CN117894882A - Optical annealing device and method for heterojunction of antimony selenide solar cell - Google Patents

Optical annealing device and method for heterojunction of antimony selenide solar cell Download PDF

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CN117894882A
CN117894882A CN202410295789.1A CN202410295789A CN117894882A CN 117894882 A CN117894882 A CN 117894882A CN 202410295789 A CN202410295789 A CN 202410295789A CN 117894882 A CN117894882 A CN 117894882A
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heterojunction
solar cell
antimony selenide
vacuum cavity
light source
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CN117894882B (en
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李志强
王新华
郭颖楠
梁晓杨
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Hebei University
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00Semiconductor 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
    • H01L31/18Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • H01L31/186Particular post-treatment for the devices, e.g. annealing, impurity gettering, short-circuit elimination, recrystallisation
    • H01L31/1864Annealing
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/67Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
    • H01L21/67005Apparatus not specifically provided for elsewhere
    • H01L21/67242Apparatus for monitoring, sorting or marking
    • H01L21/67248Temperature monitoring
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/67Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
    • H01L21/67005Apparatus not specifically provided for elsewhere
    • H01L21/67242Apparatus for monitoring, sorting or marking
    • H01L21/67253Process monitoring, e.g. flow or thickness monitoring
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50Manufacturing or production processes characterised by the final manufactured product

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  • Condensed Matter Physics & Semiconductors (AREA)
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  • Photovoltaic Devices (AREA)

Abstract

The invention provides an optical annealing device and method for an antimony selenide solar cell heterojunction. The device comprises a vacuum cavity, wherein a sample table is arranged in the vacuum cavity, and the sample table is provided with a thermometer for monitoring temperature; the two sides of the vacuum cavity are provided with a vacuum extraction opening and an air inlet pipeline, and the air inlet pipeline is provided with an inflation valve; a light source component is arranged above the vacuum cavity. The optical annealing device is applied to Sb 2 Se 3 And (3) carrying out optical annealing treatment on the CdS heterojunction through a light source assembly above the vacuum cavity in an argon atmosphere, and then preparing a window layer and a top electrode. Through heterojunction light annealing treatment, interface defect density and bulk defect density of a heterojunction interface are reduced, transmission and collection of photo-generated carriers are promoted, external quantum efficiency of the solar cell in a long wave band (600 nm-1100 nm) is greatly improved, short-circuit current is improved, and antimony selenide thin film solar electricity is further improvedPhotoelectric conversion efficiency of the cell.

Description

Optical annealing device and method for heterojunction of antimony selenide solar cell
Technical Field
The invention relates to the technical field of solar cells, in particular to an optical annealing device and method for an antimony selenide solar cell heterojunction.
Background
At present, widely studied photovoltaic devices include crystalline silicon solar cells, thin film solar cells, organic solar cells, quantum dot solar cells and the like, wherein the thin film solar cells become research hot spots due to the advantages of low preparation cost, simple process, easy flexibility, portability, suitability for building integration and the like. Antimony selenide (Sb) 2 Se 3 ) As an inorganic semiconductor material having good stability and high resistance to oxygen and ultraviolet rays, reserves are abundant in nature. Sb (Sb) 2 Se 3 The material is a quasi-direct band gap material with proper band gap (1.1-1.3 eV) and absorption coefficient greater than 10 5 cm -1 Is a very ideal photovoltaic material. According to the Shockley-Queisser limit theory, single junction Sb 2 Se 3 The photoelectric conversion efficiency of the solar cell is above 30%, and the solar cell has great development potential.
Over the last decade, the efficiency of antimony selenide solar cells has gradually increased. The highest efficiency of the currently reported antimony selenide solar cell is 10.57%, which proves that the antimony selenide solar cell has good application prospect. However, compared with the crystalline silicon solar cell, the conversion efficiency of the currently prepared antimony selenide solar cell is still lower, and certain theoretical and experimental results indicate that Sb 2 Se 3 High density of interfacial defects (10) between/CdS 11 cm -3 ) The problems of undesirable Conduction Band Offset (CBO) at the heterojunction, excessive diffusion of elements and the like seriously restrict the improvement of photoelectric conversion efficiency. At present, the existing equipment cannot meet the requirements of preparing a heterojunction interface with low interface defects and high quality, and the photoelectric conversion efficiency of the antimony selenide solar cell is more difficult to further improve.
Disclosure of Invention
The invention aims to provide an optical annealing device and method for heterojunction of an antimony selenide solar cell, which reduce interface defect density and bulk defect density of the heterojunction through heterojunction optical annealing treatment, promote transmission and collection of photo-generated carriers, greatly improve external quantum efficiency of the solar cell in a long wave band (600 nm-1100 nm), and promote short circuit current, thereby improving photoelectric conversion efficiency of the antimony selenide thin film solar cell.
The invention is realized in the following way:
an optical annealing device for heterojunction of antimony selenide solar cell, which structurally comprises: the vacuum cavity is internally provided with a sample table and a thermometer for monitoring the temperature of the sample table; the two sides of the vacuum cavity are provided with a vacuum extraction opening and an air inlet pipeline, and the air inlet pipeline is provided with an inflation valve; a light source component is arranged above the vacuum cavity.
The optical annealing device provided by the invention is used for carrying out optical annealing on the heterojunction of the antimony selenide solar cell, the sample in the vacuum cavity is irradiated by the light source component which emits light through the light source component above the vacuum cavity, and the sample is subjected to optical annealing treatment under the argon atmosphere. And preparing the window layer and the top electrode after the optical annealing treatment.
Preferably, the heterojunction of the antimony selenide solar cell is specifically Sb 2 Se 3 a/CdS heterojunction.
Preferably, the vacuum chamber is composed of a quartz tube equipped with a mechanical pump for evacuating.
Preferably, the gas introduced into the air inlet pipeline is high-purity argon (99.999%).
Preferably, the light source component is a light heating lamp tube and is provided with a control module, and the control module controls the irradiation intensity and time of the light source component.
Preferably, the light source assembly is longitudinally aligned with the center of the sample stage, and the light source assembly is spaced from the sample stage by 20cm.
The invention also provides an optical annealing method for the heterojunction of the antimony selenide solar cell, which comprises the following steps:
(1) Setting the light annealing device;
(2) Fixing the sample on a sample stage, and longitudinally aligning the light source component with the center of the sample stage;
(3) Vacuumizing to 110 -1 Closing a mechanical pump and introducing high-purity argon when Pa;
(4) Turning on a light source assembly, and controlling the irradiation intensity and the irradiation time;
(5) And cooling after the light source assembly irradiates for a specified time, and taking out the sample.
The gas pressure of the high-purity argon introduced in the step (3) is not lower than 50kPa, and is usually set to be 50-200kPa.
In the step (4), the irradiation time of the light source component is 20-40 min, and the irradiation power is 100-150W.
And (5) after the light source component reaches the irradiation time, taking out the sample after the temperature of the sample stage is reduced to 50 .
In the heterojunction treatment process, the antimony selenide solar cell with low interface defect, low bulk defect and high carrier transmission efficiency is obtained by regulating and controlling the irradiation intensity and time irradiation time of the light source assembly, and the device and the process are simple in operation, controllable in condition, efficient and stable in treatment process and suitable for further popularization and application.
The optical annealing device and the method for the heterojunction of the antimony selenide solar cell, which are provided by the invention, are one of effective means for improving the current of the solar cell and preparing the high-efficiency antimony selenide solar cell, and compared with the prior art, have the advantages that:
(1) The process is simple and efficient. The temperature of the sample is low (about 90-120 ) in the treatment process, the area of the treated sample is large (the area of the sample can be as large as the area of a sample table in the light allowable range), and the promotion of the industrialization of the antimony selenide solar cell is facilitated.
(2) Stable and strong controllability. Under the high-purity argon atmosphere, the control module is not easily influenced by other external factors, and the control module controls the light source to irradiate in the whole process, so that the high-purity argon atmosphere has low irradiation intensity and low irradiation time.
(3) The problems of large interface defects at the heterojunction interface, excessive diffusion of elements and the like are effectively solved, and the preparation of the high-efficiency antimony selenide solar cell is realized.
Drawings
Fig. 1 is a schematic structural diagram of an optical annealing device for heterojunction of an antimony selenide solar cell according to the present invention.
Fig. 2 is a schematic structural diagram of an antimony selenide solar cell prepared according to the present invention.
Fig. 3 is a graph showing External Quantum Efficiency (EQE) and capacitance voltage and driver stage capacitance analysis (CV/DLCP) test patterns of the antimony selenide solar cells prepared in example 2 and comparative example 1 of the present invention.
Fig. 4 is a graph of the photovoltaic performance of the device of the present invention at various light irradiation times.
Fig. 5 is a graph of the photovoltaic performance of the device of the present invention at different light illumination powers.
Detailed Description
For a further understanding of the present invention, preferred embodiments of the invention are described below in conjunction with the examples, but it is to be understood that these descriptions are merely intended to illustrate further the features and advantages of the invention and are not limiting of the invention.
Example 1, an optical annealing apparatus for heterojunction of antimony selenide solar cell.
As shown in fig. 1, the structure of the optical annealing device provided by the invention comprises a vacuum cavity 1, wherein the vacuum cavity 1 is specifically a quartz tube; a sample stage 4 is arranged in the vacuum cavity 1 (the area of the sample stage 4 is 10cm multiplied by 10cm in the embodiment), and the sample stage 4 is used for placing a sample; a thermometer 6 for monitoring the temperature of the sample stage 4 is arranged at the sample stage, and the thermometer 6 can be a thermocouple thermometer; the two sides of the vacuum cavity 1 are provided with a vacuum extraction opening 2 and an air inlet pipeline 3, and high-purity argon is required to be introduced into the vacuum cavity 1 during optical annealing. A light source assembly 5 is arranged above the vacuum cavity 1, the light source assembly 5 is a light heating lamp tube, the light source assembly 5 is provided with a control module, and the irradiation intensity and the irradiation time of the light source assembly are controlled by the control module. The light source component 5 is opposite to the sample stage 4 in the vacuum cavity 1, the sample stage 4 in the vacuum cavity 1 is irradiated by the light emitted by the light source component 5, and the sample stage 4 and the sample on the sample stage are heated in a light mode, so that the light annealing of the sample is realized.
Example 2 preparation of antimony selenide solar cell.
As shown in fig. 2, the structure of the antimony selenide solar cell provided by the invention is as follows from bottom to top: a substrate, a back electrode, an antimony selenide absorber layer (corresponding to Sb in FIG. 2) 2 Se 3 ) A buffer layer, a window layer, and a top electrode. Selenization ofThe heterojunction of the antimony solar cell is in a structure formed by an antimony selenide absorption layer and a buffer layer, and the heterojunction of the antimony selenide solar cell is treated by adopting an optical annealing method. Referring to fig. 2, the substrate is preferably soda lime Glass (Glass), the back electrode is preferably molybdenum back electrode (Mo), the buffer layer is preferably cadmium sulfide (CdS), the window layer is preferably intrinsic zinc oxide and aluminum doped zinc oxide (ZnO/AZO), and the top electrode is preferably silver electrode (Ag).
The preparation method of the antimony selenide solar cell comprises the following specific steps:
(1) Cleaning a substrate
The method comprises the steps of using soda lime glass as a substrate, firstly using a semiconductor cleaning agent to carry out ultrasonic oscillation cleaning, then using deionized water to wash the surface of the soda lime glass, and then using a nitrogen gun to blow-dry the surface of the substrate.
(2) Preparation of molybdenum Back electrode
The magnetron sputtering technology is adopted to deposit the Mo back electrode, the target material is high-purity molybdenum (99.999 percent), the sputtering technology of the molybdenum target material adopts a 1200W direct current power supply, and the power density is 4.0W/cm 2 The sputtering working gas is high-purity argon (99.999%), the sputtering air pressure is 0.3 Pa, the thickness of the prepared Mo film is 800nm, and the resistivity is 1 multiplied by 10 -5 cm
(3) Preparation of antimony selenide absorber layer
The antimony selenide absorbing layer was prepared by jet vapor deposition technique, the substrate temperature was set to 370 , the evaporation source temperature was set to 470 , the argon flow was set to 10sccm, and the thickness of the prepared antimony selenide absorbing layer was 1.5 m.
(4) Preparation of cadmium sulfide buffer layer
The cadmium sulfide buffer layer is prepared by adopting a chemical water bath method, cadmium sulfate is used as a cadmium source, thiourea is used as a sulfur source, ammonia water is added to regulate the reaction environment, the water bath reaction temperature is set to 70 , the reaction time is 12 minutes, and the thickness of the prepared cadmium sulfide buffer layer is 60 nm.
(5) Optical annealing treatment of antimony selenide heterojunction
The light annealing device of the invention is adopted to carry out the annealing on Sb 2 Se 3 Treatment is carried out on the/CdS heterojunction, the light annealing working gas is high-purity argon (99.999%) with the pressure of 50kPa, and the light source groupThe piece was longitudinally aligned with the center point of the sample stage, the light source assembly was 20cm from the sample stage, the illumination power of the light source assembly (emitting yellow light) was 150W, and the illumination time was 30 minutes. Under the irradiation of 150W, the irradiation is carried out for 30min, and the temperature of the sample stage is about 100 . After irradiation for 30 minutes, the light source assembly is turned off, and the sample is taken out after the temperature of the sample stage is reduced to 50 .
(6) Preparation of Zinc oxide and aluminum doped Zinc oxide Window layer
The intrinsic zinc oxide and the aluminum-doped zinc oxide are deposited by adopting a radio frequency magnetron sputtering method, the sputtering target material adopts a high-purity zinc oxide target material and an aluminum-doped zinc oxide target material, and the sputtering power density is 0.8W/cm respectively 2 1.6 W/cm 2 The sputtering working gas is high-purity argon, the sputtering air pressure is 0.5 Pa and 0.2 Pa respectively, the substrate temperature is normal temperature, and the thicknesses of the intrinsic zinc oxide and the aluminum-doped zinc oxide are 70 nm and 300 nm respectively.
(7) Preparation of silver top electrode
The silver top electrode layer is deposited by adopting a thermal evaporation technology, high-purity silver particles are used as evaporation sources, the evaporation rate is 0.5nm/s, and the thickness of the prepared Ag electrode is 150 nm.
Comparative example 1
In this comparative example, the heterojunction of the antimony selenide solar cell was not treated by the light annealing device, and other process parameters were the same as in example 2.
External quantum efficiency test and capacitance-voltage test were performed on the heterojunction interfaces prepared in this comparative example and example 2, and the results are shown in fig. 3. In fig. 3, (a) is External Quantum Efficiency (EQE) test data of example 2 and comparative example 1, and (b) is Capacitance Voltage (CV) and driver stage capacitance analysis (DLCP) test chart of example 2 and comparative example 1. As can be seen from fig. 3, the sample after the optical annealing treatment in example 2 has reduced interface defect density and bulk defect density of the heterojunction, promoted transmission and collection of photogenerated carriers, greatly improved external quantum efficiency of the solar cell in a long wavelength band (600 nm-1100 nm), improved short-circuit current, and further improved photoelectric conversion efficiency of the antimony selenide thin-film solar cell, compared with the sample not treated by the optical annealing method in comparative example 1.
The following table 1 shows specific CV/DLCP test values of the antimony selenide solar cells prepared in example 2 and comparative example 1.
TABLE 1 CV/DLCP specific test values of the antimony selenide solar cells prepared in example 2 and comparative example 1
By free carrier defect density N CV And bulk defect density N DLCP The difference between the two can obtain the interface defect density N between the interfaces i N i The smaller the value is, the better the interface defect is. Therefore, after the optical annealing, the heterojunction interface defects are greatly reduced.
On the basis of example 2, the irradiation power of the light source module in step (5) was fixed at 150W, the irradiation time was changed to 0min, 3min and 3h, respectively, and the resulting samples were subjected to the photoelectric property test together with the samples in example 2, and the results are shown in fig. 4. As can be seen from fig. 4, as the irradiation time increases, the device performance tends to rise and then fall, and the optimal irradiation time is 30min. When the light irradiation time is 3min, the Sb cannot be effectively passivated in a shorter treatment time 2 Se 3 Recombination centers between the/CdS thin films; when the light irradiation time is 3 hours, sb may be caused by excessively long light annealing time 2 Se 3 The excessive diffusion of the element at the/CdS heterojunction interface forms a new defect recombination center, resulting in a significant decrease in the photoelectric conversion efficiency of the light annealing device.
On the basis of example 2, the light irradiation time in step (5) was fixed for 30min, the light irradiation power was changed to 0W, 100W and 200W, respectively, and the resulting samples were subjected to the photoelectric property test together with the samples in example 2, and the results are shown in fig. 5. As can be seen from FIG. 5, the device performance trend is that the irradiation power is increased and then decreased, when the irradiation power is 200W, the irradiation power is too high, so that the sample surface has higher temperature, resulting in Sb 2 Se 3 Film surface SThe precipitation of e element greatly reduces the photoelectric conversion efficiency of the optical annealing device.
In summary, the appropriate light annealing treatment can greatly improve the open-circuit voltage and the short-circuit current density of the solar cell, thereby improving the photoelectric conversion efficiency of the solar cell.

Claims (7)

1. The optical annealing device for the heterojunction of the antimony selenide solar cell is characterized by comprising a vacuum cavity, wherein a sample table and a thermometer for monitoring the temperature of the sample table are arranged in the vacuum cavity, the sample table is used for bearing a sample, and the sample is the heterojunction of the antimony selenide solar cell; the two sides of the vacuum cavity are provided with a vacuum extraction opening and an air inlet pipeline, and argon can be introduced into the vacuum cavity through the vacuum extraction opening and the air inlet pipeline; a light source component is arranged above the vacuum cavity and is opposite to the sample table in the vacuum cavity, and the light source component is used for irradiating a sample to carry out optical annealing on the heterojunction of the antimony selenide solar cell in an argon environment.
2. The optical annealing device for an antimony selenide solar cell heterojunction of claim 1, wherein the vacuum chamber is a quartz tube.
3. The optical annealing device for an antimony selenide solar cell heterojunction as claimed in claim 1, wherein the light source assembly is an optical heating lamp, and the optical heating lamp is equipped with a control module for controlling the irradiation intensity and irradiation time of the optical heating lamp.
4. The optical annealing device for an antimony selenide solar cell heterojunction of claim 1, wherein the thermometer is a thermocouple thermometer.
5. An optical annealing method for heterojunction of an antimony selenide solar cell is characterized by comprising the following steps:
(1) Providing the light annealing device of claim 1;
(2) Fixing the sample on a sample stage;
(3) Vacuumizing to 110 -1 Stopping vacuumizing in Pa, and then introducing argon;
(4) Turning on a light source assembly, and controlling the irradiation intensity and the irradiation time;
(5) And cooling after the light source assembly irradiates for a set time, and taking out the sample.
6. The method for optical annealing of heterojunction for antimony selenide solar cell according to claim 5, wherein the gas pressure in the vacuum chamber after introducing argon in step (3) is 50-200kPa.
7. The method for optical annealing of heterojunction for antimony selenide solar cell according to claim 5, wherein in step (4), the irradiation time of the light source assembly is controlled to be 20-40 min, and the irradiation power is controlled to be 100-150 w.
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Citations (10)

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JPH06107433A (en) * 1992-09-28 1994-04-19 Hoya Corp Production of particulate dispersed glass
JP2000031082A (en) * 1998-07-10 2000-01-28 Sanyo Electric Co Ltd Laser annealer
US20060216875A1 (en) * 2005-03-28 2006-09-28 Takayuki Ito Method for annealing and method for manufacturing a semiconductor device
CN101719464A (en) * 2009-11-16 2010-06-02 江苏华创光电科技有限公司 Method for preparing ultra-shallow junction on surface of semiconductor chip through laser
US20170062223A1 (en) * 2015-08-26 2017-03-02 SCREEN Holdings Co., Ltd. Light irradiation type heat treatment method and heat treatment apparatus
CN107546289A (en) * 2017-08-01 2018-01-05 华中科技大学 A kind of antimony selenide thin-film solar cells and preparation method thereof
CN110649888A (en) * 2019-10-21 2020-01-03 华东师范大学 Perovskite photovoltaic cell degradation testing arrangement
CN113078239A (en) * 2021-03-29 2021-07-06 深圳大学 Antimony selenide thin film solar cell and preparation method thereof
CN115663041A (en) * 2022-10-31 2023-01-31 河北大学 Gradient band gap selenium antimony sulfide solar cell and preparation method thereof
WO2023040660A1 (en) * 2021-09-20 2023-03-23 上海大学 Reducing agent-free vacuum iron production method

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06107433A (en) * 1992-09-28 1994-04-19 Hoya Corp Production of particulate dispersed glass
JP2000031082A (en) * 1998-07-10 2000-01-28 Sanyo Electric Co Ltd Laser annealer
US20060216875A1 (en) * 2005-03-28 2006-09-28 Takayuki Ito Method for annealing and method for manufacturing a semiconductor device
CN101719464A (en) * 2009-11-16 2010-06-02 江苏华创光电科技有限公司 Method for preparing ultra-shallow junction on surface of semiconductor chip through laser
US20170062223A1 (en) * 2015-08-26 2017-03-02 SCREEN Holdings Co., Ltd. Light irradiation type heat treatment method and heat treatment apparatus
CN107546289A (en) * 2017-08-01 2018-01-05 华中科技大学 A kind of antimony selenide thin-film solar cells and preparation method thereof
CN110649888A (en) * 2019-10-21 2020-01-03 华东师范大学 Perovskite photovoltaic cell degradation testing arrangement
CN113078239A (en) * 2021-03-29 2021-07-06 深圳大学 Antimony selenide thin film solar cell and preparation method thereof
WO2023040660A1 (en) * 2021-09-20 2023-03-23 上海大学 Reducing agent-free vacuum iron production method
CN115663041A (en) * 2022-10-31 2023-01-31 河北大学 Gradient band gap selenium antimony sulfide solar cell and preparation method thereof

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