CN111403558B - High-efficiency flexible laminated thin-film solar cell and preparation method thereof - Google Patents

High-efficiency flexible laminated thin-film solar cell and preparation method thereof Download PDF

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CN111403558B
CN111403558B CN202010254952.1A CN202010254952A CN111403558B CN 111403558 B CN111403558 B CN 111403558B CN 202010254952 A CN202010254952 A CN 202010254952A CN 111403558 B CN111403558 B CN 111403558B
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cell
layer
solar cell
copper indium
substrate
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CN111403558A (en
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姚琳
李伟民
杨春雷
杨兵
许述达
李文杰
冯叶
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Shenzhen Institute of Advanced Technology of CAS
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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
    • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • 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
    • H01L31/036—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
    • H01L31/03926—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 comprising a flexible substrate
    • H01L31/03928—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 comprising a flexible substrate including AIBIIICVI compound, e.g. CIS, CIGS deposited on metal or polymer foils
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/042—PV modules or arrays of single PV cells
    • H01L31/043—Mechanically stacked PV cells
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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
    • H01L31/042—PV modules or arrays of single PV cells
    • H01L31/0445—PV modules or arrays of single PV cells including thin film solar cells, e.g. single thin film a-Si, CIS or CdTe solar cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/541—CuInSe2 material PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention discloses a high-efficiency flexible laminated thin-film solar cell and a preparation method thereof. The bottom cell adopts a narrow-forbidden band copper indium selenium solar cell, can prepare flexible cells by taking various flexible materials as a substrate, combines the narrow-forbidden band copper indium selenium solar cell and a wide-forbidden band solar cell to grow on the flexible substrate, forms a laminated cell by adjusting the forbidden band width, and is formed by laminating the solar cells according to the band gap width, thereby achieving the purpose of covering different absorption wavelength ranges, optimizing the efficiency of the flexible and bendable laminated cell, flexibly selecting the forbidden band width to distribute the light absorption effect by adopting a mechanical stacking method, having no need of current matching and having simpler preparation process.

Description

High-efficiency flexible laminated thin-film solar cell and preparation method thereof
Technical Field
The invention relates to the technical field of solar cells, in particular to a high-efficiency flexible laminated thin-film solar cell and a preparation method thereof.
Background
The efficiency of the existing single-layer cell is close to the theoretical limit efficiency, the lifting space is smaller, the technology of serially connecting solar cells provides an effective method for improving the efficiency of the solar cell, and solar radiation with wider wavelength is obtained by combining two or more solar cells with different absorption wave bands.
An effective way to increase the efficiency of polymer solar cells is also to use a tandem configuration to minimize thermalization losses of photon energy by utilizing a broader spectrum of solar radiation. However, for polymer solar cells, the performance of tandem devices is significantly behind that of single layer solar cells due to the lack of suitable low bandgap polymers. In addition, the laminated cell of the bottom cell made of crystalline silicon, which is generally adopted at present, has the defect that a silicon wafer is thick and cannot be bent, so that the application range of the laminated cell is limited.
Disclosure of Invention
In view of the defects in the prior art, the invention provides the high-efficiency flexible laminated thin-film solar cell and the preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a high-efficiency flexible laminated thin-film solar cell comprises the following steps:
preparing a bottom battery, wherein a P-type semiconductor absorption layer of the bottom battery is a copper indium selenium absorption layer;
preparing a top cell, wherein the band gap of the top cell is wider than that of the bottom cell;
stacking the top cell on the bottom cell using a mechanical stacking method.
As one embodiment, the step of preparing the bottom cell includes:
providing a flexible first substrate;
forming a back electrode on the first substrate;
preparing the copper indium selenium absorption layer on the back electrode by adopting a three-step co-evaporation method;
and carrying out alkali metal post-deposition treatment on the copper indium selenide absorption layer, and sequentially preparing a first semiconductor buffer layer, a first window layer and a first transparent front electrode above the treated copper indium selenide absorption layer.
As one embodiment, the step of preparing the bottom cell includes:
growing indium in the first stage of the copper indium selenide absorption layer prepared by a three-step co-evaporation method, growing copper in the second stage, and growing indium in the third stage to form a copper-poor phase;
wherein, sodium fluoride is added in the growth process of the third stage, and rubidium fluoride is added in the post-deposition treatment process of the alkali metal after the growth of the third stage is finished.
As one embodiment, the first stage growth process comprises: at 5.0X 10 -5 Pa～1.0×10 -4 In and Se are simultaneously evaporated on the back electrode under the background vacuum condition of Pa, the evaporation source temperatures of the In and Se are 810-830 ℃ and 240-300 ℃ respectively, the temperature of the first substrate is 350-400 ℃, and the deposition time is 25-40min;
the growth process of the second stage comprises the following steps: at 1.0X 10 -2 Pa～2.0×10 -2 Simultaneously evaporating two elements of Cu and Se on the basis of the previous stage under the vacuum condition of Pa, wherein the evaporation source temperatures of the two elements of Cu and Se are 1150-1300 ℃ and 240-300 ℃, respectively, the temperature of the first substrate is 500-600 ℃, and the deposition time is 15-25min;
the growth process of the third stage comprises the following steps: at 2.0X 10 -2 Pa～3.0×10 -2 And In and Se are simultaneously evaporated on the film layer formed In the first two stages under the vacuum condition Pa, the evaporation source temperatures of the In element and the Se element are 730-770 ℃ and 240-300 ℃ respectively, the temperature of the first substrate is 500-600 ℃, and the deposition time is 15-30min.
As one embodiment, the process of adding sodium fluoride during the third stage growth process is: under vacuum of 2.0X 1 0-2 Pa～3.0×10 -2 Pa, introducing a sodium fluoride source in the Se environment under the condition that the temperature of the first substrate reaches 380 ℃, and depositing for 8-15min;
the process of adding rubidium fluoride in the post-deposition treatment process of alkali metal comprises the following steps: and when the temperature of the first substrate reaches 320 ℃, introducing a rubidium fluoride source in a Se environment, and depositing for 15-20min.
Another object of the present invention is to provide a high efficiency flexible laminated thin film solar cell, which includes a bottom cell and a top cell stacked on the bottom cell, wherein the P-type semiconductor absorption layer of the bottom cell is a copper indium selenide absorption layer, and the band gap of the top cell is wider than that of the bottom cell.
As one of the embodiments, the upper surface of the copper indium selenide absorption layer of the bottom cell facing the top cell is covered with an alkali metal compound deposition layer.
In one embodiment, the alkali metal compound deposition layer is formed by depositing sodium fluoride and rubidium fluoride.
As one embodiment, the bottom cell includes a copper indium selenium absorption layer, a back electrode disposed below the copper indium selenium absorption layer, and the alkali metal compound deposition layer, the first semiconductor buffer layer, the first window layer, and the first transparent front electrode sequentially stacked from bottom to top on the copper indium selenium absorption layer.
As one of the embodiments, the semiconductor absorber layer of the top cell is a copper gallium selenium absorber layer (20), a perovskite absorber layer, or CdTe.
The bottom cell adopts a narrow-forbidden band copper indium selenium solar cell, can prepare flexible cells by taking various flexible materials as a substrate, combines the narrow-forbidden band copper indium selenium solar cell and a wide-forbidden band solar cell to grow on the flexible substrate, forms a laminated cell by adjusting the forbidden band width, and is formed by laminating the solar cells according to the band gap width, thereby achieving the purpose of covering different absorption wavelength ranges, optimizing the efficiency of the flexible and bendable laminated cell, flexibly selecting the forbidden band width to distribute the light absorption effect by adopting a mechanical stacking method, having no need of current matching and having simpler preparation process.
In addition, the invention improves the hole concentration by utilizing an alkali metal post-deposition treatment method in the absorption layer of the narrow-bandgap copper indium selenide solar cell, so as to improve the open-circuit voltage, thereby obviously improving the efficiency of the narrow-bandgap copper indium selenide solar cell.
Drawings
Fig. 1 is a schematic structural diagram of a high-efficiency flexible laminated thin-film solar cell according to embodiment 1 of the present invention;
fig. 2 is a flowchart of a method for manufacturing a high-efficiency flexible laminated thin-film solar cell according to embodiment 1 of the present invention;
fig. 3 is a flowchart of a method for manufacturing a copper indium selenium bottom cell according to example 1 of the present invention;
fig. 4 is a schematic structural view of a top battery of embodiment 2 of the invention;
the numbers in the figures are illustrated as follows:
1-bottom cell;
1 a-a back electrode;
10-a copper indium selenium absorbing layer;
11-an alkali metal compound deposit layer;
12-a first semiconductor buffer layer;
13-a first window layer;
14-a first transparent front electrode;
2-top battery;
2 a-a transparent electrode;
20-a copper gallium selenium absorption layer;
21-a second semiconductor buffer layer;
22-a second window layer;
23-a second transparent front electrode;
201-a photoanode;
202-electron transport layer;
203-perovskite absorption layer;
204-a hole transport layer;
205-back electrode;
a-a first substrate;
b-a second substrate.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
Referring to fig. 1 and 2, the present invention provides a high efficiency flexible laminated thin film solar cell and a method for manufacturing the same, the method comprising:
s01, preparing a bottom battery 1, wherein a P-type semiconductor absorption layer of the bottom battery 1 is a copper indium selenium absorption layer 10;
s02, preparing a top battery 2, wherein the band gap of the top battery 2 is wider than that of the bottom battery 1;
and S03, stacking the top battery 2 on the bottom battery 1 by adopting a mechanical stacking method.
In this embodiment, the narrow bandgap bottom cell 1 and the wide bandgap top cell 2 may be fabricated separately and then formed by a mechanical stacking method according to a 4-terminal stacking structure, which not only can flexibly select a forbidden bandwidth to distribute light absorption, but also does not require current matching, and is easier to fabricate. After the top cell 2 is stacked on the bottom cell 1, a top ohmic contact electrode is prepared on the top cell 2 to be used as a collecting electrode, and then the preparation of the laminated thin film solar cell is completed. The top ohmic contact electrode can be prepared by adopting an electron beam evaporation method and a screen printing method.
According to the embodiment, the absorption spectrum is complementary and the spectrum utilization rate is enlarged according to the difference of band gaps and the difference of absorption spectrum ranges of the two sub-batteries, so that the battery efficiency is improved. Due to copper indium selenide (CuInSe) 2 CIS for short) is a direct band gap material with light absorption rate as high as 10 5 The thickness of the manufactured battery can be 2-3 mu m, and the manufactured battery is very suitable for thinning a solar battery, so that the consumption of expensive materials is reduced, the flexible battery can be prepared by taking stainless steel or high-temperature-resistant polymer as a substrate, can be suitable for curved roofs and other places of buildings, can be made into a folding power supply, is convenient to carry, can be used for mobile equipment in the fields of small-sized instruments, computers, military communication GPS and the like, and can greatly expand the application field of the flexible battery.
As shown in fig. 1, the bottom cell 1 includes a flexible first substrate a, and a back electrode 1a, a copper indium selenium absorbing layer 10, an alkali metal compound deposition layer 11, a first semiconductor buffer layer 12, a first window layer 13, and a first transparent front electrode 14, which are sequentially stacked on the first substrate a from bottom to top.
As shown in fig. 3, in the present embodiment, the step of preparing the bottom cell 1 mainly includes:
s011, providing a flexible first substrate A, wherein the first substrate A is preferably made of flexible stainless steel materials.
Firstly, cleaning 10 × 10 flexible stainless steel by warm deionized water and an alkaline cleaning agent, cleaning for 15 minutes by absolute ethyl alcohol in an ultrasonic machine, blowing off excessive moisture on the surface by a nitrogen air gun at a low speed, and then putting the stainless steel into an oven for drying.
Then, the first substrate a is placed in a vacuum chamber at a predetermined center position in a substrate holder.
S012, the back electrode 1a is formed on the first substrate a.
The material of the back electrode 1a is preferably molybdenum (Mo), and the back electrode 1a is formed on the first substrate a by evaporating Mo. Parameters used for evaporating Mo are 2.0Pa, 350W and 20 times of the first layer; the second layer is 0.3Pa, 1000w, 10 times, and the thickness of the back electrode 1a is about 1.1 μm; the XRF (X Ray Fluorescence, X-Ray Fluorescence spectroscopy) count was 1044.
S013, preparing the copper indium selenium absorption layer 10 on the back electrode 1a by adopting a three-step co-evaporation method.
In the first stage of preparing the copper indium selenide absorption layer 10 by the three-step co-evaporation method, indium grows, copper grows in the second stage, indium grows in the third stage to form a copper-poor phase, and sodium fluoride is added in the growth process of the third stage. The sodium fluoride is added in the third-stage growth process, and the open-circuit voltage and the filling factor can be improved on the premise that the influence of the doping of the sodium fluoride on the crystallinity of the surface of the film in the third stage is small, so that the corresponding solar cell can show better performance.
Specifically, the growth process of the first stage of the three-step co-evaporation method comprises: the back electrode 1a was placed at 5.0X 10 -5 Pa～1.0×10 -4 Pa, in a chamber under a background vacuum conditionThen, simultaneously evaporating two elements of In and Se on the back electrode 1a, wherein the evaporation source temperatures of the In and Se are 810-830 ℃ and 240-300 ℃ respectively, the temperature of the first substrate A is 350-400 ℃, and the deposition time is 25-40min;
the growth process of the second stage comprises the following steps: at 1.0X 10 -2 Pa～2.0×10 -2 Simultaneously evaporating and plating two elements of Cu and Se on the basis of the previous stage under the vacuum condition of Pa, wherein the evaporation source temperatures of the two elements of Cu and Se are 1150-1300 ℃ and 240-300 ℃, the temperature of the first substrate A is 500-600 ℃, and the deposition time is 15-25min;
the growth process of the third stage comprises the following steps: at 2.0X 10 -2 Pa～3.0×10 -2 And (2) simultaneously evaporating In and Se on the film layer formed In the first two stages under the vacuum condition of Pa, wherein the evaporation source temperatures of the In element and the Se element are 730-770 ℃ and 240-300 ℃ respectively, the temperature of the first substrate A is 500-600 ℃, and the deposition time is 15-30min.
The process of adding sodium fluoride in the third stage growth process is as follows: under vacuum of 2.0X 1 0-2 Pa～3.0×10 - 2 Pa, the temperature of the first substrate A reaches 380 ℃, and a sodium fluoride (NaF) source is introduced in the Se environment, and the deposition time is 8-15min.
S014, an alkali metal post-deposition treatment is performed on the copper indium selenide absorber layer 10, in which rubidium fluoride is added.
In the embodiment, the rubidium fluoride is added after the growth of the absorption layer is finished, so that RbInSe is formed at the grain boundary by heavier alkali metal 2 Thereby acting to passivate the defect.
The process of adding rubidium fluoride in the post-deposition treatment process of alkali metal specifically comprises the following steps: when the temperature of the first substrate A reaches 320 ℃, introducing a rubidium fluoride source in a Se environment, and depositing for 15-20min.
S015, sequentially preparing a first semiconductor buffer layer 12, a first window layer 13, and a first transparent front electrode 14 on the processed copper indium selenide absorption layer 10.
The first semiconductor buffer layer 12 material of N-type may be: cadmium sulfide, zinc sulfide, cadmium-doped zinc sulfide, zinc magnesium oxide, zinc sulfur oxide and indium selenide, and the thickness is 50nm-80nm. Here, cadmium sulfide (CdS) is preferably used. The first semiconductor buffer layer 12 may be prepared using a chemical water bath, magnetron sputtering, or atomic layer deposition method.
The first semiconductor buffer layer 12 is preferably prepared by a chemical water bath method, which specifically comprises the following steps: 0.184g of cadmium sulfate is dissolved in 60ml of deionized water, 5.694g of thiourea is dissolved in 150ml of deionized water, the surface of the copper indium selenium absorption layer 10 is washed by the deionized water and then placed in a big beaker, 45ml of concentrated ammonia water (28-30%) is mixed with the cadmium sulfate solution and poured into the big beaker, the thiourea solution is also poured into the big beaker, then the big beaker is placed in a water bath kettle at 69 ℃, stirred for 9min at constant speed by a magnetic stirrer, taken out and washed by the deionized water, then dried by high-purity nitrogen and quickly placed in an oven at 160 ℃ for annealing for 2min.
The thickness of the copper indium selenium absorption layer 10 is 2-3 μm, the thickness of the first semiconductor buffer layer 12 of cadmium sulfide is 50nm, the thickness of the grid-type collecting electrode (ohmic contact electrode) is a nickel/aluminum/nickel (Ni/Al/Ni) three-layer lamination or chromium/nickel/gold (Cr/Ni/Au), the thickness of the nickel/aluminum/nickel (or chromium/nickel/gold) is 100nm/8000nm/100nm respectively, and the copper indium selenium absorption layer and the cadmium sulfide first semiconductor buffer layer can be sequentially overlapped by evaporation through an electron beam evaporation method. When the Ni/Al/Ni grid-type collecting electrode is prepared by an electron beam thermal evaporation method, the uppermost layer of Ni can prevent the second layer of Al from being oxidized by reaction with air, and the lowermost layer of Ni can prevent the electrode from falling off easily.
The first window layer 13 preferably employs zinc oxide (ZnO) having a thickness of 100nm. The first transparent front electrode 14 is preferably aluminum-doped zinc oxide, the aluminum doping proportion is 0.2%, the thickness is 200nm-400nm, the transmittance is more than 85%, and the conductivity is less than 6 multiplied by 10 -4 Ω.cm 2 。
The first window layer 13 and the first transparent front electrode 14 can be formed by magnetron sputtering, for example, when the first window layer 13 is manufactured, the flow rate of argon is 20sccm, the flow rate of oxygen is 2.0sccm, sputtering is performed for 4 times under the condition of 120W sputtering power, and then the power is adjusted to 220W sputtering for 16 times. When the first transparent front electrode 14 was sputtered, the first substrate a was heated to 90 ℃, the argon flow rate was 20sccm, the hydrogen flow rate was 2.5sccm, and the sputtering power was 750W, and 12 times of sputtering was performed.
The top cell 2 of this example is a Copper Gallium Selenide (CGS) solar cell, the semiconductor absorber layer of which is a copper gallium selenide absorber layer 20 made of three raw materials, copper, gallium, selenium, the thickness of the resulting absorber layer being 2-3 μm. The top cell 2 mainly includes a second substrate B, and a transparent electrode 2a, a copper-gallium-selenium absorption layer 20, a second semiconductor buffer layer 21, a second window layer 22, and a second transparent front electrode 23, which are sequentially stacked on the second substrate B from bottom to top.
The transparent electrode 2a can be fully transparent or semitransparent ITO, the light transmittance is more than or equal to 85 percent, and the used material is a zinc oxide aluminum-doped transparent conductive film with the thickness of 150nm. The materials and thicknesses of the second substrate B, the second semiconductor buffer layer 21, the second window layer 22, and the second transparent front electrode 23, and the processes may be the same as those of the first substrate a, the first semiconductor buffer layer 12, the first window layer 13, and the first transparent front electrode 14 in the bottom cell 1.
The copper-gallium-selenium absorption layer 20 is prepared by adopting a copper element, gallium element and selenium element three-step co-evaporation method, the substrate temperature is detected through a thermocouple at the back of the substrate, the substrate temperature in the first step is 450 ℃, the substrate temperature in the second step is 600 ℃, the substrate temperature in the third step is 600 ℃, the deposition rate of Ga is 4A DEG/s, the deposition rate of Cu is 3A DEG/s, and the deposition rate of Se is stably maintained at 30A DEG/s in the three steps. The substrate temperature is reduced by 2 ℃ to form a copper-rich phase at the end of the second step, and the substrate temperature is increased by 2 ℃ in the third step, and Ga is added to form a copper-poor phase. Because the thermocouple is at a certain distance from the substrate, the temperature of the substrate detected by the thermocouple is 30-50 ℃ lower than the temperature of the actual substrate surface.
Another object of the present invention is to provide a high efficiency flexible laminated thin film solar cell, which comprises a bottom cell 1 and a top cell 2 stacked on the bottom cell 1, wherein the P-type semiconductor absorption layer of the bottom cell 1 is a copper indium selenium absorption layer 10, and the band gap of the top cell 2 is wider than that of the bottom cell 1.
Accordingly, the upper surface of the copper indium selenide absorption layer 10 of the bottom cell 1 facing the top cell 2 is covered with an alkali metal compound deposition layer 11. The alkali metal compound deposition layer 11 is formed by depositing sodium fluoride and rubidium fluoride.
Example 2
Unlike example 1, the top cell 2 of the stacked thin-film solar cell of this embodiment may be a perovskite (perovskite) cell or a cadmium telluride (CdTe) cell, and the semiconductor absorber layer corresponding to the top cell 2 is a perovskite absorber layer or CdTe. The CIS flexible cell with the forbidden band width of about 1.0eV is used as a bottom cell 1, and is combined with a wide forbidden band flexible perovskite with the forbidden band width of about 1.7eV and a cadmium telluride thin film solar front cell to form a double-section laminated flexible solar cell with the efficiency of more than 30%.
Fig. 4 is a schematic view of the perovskite roof battery.
The perovskite top cell 2 is mainly composed of a photo-anode 201, an Electron Transport Layer (ETL) 202, a perovskite absorption layer 203, a Hole Transport Layer (HTL) 204, and a back electrode 205. Wherein the photo-anode 201 is typically fluorine doped oxide (FTO) and the back electrode 205 is typically a gold (Au) or silver (Ag) electrode.
The preparation method of the perovskite absorption layer 203 adopts a solution method which has simple process and does not need vacuum, and particularly relates to a two-step method. A metal halide (typically lead iodide PbI 2) is first deposited on the film and then reacted with a cationic halide (MAI, FAI, etc.) by a gas or liquid phase process to form the perovskite absorption layer 203.
The specific implementation method comprises the following steps: firstly, preparing ammonium potassium iodide (MAI) powder, mixing a hydriodic acid aqueous solution and a methylamine methanol solution, stirring for two hours under a bath condition, then performing rotary evaporation for one hour under a 50 ℃ condition, washing for 3 times by using diethyl ether, and then performing vacuum drying to obtain the MAI powder. Then PbI was added at a concentration of 1.2M 2 Dissolving in polar solvent DMF, stirring to dissolve completely, and adding 40 μ L of PbI 2 Dropping the solution to TiO 2 After 30 seconds of residence time on the film, the film was spin-coated at 2000rpm for 60 seconds. After the completion of spin coating, the film was placed on a 90 ℃ hot plate and heated for 5min to remove the solvent remaining in the film. After cooling to room temperature, the membrane was immersed in a 10mg/mL concentration MAI solution (in isopropanol) in PbI 2 After being converted into MAPbI3, the mixture is cleaned by isopropanol and annealed on a hot bench at 90 ℃ for 40min to obtain MAPbI 3 A perovskite absorption layer 203.
And directly stacking the perovskite battery on the CIS battery according to a 4-end stacking structure by using the prepared perovskite battery as a top battery of the tandem battery and the prepared CIS bottom battery to obtain the perovskite/copper indium selenium tandem solar battery.
In summary, the bottom cell of the present invention employs a narrow bandgap copper indium selenium solar cell, and can use various flexible materials as substrates to prepare flexible cells, and the narrow bandgap copper indium selenium solar cell and the wide bandgap solar cell are grown on the flexible substrates in combination, and a stacked cell is formed by adjusting the bandgap width, and the solar cells are stacked according to the bandgap width, thereby achieving the purpose of covering different absorption wavelength ranges, optimizing the efficiency of the flexible stacked cell, and by using a mechanical stacking method, the bandgap width can be flexibly selected to distribute the light absorption effect, and no current matching is needed, and the preparation process is simpler. In addition, the hole concentration is improved by utilizing an alkali metal post-deposition treatment method in the absorption layer of the narrow bandgap copper indium selenide solar cell, and then the open-circuit voltage is improved, so that the efficiency of the narrow bandgap copper indium selenide solar cell is obviously improved.
The foregoing is directed to embodiments of the present application and it is noted that numerous modifications and adaptations may be made by those skilled in the art without departing from the principles of the present application and are intended to be within the scope of the present application.

Claims (7)

1. A preparation method of a high-efficiency flexible laminated thin-film solar cell is characterized by comprising the following steps:
preparing a bottom battery (1), wherein a P-type semiconductor absorption layer of the bottom battery (1) is a copper indium selenium absorption layer (10);
preparing a top cell (2), wherein the band gap of the top cell (2) is wider than that of the bottom cell (1);
stacking the top cell (2) on the bottom cell (1) using a mechanical stacking method;
wherein the step of preparing the bottom cell (1) comprises:
providing a flexible first substrate (a);
forming a back electrode (1 a) on the first substrate (a);
preparing the copper indium selenium absorption layer (10) on the back electrode (1 a) by adopting a three-step coevaporation method;
carrying out alkali metal post-deposition treatment on the copper indium selenide absorption layer (10), and sequentially preparing a first semiconductor buffer layer (12), a first window layer (13) and a first transparent front electrode (14) above the treated copper indium selenide absorption layer (10);
wherein the step of preparing the bottom cell (1) comprises:
growing indium in the first stage of preparing the copper indium selenide absorption layer (10) by a three-step co-evaporation method, growing copper in the second stage, and growing indium in the third stage to form a copper-poor phase; adding sodium fluoride in the third-stage growth process, and adding rubidium fluoride in the post-deposition treatment process of the alkali metal after the third-stage growth;
wherein the growth process of the first stage comprises: at 5.0X 10 -5 Pa~1.0×10 -4 In and Se are simultaneously evaporated on the back electrode (1 a) under the background vacuum condition of Pa, the evaporation source temperatures of the In and Se are 810-830 ℃ and 240-300 ℃, the temperature of the first substrate (A) is 350-400 ℃, and the deposition time is 25-40min;
the growth process of the second stage comprises the following steps: at 1.0X 10 -2 Pa~2.0×10 -2 Simultaneously evaporating and plating two elements of Cu and Se on the basis of the previous stage under the vacuum condition of Pa, wherein the evaporation source temperatures of the two elements of Cu and Se are 1150-1300 ℃ and 240-300 ℃, the temperature of the first substrate (A) is 500-600 ℃, and the deposition time is 15-25min;
the growth process of the third stage comprises: at 2.0X 10 -2 Pa~3.0×10 -2 And (2) simultaneously evaporating In and Se on the film layer formed In the first two stages under the vacuum condition of Pa, wherein the evaporation source temperatures of the In element and the Se element are 730-770 ℃ and 240-300 ℃ respectively, the temperature of the first substrate (A) is 500-600 ℃, and the deposition time is 15-30min.
2. The method according to claim 1, wherein the flexible laminated thin-film solar cell is characterized in that,
the process of adding sodium fluoride in the third stage growth process is as follows: under vacuum of 2.0X 1 0-2 Pa~3.0×10 -2 Pa, introducing a sodium fluoride source in the Se environment under the condition that the temperature of the first substrate (A) reaches 380 ℃, and depositing for 8-15min;
the process of adding rubidium fluoride in the post-deposition treatment process of alkali metal comprises the following steps: when the temperature of the first substrate (A) reaches 320 ℃, introducing a rubidium fluoride source in a Se environment, and the deposition time is 15-20min.
3. A high-efficiency flexible laminated thin-film solar cell prepared by the preparation method of claim 1 or 2, wherein the high-efficiency flexible laminated thin-film solar cell comprises a bottom cell (1) and a top cell (2) stacked on the bottom cell (1), the P-type semiconductor absorption layer of the bottom cell (1) is a copper indium selenium absorption layer (10), the band gap of the top cell (2) is wider than that of the bottom cell (1), and the copper indium selenium absorption layer (10) is prepared by a three-step co-evaporation method.
4. High efficiency flexible laminated thin film solar cell according to claim 3, characterized in that the upper surface of the copper indium selenium absorber layer (10) of the bottom cell (1) facing the top cell (2) is covered with an alkali metal compound deposition layer (11).
5. The high efficiency flexible laminated thin film solar cell according to claim 4, characterized in that the alkali metal compound deposition layer (11) is formed by sodium fluoride and rubidium fluoride deposition.
6. The high efficiency flexible laminated thin film solar cell according to claim 4, wherein the bottom cell (1) comprises a copper indium selenium absorber layer (10), a back electrode (1 a) disposed below the copper indium selenium absorber layer (10), and the alkali metal compound deposition layer (11), the first semiconductor buffer layer (12), the first window layer (13), and the first transparent front electrode (14) sequentially stacked from bottom to top on the copper indium selenium absorber layer (10).
7. The high-efficiency flexible laminated thin-film solar cell according to any one of claims 3 to 6, characterized in that a semiconductor absorption layer of the top cell (2) is a copper gallium selenium absorption layer (20), a perovskite absorption layer or CdTe.
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