CN112993062A - Flexible CIGS thin film battery with embedded grid line electrode - Google Patents
Flexible CIGS thin film battery with embedded grid line electrode Download PDFInfo
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- CN112993062A CN112993062A CN202011397877.0A CN202011397877A CN112993062A CN 112993062 A CN112993062 A CN 112993062A CN 202011397877 A CN202011397877 A CN 202011397877A CN 112993062 A CN112993062 A CN 112993062A
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- 239000010409 thin film Substances 0.000 title claims abstract description 42
- 230000031700 light absorption Effects 0.000 claims abstract description 33
- 238000002955 isolation Methods 0.000 claims description 25
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 20
- 229910052709 silver Inorganic materials 0.000 claims description 19
- 239000004332 silver Substances 0.000 claims description 19
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 14
- 229910052708 sodium Inorganic materials 0.000 claims description 14
- 239000011734 sodium Substances 0.000 claims description 14
- 239000000758 substrate Substances 0.000 claims description 12
- 239000011159 matrix material Substances 0.000 claims description 6
- 239000003292 glue Substances 0.000 claims description 4
- 239000000463 material Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000010408 film Substances 0.000 description 7
- 230000007547 defect Effects 0.000 description 5
- 238000000151 deposition Methods 0.000 description 5
- 238000001755 magnetron sputter deposition Methods 0.000 description 5
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- 239000010935 stainless steel Substances 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 238000005530 etching Methods 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 238000010329 laser etching Methods 0.000 description 3
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- 238000010521 absorption reaction Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- 239000013077 target material Substances 0.000 description 2
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical group OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 1
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical group [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
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- 238000000576 coating method Methods 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 229910001325 element alloy Inorganic materials 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- HRHKULZDDYWVBE-UHFFFAOYSA-N indium;oxozinc;tin Chemical compound [In].[Sn].[Zn]=O HRHKULZDDYWVBE-UHFFFAOYSA-N 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
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- 238000004806 packaging method and process Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- KIIUTKAWYISOAM-UHFFFAOYSA-N silver sodium Chemical compound [Na].[Ag] KIIUTKAWYISOAM-UHFFFAOYSA-N 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- PVGBHEUCHKGFQP-UHFFFAOYSA-N sodium;n-[5-amino-2-(4-aminophenyl)sulfonylphenyl]sulfonylacetamide Chemical compound [Na+].CC(=O)NS(=O)(=O)C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 PVGBHEUCHKGFQP-UHFFFAOYSA-N 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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- 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
- H01L31/0224—Electrodes
- H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
- H01L31/022433—Particular geometry of the grid contacts
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- 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
- H01L31/02363—Special surface textures of the semiconductor body itself, e.g. textured active layers
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- H—ELECTRICITY
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- 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
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- 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
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- 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
- H01L31/052—Cooling means directly associated or integrated with the PV cell, e.g. integrated Peltier elements for active cooling or heat sinks directly associated with the PV cells
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- 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
- H01L31/06—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 characterised by potential barriers
- H01L31/072—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 characterised by potential barriers the potential barriers being only of the PN heterojunction type
- H01L31/0749—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 characterised by potential barriers the potential barriers being only of the PN heterojunction type including a AIBIIICVI compound, e.g. CdS/CulnSe2 [CIS] heterojunction solar cells
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Abstract
The invention discloses a flexible CIGS thin-film battery with an embedded grid line electrode, which comprises a CIGS light absorption layer and a transparent surface electrode layer, wherein the CIGS light absorption layer of the thin-film battery is etched with a wire groove structure at the position of a silk-screen conductive grid line, the transparent surface electrode layer is provided with a downward convex linear groove at the position corresponding to the wire groove structure, the downward convex linear groove is embedded into the wire groove structure of the CIGS light absorption layer, the lower end part of the conductive grid line is embedded into the linear groove, and the upper end part of the conductive grid line extends upwards to the outside of the linear groove. The thin film battery has the advantages that the contact area between the grid line electrode and the transparent surface electrode layer is increased, so that the thin film battery has low resistance and good conductivity under the condition that the grid line electrode on the upper surface of the battery is small in size.
Description
Technical Field
The invention relates to a flexible CIGS thin film battery with an embedded grid line electrode.
Background
The solar cell can convert light into electric energy, and each independent cell unit is connected in series to form integral electric energy output outwards. The most direct index for evaluating the performance of a battery is the photoelectric conversion efficiency, and various factors influencing the photoelectric conversion efficiency of the photovoltaic battery are provided, such as the difference of different types of photovoltaic materials, the preparation process, the effective light receiving area, the power loss of the battery and the like. Increasing the effective light receiving area of the battery or reducing the power loss of the battery is considered to be a method for easily improving the photoelectric conversion efficiency of the battery. At present, most photovoltaic cells adopt a method of printing electrodes on a top layer to prepare a cell output electrode, the top layer electrode plays a role in collecting charges and conducting out electric energy converted by the cell, the lower the resistance of the top layer electrode is, the smaller the power of the cell is, so that the thicker and wider the electrode grid lines are required to be, the better the electrode grid lines are, but because the electrode grid lines are positioned on the top layer of the cell, the wider grid lines can shield more light rays, the effective light receiving area of the cell is influenced, and conversely, the thinner the electrode grid lines are required to be, the better the electrode grid lines are. To solve this problem, the prior art adopts adjusting the aspect ratio of the gate lines (i.e. the gate lines become narrower but the height increases), or adopts a main-gate-free perforated back contact cell (often seen in a crystalline silicon cell) or adopts an ultra-dense main-gate-free structure to solve the problem that the resistance of the gate lines and the shading area are restricted with each other. The back contact battery omits the main grid, although the shading area is greatly reduced, the hidden crack risk is increased because the battery is tunneled by the laser opening; the height-width ratio of the grid line is adjusted, namely the height-width ratio is increased on the existing printed pattern, so that the grid line is narrowed but the height is increased, the light source is over against the battery when the standard battery efficiency is detected, the shading is mainly influenced by the width of the grid line and is irrelevant to the height, but when the actual photovoltaic product is installed in outdoor application, sunlight is always changed from the morning to the evening, the height of the grid line can influence light rays at the moment, and more oblique light rays can be shielded by the aid of the thickness of the welding strip and the main grid after the height is increased.
Disclosure of Invention
The purpose of the invention is as follows: aiming at solving the problem that the mutual restriction between the resistance of a grid line electrode and the shading area of a battery exists in the prior art, the invention provides a flexible CIGS thin-film battery with an embedded grid line electrode, which realizes low resistance and good conductivity under the condition that the grid line electrode on the upper surface of the battery is very small in size by increasing the contact area between the grid line electrode and a transparent surface electrode layer.
The technical scheme is as follows: the flexible CIGS thin-film battery with the embedded grid line electrode comprises a CIGS light absorption layer and a transparent surface electrode layer, wherein a wire groove structure is etched on the position of a silk-screen conductive grid line of the CIGS light absorption layer of the thin-film battery, a downward convex linear groove is arranged on the position, corresponding to the wire groove structure, of the transparent surface electrode layer, the downward convex linear groove is embedded into the wire groove structure of the CIGS light absorption layer, the lower end part of the conductive grid line is embedded into the linear groove, and the upper end part of the conductive grid line extends upwards to the outside of the linear groove.
The thin film battery sequentially comprises a substrate, a back electrode layer, a reflecting layer, a CIGS light absorption layer, a buffer layer and a transparent surface electrode layer from bottom to top along the longitudinal direction; the transparent surface electrode layer sequentially comprises a transparent surface electrode high-impedance layer and a transparent surface electrode low-impedance layer, the conductive grid line comprises a lower end portion located in the linear groove and an upper end portion extending out of the linear groove, the upper end portion of the conductive grid line is connected with the low-impedance layer, and the lower end portion of the conductive grid line is connected with the high-impedance layer.
The cross section of the upper end part of the conductive grid line is semicircular or rectangular, and the cross section of the lower end part of the conductive grid line is rectangular.
The upper end part of the conductive grid line is a silver grid line; the lower end part of the conductive grid line is a silver grid line or a silver grid line doped with sodium, and when the conductive grid line is the silver grid line doped with sodium, the sodium is doped at the lower end of the silver grid line.
The conductive grid lines are printed on the battery in a silk-screen mode to form grid line electrodes; the grid line electrode is a grid line electrode containing at least one main grid line or a grid line electrode without the main grid line.
Wherein the inner diameter of the linear groove corresponding to the thin grid line in the grid line electrode is 49-79 um, and the depth is 1.75-2.25 um; the inner diameter of the linear groove corresponding to the main grid line in the grid line electrode is 999-1499 um, and the depth is 1.75-2.25 um.
The upper surface of the CIGS light absorption layer is also etched with a plurality of concave tooth structures, the plurality of concave tooth structures are arranged in a matrix manner, and the plurality of concave tooth structures arranged in the matrix manner are arranged between the adjacent wire slot structures; the high-impedance layer is provided with a plurality of protruding structures corresponding to the concave tooth structures, the top of each protruding structure is open and protrudes downwards, the protruding structures of the high-impedance layer are embedded into the concave tooth structures on the upper surface of the CIGS light absorption layer, a plurality of protruding blocks corresponding to the protruding structures are formed on the lower surface of the low-impedance layer, the protruding blocks are embedded into the protruding structures of the top opening, and the upper surface of the low-impedance layer is of a continuous smooth structure.
Wherein, the cross section of the concave tooth structure is rectangular or conical.
The isolation belt is arranged at a position 0.1-1 mm away from the outer edge of the battery, the isolation belt is parallel to the corresponding battery edge, and the isolation belt surrounds the periphery of the battery to form a ring; the width of the isolation belt is 0.02-0.05mm, and the depth of the isolation belt is from the upper surface of the battery to the upper surface of the substrate.
Wherein, the isolation strip is filled with insulating glue.
Has the advantages that: according to the thin film battery, the grid line electrode is embedded into the transparent surface electrode layer and the inside of the battery (CIGS absorption layer), so that the contact area between the grid line electrode and the transparent surface electrode layer is effectively increased, the grid line electrode is more beneficial to collecting electrons from the deep part of the transparent electrode layer, the internal resistance of the battery is reduced in such a way, namely, the power loss of the battery is reduced, the output power of the battery is improved, and the photoelectric conversion efficiency is improved; in addition, the conductivity of the grid line electrode is enhanced after the grid line electrode is embedded into the battery, so that the resistance is not increased under the condition that the sizes of the main grid line and the fine grid line of the grid line electrode are smaller, and the thickness of the grid line on the surface of the battery can be reduced, so that the shading influence of the grid line on the surface of the battery on vertical illumination and oblique illumination can be effectively reduced, and the effective light receiving area of the battery is further improved; therefore, the non-main-gate battery or the multi-main-gate battery manufactured by adopting the embedded grid line electrode can ensure the conductivity of the electrode while obviously increasing the light receiving area, thereby increasing the photoelectric conversion efficiency of the battery; finally, the grid line electrode structure can enhance the heat dissipation performance of the battery, and because the silver grid lines have good electric conduction and heat conduction performance, the grid line electrodes embedded in the battery film layer can quickly conduct heat generated by the battery during working from the inside to the surface of the battery to be dissipated, so that the temperature of the battery can be effectively reduced, and the stability of the power generation performance of the battery is guaranteed.
Drawings
Fig. 1 is a schematic structural view of a thin film battery according to example 1 of the present invention;
FIG. 2 is a cross-sectional view of FIGS. 1 a-a;
FIG. 3 is a cross-sectional view of FIG. 2 b-b;
FIG. 4 is a schematic structural view of a thin film battery according to example 2 of the present invention;
FIG. 5 is a cross-sectional view of FIGS. 4 c-c;
FIG. 6 is a cross-sectional view of FIGS. 5 d-d;
FIG. 7 is a schematic structural view of a thin film battery according to example 3 of the present invention;
FIG. 8 is a cross-sectional view of FIGS. 7 e-e;
FIG. 9 is a cross-sectional view of FIGS. 8 f-f;
fig. 10 shows a light shielding condition of the embedded gate line electrode;
fig. 11 is a comparison of shading of oblique illumination by conventional gate lines and gate lines of the present invention;
FIG. 12 is a schematic diagram of light entering the light absorbing layer after being reflected multiple times in the light trapping structure;
FIG. 13 is a schematic diagram of a light trapping structure effectively increasing the area of the PN junction interface between the transparent surface electrode layer and the light absorbing layer;
fig. 14 is a top view of a thin film battery of the present invention;
FIG. 15 is a cross-sectional view of FIGS. 14G-G;
fig. 16 is a schematic diagram of sodium diffusion of a sodium silver doped grid line.
Detailed Description
The technical solution of the present invention is further explained with reference to the accompanying drawings and specific embodiments.
Example 1
As shown in fig. 1 to 3, in the flexible CIGS thin film battery 100 with an embedded gate line electrode according to the present invention, the thin film battery 100 sequentially includes a substrate 1, a back electrode layer 2, a reflective layer 3, a CIGS light absorbing layer 4, a buffer layer 5, and a transparent surface electrode layer from bottom to top along a longitudinal direction; wherein, the transparent surface electrode layer comprises a transparent surface electrode high-impedance layer 6 and a transparent surface electrode low-impedance layer 7; the CIGS light absorption layer 4 is etched with a wire groove structure 4-1 at the position of the silk-screen conductive grid line 10, and after a buffer layer 5 and a transparent surface electrode layer are sequentially deposited on the inner side wall and the bottom of the wire groove structure 4-1, a downward convex linear groove 62 is formed in the position of the transparent surface electrode layer corresponding to the wire groove structure 4-1, the downward convex linear groove 62 is positioned in the wire groove structure 4-1 of the CIGS light absorption layer, and the conductive grid line 10 is silk-screen printed in the linear groove 62. The conductive grid line 10 comprises a part, namely an upper end part 10-2, extending out of the linear groove 62 and a part, namely a lower end part 10-1, positioned in the linear groove 62, wherein the lower end part 10-1 of the conductive grid line 10 is embedded in the linear groove 62, and the upper end part 10-2 of the conductive grid line 10 extends upwards to the outside of the linear groove 62 (the upper end part 10-2 of the conductive grid line 10 is positioned on the upper surface of the thin film battery). The upper end portion 10-2 of the conductive grid line 10 is connected with the low impedance layer 7, and the lower end portion 10-1 of the conductive grid line 10 is connected with the high impedance layer 6.
A plurality of concave tooth structures 4-2 are further etched on the upper surface of the CIGS light absorption layer 4, the concave tooth structures 4-2 are arranged in a matrix manner, and the concave tooth structures 4-2 arranged in the matrix manner are arranged between the adjacent wire slot structures 4-1 (the adjacent wire slot structures 4-1 are arranged in parallel); the high-resistance layer 6 is provided with a plurality of convex structures 61 corresponding to the concave tooth structures 4-2, the top of each convex structure 61 is open and protrudes downwards, the convex structures 61 of the high-resistance layer 6 are embedded into the concave tooth structures 4-2 on the upper surface of the CIGS light absorption layer 4, a plurality of convex blocks 71 corresponding to the convex structures 61 are formed on the lower surface of the low-resistance layer 7, the convex blocks 71 are embedded into the convex structures 61 with the top open, the upper surface of the low-resistance layer 7 is a flat continuous structure in an area 4-3 where the CIGS light absorption layer 4 is provided with a plurality of concave tooth structures 4-2, and the concave tooth structures 4-2 are filled with transparent surface conducting layers after a buffer layer is deposited in the concave tooth structures 4-2.
As shown in fig. 12-13, the thin film battery of the invention forms a plurality of light trapping structures by the concave tooth structure 4-2, that is, the transparent surface electrode layer and the light absorbing layer are not in plane contact any more, but are in a mutually inserted engaged contact structure, that is, the transparent surface electrode layer has a plurality of convex structures recessed downward and deep into the light absorbing layer, and also the light absorbing layer has a plurality of structures protruding upward and inserted into the adjacent convex structures on the transparent surface electrode layer, the tooth depths of the two microstructures are the same (the depth of the convex structure is the same as that of the protruding structure), wherein the low impedance layer of the transparent surface electrode layer also has a convex block structure inserted downward into the convex structure recessed downward on the high impedance layer. The meshing structure forms a microscopic light trapping structure in the thin film battery, and light rays are reflected for multiple times through a meshing interface when entering the meshing structure, so that light absorption can be increased; light that passes through the light-absorbing layer without being completely absorbed is reflected by the reflective layer at the bottom of the light-absorbing layer and re-enters the light-absorbing layer, and then is reflected again a part of the way to increase light absorption if there are still unabsorbed light that escapes the light-absorbing layer and passes through the ratcheting interface again. The light trapping structure is positioned in the battery, and the surface of the battery is only provided with a slight pit structure, so that the light trapping effect is increased, and the conductivity of a surface electrode layer is not reduced. Meanwhile, the film layer meshing structure in the cell greatly increases the area of a PN junction interface, the PN junction interface is formed on the upper surface and the lower surface of each tooth structure, and the PN junction interface can also be formed on the side surface of each tooth structure, so that excitons or current carriers in the tooth structure on the upper part of the light absorption layer have more chances to diffuse to the PN junction interface to form photovoltaic current. Secondly, because the downward tooth structure of the transparent surface electrode layer is deep into the lower part of the light absorption layer (namely, the PN junction formed at the bottom of the tooth structure is deep into the lower part of the light absorption layer), excitons or carriers which are difficult to migrate remotely in the lower part of the light absorption layer in the past also have the opportunity to approach the PN junction to generate current. Finally, more carriers have more opportunities to participate in power generation, the carrier utilization rate is greatly improved, and meanwhile, the current density is increased, and the short-circuit current of the battery is increased. The transparent electrode high-impedance layer tooth structure extending into the light absorption layer and the low-impedance layer tooth structure extending into the high-impedance layer tooth structure have better transportation effect on electrons collected from the inside of the light absorption layer, so that the internal resistance of the thin film battery is reduced again, the output power of the battery is increased, and the filling factor is improved. The concave-convex structure can also reduce the material consumption of the transparent electrode layer, save the target material cost, and the thinner surface transparent electrode layer can further increase the incident light. The thin film battery has the characteristic of high carrier utilization rate.
In fig. 2, the cross section of the upper end portion 10-2 of the conductive gate line 10 is semicircular, and the cross section of the lower end portion 10-1 of the conductive gate line 10 is rectangular. The conductive grid line 10 is a silver grid line, or the upper end portion 10-2 of the conductive grid line 10 is a silver grid line, and the lower end portion 10-1 of the conductive grid line 10 is a silver grid line doped with sodium. As shown in fig. 16, sodium is doped at the end of the lower end 10-1 of the conductive gate line 10, the sodium source is located in the concave teeth 4-2 of the CIGS light absorbing layer 4, sodium can directly diffuse to the inner depth of the CIGS light absorbing layer 4, and can diffuse from the side surfaces of the concave teeth 4-2 to the periphery (diffuse in the CIGS light absorbing layer 4) in addition to the downward diffusion, and finally, sodium doping with a deeper depth and a wider range is formed in the CIGS light absorbing layer 4, so that the defect density of the CIGS light absorbing layer 4 is reduced, the carrier concentration is increased, and the cell efficiency is further improved. The doped sodium is concentrated at the tail end of the silver grid line, the upper end silver grid line does not contain sodium, and the problem that the structural stability of the transparent electrode layer is influenced by the transverse diffusion of the sodium on the transparent electrode layer on the surface of the battery is avoided.
The conductive grid lines 10 are silk-screened on the battery to form grid line electrodes 80; the embodiment is a grid line electrode 80 containing a main grid 11, wherein the inner diameter of a wire groove structure corresponding to a thin grid line 12 in the grid line electrode 80 is 49-79 um, and the depth is 1.75-2.25 um; the inner diameter of the trunking structure corresponding to the main grid line 11 in the grid line electrode 80 is 999-1499 um, and the depth is 1.75-2.25 um.
The flexible CIGS thin film battery is prepared by the following method, and the specific steps are as follows:
(1) selecting a stainless steel substrate with the thickness of 0.05-0.2 mm, preferably 0.1-0.15 mm, and scrubbing and cleaning the stainless steel substrate by using acetone to facilitate film coating;
(2) depositing 0.5-1.5 um, preferably 0.8-1 um thick metal molybdenum (Mo) on a stainless steel substrate by adopting a magnetron sputtering method to serve as a back electrode layer, and then depositing a 0.1um thick conductive reflecting layer on the back electrode layer;
(3) a CIGS light absorption layer with the thickness of 1.5-2.5 um, preferably 2um, is deposited on the conductive reflecting layer by adopting a low-temperature vacuum magnetron sputtering method and using CIGS multi-element alloy as a target material;
(4) in a vacuum environment, a pulse laser etching process is adopted, a plurality of concave tooth structures are uniformly etched on the upper surface of a CIGS light absorption layer according to a designed etching pattern, each concave tooth structure is an independent structure, the inner diameter of each concave tooth is 10 micrometers, the distance between every two adjacent concave teeth is 10 micrometers, and the depth of each concave tooth is 0.75-1.25 micrometers; meanwhile, a wire groove with the depth of 0.75-1.25 um and the width of 50-80 um is etched on the upper surface of the CIGS light absorption layer in the area right below the conductive grid line, wherein the width of the wire groove below the main grid is 1000-1500 um, and finally formed wire groove patterns correspond to the top conductive grid line patterns one by one and the vertical projections of the wire groove patterns are overlapped;
(5) depositing a buffer layer with the thickness of 50-100 nm on a CIGS light absorption layer with a concave tooth structure and a slot structure in a magnetron sputtering way, wherein the material of the buffer layer is cadmium sulfide or other cadmium-free materials, etching the buffer layer material in the concave tooth and the slot by adopting pulse laser, only leaving the buffer layer with the thickness of 50-100 nm, at the moment, the inner diameter of the concave tooth is changed to 9.8-9.9 um, the width of the corresponding slot is also narrowed a little, and finally forming the concave tooth and the upper surface of the slot uniformly coated with the buffer layer;
(6) depositing a transparent surface electrode sublayer-high-resistance layer with the thickness of about 0.5um on the buffer layer by utilizing vacuum magnetron sputtering, wherein the material can be selected from intrinsic zinc oxide (ZnO) or Indium Tin Oxide (ITO), etching part of high-resistance material in the concave teeth by adopting pulse laser, only leaving the high-resistance layer with the thickness of about 0.5um, further reducing the diameter of the concave teeth to 8.8 um-8.9 um, and etching the high-resistance material in the wire grooves in the step is not needed;
(7) and depositing a transparent surface electrode sublayer with the thickness of about 1um, namely a low-impedance layer on the high-impedance layer by adopting a vacuum magnetron sputtering method, wherein concave teeth are filled with the transparent surface electrode sublayer, slight pits are left on the upper surface of the battery, and the material can be aluminum-doped zinc oxide ZAO or indium zinc tin oxide IZTO. And then, carrying out vacuum high-temperature annealing treatment to reconstruct and crystallize the materials of all film layers in the battery, wherein the absorption layer has a chalcopyrite structure, and the sputtering coating process is finished.
(8) And (3) slotting from the low impedance layer to the high impedance layer in the grid line electrode area on the low impedance layer of the transparent surface electrode again through a pulse laser etching process, wherein the depth of the slotting is directly reached to the bottom of the slot of the high impedance layer, but both sides and the bottom of the slot are not contacted with the buffer layer, and finally, small slots with the width of 49-79 um, the depth of 1.75-2.25 um, and large slots with the width of 999 um-1499 um and the depth of 1.75-2.25 um are formed.
(9) The method comprises the steps of selecting low-temperature conductive silver paste as a grid line electrode material, carrying out first screen printing by adopting a printing screen plate (the screen plate line width is slightly narrower than a wire groove) which is consistent with a wire groove pattern on the surface of a battery, carrying out second screen printing by adopting a printing screen plate which is slightly wider than the wire groove after short-time drying, finishing electrode printing on the surface of the battery, completely filling the wire groove with silver paste, forming a T-shaped structure-like grid line electrode, treating the printed battery piece by utilizing low-frequency ultrasonic equipment in the two-time printing, and contributing to fully embedding the silver paste into the wire.
(10) And (4) sintering the printed battery piece at low temperature of about 200 ℃ to dry, solidify and mold the silver paste and form ohmic contact with the transparent conductive layer of the thin film battery.
(11) Finally, a full-automatic graphical scribing machine is used, a high-precision needle head is used for scribing along the periphery of the battery at a position (preferably 0.2-0.5mm, most preferably 0.3mm) 0.1mm-1mm away from the edge of the battery, and an isolation zone 90 (shown in figures 14-15) with the width of 0.02-0.05mm and the depth of the isolation zone reaching the upper surface of the stainless steel substrate is scribed, so that the battery is prepared.
Most of leakage current caused by edge defects is that the resistance is too low due to too thin film layers or defects on the vertical surfaces of all the film layers are staggered to cause the conduction of an upper transparent conductive layer and a back electrode layer or a stainless steel substrate, a battery with a circle of isolation strips 90 (the width of the isolation strips 90 is 0.02-0.05mm, the depth of the isolation strips is 2-4 um or the depth of the isolation strips is determined according to the total thickness of the plating layers) can be obtained by removing the plating films at the positions 0.1-1 mm away from the edges of the battery from the substrate along a path parallel to the edges of the battery, the isolation strips 90 are deep and reach the upper surface of the substrate 1, a molten glue film of the battery is filled into the isolation strips 90 in the subsequent assembly packaging stage, so that the glue film layers are filled in the isolation strips 90, the insulation isolation effect of the battery is further enhanced, the edge defects do not influence the middle normal. Therefore, the isolation strip structure can effectively avoid the influence of edge defects on the central normal area of the battery, effectively reduce the leakage current of the whole battery, improve the parallel resistance of the battery, further improve the photoelectric conversion efficiency of the battery in cooperation, reduce hot spots caused by edge leakage and prolong the service life of the battery. A large number of tests prove that the conversion efficiency of the battery with the isolation band structure can be further improved by over 0.2 percent, and the phenomenon of edge leakage and hot spots is also obviously improved.
The pulse laser etching in the steps can be replaced by a chemical etching process of a graphical mask plate, and the required concave teeth and the required line groove structure can be manufactured; the laser scribing machine can also be used for replacing a high-precision needle head to scribe, and an edge isolation belt can also be formed.
Example 2
As shown in fig. 4 to 6, the only differences between the thin film batteries of example 2 and example 1 are: the gate line electrode 80 of embodiment 2 does not have the main gate line 11. When the grid line electrode 80 does not contain the main grid line 11, the light receiving area of the battery is further increased, and due to the adoption of the embedded grid line electrode, the conductive performance of the grid line electrode is not greatly influenced after the main grid line is not provided, and compared with the existing grid line electrode containing the main grid line, the conductive performance is not greatly different, but is far larger than the conductive performance of the existing non-main-grid battery.
Example 3
As shown in fig. 7 to 9, the only differences between the thin film battery of example 3 and the thin film battery of example 1 are: the cross-section of the indented structure on the CIGS light absorbing layer in example 1 is rectangular (the indented structure 4-2 is circular in plan view 3), and the cross-section of the indented structure on the CIGS light absorbing layer in example 3 is tapered (the indented structure 4-2 is square in plan view 9).
As shown in fig. 10, the lower end portions of the embedded grid line electrodes (i.e., the portions of the grid line electrodes with increased areas) are embedded in the battery, and the areas originally belong to areas where light is difficult to irradiate, so that the increased areas of the grid line electrodes have no additional influence on the light absorption of the battery.
As shown in fig. 11, compared with the cross section of the gate line of the present invention, the vertical light shielding area S3 and the oblique light shielding area S4 of the gate line structure of the present invention are both smaller than the vertical light shielding area S1 and the oblique light shielding area S2 of the conventional gate line.
Claims (10)
1. A flexible CIGS thin film battery with embedded grid line electrodes, characterized by: the thin film battery comprises a CIGS light absorption layer and a transparent surface electrode layer, wherein a wire groove structure is etched on the CIGS light absorption layer of the thin film battery at the position of a silk-screen conductive grid line, a downward convex linear groove is arranged on the transparent surface electrode layer at the position corresponding to the wire groove structure, the downward convex linear groove is embedded into the wire groove structure of the CIGS light absorption layer, the lower end part of the conductive grid line is embedded into the linear groove, and the upper end part of the conductive grid line extends upwards to the outside of the linear groove.
2. The flexible CIGS thin film battery with embedded grid line electrodes as claimed in claim 1 wherein: the thin film battery sequentially comprises a substrate, a back electrode layer, a reflecting layer, a CIGS light absorption layer, a buffer layer and a transparent surface electrode layer from bottom to top along the longitudinal direction; the transparent surface electrode layer sequentially comprises a transparent surface electrode high-impedance layer and a transparent surface electrode low-impedance layer, the conductive grid line comprises a lower end portion located in the linear groove and an upper end portion extending out of the linear groove, the upper end portion of the conductive grid line is connected with the low-impedance layer, and the lower end portion of the conductive grid line is connected with the high-impedance layer.
3. The flexible CIGS thin film battery with embedded grid line electrodes as claimed in claim 2 wherein: the cross section of the upper end part of the conductive grid line is semicircular or rectangular, and the cross section of the lower end part of the conductive grid line is rectangular.
4. A flexible CIGS thin film battery with embedded grid line electrodes as claimed in claim 3 wherein: the end part of the conductive grid line is a silver grid line; the lower end part of the conductive grid line is a silver grid line or a silver grid line doped with sodium, and when the conductive grid line is the silver grid line doped with sodium, the sodium is doped at the lower end of the silver grid line.
5. The flexible CIGS thin film battery with embedded grid line electrodes as claimed in claim 1 wherein: the conductive grid lines are printed on the battery in a silk-screen mode to form grid line electrodes; the grid line electrode is a grid line electrode containing at least one main grid line or a grid line electrode without the main grid line.
6. The flexible CIGS thin film battery with embedded grid line electrodes as claimed in claim 5, wherein: the inner diameter of a linear groove corresponding to a thin grid line in the grid line electrode is 49-79 um, and the depth is 1.75-2.25 um; the inner diameter of the linear groove corresponding to the main grid line in the grid line electrode is 999-1499 um, and the depth is 1.75-2.25 um.
7. The flexible CIGS thin film battery with embedded grid line electrodes as claimed in claim 5, wherein: the upper surface of the CIGS light absorption layer is also etched with a plurality of concave tooth structures which are arranged in a matrix manner, and the plurality of concave tooth structures arranged in the matrix manner are arranged between the adjacent wire slot structures; the high-impedance layer is provided with a plurality of protruding structures corresponding to the concave tooth structures, the top of each protruding structure is open and protrudes downwards, the protruding structures of the high-impedance layer are embedded into the concave tooth structures on the upper surface of the CIGS light absorption layer, a plurality of protruding blocks corresponding to the protruding structures are formed on the lower surface of the low-impedance layer, the protruding blocks are embedded into the protruding structures of the top opening, and the upper surface of the low-impedance layer is of a continuous smooth structure.
8. The flexible CIGS thin film battery with embedded grid line electrodes as claimed in claim 7, wherein: the cross section of the concave tooth structure is rectangular or conical.
9. The flexible CIGS thin film battery with embedded grid line electrodes as claimed in claim 1 wherein: arranging an isolation belt at a position 0.1-1 mm away from the outer edge of the battery, wherein the isolation belt is parallel to the corresponding battery edge, and the isolation belt surrounds the periphery of the battery to form a ring shape; the width of the isolation belt is 0.02-0.05mm, and the depth of the isolation belt is from the upper surface of the battery to the upper surface of the substrate.
10. The flexible CIGS thin film battery with embedded grid line electrodes as claimed in claim 9 wherein: and the isolation belt is internally filled with insulating glue.
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