnO film was formed by Ar sputtering with a thickness of 0.6μm. After forming the upper electrode, mechanical scribing using a scriber blade was performed on the upper electrode using the same apparatus as that used for forming the second separation grooves to form a plurality of third
separation grooves with a depth of about 3.2 μm and a width of about 140 urn, whereby the upper electrode was divided into 24 cells. Viewed in a width direction of the substrate, a plurality of second separation grooves was formed with a pitch of 10 mm, whereby the upper electrode was divided into 24 cells. The scribing blade used and conditions for brining the scriber blade into contact with the substrate were identical to those for forming the second separation grooves .
Then, mechanical scribing using a scriber blade was performed on the photoelectric conversion layer, buffer layer and upper electrode using the apparatus shown in Figure 2 to form a plurality of fourth separation grooves with a depth of about 3.2 μm and a width of about 200 μm. The substrate was conveyed by intermittent conveyance and each of the fourth separation grooves was formed by scanning the scriber blade in a width direction of the substrate while the conveyance was stopped. A flat diamond scriber blade with a cutting edge width of 160μm was used. The angle and loading conditions when the scriber blade was brought into contact with the substrate were identical to those for forming the second separation grooves. Formation of the plurality of fourth separation grooves results in the stack of the photoelectric conversion layer, buffer layer, and upper electrode to be divided into cell units of 24 cells arranged in a width direction of the substrate.
Thereafter, the substrate was cut into a plurality of 240 mm square devices and Al was deposited to form drawing-out external electrodes, whereby photoelectric conversion devices were obtained. Finally, a transparent resin for sealing was laminated, whereby a solar cell module was obtained. A total of 20 solar cell modules were produced under the same condition. Each module has a structure in which three cell units, each having 24 cells connected in series, are connected in parallel.
The first to fourth separation grooves were formed under the same conditions with respect to the radius of the pressing roller, tensile strength Tn and pressing force P, Tn x P, applied to the flexible substrate per unit cross-sectional area at the time of
scribing. These data are shown in Table 1.
<Photoelectric Conversion Efficiency and Yield Rate Evaluations>
Photoelectric conversion efficiency was evaluated for each produced solar cell module using pseudo sunlight of Air Mass (AM) = 1.5, 100mW/cm2. Photoelectric conversion efficiency was measured for 20 samples, and those having photoelectric conversion efficiency of 80% or more of a maximum value among them were evaluated as acceptable products and those other than the acceptable products were evaluated as unacceptable products. Then, an average value of photoelectric conversion efficiency of the acceptable products was obtained as the photoelectric conversion efficiency. Further, the yield rate was obtained by the formula below.
Yield Rate = number of acceptable products/total number of evaluated samples (%) . (Examples 2 to 11, Comparative Examples 1 to 3)
Solar cell modules were obtained and evaluated in a similar manner to that of Example 1 other than that the conditions with respect to the radius of the pressing roller, tensile strength Tn and pressing force P, Tn x P, applied to the flexible substrate per unit cross-sectional area at the time of scribing were changed to those shown in Table 1. (Results)
As shown in Table 1, Examples 1 to 11 produced by setting conditions with respect to the radius of the pressing roller, tensile strength Tn and pressing force P, Tn x P, applied to the flexible substrate per unit cross-sectional area at the time of scribing within the ranges of the present invention has higher photoelectric conversion efficiency and yield rate in comparison with Comparative
Examples 1 to 3 produced by setting the parameters outside of the ranges of the present invention, meaning that photoelectric conversion devices having excellent properties were produced stably.
For Examples 1 to 11, the radius of the pressing roller was set within the range from 40 to 300 mm, which provided favorable results . Note that the manufacture of a pressing roller with a radius greater than 300 mm was difficult and evaluation thereof was not
conducted. (Example 12)
Solar cell modules were obtained and evaluated in the same manner as that for Example 5 other than that the second and third separation grooves were formed in two steps using the apparatus shown in Figure 4. The clearance between the scriber blade and pressing roller of each of two pairs was adjusted such that the first scribing depth corresponds to 70% of a desired depth and the second scribing provides the desired depth. Manufacturing conditions and evaluation results of Examples 5 and 12 are shown in Table 2. As shown in Table
2, Example 12 in which scribing was performed in two steps for one separation groove has favorable results, that is, has higher photoelectric conversion efficiency and yield rate in comparison with Example 5 in which scribing was performed in single step for one separation groove. This shows that it is more preferable to perform scribing in a plurality of steps.
(Examples 13 and 14)
Solar cell modules were obtained and evaluated in the same manner as that for Example 5 other than that the materials of scriber blade were changed to those shown below.
Example 13: boron nitride sintered body (BN)
Example 14: WC-TiC-TaC-Co alloy (equivalent to JIS-K-IO material) Manufacturing conditions and evaluation results of Examples 5, 13, and 14 are shown in Table 3. As Table 3 shows, diamond is particularly preferable as the material of the scriber blade. (Examples 15 to 22)
Solar cell modules were obtained and evaluated in the same manner as that for Example 5 other than that the conditions for brining the scriber blade into contact with the substrate were changed to those shown in Table 4. As shown in Table 4, Examples 15 to 22 produced by setting the rake angle α to -80 to 35° provided favorable results. More favorable results were obtained when the rake angle α was set to -70 to -5°, more preferably to -60 to -35°.
(Examples 23) Solar cell modules were obtained and evaluated in the same
manner as that for Examples 1 to 11 other than that the second to fourth separation grooves were formed by laser scribing using the apparatus shown in Figure 3. As for the laser, a third harmonic of YAG with a center wavelength of 355 nm was used. Each module showed identical results to those of Examples 1 to 11.
Table 1
Table 3
Table 4
The scribing apparatus of the present invention may be used for scribing any target scribing film, and may be used for scribing a semiconductor film, a conductive film, a laminated film of these films, and the like of devices such as a photoelectric conversion device and the like.
Claims
1. A scribing apparatus, comprising: a conveyance means for conveying a web of strip-like continuous flexible substrate on which a target scribing film is formed by applying a tensile strength to the flexible substrate; a pressing means, having a convex curved surface, for pressing the flexible substrate by bringing the convex curved surface into contact with the flexible substrate from a side on which the target subscribing film is not formed; and a scribing means for performing scribing on the target scribing film formed on the surface of a portion of the flexible substrate pressed by the pressing means, wherein a tensile strength Tn and a pressing force P applied to the flexible substrate per unit cross-sectional area during the scribing satisfy Formulae (1) to (3) below: 1.5 MPa < Tn < 25 MPa (1)
4 kPa < P < 50 kPa (2)
5 GPa2 < Tn x P < 800 GPa2 (3)
The tensile strength Tn and pressing force P are parameters represented by the following formulae:
Tn = T/Ss (Pa), P = T/ (W x R) (Pa)
(where, T represents the tensile strength applied the entire cross-section of the flexible substrate, Ss represents the cross-sectional area of the flexible substrate, W represents the width of the flexible substrate, and R represents the radius of curvature of the convex curved surface.)
2. The scribing apparatus of claim 1, wherein: the conveyance means includes a first roller for paying out the flexible substrate and a second roller for rolling up the flexible substrate after subjected to the scribing; and the pressing means includes a pressing roller for pressing the flexible substrate.
3. The scribing apparatus of claim 2, wherein the pressing roller has a radius of 40 to 300 mm.
4. The scribing apparatus of any of claims 1 to 3, wherein the position of the convex curved surface is changeable with respect to the flexible substrate.
5. The scribing apparatus of any of claims 1 to 4, wherein the scribing means is a means that has a scriber blade and performs mechanical scribing.
6. The scribing apparatus of claim 5, wherein the material of the scriber blade is diamond.
7. The scribing apparatus of claim 5 or 6, wherein an angle α formed between a face of the scriber blade on the side that moves relative to the flexible substrate and a normal line to the surface of the flexible substrate is -80° < α < 35°.
8. The scribing apparatus of claim 5 or 6, wherein an angle α formed between a face of the scriber blade on the side that moves relative to the flexible substrate and a normal line to the surface of the flexible substrate is -70° < α ≤ 0°.
9. The scribing apparatus of any of claims 1 to 4, wherein the scribing means is a means that has a laser light emission optical system and performs laser scribing.
10. The scribing apparatus of any of claims 1 to 9, wherein the apparatus is an apparatus, comprising a plurality of sets of the pressing means and scribing means to increase the depth and/or width of a separation groove to be formed in the target scribing film in a stepwise manner.
11. The scribing apparatus of any of claims 1 to 10, wherein: the flexible substrate is a substrate of a metal base on which an insulation film is formed; and the target scribing film is a semiconductor film, a conductive film, or a laminated film of these films.
12. The scribing apparatus of any of claims 1 to 11, wherein the apparatus is an apparatus for manufacturing a photoelectric conversion device.
13. The scribing apparatus of claim 12, wherein the apparatus is an apparatus for manufacturing a photoelectric conversion device having a photoelectric conversion layer that includes a compound semiconductor formed of a group Ib element, a group IHb element, and a group VIb element.
14. The scribing apparatus of claim 13, wherein the apparatus is an apparatus for manufacturing a photoelectric conversion device having a photoelectric conversion layer that includes a compound semiconductor formed of at least one type of group Ib element selected from the group consisting of Cu and Ag, at least one type of Ilib element selected from the group consisting of Al, Ga, and In, and at least one type of VIb element selected from the group consisting of S, Se, and Te.
15. A scribing method for performing scribing, while conveying a web of strip-like continuous flexible substrate on which a target scribing film is formed by applying a tensile strength to the flexible substrate, on the target scribing film with the flexible substrate being pressed by a convex curved surface by bringing the convex curved surface into contact with the flexible substrate from a side on which the target subscribing film is not formed, wherein a tensile strength Tn and a pressing force P applied to the flexible substrate per unit cross-sectional area during the scribing satisfy Formulae (1) to (3) below: 1.5 MPa < Tn < 25 MPa (1)
4 kPa < P < 50 kPa (2)
5 GPa2 < Tn * P ≤ 800 GPa2 (3)
The tensile strength Tn and pressing force P are parameters represented by the following formulae: Tn = T/Ss (Pa), P = T/ (W * R) (Pa)
(where, T represents the tensile strength applied the entire cross-section of the flexible substrate, Ss represents the cross-sectional area of the flexible substrate, W represents the width of the flexible substrate, and R represents the radius of curvature of the convex curved surface.)
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010800046749A CN102334200A (en) | 2009-01-16 | 2010-01-12 | Scribing apparatus and scribing method |
| EP10731313A EP2380214A4 (en) | 2009-01-16 | 2010-01-12 | Scribing apparatus and scribing method |
| US13/145,048 US20110278267A1 (en) | 2009-01-16 | 2010-01-12 | Scribing apparatus and scribing method |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009007136A JP2010165879A (en) | 2009-01-16 | 2009-01-16 | Scribing apparatus and scribing method |
| JP2009-007136 | 2009-01-16 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2010082644A1 true WO2010082644A1 (en) | 2010-07-22 |
Family
ID=42339897
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP2010/050457 WO2010082644A1 (en) | 2009-01-16 | 2010-01-12 | Scribing apparatus and scribing method |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US20110278267A1 (en) |
| EP (1) | EP2380214A4 (en) |
| JP (1) | JP2010165879A (en) |
| KR (1) | KR20110105389A (en) |
| CN (1) | CN102334200A (en) |
| WO (1) | WO2010082644A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102010038259A1 (en) * | 2010-10-19 | 2012-04-19 | 4Jet Sales + Service Gmbh | Method and apparatus for engraving a flexible belt |
| EP2618384A1 (en) * | 2010-09-16 | 2013-07-24 | LG Innotek Co., Ltd. | Solar photovoltaic device and a production method therefor |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102581492A (en) * | 2012-01-31 | 2012-07-18 | 武汉吉事达激光技术有限公司 | Laser etcher capable of automatically feeding roll materials |
| CN102717191B (en) * | 2012-06-07 | 2015-06-10 | 江阴德力激光设备有限公司 | Device and method for pulse laser etching of roll-to-roll flexible conducting films |
| TW201409720A (en) * | 2012-08-17 | 2014-03-01 | M U Technologies Corp | Scribing apparatus |
| JP5486057B2 (en) * | 2012-09-10 | 2014-05-07 | 昭和シェル石油株式会社 | Method for manufacturing thin film solar cell |
| KR101403284B1 (en) * | 2012-10-23 | 2014-06-03 | 주식회사 포스코 | Method for patterning of substrate for solar cell using static roll-to-roll process |
| CN103050578B (en) * | 2013-01-04 | 2015-09-16 | 普尼太阳能(杭州)有限公司 | A kind of cutting equipment of flexible thin-film solar cell and cutting method |
| US9381661B2 (en) * | 2013-10-07 | 2016-07-05 | Curt G. Joa, Inc. | Corrosion protected anvil and knife cutting assembly |
| JP6547397B2 (en) * | 2015-04-30 | 2019-07-24 | 三星ダイヤモンド工業株式会社 | Thin film solar cell processing apparatus and thin film solar cell processing method |
| CN106670655B (en) * | 2017-01-22 | 2019-07-05 | 旭科新能源股份有限公司 | For manufacturing the control method of the laser scoring system of flexible substrate solar battery |
| CN109791319B (en) * | 2017-07-10 | 2022-05-17 | 深圳市柔宇科技股份有限公司 | Method and apparatus for peeling flexible substrate |
| KR102203250B1 (en) | 2017-11-29 | 2021-01-13 | 주식회사 엘지화학 | Battery Module Having End Frame |
| CN111566822A (en) * | 2018-03-27 | 2020-08-21 | 积水化学工业株式会社 | Method for manufacturing solar cell and solar cell |
| CN112277034A (en) * | 2020-09-28 | 2021-01-29 | 李银玲 | Film scribing device for Chinese patent medicine development and using method thereof |
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| JP2714247B2 (en) * | 1990-10-29 | 1998-02-16 | キヤノン株式会社 | Method and apparatus for continuously forming large-area functional deposited film by microwave plasma CVD |
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- 2010-01-12 KR KR1020117017433A patent/KR20110105389A/en not_active Application Discontinuation
- 2010-01-12 CN CN2010800046749A patent/CN102334200A/en active Pending
- 2010-01-12 WO PCT/JP2010/050457 patent/WO2010082644A1/en active Application Filing
- 2010-01-12 US US13/145,048 patent/US20110278267A1/en not_active Abandoned
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| EP2618384A1 (en) * | 2010-09-16 | 2013-07-24 | LG Innotek Co., Ltd. | Solar photovoltaic device and a production method therefor |
| EP2618384A4 (en) * | 2010-09-16 | 2014-04-16 | Lg Innotek Co Ltd | Solar photovoltaic device and a production method therefor |
| DE102010038259A1 (en) * | 2010-10-19 | 2012-04-19 | 4Jet Sales + Service Gmbh | Method and apparatus for engraving a flexible belt |
| DE102010038259B4 (en) * | 2010-10-19 | 2013-02-07 | 4Jet Sales + Service Gmbh | Method and apparatus for engraving a flexible belt |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20110105389A (en) | 2011-09-26 |
| JP2010165879A (en) | 2010-07-29 |
| CN102334200A (en) | 2012-01-25 |
| EP2380214A1 (en) | 2011-10-26 |
| EP2380214A4 (en) | 2012-07-18 |
| US20110278267A1 (en) | 2011-11-17 |
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