WO2013073778A1 - 텍스처 구조를 갖는 열팽창 제어형 플렉서블 금속 기판재 - Google Patents
텍스처 구조를 갖는 열팽창 제어형 플렉서블 금속 기판재 Download PDFInfo
- Publication number
- WO2013073778A1 WO2013073778A1 PCT/KR2012/008429 KR2012008429W WO2013073778A1 WO 2013073778 A1 WO2013073778 A1 WO 2013073778A1 KR 2012008429 W KR2012008429 W KR 2012008429W WO 2013073778 A1 WO2013073778 A1 WO 2013073778A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- metal substrate
- substrate material
- flexible metal
- flexible
- present
- Prior art date
Links
- 239000000758 substrate Substances 0.000 title claims abstract description 132
- 239000002184 metal Substances 0.000 title claims abstract description 97
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 97
- 239000000463 material Substances 0.000 title claims abstract description 94
- 230000009975 flexible effect Effects 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 claims abstract description 54
- 238000007747 plating Methods 0.000 claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 claims abstract description 18
- 239000011888 foil Substances 0.000 claims description 32
- 229910052759 nickel Inorganic materials 0.000 claims description 18
- 229910000990 Ni alloy Inorganic materials 0.000 claims description 10
- 238000005323 electroforming Methods 0.000 claims description 9
- 239000013078 crystal Substances 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 abstract description 19
- 239000010703 silicon Substances 0.000 abstract description 19
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 18
- 239000010409 thin film Substances 0.000 abstract description 15
- 239000000956 alloy Substances 0.000 abstract description 10
- 230000003287 optical effect Effects 0.000 abstract description 10
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 abstract description 6
- 229910045601 alloy Inorganic materials 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 238000005275 alloying Methods 0.000 abstract description 2
- 230000037361 pathway Effects 0.000 abstract 1
- 230000006641 stabilisation Effects 0.000 description 29
- 238000011105 stabilization Methods 0.000 description 29
- 238000010438 heat treatment Methods 0.000 description 21
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 17
- 239000008151 electrolyte solution Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- 238000005096 rolling process Methods 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 238000005259 measurement Methods 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 4
- 238000009713 electroplating Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- KERTUBUCQCSNJU-UHFFFAOYSA-L nickel(2+);disulfamate Chemical compound [Ni+2].NS([O-])(=O)=O.NS([O-])(=O)=O KERTUBUCQCSNJU-UHFFFAOYSA-L 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 230000008602 contraction Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 230000000930 thermomechanical effect Effects 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- 229910000640 Fe alloy Inorganic materials 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 229960002089 ferrous chloride Drugs 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000002159 nanocrystal Substances 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- CVHZOJJKTDOEJC-UHFFFAOYSA-N saccharin Chemical compound C1=CC=C2C(=O)NS(=O)(=O)C2=C1 CVHZOJJKTDOEJC-UHFFFAOYSA-N 0.000 description 2
- 229940081974 saccharin Drugs 0.000 description 2
- 235000019204 saccharin Nutrition 0.000 description 2
- 239000000901 saccharin and its Na,K and Ca salt Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 1
- 239000002211 L-ascorbic acid Substances 0.000 description 1
- 235000000069 L-ascorbic acid Nutrition 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 229920002457 flexible plastic Polymers 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 239000002648 laminated material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000002707 nanocrystalline material Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000006174 pH buffer Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- -1 polyethylene terephthalate Polymers 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 150000003376 silicon Chemical class 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D1/00—Electroforming
- C25D1/04—Wires; Strips; Foils
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/06—Wires; Strips; Foils
- C25D7/0607—Wires
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/06—Wires; Strips; Foils
- C25D7/0614—Strips or foils
- C25D7/0635—In radial cells
-
- 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
- H01L31/02—Details
- H01L31/0236—Special surface textures
- H01L31/02366—Special surface textures of the substrate or of a layer on the substrate, e.g. textured ITO/glass substrate or superstrate, textured polymer layer on glass substrate
-
- 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
Definitions
- the present invention relates to a flexible metal substrate having a concave-convex structure similar to the texture structure of a silicon crystalline solar cell. More specifically, the present invention relates to a flexible metal substrate material for a solar cell having a texture structure having a thermal expansion behavior similar to that of a stacked thin film cell.
- the substrate material for a flexible solar cell should have excellent mechanical strength, and preferably have a thermal expansion behavior similar to that of a thin film cell material laminated at a solar cell manufacturing process temperature. Substrates that meet these requirements can reduce efficiency degradation due to delamination between the substrate and the laminated material.
- plastic substrates such as polyimide (PI) and polyethylene terephthalate (PET), and metal foil substrates such as Ti, Mo, SS, and kover.
- plastic substrates are weak to heat, have a high coefficient of thermal expansion (CTE), low strength, and are vulnerable to chemicals, oxygen and moisture.
- a metal substrate can compensate for the problem of the plastic substrate.
- Metal substrates have to be thin in order to exhibit flexible characteristics, and for this purpose, rolling process technology is used.
- the sheet metal is processed into thin sheets through a facility equipped with a 20-stage rolling mill.
- the rolling process technology has a limitation in widening the width of the metal substrate to be processed, and the sheet thickness is also less than 0.1 mm level.
- the coefficient of thermal expansion cannot be controlled, and it has disadvantages such as difficulty in handling thin plates.
- a silicon solar cell undergoes so-called texturing to make pyramidal irregularities on its surface because incident solar rays have a long optical path in the light absorbing layer to increase photoelectric conversion efficiency.
- a silicon thin film solar cell for this purpose, a thin film layer having an uneven structure is laminated on a substrate.
- these processes have a problem in that manufacturing cost increases due to additional efforts and costs.
- a flexible thin metal substrate material may be used to manufacture a display device or a grating device requiring a fine concavo-convex structure.
- a manufacturing technology capable of manufacturing a thin metal substrate having a wide range of flexible properties in a wide range and providing a more inexpensive and convenient handling.
- An object of the present invention is to provide a flexible metal substrate material for solar cells having a low manufacturing cost and a textured structure.
- it can be used in silicon thin film solar cells, display devices, grating devices, etc., and an object of the present invention is to manufacture a wide flexible metal substrate material using a more convenient equipment.
- Another object of the present invention is to provide a flexible metal substrate material having a similar thermal expansion characteristics and flexibility that is most suitable for a silicon solar cell by controlling the alloy composition, grain size and structure of the metal substrate material, and improve the photoelectric conversion efficiency will be.
- the texture structure is a plating drum or plate having an uneven structure on the surface by an electroforming method It is formed using.
- the flexible metal substrate material is Fe-40wt% Ni to Fe-45wt% Ni alloy foil substrate material.
- the flexible metal substrate material is manufactured by a pole casting method, and then heat treated at 350 to 1000 ° C. for 30 minutes to 2 hours to form micro-sized grains.
- the flexible metal substrate material has a grain size of 0.1 ⁇ m to 10 ⁇ m, and has a single-phase structure of face-centered cubic crystal.
- the flexible metal substrate material has a coefficient of thermal expansion of 2 ⁇ 10 ⁇ 6 / ° C. to 6 ⁇ 10 ⁇ 6 / ° C.
- the flexible metal substrate material has a thickness of 1 ⁇ m to 100 ⁇ m.
- the method includes: forming a metal substrate having a textured structure on a surface by using a plating drum or plate having an uneven structure on the surface by an electroforming method; And it provides a method for producing a flexible metal substrate material for a solar cell comprising the step of heat-treating the metal substrate prepared by the pole method to form micro-sized grains.
- a flexible metal for grating composed of Fe-40wt% Ni to Fe-45wt% Ni alloy and having a coefficient of thermal expansion of 2 ⁇ 10 ⁇ 6 / ° C. to 6 ⁇ 10 ⁇ 6 / ° C.
- a substrate material a flexible metal for grating composed of Fe-40wt% Ni to Fe-45wt% Ni alloy and having a coefficient of thermal expansion of 2 ⁇ 10 ⁇ 6 / ° C. to 6 ⁇ 10 ⁇ 6 / ° C.
- the grating flexible metal substrate material is characterized in that the uneven structure forming a grating (gratting) is formed on the surface, or has a texture structure on the surface.
- the present invention it is possible to produce a thin flexible metal substrate material having a width of a desired size manufactured using a pole. Further, according to the present invention, by controlling the electrolyte component, the thin metal substrate material made of Fe-Ni alloy has a predetermined coefficient of thermal expansion. In addition, according to the present invention, a simple structure has a texture structure on the surface of the thin flexible metal substrate material. In addition, according to the present invention, by using a flexible metal substrate having a textured structure, a relatively thin silicon thin film solar cell, a compound semiconductor solar cell such as CIGS, a grating element, a display element, etc., which can improve photoelectric conversion efficiency, are relatively low. It can manufacture at unit price.
- FIG. 2 is a conceptual diagram illustrating an extended optical path in a pyramidal uneven structure (a flexible metal substrate having an inclination angle of 60 °) similar to a texture structure for a silicon thin film solar cell manufactured according to a preferred embodiment of the present invention.
- FIG. 3 is a schematic view of a flexible metal substrate having a concavo-convex structure for a grating device manufactured according to a preferred embodiment of the present invention.
- Figure 4 shows the coefficient of thermal expansion according to the temperature of the stabilization process in the metal foil substrate material of Fe-40wt% Ni.
- Figure 5 shows the coefficient of thermal expansion according to the tissue stabilization process temperature in the metal foil substrate material Fe-42wt% Ni.
- Figure 6 shows the XRD peak with the heat treatment temperature of the metal foil substrate material Fe-42wt% Ni.
- Figure 7 shows the coefficient of thermal expansion according to the temperature of the tissue stabilization process in the metal foil substrate material Fe-44wt% Ni.
- Figure 8b is a texture structure is formed on the surface, the inclination angle of the V-shape uneven structure is 30 ° (a), 45 ° (b), 60 ° (c) substrate material, respectively, the inclination angle in the pyramidal uneven structure, respectively It is the result of measuring the surface reflectivity of the board
- substrate material which is 30 degrees (d), 45 degrees (e), and 60 degrees (f).
- Figure 9 shows the results of measuring the hardness according to the heat treatment temperature of the metal foil substrate material Fe-42wt% Ni.
- FIG. 1 illustrates an embodiment of manufacturing a flexible metal substrate material using electroforming according to the present invention.
- an electrolyte solution is filled in an electrolytic cell 100 made of a conductive metal such as SUS (Steel Use Stainless), and the plating drum 200 and the anode electrode 400 having the conductive metal surface are immersed therein.
- a voltage is applied to the anode electrode 400 and the plating drum 200, metal is deposited on the surface of the plating drum 200 according to the electroplating principle to form a metal foil.
- the metal foil produced is flexible and can control its thickness. The thickness of the metal foil is adjusted to prepare a flexible metal substrate.
- the plating drum 200 is connected to the negative electrode of the voltage supply source, the positive electrode 400 is connected to the positive electrode, and the electrolyte solution containing the metal ions to be plated is filled in the electrolytic cell 100, and
- the metal foil to be electroplated by the composition can be made of an alloying material.
- the uneven structure is formed on the surface of the plating drum 200 so that the metal foil manufactured by electroplating has the same uneven structure on the surface.
- the concave-convex structure is used in the sense that the cross-sectional shape collectively refers to the concave-convex structure of various forms such as V-shaped, U-shaped.
- the method of forming the surface of the plating drum 200 into an uneven structure may be selected from various well-known methods such as physical and chemical methods and surface treatment techniques.
- metal foils produced by electroforming are advantageous compared to the rolling process because the width of the metal foil can be widened to a desired degree by increasing the drum size.
- a plate having a textured structure may be connected to the negative electrode and immersed in an electrolytic cell to produce a flexible metal substrate having a textured structure in a batch method.
- the metal substrate may be manufactured to a desired width and thickness.
- the inventors have also found the thermal expansion behavior according to the iron and nickel alloy composition ratios after a considerable period of in-depth study on the thermal expansion behavior of iron and nickel alloy foils by electroforming. As a result, it was found that the thermal expansion coefficient of Fe-40 ⁇ 45wt% Ni alloy material is almost the same as that of the silicon (Si) thin film solar cell device.
- the thermal expansion coefficient between layers is different, which causes side effects such as distortion between layers and peeling during the manufacturing process.
- thermal deformation due to use becomes another problem.
- the substrate of Fe-40 ⁇ 45wt% Ni alloy material of the present invention has a thermal expansion property similar to that of a silicon thin film, it is possible to use a device at high temperature with high efficiency without using special low temperature deposition equipment in the manufacturing process. I can make it.
- Fe-40 ⁇ 45wt% Ni alloy material produced in the present invention has a thermal expansion coefficient of 2 ⁇ 10 -6 / °C to 6 ⁇ 10 -6 / °C, further more precisely by controlling the alloy composition ratio of 4 ⁇ 10 -6 / It can be brought to °C.
- the electrolyte solution may be used by mixing a salt containing iron and a salt containing nickel as the electrolyte.
- the electrolyte may be iron sulfate, ferrous chloride, nickel sulfate, nickel chloride, nickel sulfamate, and more preferably ferrous chloride and nickel sulfamate.
- the electrolyte solution preferably includes 100 to 300 g / L of nickel sulfamate and 10 to 40 g / L of iron chloride.
- the electrolyte solution has an acidity of pH 2.5 to pH 3.5, a temperature of 45 ° C. to 60 ° C., and a current density of 50 to 120 mA / cm 2 .
- the conditions associated with the electrolyte solution can be appropriately adjusted depending on the situation.
- additives such as brightener stress relaxers, pH buffers together with the electrolytes described above. It is preferable to contain 1-10 g / L saccharin, 0.1-5 g / L ascorbic acid, 10-40 g / L boric acid, and 0.1-5 g / L sodium dodecyl sulfate.
- the plating drum 200 is rotated at a predetermined speed and the foil formed by electroplating can be easily recovered by winding the roller 300 installed outside the electrolytic cell 100.
- the thickness of the metal foil is related to the rotational speed of the plating drum 200, By adjusting the rotational speed of the plating drum differently according to the size and current density of the cathode drum, the desired thickness can be produced.
- the thickness of the Fe—Ni metal foil substrate material is preferably 1 to 100 ⁇ m, more preferably 10 ⁇ m to 50 ⁇ m. If the thickness of the substrate material is more than 100 ⁇ m there is no problem in the application but there is a disadvantage that the productivity worsens. Since the thin metal foil substrate material has flexible characteristics, the thin metal foil substrate material may be used in solar cells, display devices, and the like, which require flexible characteristics.
- the concave-convex structure substrate 500 may form a three-dimensional texture structure such as triangular pyramids and square pyramids (pyramid, 600) in addition to the V-shaped pillars on the surface thereof, which is used as a substrate of a silicon thin film solar cell.
- the photoelectric conversion efficiency can be increased by extending the optical path incident on the manufactured solar cell.
- the angle of inclination is set to 60 ° or more in a texture structure having a V-shaped cross section
- the optical path of the vertically incident light is returned along the incident path after three reflections, thereby greatly expanding the optical path.
- a grating substrate 700 manufactured using a plating drum having a concave-convex texture structure of a certain shape is also an embodiment of the present invention.
- the metal foil substrate material prepared in the present invention is another embodiment of the metal foil substrate material prepared in the present invention, a metal substrate material having a textured structure manufactured by electro-forming a grating element for diffraction and interference of light to make a holographic label, etc. It is shown.
- the alloy material does not need to be made of iron and nickel, but may be made of a material having desired physical properties as necessary.
- the flexible metal substrate material manufactured in a shape having a texture structure in a desired size at a low cost by using electric poles may be used as a solar cell, a display device, and a grating device substrate.
- the metal foil substrate material produced by the above electroforming process is a nanocrystalline material, and the grain size is about 10 nm to 30 nm.
- Such nanocrystalline substrate materials have higher mechanical properties than bulk materials of the same composition produced by conventional rolling processes.
- the uniform size of the nano-sized grains was 0.1 ⁇ m to 10 ⁇ m through the structure stabilization process, that is, heat treatment, thereby exhibiting uniform thermal expansion behavior.
- the structure of the substrate material also changes. That is, it has a structure of face centered cubic single phase (FCC). Nanocrystals generally consist of different tissues with body-centered cubic and face-centered cubic crystals.
- the substrate material of the present invention has a single-phase structure of face-centered cubic crystals, it exhibits specific thermal expansion characteristics.
- the substrate material has a thermal expansion coefficient of 2 ⁇ 10 ⁇ 6 / ° C. to 6 ⁇ 10 ⁇ 6 / ° C.
- the above coefficient of thermal expansion is a thermal expansion characteristic almost similar to that of silicon, and the substrate material of the present invention can be most preferably used for a silicon solar cell.
- the tensile strength decreases as the grain size grows in the stabilized tissue, the flexibility, that is, the flexibility increases, so it can be advantageously used for the substrate material for silicon solar cells.
- the tensile strength is superior to that of the substrate material manufactured in the conventional rolling process.
- substrate material is 0.1 micrometer-10 micrometers.
- the grain size is less than 0.1 mu m, the coefficient of thermal expansion changes abruptly with temperature, and thus does not have a stable coefficient of thermal expansion. If the size of the crystal grains exceeds 10 ⁇ m, there is a problem that the strength is too low. In this case, handling becomes difficult.
- Fe-40wt% Ni metal substrate material was prepared by using an electroplating apparatus equipped with a plating drum having a pyramidal texture texture as shown in Figure 1 using an electrolyte solution having the following composition.
- the metal electrolyte solution is 30 g / L of iron (II) chloride 4. hydrate, 200 g / L nickel sulfamate, 20 g / L boric acid, 1 g / L sodium dodecyl sulfate, 2 g / L saccharin, 1 g / L antioxidant It was prepared to include.
- the temperature of the electrolyte solution was maintained at 60, the current density was adjusted to 56 mA / cm 2 , and the thickness was 30 ⁇ m to prepare a metal substrate material of Fe-40wt% Ni.
- the concave-convex structure of the prepared substrate material had an inclination angle of 60 ° and a grain size of 15-20 nm. After performing the structure stabilization process by heat treatment at 400 °C to 1000 °C for 1 hour, the grain size was grown to 0.1 ⁇ m ⁇ 10 ⁇ m.
- the thermal expansion coefficient of the Fe-Ni metal foil substrate material according to the temperature was measured by the thermo mechanical analysis (TMA), The measurement results are shown in FIG. 4.
- TMA thermo mechanical analysis
- the electrolyte solution composition was adjusted to prepare Fe-42wt% Ni metal foil in a similar manner to Example 1.
- substrate material is a pyramid shape with an inclination angle of 60 degrees.
- After treating the tissue stabilization process at 400 °C to 1000 °C grain size was grown to 0.1 ⁇ m to 10 ⁇ m.
- the thermal expansion coefficient of the Fe-Ni metal foil substrate material with temperature was measured using Thermo mechanical Analysis (TMA), and the measurement results are shown in FIG. 5.
- TMA Thermo mechanical Analysis
- the coefficient of thermal expansion was measured under the condition that the temperature increase rate of 5 °C / min at 25 ⁇ 520 °C. 5 shows a rapid thermal change at about 375 °C when the tissue stabilization process is not performed.
- the structure stabilization process at 400 °C can be seen that the rapid thermal contraction phenomenon occurred at 400 °C point.
- the tissue stabilization process is performed at 600 °C, it can be seen that the average of CTE up to 350 °C is 4.94 ⁇ 10 -6 / °C.
- the structure of the structure was confirmed by measuring the XRD peak according to the heat treatment temperature of the prepared substrate material. The results are shown in FIG. Referring to FIG. 6, as the heat treatment temperature increases, peaks of the FCC 111 and the FCC 200 showing the face-centered cubic structure are clearly seen. On the other hand, the peak of FCC (110) disappeared when the heat treatment at 600 °C or more.
- the grain size was constantly increased as the heat treatment temperature was increased, and the specimens heat-treated at 800 ° C. grew to 4.3 ⁇ m when observed by optical structure and 4.5 ⁇ m when observed by SEM.
- the electrolyte solution composition was adjusted to prepare Fe-44wt% Ni metal foil in a similar manner to Example 1.
- the texture structure of the manufactured substrate material is pyramidal shape with an inclination angle of 60 degrees. After the tissue stabilization process of 400 °C to 1000 °C grain size was grown to 0.1 ⁇ m ⁇ 10 ⁇ m.
- the thermal expansion coefficient of the Fe-Ni metal foil substrate material with temperature was measured using Thermo mechanical Analysis (TMA), and the measurement results are shown in FIG. 7.
- TMA Thermo mechanical Analysis
- An Fe-42 wt% Ni metal foil was prepared using an electrolytic solution and pole apparatus with the composition of Example 2.
- the texture structure of the substrate material was manufactured in a pyramid shape having a V-shape having an inclination angle of 30 °, 45 °, and 60 °, respectively, and having an inclination angle of 30 °, 45 °, and 60 °, respectively.
- Surface reflectances of the prepared substrate materials were measured and shown in FIGS. 8A and 8B.
- FIG. 8A is a result of measuring the total reflectance of the substrate material having no texture structure formed
- FIG. 8B shows the texture structure formed on the surface, and the inclination angles of the V-shape texture structure were 30 ° (a) and 45 ° (b), respectively.
- FIG. Figure 9 shows the maximum, minimum, average value of the hardness according to the heat treatment temperature.
- the average value of the hardness of the substrate material manufactured after the pole casting process is 472.02 Hz, but after the heat treatment at 350 °C can be seen that the hardness value significantly increased to 592.5 Hz. Since the heat treatment temperature increases it can be seen that the decrease to 193.6Hz at 800 °C. This is believed to be due to the growth of grains according to the heat treatment temperature. In the case of micro-sized grains, dislocations can be generated and moved within the grains, and thus, the heat treated specimens are expected to be softer than those of the electrodeposition material in the nanocrystalline state, which has little ductility.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Materials Engineering (AREA)
- Electrochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Physics & Mathematics (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Computer Hardware Design (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Photovoltaic Devices (AREA)
Abstract
Description
열처리 온도 (℃) | 결정립 크기 (㎛) | |
Optical | SEM | |
400 | 1.73 | 1.77 |
600 | 2.56 | 2.13 |
800 | 4.27 | 4.50 |
Claims (12)
- 표면에 텍스처 구조를 갖는 태양전지용 플렉서블 금속 기판재로서,상기 텍스처 구조는 전주 방법에 의해, 표면에 요철구조를 갖는 도금용 드럼 또는 플레이트를 이용하여 형성된 태양전지용 플렉서블 금속 기판재.
- 청구항 1에 있어서, 상기 플렉서블 금속 기판재는 Fe-40wt% Ni 내지 Fe-45wt% Ni 합금 포일 기판재인 것을 특징으로 하는 태양전지용 플렉서블 금속 기판재.
- 청구항 1에 있어서, 상기 플렉서블 금속 기판재는 350℃ 내지 1000℃에서 30분 내지 2시간 동안 열처리하여 마이크로 크기의 결정립이 형성되는 것을 특징으로 하는 태양전지용 플렉서블 금속 기판재.
- 청구항 1 내지 청구항 3 중 어느 한 항에 있어서, 상기 플렉서블 금속 기판재의 결정립 크기는 0.1 ㎛ 내지 10 ㎛이고, 면심 입방정의 단일상 구조를 갖는 것을 특징으로 하는 태양전지용 플렉서블 금속 기판재.
- 청구항 1 내지 청구항 3 중 어느 한 항에 있어서, 상기 플렉서블 금속 기판재의 열팽창계수는 2×10-6/℃ 내지 6×10-6/℃ 인 것을 특징으로 하는 태양전지용 플렉서블 금속 기판재.
- 청구항 1 내지 청구항 3 중 어느 한 항에 있어서, 상기 플렉서블 금속 기판재의 두께는 1 ㎛ 내지 100 ㎛인 것을 특징으로 하는 태양전지용 플렉서블 금속 기판재.
- 전주 방법으로 표면에 요철 구조를 갖는 도금용 드럼 또는 플레이트를 이용하여 표면에 텍스처 구조를 갖는 금속 기판을 형성하는 단계; 및상기 전주 방법으로 제조된 금속 기판을 열처리하여 마이크로 크기의 결정립을 형성하는 단계를 포함하는 태양전지용 플렉서블 금속 기판재의 제조방법.
- 청구항 7에 있어서, 상기 금속 기판은 Fe-40wt% Ni 내지 Fe-45wt% Ni 합금인 것을 특징으로 하는 태양전지용 플렉서블 금속 기판재의 제조방법.
- Fe-40wt% Ni 내지 Fe-45wt% Ni 합금으로 이루어지고, 열팽창계수가 2×10-6/℃ 내지 6×10-6/℃인 그래팅용 플렉서블 금속 기판재.
- 청구항 9에 있어서, 상기 플렉서블 금속 기판재는 표면에 그래팅(gratting)을 이루는 요철 구조가 형성된 것을 특징으로 하는 그래팅용 플렉서블 금속 기판재.
- 청구항 9에 있어서, 상기 플렉서블 금속 기판재는 표면에 텍스처 구조를 갖는 것을 특징으로 하는 그래팅용 플렉서블 금속 기판재.
- 청구항 9에 있어서, 상기 플렉서블 금속 기판재는 결정립 크기가 0.1 ㎛ 내지 10 ㎛인 것을 특징으로 하는 그래팅용 플렉서블 금속 기판재.
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2014542224A JP6246727B2 (ja) | 2011-11-17 | 2012-10-16 | テクスチャ構造を有する熱膨張制御型フレキシブル金属基板材 |
US14/358,138 US20140332069A1 (en) | 2011-11-17 | 2012-10-16 | Controlled expansion flexible metal substrate material having a textured structure |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR10-2011-0120181 | 2011-11-17 | ||
KR20110120181 | 2011-11-17 | ||
KR1020120114243A KR101422609B1 (ko) | 2011-11-17 | 2012-10-15 | 텍스처 구조를 갖는 열팽창 제어형 플렉서블 금속 기판재 |
KR10-2012-0114243 | 2012-10-15 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2013073778A1 true WO2013073778A1 (ko) | 2013-05-23 |
Family
ID=48429806
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/KR2012/008429 WO2013073778A1 (ko) | 2011-11-17 | 2012-10-16 | 텍스처 구조를 갖는 열팽창 제어형 플렉서블 금속 기판재 |
Country Status (1)
Country | Link |
---|---|
WO (1) | WO2013073778A1 (ko) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2018506641A (ja) * | 2014-12-23 | 2018-03-08 | ポスコPosco | 熱復元性に優れたFe−Ni系合金金属箔及びその製造方法 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH1082000A (ja) * | 1996-09-05 | 1998-03-31 | Nisshin Steel Co Ltd | 太陽電池基板用ステンレス鋼の製造方法、太陽電池用基板,太陽電池及び太陽電池の製造方法 |
JP2009021479A (ja) * | 2007-07-13 | 2009-01-29 | Omron Corp | Cis系太陽電池及びその製造方法 |
JP2011511477A (ja) * | 2008-02-06 | 2011-04-07 | ソロパワー、インコーポレイテッド | 太陽電池吸収体を形成するための前駆体膜のリール・ツー・リール反応 |
-
2012
- 2012-10-16 WO PCT/KR2012/008429 patent/WO2013073778A1/ko active Application Filing
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH1082000A (ja) * | 1996-09-05 | 1998-03-31 | Nisshin Steel Co Ltd | 太陽電池基板用ステンレス鋼の製造方法、太陽電池用基板,太陽電池及び太陽電池の製造方法 |
JP2009021479A (ja) * | 2007-07-13 | 2009-01-29 | Omron Corp | Cis系太陽電池及びその製造方法 |
JP2011511477A (ja) * | 2008-02-06 | 2011-04-07 | ソロパワー、インコーポレイテッド | 太陽電池吸収体を形成するための前駆体膜のリール・ツー・リール反応 |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2018506641A (ja) * | 2014-12-23 | 2018-03-08 | ポスコPosco | 熱復元性に優れたFe−Ni系合金金属箔及びその製造方法 |
EP3239363B1 (en) * | 2014-12-23 | 2019-05-08 | Posco | Fe-ni alloy metal foil having excellent heat resilience and method for manufacturing same |
US10458031B2 (en) | 2014-12-23 | 2019-10-29 | Posco | Fe—Ni alloy metal foil having excellent heat resilience and method for manufacturing same |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
KR101422609B1 (ko) | 텍스처 구조를 갖는 열팽창 제어형 플렉서블 금속 기판재 | |
TWI684679B (zh) | 免於起皺的銅箔、包含其的電極、包含其的二次電池及其製造方法 | |
KR20010063692A (ko) | 전기도금법에 의한 2축 집합조직을 갖는 니켈 도금층 및이의 제조방법과 제조장치 | |
CN101931097B (zh) | LiCoO2的沉积 | |
CN113621999B (zh) | 一种高延伸性电解铜箔及其制备方法 | |
KR102413056B1 (ko) | 주름이 방지되고 우수한 충방전 특성을 갖는 동박, 그것을 포함하는 전극, 그것을 포함하는 이차전지, 및 그것의 제조방법 | |
CN106507689A (zh) | 用于锂二次电池的电解铜箔及包含该电解铜箔的锂二次电池 | |
US20020015833A1 (en) | Manufacturing method of electrodeposited copper foil and electrodeposited copper foil | |
WO2013073738A1 (ko) | Cigs 태양전지용 철-니켈 합금 금속 포일 기판재 | |
KR100516126B1 (ko) | 이축집합조직을 갖는 금속 도금층의 제조방법 | |
EP1065298A2 (en) | Method of manfacturing electrodeposited copper foil and electrodeposited copper foil | |
KR20230038679A (ko) | 고용량 이차전지 제조를 가능하게 하는 동박, 그것을 포함하는 전극, 그것을 포함하는 이차전지, 및 그것의 제조방법 | |
WO2013073778A1 (ko) | 텍스처 구조를 갖는 열팽창 제어형 플렉서블 금속 기판재 | |
JP7326668B2 (ja) | シワの発生が防止された銅箔、それを含む電極、それを含む二次電池、およびその製造方法 | |
KR101165354B1 (ko) | 단일 방위의 면을 가지는 면심입방격자 금속촉매상에서 그래핀을 제조하는 방법 | |
KR20190030987A (ko) | 핸들링성이 우수한 고용량 이차전지용 동박, 그것을 포함하는 전극, 그것을 포함하는 이차전지, 및 그것의 제조방법 | |
WO2019124696A1 (ko) | 내굴곡성이 우수한 철-니켈 합금박 | |
CN112118672A (zh) | 具有长岛状微结构的进阶反转电解铜箔及应用其的铜箔基板 | |
KR20090114126A (ko) | 음극용 리드탭 및 그 제조방법 | |
KR20120045910A (ko) | 그래핀 박막 및 이를 제조하는 방법 | |
Nam et al. | Recrystallization textures of silver electrodeposits | |
KR101502373B1 (ko) | 전해동박, 이를 포함하는 전기부품 및 전지 | |
KR101478464B1 (ko) | 전해동박, 이를 포함하는 전기부품 및 전지 | |
Saitou | Phase Diagram and Tin Whisker Growth During Electrodeposition | |
CN116180162A (zh) | 一种铜箔及其制备方法和应用 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 12850725 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 14358138 Country of ref document: US |
|
ENP | Entry into the national phase |
Ref document number: 2014542224 Country of ref document: JP Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 12850725 Country of ref document: EP Kind code of ref document: A1 |