CN113571594A - Copper indium gallium selenide battery and manufacturing method thereof - Google Patents
Copper indium gallium selenide battery and manufacturing method thereof Download PDFInfo
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- KTSFMFGEAAANTF-UHFFFAOYSA-N [Cu].[Se].[Se].[In] Chemical compound [Cu].[Se].[Se].[In] KTSFMFGEAAANTF-UHFFFAOYSA-N 0.000 title description 55
- 238000009826 distribution Methods 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims description 29
- 239000010409 thin film Substances 0.000 claims description 29
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 18
- 239000010408 film Substances 0.000 claims description 17
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 11
- 239000000758 substrate Substances 0.000 claims description 10
- 229910052783 alkali metal Inorganic materials 0.000 claims description 9
- 238000001704 evaporation Methods 0.000 claims description 9
- 239000011787 zinc oxide Substances 0.000 claims description 9
- 150000001340 alkali metals Chemical class 0.000 claims description 8
- 238000000151 deposition Methods 0.000 claims description 8
- 229910052733 gallium Inorganic materials 0.000 claims description 8
- 230000008020 evaporation Effects 0.000 claims description 7
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 6
- 230000005540 biological transmission Effects 0.000 claims description 6
- 229910052738 indium Inorganic materials 0.000 claims description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- 239000011733 molybdenum Substances 0.000 claims description 6
- 230000001105 regulatory effect Effects 0.000 claims description 6
- 238000000224 chemical solution deposition Methods 0.000 claims description 4
- 238000010549 co-Evaporation Methods 0.000 claims description 4
- 230000001276 controlling effect Effects 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 238000010521 absorption reaction Methods 0.000 abstract description 6
- 239000010949 copper Substances 0.000 description 5
- 238000010586 diagram Methods 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- HVMJUDPAXRRVQO-UHFFFAOYSA-N copper indium Chemical compound [Cu].[In] HVMJUDPAXRRVQO-UHFFFAOYSA-N 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 229910052711 selenium Inorganic materials 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
- -1 uniformity Substances 0.000 description 1
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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
- 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 at least one potential-jump barrier or surface barrier
- 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 at least one potential-jump barrier or surface barrier 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 at least one potential-jump barrier or surface barrier 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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- 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
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022466—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers
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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
- H01L31/0248—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 characterised by their semiconductor bodies
- H01L31/0256—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 characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
- H01L31/0322—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising only AIBIIICVI chalcopyrite compounds, e.g. Cu In Se2, Cu Ga Se2, Cu In Ga Se2
- H01L31/0323—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising only AIBIIICVI chalcopyrite compounds, e.g. Cu In Se2, Cu Ga Se2, Cu In Ga Se2 characterised by the doping material
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- H01L31/0248—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 characterised by their semiconductor bodies
- H01L31/036—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 characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes
- H01L31/0392—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 characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate
- H01L31/03923—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 characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate including AIBIIICVI compound materials, e.g. CIS, CIGS
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- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1884—Manufacture of transparent electrodes, e.g. TCO, ITO
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/541—CuInSe2 material PV cells
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention provides a CIGS battery and a manufacturing method thereof, wherein the CIGS battery comprises a CIGS film, the CIGS film is from the front surface close to the side of a buffer layer to the rear surface close to the side of a back electrode, the Ga gradient comprises two minimum values, and the GGI value and the band gap gradient of the CIGS film are both in W-shaped distribution. Effectively improves the open-circuit voltage VOCImproving carrier collection efficiency and short-circuit current JSCMeanwhile, the W-shaped gradient contains two areas with low GGI, so that the absorption probability of long-wavelength photons is increased.
Description
Technical Field
The invention relates to the technical field of solar cells, in particular to a copper indium gallium selenide cell and a manufacturing method thereof.
Background
In the process of depositing the CIGS thin film by the co-evaporation method, the properties of the thin film material such as uniformity, crystal structure and the like are related to the evaporation rate of the constituent elements. Different kinds of gradient distribution are realized, and the longitudinal distribution of the Ga content in the film can be controlled by changing the evaporation rate of Ga element by changing the evaporation temperature of a Ga source under the condition that the rest evaporation conditions are the same. In a cigs solar cell, the deep band gap variation due to the variation of the Ga content (GGI, i.e., Ga/(Ga + In)) ratio is generally referred to as a Ga gradient. The absorption band gap of the CIGS thin film can change according to a fixed proportion along with the proportion of Ga content to form a band gap gradient, and the change of the Ga gradient in the thin film can bring about the change of the band gap gradient. The GGI gradient distribution categories currently fall into three main categories, flat gradient, single gradient, and "V" double gradient.
Figure 1 shows three band gap curves for a Copper Indium Gallium Selenide (CIGS) cell. The flat gradient bandgap profile, where (a) denotes, is limited in the drift of photo-generated electrons generated in other regions than electrons generated in or near the depletion layer due to the zero gradient of the potential. In contrast, in the case where a band gap gradient exists as shown in (b), (c), photoelectrons can easily reach the depletion region, thereby improving carrier collection efficiency. At present, the copper indium gallium selenide solar cell with a V-shaped double-gradient band gap structure as shown in (c) has the highest efficiency: the increase of the band gaps on the surface and the back surface inhibits the recombination of the absorption region of the battery and effectively improves the open-circuit voltage VOC(ii) a The middle narrow band gap can reduce the spectral response loss of the battery in a long wave band, so that the short-circuit current J is enabledSCThe loss of (2) is minimized.
In the optimization process of the gradient distribution of the band gap of the CIGS battery from a flat band gap to a single band gap to a V-shaped double band gap, the gain optimization of the battery performance is improved all the time. However, in the prior art, compared with the Shockley-Queisser (S-Q) efficiency limit, the loss of the open-circuit voltage of the CIGS battery still reaches more than 350mV, the short-circuit current loss is also the largest in the third-generation thin-film solar battery and reaches more than 10%, and the battery performance also has a great promotion space.
Disclosure of Invention
The invention provides a copper indium gallium selenide battery and a manufacturing method thereof, which aim to solve the defects in the prior art.
In order to achieve the purpose, the invention adopts the following technical scheme.
A CIGS cell includes a CIGS film from a front surface near a buffer layer side to a rear surface near a back electrode side, a Ga gradient includes two minima, and both a GGI value and a band gap gradient of the CIGS film exhibit a W-type distribution.
Preferably, the cell comprises a substrate, a back electrode, a CIGS thin film, a buffer layer, an electron transport layer, and a transparent front electrode.
Preferably, the GGI value of the front surface of the CIGS thin film is 0.25-0.65, and the band gap of the front surface of the CIGS thin film and the conduction band offset value CBO of the n-type buffer layer of the CIGS cell are kept at-0.05-0.1 eV.
Preferably, the minimum value of GGI of the band gap gradient is 0.1-0.5.
Preferably, the rear surface GGI value of the CIGS thin film is 0.5-1.
Another aspect of the present invention provides a method for manufacturing the copper indium gallium selenide battery, including:
preparing a molybdenum electrode layer with the thickness of 100-1000 nanometers on a battery substrate by adopting a direct-current magnetron sputtering method;
depositing a CIGS thin film with the thickness of 0.5-5 microns on the molybdenum electrode layer by adopting a three-step co-evaporation method; GGI is regulated and controlled by controlling the evaporation rates of Ga and In sources at different stages, so that the band gap of CIGS is regulated to form W-shaped band gap gradient distribution;
performing alkali metal post-treatment on CIGS by using NaF, KF, RbF or CsF alkali metal source materials;
depositing an n-type thin film with the thickness of 10-100 nanometers on the CIGS layer subjected to the alkali metal post-treatment by adopting a chemical bath deposition method to serve as a buffer layer;
preparing a zinc oxide layer with the thickness of 50-500 nanometers on the buffer layer by adopting a direct-current magnetron sputtering method to serve as an electron transmission layer;
and preparing an AZO layer with the thickness of 150-1000 nanometers on the electron transmission layer by adopting a direct current magnetron sputtering method to serve as a transparent front electrode.
Preferably, the AZO is aluminum-doped zinc oxide.
The technical scheme provided by the CIGS battery and the manufacturing method thereof can be seen that the invention optimizes the gradient distribution of the band gap aiming at the problem of device performance loss in the conventional CIGS battery, under the condition that the total content of Ga in the CIGS film is the same, the GGI value in the CIGS film is distributed from the front surface close to the buffer layer side to the rear surface close to the back electrode side, the Ga gradient comprises two minimum values, the GGI and the band gap gradient of the CIGS film are in W-shaped distribution, so that the battery is relatively higher than the conventional flat gradient, single gradient and V-shaped double gradient, the GGI value of the front surface and the GGI value of the rear surface of the CIGS film, the combination of the W-shaped gradient on the wide band gap of the CIGS surface and the wide band gap of the back surface of the CIGS film is inhibited, and the open-circuit voltage V is effectively improvedOC(ii) a The increase of the GGI value of the rear surface forms a high back electric field, improves the carrier collection efficiency and improves the short-circuit current JSCAnd an open circuit voltage VOCMeanwhile, the W-shaped gradient contains two areas with low GGI, so that the absorption probability of long-wavelength photons is increased.
Additional aspects and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
Fig. 1 is a schematic diagram of three band gap curves for a Copper Indium Gallium Selenide (CIGS) cell;
FIG. 2 is a schematic diagram of an example CIGS thin film band gap gradient design of a CIGS thin film;
fig. 3 is a flowchart of a method for manufacturing a copper indium gallium selenide cell according to an embodiment.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the accompanying drawings are illustrative only for the purpose of explaining the present invention, and are not to be construed as limiting the present invention.
As used herein, the singular forms "a", "an", "the" and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise. It will be further understood that the terms "comprises" and/or "comprising," when used in this specification, specify the presence of stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof. It should be understood that "connected" or "coupled" as used herein may include wirelessly connected or coupled. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
It will be understood by those skilled in the art that, unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the prior art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
For the convenience of understanding of the embodiments of the present invention, the following description will be further explained by taking specific embodiments as examples with reference to the drawings, and the embodiments of the present invention are not limited thereto.
Examples
The present embodiment provides a CIGS cell, including a CIGS thin film, fig. 2 is a schematic diagram illustrating a design of a band gap gradient of the CIGS thin film of the CIGS cell of the present embodiment, referring to fig. 2, a Ga gradient includes two minimum values from a front surface near a buffer layer side to a rear surface near a back electrode side, and both a GGI value and a band gap gradient of the CIGS thin film exhibit a "W" type distribution. GGI is Ga content, GGI ═ Ga/(Ga + In).
The cell of this embodiment includes a substrate, a back electrode, a CIGS thin film, a buffer layer, an electron transport layer, and a transparent front electrode.
The GGI value of the front surface of the CIGS thin film is 0.25-0.65, and the band gap of the front surface of the CIGS thin film and the conduction band detuning value CBO of the n-type buffer layer of the CIGS battery are kept at-0.05-0.1 eV. The CIGS cell band gap gradient design is applicable to different n-type buffer layers including CdS, Zn (O, S) and In2S3、ZnS、Zn1-xMgxO, gain is universal.
The minimum value of GGI of the band gap gradient is 0.1-0.5, and the value of GGI of the rear surface of the CIGS film is 0.5-1.
Another aspect of the present invention provides a method for manufacturing a copper indium gallium selenide battery, and fig. 3 is a flowchart of the method for manufacturing the copper indium gallium selenide battery, and with reference to fig. 3, the method includes the following steps:
s101: and preparing a molybdenum electrode layer with the thickness of 500 nanometers on the battery substrate by adopting a direct-current magnetron sputtering method.
The cell substrate of this example was 3mm glass.
S102: and depositing a W-shaped band gap gradient copper indium gallium selenide film with the thickness of 1 micron on the molybdenum electrode layer by adopting a three-step co-evaporation method.
The GGI ratio is regulated and controlled by controlling the evaporation rates of Ga and In sources at different stages, so that the band gap of CIGS is regulated to form W-shaped band gap gradient distribution.
In particular, the deposition process needs to be carried out in a sufficient amount of Se atmosphere, in a first step, inEvaporating and depositing In, Ga and Se at a lower substrate temperature (260-400 ℃) to form a compound prefabricated layer consisting of the In, Ga and Se; and step two, closing the In source and the Ga source, and opening the Cu source at a higher substrate temperature (550-600 ℃) to prepare a copper-rich CIGS layer, wherein at a high temperature, copper is used as Cu2-xThe Se secondary phase exists in a liquid state; finally, evaporating the In, Ga source, and Cu while the substrate is still at the elevated temperature2-xSe reacts to finally form a CIGS thin film with the thickness of 1 micron.
The step provides a high-efficiency W-shaped Ga gradient distribution value, the total GGI value is 0.58, the ratio of the GGI values of the front surface of the CIGS film is 0.51-0.62, the minimum value ratio of the first GGI value is 0.49-0.51, the ratio of the middle GGI value is 0.51-0.62, the minimum value ratio of the second GGI value is 0.49-0.51, and the ratio of the GGI values of the rear surface of the CIGS film is 0.74-0.96.
S103: and (3) evaporating 5 nm CsF on the top of the CIGS film by thermal evaporation to perform alkali metal post-treatment, and then performing annealing treatment.
Diffusing alkali metal elements to the surface or inside of the CIGS thin film through a post annealing process at 350 ℃;
and S104, depositing cadmium sulfide with the thickness of 50 nanometers on the CIGS thin film subjected to the alkali metal post-treatment by adopting a Chemical Bath Deposition (CBD) method to serve as a buffer layer.
And S105, preparing a zinc oxide layer with the thickness of 100 nanometers on the buffer layer by adopting a direct-current magnetron sputtering method. Wherein the zinc oxide layer is an electron transport layer, the electron transport layer adopts zinc oxide, and the zinc oxide layer with the thickness of 100 nanometers is prepared on the perovskite layer by adopting a magnetron sputtering method.
S106: and preparing an AZO layer with the thickness of 200 nanometers on the electron transmission layer by adopting a direct current magnetron sputtering method to serve as a transparent front electrode.
In the step, the transparent front electrode adopts AZO, the AZO is aluminum-doped zinc oxide, and an AZO layer with the thickness of 200 nanometers is prepared on the electron transmission layer by adopting a magnetron sputtering method.
In summary, the CIGS cell and the method for manufacturing the same according to the present embodiment effectively increase the open-circuit voltage V by suppressing the recombination of the absorption region of the cell by increasing the band gap of the front surface of the CIGS thin filmOC(ii) a The increase of the band gap of the back surface of the CIGS film is utilized to form a high back electric field, the carrier collection efficiency is improved, and the short-circuit current J is improvedSCAnd an open circuit voltage VOC(ii) a The use of two low-GGI regions reduces the loss of spectral response of the cell in the long wavelength band, while increasing the absorption probability of long wavelength photons. Compared with the highest efficiency achieved by the current V-shaped double gradient, the copper indium gallium selenide solar cell can achieve the photoelectric conversion efficiency higher than 23.35%.
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. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (7)
1. A CIGS battery comprises a CIGS film, and is characterized in that the CIGS film is from the front surface close to the side of a buffer layer to the back surface close to the side of a back electrode, the Ga gradient comprises two minimum values, and the GGI value and the band gap gradient of the CIGS film both show W-shaped distribution.
2. The CIGS cell of claim 1, wherein the cell comprises a substrate, a back electrode, a CIGS thin film, a buffer layer, an electron transport layer, and a transparent front electrode.
3. The CIGS cell of claim 1, wherein the GGI value of the front surface of the CIGS thin film is 0.25-0.65, and the band gap of the front surface of the CIGS thin film and the CBO value of the n-type buffer layer of the CIGS cell are maintained at-0.05-0.1 eV.
4. The CIGS battery of claim 1, wherein the GGI minimum value of the band gap gradient is 0.1-0.5.
5. The CIGS cell of claim 1, wherein the rear surface of the CIGS thin film has a GGI value of 0.5 to 1.
6. A method for manufacturing the CIGS battery according to any one of claims 1 to 5, comprising:
preparing a molybdenum electrode layer with the thickness of 100-1000 nanometers on a battery substrate by adopting a direct-current magnetron sputtering method;
depositing a CIGS thin film with the thickness of 0.5-5 microns on the molybdenum electrode layer by adopting a three-step co-evaporation method; GGI is regulated and controlled by controlling the evaporation rates of Ga and In sources at different stages, so that the band gap of CIGS is regulated to form W-shaped band gap gradient distribution;
performing alkali metal post-treatment on CIGS by using NaF, KF, RbF or CsF alkali metal source materials;
depositing an n-type thin film with the thickness of 10-100 nanometers on the CIGS layer subjected to the alkali metal post-treatment by adopting a chemical bath deposition method to serve as a buffer layer;
preparing a zinc oxide layer with the thickness of 50-500 nanometers on the buffer layer by adopting a direct-current magnetron sputtering method to serve as an electron transmission layer;
and preparing an AZO layer with the thickness of 150-1000 nanometers on the electron transmission layer by adopting a direct current magnetron sputtering method to serve as a transparent front electrode.
7. The method of claim 6, wherein the AZO is aluminum-doped zinc oxide.
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