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CN110061075B - CIGS solar cell doped with metal Na and preparation method thereof - Google Patents

CIGS solar cell doped with metal Na and preparation method thereof Download PDF

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CN110061075B
CN110061075B CN201910346322.4A CN201910346322A CN110061075B CN 110061075 B CN110061075 B CN 110061075B CN 201910346322 A CN201910346322 A CN 201910346322A CN 110061075 B CN110061075 B CN 110061075B
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CN110061075A (en
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张准
王磊
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Sunflare Nanjing Energy Technology Co ltd
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    • H—ELECTRICITY
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    • 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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    • H01L31/022408—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
    • H01L31/022441—Electrode arrangements specially adapted for back-contact solar 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
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • 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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Abstract

The invention discloses a CIGS solar cell doped with metal Na and a preparation method thereof, belongs to the technical field of CIGS solar cell thin film materials, and solves the problem that new impurity elements are introduced when a CIGS layer or a back electrode layer is doped with Na compounds in the prior art. The CIGS solar cell doped with the metal Na comprises a substrate, and a back electrode layer, a CIGS layer, a buffer layer and a transparent surface electrode layer which are sequentially stacked on the substrate; the back electrode layer is doped with metal Na, and the doping amount of Na in the back electrode layer increases in a gradient manner from the substrate to the transparent surface electrode layer. The preparation method comprises the following steps: sequentially forming a back electrode layer, a CIGS layer, a buffer layer and a surface electrode layer on a substrate; the forming method of the back electrode layer comprises the following steps: and sequentially forming a third electrode sublayer, a second electrode sublayer and a third electrode sublayer on the substrate by adopting a target assembly and a magnetron sputtering process. The CIGS solar cell doped with the metal Na and the preparation method thereof can be used for solar power generation.

Description

CIGS solar cell doped with metal Na and preparation method thereof
Technical Field
The invention relates to an energy-saving, environment-friendly and clean energy technology, in particular to a CIGS solar cell thin film material technology, and especially relates to a CIGS solar cell doped with metal Na and a preparation method thereof.
Background
Energy crisis and environmental pollution are major challenges facing human beings, and the development of new energy and renewable clean energy is an important means for effectively solving the energy crisis and environmental pollution, and becomes one of the emerging industries with the fastest global development. The CIGS solar cell is a multilayer film structure mainly made of Cu (copper), In (indium), Ga (gallium), Se (selenium) and the like, can effectively utilize solar energy to generate electric energy, and has the advantages of strong light absorption capacity, good power generation stability, high conversion efficiency, long power generation time In the daytime, high power generation amount, low production cost, short energy recovery period and the like.
In the prior art, a CIGS solar cell generally includes a substrate, and a back electrode layer, a CIGS layer, a buffer layer and a transparent front electrode layer sequentially stacked on the substrate, wherein the CIGS layer is made of Cu (In, Ga) Se2The resulting film material, in order to reduce the defect density of the CIGS layer and increase the carrier concentration, is typically doped with a Na compound, e.g., Na, in the CIGS layer or in the back electrode layer adjacent thereto2Se、Na2S、Na2SeO3Or NaNbO3And the like.
However, doping a film material such as a CIGS layer or a back electrode layer with a Na compound introduces a new impurity element such as Se, S, or Nb, which affects the performance of the CIGS solar cell. Therefore, it is required to develop a new film material to reduce the introduction of impurity elements and improve the energy conversion efficiency of the solar cell.
Disclosure of Invention
In view of the foregoing analysis, the present invention aims to provide a CIGS solar cell doped with metallic Na and a method for manufacturing the same, which solve the problem in the prior art that doping a CIGS layer or a back electrode layer with a Na compound introduces a new impurity element.
The purpose of the invention is mainly realized by the following technical scheme:
the invention provides a CIGS solar cell doped with metal Na, which comprises a substrate, and a back electrode layer, a CIGS layer, a buffer layer and a transparent surface electrode layer which are sequentially stacked on the substrate; the back electrode layer is doped with metal Na, and the doping amount of Na in the back electrode layer increases in a gradient manner from the substrate to the transparent surface electrode layer.
In one possible design, the back electrode layer sequentially comprises a first electrode sublayer, a second electrode sublayer and a third electrode sublayer from the transparent surface electrode layer to the substrate, and the Na doping amount of the first electrode sublayer is greater than the Na doping amount of the second electrode sublayer and greater than the Na doping amount of the third electrode sublayer.
In one possible design, the thickness ratio of the first electrode sublayer to the second electrode sublayer to the third electrode sublayer is 2-2.5: 1-1.2: 2-2.5.
In one possible design, the transparent surface electrode layer includes a first surface electrode layer and a second surface electrode layer which are laminated, and a shape memory alloy fiber layer is provided between the first surface electrode layer and the second surface electrode layer.
In one possible design, the first surface electrode layer includes a continuous first ITO region and a plurality of first IZTO regions located in the first ITO region and distributed in a matrix.
In one possible design, the second surface electrode layer may include a continuous second IZTO region and a plurality of second ITO regions in a matrix in the second IZTO region.
The invention also provides a preparation method of the CIGS solar cell doped with the metal Na, which is used for preparing the CIGS solar cell doped with the metal Na, and the preparation method comprises the following steps: sequentially forming a back electrode layer, a CIGS layer, a buffer layer and a surface electrode layer on a substrate; the method for forming the back electrode layer comprises the following steps: and sequentially forming a third electrode sublayer, a second electrode sublayer and a first electrode sublayer on the substrate by adopting a target assembly and a magnetron sputtering process.
In one possible design, the target assembly includes a first target and a second target, each of the first target and the second target includes a Mo layer and a Na doping layer stacked, and a Na doping amount of the Na doping layer is the same as a Na doping amount of the third electrode sublayer.
In one possible design, the method for forming the back electrode layer includes the steps of:
step 1: placing the Mo layer of the first target material and the Na doping layer of the second target material in a film forming area, adjusting the magnetic field intensity corresponding to the Na doping layer of the second target material, and forming a third electrode sublayer on the substrate by adopting a magnetron sputtering process so that the Na doping amount of the third electrode sublayer reaches the design amount;
step 2: increasing the magnetic field intensity corresponding to the Na doping layer of the second target, and forming a second electrode sublayer on the third electrode sublayer by adopting a magnetron sputtering process, so that the Na doping amount of the second electrode sublayer reaches the design amount;
and step 3: and (3) placing the Mo layer of the first target material in the non-film forming region, placing the Na doped layers of the first target material and the second target material in the film forming region, and forming a first electrode sublayer on the second electrode sublayer by adopting a magnetron sputtering process, so that the Na doping amount of the first electrode sublayer reaches the design amount.
In one possible design, the method for forming the back electrode layer includes the steps of:
step 1: placing the Mo layer of the first target material and the Na doping layer of the second target material in a film forming area, adjusting the magnetic field intensity corresponding to the Na doping layer of the second target material, and forming a third electrode sublayer on the substrate by adopting a magnetron sputtering process so that the Na doping amount of the third electrode sublayer reaches the design amount;
step 2: reducing the magnetic field intensity corresponding to the Mo layer of the first target, and forming a second electrode sublayer on the third electrode sublayer by adopting a magnetron sputtering process, so that the Na doping amount of the second electrode sublayer reaches the design amount;
and step 3: and (3) placing the Mo layer of the first target material in the non-film forming region, placing the Na doped layers of the first target material and the second target material in the film forming region, and forming a first electrode sublayer on the second electrode sublayer by adopting a magnetron sputtering process, so that the Na doping amount of the first electrode sublayer reaches the design amount.
In one possible design, the method for forming the surface electrode layer includes the following steps: and forming a first surface electrode layer and a second surface electrode layer on the surface of the buffer layer.
In one possible design, the first surface electrode layer is prepared by the following method: the method comprises the steps of forming an ITO layer by adopting a sputtering process, forming a plurality of IZTO accommodating grooves distributed in a matrix mode on the ITO layer by adopting an etching process, forming a first IZTO area in the plurality of IZTO accommodating grooves by adopting the sputtering process, and enabling the non-etched part of the ITO layer to be the first ITO area.
In one possible design, the second surface electrode layer is prepared by the following method: the method comprises the steps of forming an IZTO layer by adopting a sputtering process, forming a plurality of ITO containing grooves which are distributed in a matrix mode on the IZTO layer by adopting an etching process, forming second ITO areas in the plurality of ITO containing grooves by adopting the sputtering process, and enabling the non-etched parts of the IZTO layer to be the second IZTO areas.
In one possible design, the method for forming the surface electrode layer includes the following steps:
step a: paving shape memory alloy fibers on the surface of the first surface electrode layer;
step b: carrying out hot pressing on the shape memory alloy fibers to enable part of the shape memory alloy fibers to be embedded into the first surface electrode layer, so as to obtain a shape memory alloy fiber layer;
step c: and forming a second surface electrode layer on the first surface electrode layer and the surface of the shape memory alloy fiber layer.
In one possible design, the method for forming the surface electrode layer includes the following steps:
step a': laying shape memory alloy fibers on the surface of the second surface electrode layer;
step b': carrying out hot pressing on the shape memory alloy fibers to enable part of the shape memory alloy fibers to be embedded into the second surface electrode layer, so as to obtain a shape memory alloy fiber layer;
step c': and forming a first surface electrode layer on the second surface electrode layer and the surface of the shape memory alloy fiber layer.
The invention also provides a packaging structure for packaging the CIGS solar cell, which is characterized in that the packaging structure is rectangular and comprises a protective film, a structural film and a back film which are compacted from top to bottom, and the CIGS solar cell is positioned between the structural film and the back film; the size of the structural film and the CIGS solar cell are the same; the area of the back film is larger than that of the CIGS solar cell; the protective film comprises a main body and edge portions, the main body is the same as the CIGS solar cell in size, the edge portions are arranged on four sides of the main body and are integrated with the main body into a whole, and the edge portions are sealed to tightly cover the side faces of the structural film and the CIGS solar cell and are tightly pressed with the back film.
Compared with the prior art, the invention has the following beneficial effects:
a) according to the CIGS solar cell doped with the metal Na, Na is doped in the back electrode layer (Mo), and both the Na and the Mo belong to metals, so that the Na doping is realized on the basis of basically not influencing the uniformity of the back electrode layer, and the Na can be diffused to the CIGS layer from the back electrode layer, so that the energy conversion efficiency of the solar cell is improved.
b) According to the CIGS solar cell doped with the metal Na, the back electrode layer is doped with pure metal sodium, and no new impurity element is introduced in the doping process, so that the performance of the CIGS solar cell is ensured.
c) According to the CIGS solar cell doped with metal Na provided by the invention, the Na doping amount in the back electrode layer is increased in a gradient manner from the transparent surface electrode layer to the substrate direction, and under the condition that the total Na doping amount is not changed, compared with the back electrode layer with the same Na doping amount, the Na doping amount in the electrode sub-layer close to the CIGS layer is larger, so that the Na concentration difference between the electrode sub-layer and the CIGS layer is increased, the infiltration amount and the infiltration depth of Na penetrating into the CIGS layer can be further improved, and the utilization rate of Na can be further improved
d) According to the CIGS solar cell doped with metal Na provided by the invention, the Na doping amount in the electrode sublayer close to the substrate is small, so that the infiltration amount and the infiltration depth of Na into the substrate can be reduced.
e) In general, the bonding tightness between the back electrode layer and the substrate is influenced to a certain extent by doping Na, and in the CIGS solar cell doped with Na provided by the invention, the doping amount of Na in the back electrode layer is increased in a gradient manner from the substrate to the transparent surface electrode layer, and the doping amount of Na in the electrode sublayer close to the substrate is smaller, so that the lattice matching between the substrate and the electrode sublayer can be improved, the physicochemical stress between the substrate and the electrode sublayer is reduced, and the influence of Na doping on the bonding tightness between the substrate and the electrode sublayer can be reduced as much as possible.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention will be realized and attained by the structure particularly pointed out in the written description and claims hereof as well as the appended drawings.
Drawings
The drawings are only for purposes of illustrating particular embodiments and are not to be construed as limiting the invention, wherein like reference numerals are used to designate like parts throughout.
Fig. 1 is a schematic structural diagram of a CIGS solar cell doped with Na metal according to an embodiment of the present invention;
fig. 2 is a schematic structural diagram of a back electrode layer in a CIGS solar cell doped with Na according to an embodiment of the present invention;
fig. 3 is a schematic structural diagram of a first surface electrode layer in a CIGS solar cell doped with Na according to an embodiment of the present invention;
fig. 4 is a schematic structural diagram of a second surface electrode layer in a CIGS solar cell doped with Na according to an embodiment of the present invention;
fig. 5 is a schematic position diagram of a first surface electrode layer and a shape memory alloy fiber layer in a CIGS solar cell doped with Na according to an embodiment of the present invention;
fig. 6 is a cross-sectional view of a transparent surface electrode layer in a metallic Na-doped CIGS solar cell according to an embodiment of the present invention;
fig. 7 is a schematic structural diagram of an alkali metal composite layer in a metallic Na-doped CIGS solar cell according to an embodiment of the present invention;
fig. 8 is a schematic structural diagram of a buffer layer in a metallic Na-doped CIGS solar cell according to an embodiment of the present invention;
fig. 9 is a schematic structural diagram of a target in a method for manufacturing a metallic Na-doped CIGS solar cell according to a second embodiment of the present invention.
Reference numerals:
1-a substrate; 2-a back electrode layer; 21-a first electrode sublayer; 22-a second electrode sublayer; 23 a third electrode sublayer; 3-a CIGS layer; 4-a buffer layer; 41-indium selenide layer; 42-indium sulfide layer; 5-a transparent surface electrode layer; 6-a first surface electrode layer; 61-first ITO region; 62-first IZTO zone; 7-a second surface electrode layer; 71-second ITO region; 72-second IZTO region; 8-a layer of shape memory alloy fibers; 9-Mo layer; a 10-Na doped layer; 11-an alkali metal composite layer; 111-a first alkali metal layer; 112-second alkali metal layer.
Detailed Description
The preferred embodiments of the present invention will now be described in detail with reference to the accompanying drawings, which form a part hereof, and which together with the embodiments of the invention serve to explain the principles of the invention.
Example one
The present embodiment provides a CIGS solar cell doped with metallic Na, referring to fig. 1 to 7, including a substrate 1, and a back electrode layer 2, a CIGS layer 3, a buffer layer 4 and a transparent surface electrode layer 5 sequentially stacked on the substrate 1, wherein the back electrode layer 2 is doped with metallic Na, and the doping amount of Na in the back electrode layer 2 increases in a gradient manner from the substrate 1 to the transparent surface electrode layer 5, that is, the back electrode layer 2 may have at least two layers, and in two adjacent electrode sublayers, the Na doping amount of the electrode sublayer close to the transparent surface electrode layer 5 is higher than the Na doping amount of the electrode sublayer far from the transparent surface electrode layer 5. Specifically, the Na doping amount in the multilayer electrode sublayers can be increased in a gradient manner in an equal difference and equal ratio manner.
In practical applications, although the back electrode layer 2 has a small thickness, when the doping amount gradient of Na in the back electrode layer 2 increases, Na atoms are not uniformly distributed in the back electrode layer 2 even after the storage for a long time.
Compared with the prior art, in the CIGS solar cell doped with metallic Na provided by the embodiment, Na is doped in the back electrode layer (Mo), and since both Na and Mo belong to metals, the compatibility of both Na and Mo is good, so that the doping of Na can be realized on the basis of basically not influencing the uniformity of the back electrode layer 2, and Na can be diffused from the back electrode layer 2 to the CIGS layer 3, thereby improving the energy conversion efficiency of the solar cell. In addition, since pure metal sodium is doped in the back electrode layer 2 of the CIGS solar cell, no new impurity element is introduced in the doping process, thereby ensuring the performance of the CIGS solar cell.
Meanwhile, because the doping amount of Na in the back electrode layer 2 is increased in a gradient manner from the substrate 1 to the transparent surface electrode layer 5, under the condition that the total Na doping amount is not changed, compared with the back electrode layer 2 with the same Na doping amount, in the CIGS solar cell doped with metal Na provided by the embodiment, the Na doping amount in the electrode sublayer close to the CIGS layer 3 is larger, so that the Na concentration difference between the electrode sublayer and the CIGS layer 3 is increased, the infiltration amount and the infiltration depth of Na into the CIGS layer 3 can be further increased, and the utilization rate of Na can be further increased; in addition, since the Na doping amount in the electrode sublayer near the substrate 1 is small, the amount and depth of Na penetration into the substrate 1 can be reduced.
In general, the adhesion between the back electrode layer 2 and the substrate 1 is affected to a certain extent by doping Na, and the doping amount of Na in the back electrode layer 2 increases in a gradient manner from the substrate 1 to the transparent front electrode layer 5, and the doping amount of Na in the electrode sublayer close to the substrate 1 is small, so that the lattice matching between the substrate 1 and the electrode sublayer can be improved, the physicochemical stress between the substrate 1 and the electrode sublayer can be reduced, and the influence of Na doping on the adhesion between the substrate 1 and the electrode sublayer can be reduced as much as possible.
Illustratively, the back electrode layer 2 may have a three-layer structure, and the back electrode layer 2 sequentially includes a first electrode sub-layer 21, a second electrode sub-layer 22, and a third electrode sub-layer 23 from the transparent surface electrode layer 5 to the substrate 1, where the Na doping amount of the first electrode sub-layer 21 > the Na doping amount of the second electrode sub-layer 22 > the Na doping amount of the third electrode sub-layer 23.
In order to further improve the infiltration amount and the infiltration depth of Na penetrating into the CIGS layer 3 and reduce the infiltration amount and the infiltration depth of Na penetrating into the substrate 1, the thickness ratio of the first electrode sublayer 21, the second electrode sublayer 22 and the third electrode sublayer 23 can be controlled within the range of 2-2.5: 1-1.2: 2-2.5, that is, the thicknesses of the first electrode sublayer 21 and the third electrode sublayer 23 are larger than that of the second electrode sublayer 22. This is because the Na doping amount and thickness of the first electrode sublayer 21 are large, and sufficient Na atoms can be provided to penetrate into the CIGS layer 3, and the thickness of the third electrode sublayer 23 is large, so that the first electrode sublayer 21 with a large Na doping amount is as far as possible from the substrate 1, and Na in the third electrode sublayer 23 does not substantially penetrate into the substrate 1; meanwhile, due to the difference between the arrangement of the second electrode sublayer 22 and the Na doping amount, the back electrode layer 2 is made of three different types of materials, so as to form an interface between the two different types of materials, and the interface can have a certain barrier effect on the diffusion of Na and other impurity elements due to the difference of diffusion behaviors, so that the infiltration amount and the infiltration depth of Na into the CIGS layer 3 are further increased, and the infiltration amount and the infiltration depth of Na into the substrate 1 are reduced.
In order to improve the water vapor barrier property of the CIGS layer, the transparent surface electrode layer 5 may be made of Indium Zinc Tin Oxide (IZTO). The IZTO is adopted to replace a common material ITO of the transparent surface electrode layer 5, the structural compactness of the IZTO is better than that of the ITO, and the water vapor barrier property of the IZTO is higher than that of the ITO, so that the transparent surface electrode layer 5 made of the IZTO can better protect the buffer layer 4 and the CIGS layer 3 which are sensitive to water vapor, and the working stability of the barrier CIGS solar cell is improved.
Considering that the light transmittance of IZTO is lower than that of ITO, in order to reduce the influence of IZTO on the light transmittance of the transparent surface electrode layer 5, the transparent surface electrode layer 5 may have a double-layer structure including a first surface electrode layer 6 and a second surface electrode layer 7 which are stacked, one of the layers includes IZTO, and the other layer includes ITO, that is, the transparent surface electrode layer 5 includes both IZTO and ITO, so that the transparent surface electrode layer 5 can have both good water vapor barrier property of IZTO and good light transmittance of ITO, and the water vapor barrier property can be improved without affecting the light transmittance of the transparent surface electrode layer 5. The relative positions of the first surface electrode layer 6 and the second surface electrode layer 7 may be adjusted so that the first surface electrode layer 6 is close to the buffer layer 4 or the second surface electrode layer 7 is close to the buffer layer 4.
As for the structure of the first surface electrode layer 6, specifically, it may include a continuous first ITO region 61 and a plurality of first IZTO regions 62 disposed in the first ITO region 61 and distributed in a matrix, similarly, the second surface electrode layer 7 may include a continuous second IZTO region 72 and a plurality of second ITO regions 71 disposed in the second IZTO region 72 and distributed in a matrix, so that, from the perspective of the transparent surface electrode layer 5 as a whole, it has both an IZTO structure and an ITO structure, and the structure is relatively uniform, thereby enabling to improve moisture barrier property without affecting the light transmittance of the transparent surface electrode layer 5.
In order to further improve the light transmittance and the water vapor barrier property of the barrier CIGS solar cell, the first ITO region 61 and the second ITO region 71 are projected on the solar cell substrate 1 as a continuous plane, and the first IZTO region 62 and the second IZTO region 72 are projected on the solar cell substrate 1 as a continuous plane. That is, the shape and size of the first ITO region 61 and the second IZTO region 72 are the same, and the position of the first IZTO region 62 and the second ITO region 71 are the same, so that the first IZTO region 62 and the second IZTO region 72 can form a complete film structure with good water vapor barrier property, thereby further improving the light transmittance and water vapor barrier property of the barrier CIGS solar cell.
In order to improve the uniformity of the entire transparent surface electrode layer 5, the ratio of the area of the first ITO region 61 to the total area of the plurality of first IZTO regions 62 may be controlled to be 1.2 to 1.5, and the ratio of the area of the same second IZTO region 72 to the total area of the plurality of second ITO regions 71 may be controlled to be 1.2 to 1.5.
Considering that the size and distribution density of the first IZTO regions 62 and the second ITO regions 71 also affect the uniformity of the transparent surface electrode layer 5 as a whole, when the first IZTO regions 62 and the second ITO regions 71 are square, the ratio of the gap between two adjacent first IZTO regions 62 to the side length of the first IZTO regions 62 may be controlled to be 0.4 to 0.6, and similarly, the ratio of the gap between two adjacent second ITO regions 71 to the side length of the second ITO regions 71 may be controlled to be 0.4 to 0.6.
In view of the fact that the CIGS solar cell needs to be exposed to the external environment for a long time and is sensitive to its own structure, especially for the transparent surface electrode layer 5, which is located on the surface of the CIGS solar cell and is exposed to sunlight for a long time, the transparent surface electrode layer is easily deformed under high temperature or external impact, and thus the overall operation stability of the CIGS solar cell is affected, the shape memory alloy fiber layer 8 may be disposed between the first surface electrode layer 6 and the second surface electrode layer 7. The shape memory alloy fiber has the functions of self-diagnosis, self-adaptation, self-repair and the like. When the transparent surface electrode layer 5 is deformed at a high temperature or by external impact, the shape memory alloy fibers can promote the transparent surface electrode layer 5 to be restored to an original state before the transparent surface electrode layer is deformed, so that the deformation amount of the transparent surface electrode layer 5 is reduced, the working stability of the whole CIGS solar cell is improved, and the service life of the CIGS solar cell is prolonged.
In order to reduce the influence of the addition of the shape memory alloy fiber layer 8 on the light transmittance, the shape may be a mesh shape. In this way, sunlight can enter the CIGS solar cell through the shape memory alloy fiber layer 8, and only the mesh line portions affect the sunlight, so that the effect of the addition of the shape memory alloy fiber layer 8 on the light transmittance can be minimized.
Illustratively, the grid lines of the grid-like shape memory alloy fiber layer 8 may coincide with connecting lines of the first ITO region 61, the second ITO region 71, the first IZTO region 62, and the second IZTO region 72. This is because, since the connecting lines of the first ITO region 61, the second ITO region 71, the first IZTO region 62, and the second IZTO region 72 are the junctions of the four regions, the light transmittance is relatively poor here in consideration of the influence of the processing process and the material, and the grid lines overlap with the connecting lines, and the addition of the grid-like shape memory alloy fiber layer 8 affects only the light transmittance of the connecting line portion having relatively poor light transmittance without affecting other portions of the transparent surface electrode layer 5, and the influence of the addition of the shape memory alloy fiber layer 8 on the light transmittance can be further reduced.
Considering that the electrode of the transparent surface electrode layer 5 generates heat due to resistance in the actual working process, the transparent surface electrode layer 5 may be doped with nano silver (Ag) particles, because the thermal conductivity of Ag is better than that of ITO and IZTO, and the doping of Ag in the transparent surface electrode layer 5 can improve the overall thermal conductivity of the transparent surface electrode layer 5, so that the heat generated by the electrode can be diffused into the environment more quickly, and the damage of the electrode due to resistance heating is reduced. Meanwhile, it is worth noting that the transparent surface electrode layer 5 has a high requirement on light transmittance, and in order to reduce the influence of Ag doping on the light transmittance of the transparent surface electrode layer 5, Ag nanoparticles can be used for doping, and the light absorption of the nano-sized Ag particles is small.
In order to further improve the photoelectric properties and stability of the transparent surface electrode layer 5, zirconium (Zr) may be doped therein.
In order to further improve the photoelectric conversion efficiency of the cell, an alkali metal composite layer 11 is disposed between the CIGS layer 3 and the buffer layer 4, the alkali metal composite layer 11 includes a first alkali metal layer 111 and a second alkali metal layer 112, the first alkali metal layer 111 is located at a side close to the CIGS layer 3, and the second alkali metal layer 111 is located at a side close to the buffer layer 4. Specifically, the first alkali metal layer 111 contains a fluoride, sulfide, selenide, or the like of Na, such as NaF, Na2Se、Na2S、Na2SeO3Or NaNbO3The second alkali metal layer 112 contains a fluoride, sulfide or selenide of K and Rb, preferably a fluoride, sulfide or selenide of K. The alkali metal layer 11 is designed to be a composite layer of the first alkali metal layer 111 and the second alkali metal layer 112, and the first alkali metal layer 111 is arranged between the CIGS layer 3 and the second alkali metal layer 112, so that the second alkali metal layer 112 can prevent alkali metal in the first alkali metal layer 111 from diffusing to other layers, the utilization rate of alkali metal in the first alkali metal layer 111 is improved, the defect density of the CIGS layer 3 is effectively reduced, the carrier concentration is improved, and the photoelectric conversion efficiency of the cell is improved. Meanwhile, since the second alkali metal layer 112 also contains an alkali metal, the second alkali metal layer 112 can also supply an alkali metal to the CIGS layer 3, thereby further reducing the defect density of the CIGS layer 3, increasing the carrier concentration, and further improving the photoelectric conversion efficiency of the cell.
It is emphasized that the mass percentage of the metal Na in the first alkali metal layer 111 adjacent to the CIGS layer 3 is higher than the mass percentage of the alkali metal in the second alkali metal layer 112. This is because the first alkali metal layer 111 contains a high amount of Na by mass, and the Na concentration difference between the first alkali metal layer 111 and the CIGS layer 3 is increased, so that the amount and depth of Na penetration into the CIGS layer 3 can be increased, and the Na utilization rate can be increased. Further, since the second alkali metal layer 112 close to the back electrode layer 2 contains an alkali metal in a lower percentage by mass, the amount of penetration and the depth of penetration of the alkali metal into the back electrode layer 2 can be reduced.
Meanwhile, the thickness of the second alkali metal layer 112 is smaller than that of the first alkali metal layer 111. This is because, on the one hand, the thin thickness of the second alkali metal layer 112 can improve the utilization rate of the alkali metal, thereby achieving the purpose of improving the photoelectric conversion efficiency of the cell; on the other hand, the waste of production materials caused by the fact that the thickness of the second alkali metal layer is too thick is avoided, the phenomenon that the combination tightness among all layers of the solar cell is influenced by the fact that the thickness of the second alkali metal layer is too thick is avoided, and the process difficulty is reduced.
The buffer layer 4 may specifically include an indium selenide layer 41 and three indium sulfide layers 42, the indium selenide layer 41 being located on a side close to the CIGS layer 3, and each indium sulfide layer and each indium selenide layer containing metallic sodium, as shown in fig. 8. By doping sodium in the indium sulfide layer and the indium selenide layer, the band gap and the charge carrier concentration of the buffer layer can be adjusted, so that the electronic transition from the light absorption layer to the surface electrode layer through the buffer layer is optimized, the short-circuit current of the battery is increased, and the conversion efficiency of the battery is improved.
Illustratively, the buffer layer 4 in the present embodiment has a 4-layer structure, and the buffer layer 4 of the multilayer structure has a finer band gap energy than that of the buffer layer of the single-layer structure. The finer band gap energy enables electrons and/or holes formed by external sunlight to be easily transmitted to the electrode layer and the window layer, so that the power generation efficiency of the solar cell is improved; on the other hand, the thickness of the buffer layer is reduced.
In order to reduce the reflectivity of incident light, the upper surface of the transparent surface electrode layer 5 is provided with an optical film coating, and the optical film coating sequentially comprises a first indium tin oxide layer, a nano silicon dioxide layer, a nano titanium dioxide layer and a second indium tin oxide layer from top to bottom; optical thin film coatings are used to reduce the reflection of incident light, increasing the optical path of the incident light within the CIGS solar thin film cell.
Specifically, be equipped with the optical film coating on transparent surface electrode layer 5, this optical film coating includes first indium tin oxide layer from top to bottom in proper order, the nanometer silica layer, nanometer titanium dioxide layer and second indium tin oxide layer, the porosity can be adjusted according to the angle of inclination incidence of optical film coating to the reflection system of this optical film coating, and then adjust the light reflectivity of optical film coating, through adjusting the light reflectivity of this optical film coating, the reflection condition of the incident light that can greatly reduced, reduce the reflection loss of incident light, increase the short-circuit current and the quantum efficiency of battery.
In order to prevent the incident light which is not absorbed after passing through the CIGS layer 3 from being transmitted out through the back electrode layer 2, a first light trapping structure is arranged between the flexible substrate 1 and the back electrode layer 2, and the interface between the first light trapping structure and the back electrode layer 2 is a corrugated Ag thin film; the first light trapping structure is used for increasing the optical path of incident light in the CIGS solar thin film cell. The first light trapping structure is arranged between the flexible substrate 1 and the back electrode layer 2, light transmitted through the CIGS layer 3 can be blocked, the part of transmitted light can be reflected into the CIGS layer 3 by the corrugated Ag thin film, the part of transmitted light reflected by the first light trapping structure enters the CIGS layer 3 above the back electrode layer 2 again, the optical path of incident light in the CIGS solar thin film battery is increased, and the incident light is fully absorbed, so that the incident light absorption performance is improved, and the current and the quantum efficiency of the battery are increased.
In addition, can also directly prepare the second light trapping structure on transparent surface electrode layer 5, this second light trapping structure is including evenly laying the micro-nano layer structure on transparent surface electrode layer 5, this micro-nano layer structure comprises the little nanometer ball that the particle diameter is even, plate one deck aluminium-doped zinc oxide conductive film at the upper surface of micro-nano layer structure, get rid of little nanometer ball through ultrasonic cleaning, form second light trapping structure, the incident light enters into CIGS layer 3 of below after the second light trapping structure scattering.
Example two
The embodiment provides a preparation method of a CIGS solar cell doped with metal Na, which comprises the following steps: sequentially forming a back electrode layer, a CIGS layer, a buffer layer and a surface electrode layer on a substrate;
the method for forming the back electrode layer comprises the following steps: and sequentially forming a third electrode sublayer, a second electrode sublayer and a first electrode sublayer on the substrate by adopting a target assembly and a magnetron sputtering process.
Compared with the prior art, the beneficial effects of the preparation method of the CIGS solar cell doped with metallic Na provided by the embodiment are substantially the same as those of the CIGS solar cell doped with metallic Na provided by the embodiment, and detailed description thereof is omitted here.
Specifically, the target assembly may include a first target and a second target, the first target and the second target have the same structure and size, and refer to fig. 9, and each target includes a Mo layer 9 and a Na doping layer 10 stacked together, where it is noted that the Na doping layer 10 is a Na-doped Mo layer, and the Na doping amount of the Na doping layer 10 is the same as the Na doping amount of the third electrode sublayer. The method for forming the back electrode layer comprises the following steps:
step 1: placing the Mo layer 9 of the first target and the Na doping layer 10 of the second target in a film forming region, namely placing the Na doping layer 10 of the first target and the Mo layer 9 of the second target in a non-film forming region, adjusting the magnetic field intensity corresponding to the Na doping layer 10 of the second target, and forming a third electrode sublayer on the substrate by adopting a magnetron sputtering process so that the Na doping amount of the third electrode sublayer reaches the designed amount;
step 2: increasing the magnetic field intensity corresponding to the Na doping layer 10 of the second target material or reducing the magnetic field intensity corresponding to the Mo layer 9 of the first target material, and forming a second electrode sublayer on the third electrode sublayer by adopting a magnetron sputtering process, so that the Na doping amount of the second electrode sublayer reaches the design amount;
and step 3: the Mo layer 9 of the first target material is placed in a non-film forming area, the Na doping layers 10 of the first target material and the second target material are both placed in a film forming area, and a first electrode sublayer is formed on the second electrode sublayer by adopting a magnetron sputtering process, so that the Na doping amount of the first electrode sublayer reaches the design amount.
According to the CIGS preparation method, two targets are adopted, each target comprises the laminated Mo layer 9 and the Na doping layer 10, the third electrode sublayer, the second electrode sublayer and the third electrode sublayer can be sequentially formed by adjusting the magnetic field intensity and the film layer located in the film forming area, and the targets do not need to be replaced in the forming process, so that the forming efficiency of the back electrode layer can be improved.
The method for forming the surface electrode layer comprises the following steps: forming a first surface electrode layer and a second surface electrode layer on the surface of the buffer layer; the first surface electrode layer is prepared by the following method: the method comprises the steps of forming an ITO layer by adopting a sputtering process, forming a plurality of IZTO accommodating grooves distributed in a matrix mode on the ITO layer by adopting an etching process, forming a first IZTO area in the plurality of IZTO accommodating grooves by adopting the sputtering process, and enabling the non-etched part of the ITO layer to be the first ITO area. The second surface electrode layer is prepared by the following method: the method comprises the steps of forming an IZTO layer by adopting a sputtering process, forming a plurality of ITO containing grooves which are distributed in a matrix mode on the IZTO layer by adopting an etching process, forming second ITO areas in the plurality of ITO containing grooves by adopting the sputtering process, and enabling the non-etched parts of the IZTO layer to be the second IZTO areas.
When the shape memory alloy fiber layer is arranged between the first surface electrode layer and the second surface electrode layer, the forming method of the surface electrode layer comprises the following steps:
step a: paving shape memory alloy fibers on the surface of the first surface electrode layer;
step b: carrying out hot pressing on the shape memory alloy fibers to enable part of the shape memory alloy fibers to be embedded into the first surface electrode layer, so as to obtain a shape memory alloy fiber layer;
step c: and forming a second surface electrode layer on the first surface electrode layer and the surface of the shape memory alloy fiber layer.
Alternatively, the method for forming the surface electrode layer includes the steps of:
step a': laying shape memory alloy fibers on the surface of the second surface electrode layer;
step b': carrying out hot pressing on the shape memory alloy fibers to enable part of the shape memory alloy fibers to be embedded into the second surface electrode layer, so as to obtain a shape memory alloy fiber layer;
step c': and forming a first surface electrode layer on the second surface electrode layer and the surface of the shape memory alloy fiber layer.
The shape memory alloy fibers, the first surface electrode layer and the second surface electrode layer can be tightly combined by adopting a hot pressing process, so that the phenomenon that gaps are formed among the shape memory alloy fibers, the first surface electrode layer and the second surface electrode layer, and the overall performance of the CIGS solar cell is influenced is avoided. It should be noted that the two methods are substantially the same, and only the relative positions of the first surface electrode layer and the second surface electrode layer are appropriately adjusted.
In order to make the combination of the shape memory alloy fiber and the first surface electrode layer and the second surface electrode layer more compact, the shape memory alloy fiber can be pretreated, and the pretreatment comprises the following steps: and sequentially grinding and polishing the surface of the shape memory alloy fiber, carrying out acid etching for 20-30 s, cleaning and drying. The shape memory alloy fiber is polished, so that an oxide layer on the surface of the shape memory alloy fiber can be removed, and the next step of acid etching is more sufficient. The acid etching process is substantially a process of increasing the surface area of the shape memory alloy fiber, and the acid etched shape memory alloy fiber is fully contacted in the subsequent hot pressing process, so that the first surface electrode layer, the second surface electrode layer and the shape memory alloy fiber are combined more tightly.
For the hot pressing process, the hot pressing temperature, the hot pressing pressure and the hot pressing time are important process conditions for fully stretching the shape memory alloy fibers, the hot pressing temperature is preferably 800-900 ℃, the hot pressing pressure is preferably 100-120 MPa, and the hot pressing time is preferably 3-4 h.
EXAMPLE III
The embodiment provides a packaging structure of a thin-film solar cell, which is rectangular and comprises a protective film, a structural film and a back film which are compacted from top to bottom, wherein the CIGS solar cell is positioned between the structural film and the back film; in general, a CIGS solar cell is generally formed in a rectangular shape for convenience of processing, and a CIGS solar cell is a core object of a package, so that the package structure is rectangular. The size of the structural film and the CIGS solar cell are the same; the area of the back film is larger than that of the CIGS solar cell; the protective film comprises a main body and edge portions, the main body is the same as the CIGS solar cell in size, the edge portions are arranged on four sides of the main body and are integrated with the main body into a whole, and the edge portions are sealed to tightly cover the side faces of the structural film and the CIGS solar cell and are tightly pressed with the back film. In the packaging structure, a main body of the protective film, a structural film and the CIGS solar cell are used as the core of the main laminated packaging, and the sizes of the main laminated packaging and the structural film are required to be equal; the edge of the protective film is used for packaging the side edge, so that the width of the edge is equal to that of the corresponding side edge, the length of the edge is greater than the thickness of the solar thin film cell, and the excess part is used for being bonded with the back film to realize the fixation of the edge and the internal packaging.
The packaging structure of the embodiment of the invention is equivalent to packaging the main illumination surface and the side surface of the solar thin film battery by using the protective film at the same time, and does not need to use special side packaging materials, thereby simplifying the packaging structure of the solar thin film battery.
In order to ensure that the solar thin-film battery obtains the photoelectric conversion efficiency as large as possible on the premise of ensuring the water-blocking function of the packaging structure, in the embodiment of the invention, the protective film is an ETFE film; the structural film is an EEA film; the back film is a double-layer film, one layer in contact with the CIGS is a DNP film, and the other layer is a PET film.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention.

Claims (9)

1. The CIGS solar cell doped with metal Na is characterized by comprising a substrate, and a back electrode layer, a CIGS layer, a buffer layer and a transparent surface electrode layer which are sequentially stacked on the substrate;
the back electrode layer is doped with metal Na, and the doping amount of Na in the back electrode layer is increased in a gradient manner from the substrate to the transparent surface electrode layer;
the transparent surface electrode layer includes a first surface electrode layer and a second surface electrode layer which are laminated; the first surface electrode layer comprises a continuous first ITO (indium tin oxide) area and a plurality of first IZTO areas which are positioned in the first ITO area and distributed in a matrix manner; the second surface electrode layer comprises a continuous second IZTO area and a plurality of second ITO areas which are positioned in the second IZTO area and distributed in a matrix manner; the projections of the first ITO area and the second ITO area on the solar cell substrate are continuous planes, and the projections of the first IZTO area and the second IZTO area on the solar cell substrate are continuous planes;
a shape memory alloy fiber layer is arranged between the first surface electrode layer and the second surface electrode layer; the shape of the shape memory alloy fiber layer is in a grid shape; the grid lines of the shape memory alloy fiber layer are superposed with the connecting lines of the first ITO area, the second ITO area, the first IZTO area and the second IZTO area;
the upper surface of the transparent surface electrode layer is provided with an optical film coating, and the optical film coating sequentially comprises a first indium tin oxide layer, a nano silicon dioxide layer, a nano titanium dioxide layer and a second indium tin oxide layer from top to bottom;
the substrate is a flexible substrate, a first light trapping structure is arranged between the flexible substrate and the back electrode layer, and a corrugated Ag film is arranged at the interface of the first light trapping structure and the back electrode layer;
the back electrode layer sequentially comprises a first electrode sublayer, a second electrode sublayer and a third electrode sublayer from the transparent surface electrode layer to the substrate direction, and the Na doping amount of the first electrode sublayer is larger than that of the second electrode sublayer and larger than that of the third electrode sublayer; the thickness ratio of the first electrode sublayer to the second electrode sublayer to the third electrode sublayer is 2-2.5: 1-1.2: 2-2.5.
2. A method for manufacturing a metallic Na-doped CIGS solar cell according to claim 1, comprising the steps of: sequentially forming a back electrode layer, a CIGS layer, a buffer layer and a surface electrode layer on a substrate;
the method for forming the back electrode layer comprises the following steps: sequentially forming a third electrode sublayer, a second electrode sublayer and a first electrode sublayer on the substrate by adopting a target assembly and a magnetron sputtering process;
the forming method of the surface electrode layer comprises the following steps:
step a: paving shape memory alloy fibers on the surface of the first surface electrode layer;
step b: carrying out hot pressing on the shape memory alloy fibers to enable part of the shape memory alloy fibers to be embedded into the first surface electrode layer, so as to obtain a shape memory alloy fiber layer;
step c: forming a second surface electrode layer on the surfaces of the first surface electrode layer and the shape memory alloy fiber layer;
alternatively, the method for forming the surface electrode layer includes the steps of:
step a': laying shape memory alloy fibers on the surface of the second surface electrode layer;
step b': carrying out hot pressing on the shape memory alloy fibers to enable part of the shape memory alloy fibers to be embedded into the second surface electrode layer, so as to obtain a shape memory alloy fiber layer;
step c': and forming a first surface electrode layer on the second surface electrode layer and the surface of the shape memory alloy fiber layer.
3. The method of claim 2, wherein the target assembly comprises a first target and a second target, each of the first target and the second target comprises a stacked Mo layer and a Na doped layer, and the Na doped layer has the same Na doping amount as the third electrode sublayer.
4. The method of claim 3, wherein the back electrode layer is formed by a method comprising:
step 1: placing the Mo layer of the first target material and the Na doping layer of the second target material in a film forming area, adjusting the magnetic field intensity corresponding to the Na doping layer of the second target material, and forming a third electrode sublayer on the substrate by adopting a magnetron sputtering process so that the Na doping amount of the third electrode sublayer reaches the design amount;
step 2: increasing the magnetic field intensity corresponding to the Na doping layer of the second target, and forming a second electrode sublayer on the third electrode sublayer by adopting a magnetron sputtering process, so that the Na doping amount of the second electrode sublayer reaches the design amount;
and step 3: and (3) placing the Mo layer of the first target material in the non-film forming region, placing the Na doped layers of the first target material and the second target material in the film forming region, and forming a first electrode sublayer on the second electrode sublayer by adopting a magnetron sputtering process, so that the Na doping amount of the first electrode sublayer reaches the design amount.
5. The method of claim 3, wherein the back electrode layer is formed by a method comprising:
step 1: placing the Mo layer of the first target material and the Na doping layer of the second target material in a film forming area, adjusting the magnetic field intensity corresponding to the Na doping layer of the second target material, and forming a third electrode sublayer on the substrate by adopting a magnetron sputtering process so that the Na doping amount of the third electrode sublayer reaches the design amount;
step 2: reducing the magnetic field intensity corresponding to the Mo layer of the first target, and forming a second electrode sublayer on the third electrode sublayer by adopting a magnetron sputtering process, so that the Na doping amount of the second electrode sublayer reaches the design amount;
and step 3: and (3) placing the Mo layer of the first target material in the non-film forming region, placing the Na doped layers of the first target material and the second target material in the film forming region, and forming a first electrode sublayer on the second electrode sublayer by adopting a magnetron sputtering process, so that the Na doping amount of the first electrode sublayer reaches the design amount.
6. The method of claim 2, wherein the method of forming the surface electrode layer comprises the steps of: and forming a first surface electrode layer and a second surface electrode layer on the surface of the buffer layer.
7. The method of claim 6, wherein the first surface electrode layer is formed by: the method comprises the steps of forming an ITO layer by adopting a sputtering process, forming a plurality of IZTO accommodating grooves distributed in a matrix mode on the ITO layer by adopting an etching process, forming a first IZTO area in the plurality of IZTO accommodating grooves by adopting the sputtering process, and enabling the non-etched part of the ITO layer to be the first ITO area.
8. The method of claim 6, wherein the second surface electrode layer is formed by: the method comprises the steps of forming an IZTO layer by adopting a sputtering process, forming a plurality of ITO containing grooves which are distributed in a matrix mode on the IZTO layer by adopting an etching process, forming second ITO areas in the plurality of ITO containing grooves by adopting the sputtering process, and enabling the non-etched parts of the IZTO layer to be the second IZTO areas.
9. An encapsulation structure for encapsulating the CIGS solar cell of claim 1, wherein the encapsulation structure is rectangular and comprises a protective film, a structural film and a back film which are compressed from top to bottom, the CIGS solar cell being located between the structural film and the back film;
the structural film and the CIGS solar cell are the same size;
the area of the back film is larger than that of the CIGS solar cell;
the protective film comprises a main body and edges, the size of the main body is the same as that of the CIGS solar cell, the edges are arranged on four sides of the main body and are integrated with the main body into a whole, and the edges tightly cover the side faces of the structural film and the CIGS solar cell in a sealing mode and are tightly pressed with the back film.
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