CN108550657B - Method for improving performance of cadmium telluride solar cell - Google Patents
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- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical compound C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 238000000034 method Methods 0.000 title claims abstract description 53
- 229910052751 metal Inorganic materials 0.000 claims abstract description 22
- 239000002184 metal Substances 0.000 claims abstract description 22
- 238000004806 packaging method and process Methods 0.000 claims abstract description 11
- 239000010949 copper Substances 0.000 claims description 12
- 239000011521 glass Substances 0.000 claims description 12
- 229910052802 copper Inorganic materials 0.000 claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 7
- 238000010521 absorption reaction Methods 0.000 claims description 6
- 238000005538 encapsulation Methods 0.000 claims description 3
- 229910004613 CdTe Inorganic materials 0.000 claims 2
- 239000000463 material Substances 0.000 abstract description 15
- 238000002360 preparation method Methods 0.000 abstract description 9
- 230000007547 defect Effects 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 8
- 230000006872 improvement Effects 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 abstract description 5
- 238000009826 distribution Methods 0.000 abstract description 3
- 230000005288 electromagnetic effect Effects 0.000 abstract description 3
- 230000001276 controlling effect Effects 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 239000010409 thin film Substances 0.000 description 21
- 239000010408 film Substances 0.000 description 17
- 230000008569 process Effects 0.000 description 15
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 14
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 7
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000001755 magnetron sputter deposition Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 238000000137 annealing Methods 0.000 description 4
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 description 4
- AQCDIIAORKRFCD-UHFFFAOYSA-N cadmium selenide Chemical group [Cd]=[Se] AQCDIIAORKRFCD-UHFFFAOYSA-N 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 238000002202 sandwich sublimation Methods 0.000 description 4
- 238000002207 thermal evaporation Methods 0.000 description 4
- 229910052793 cadmium Inorganic materials 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- OEDMOCYNWLHUDP-UHFFFAOYSA-N bromomethanol Chemical compound OCBr OEDMOCYNWLHUDP-UHFFFAOYSA-N 0.000 description 1
- 150000001661 cadmium Chemical class 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000013386 optimize process Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- ONWXNHPOAGOMTG-UHFFFAOYSA-N suxibuzone Chemical compound O=C1C(CCCC)(COC(=O)CCC(O)=O)C(=O)N(C=2C=CC=CC=2)N1C1=CC=CC=C1 ONWXNHPOAGOMTG-UHFFFAOYSA-N 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 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
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
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Abstract
The invention provides a method for improving the performance of a cadmium telluride solar cell, which is used for carrying out microwave treatment on the cadmium telluride solar cell without an outer metal packaging structure. The invention introduces the microwave technology into the field of preparation and performance improvement of solar cells, utilizes the penetrability of microwaves to penetrate into devices, changes the concentration and distribution of point defects in materials through the specific thermal effect and electromagnetic effect of the microwaves, further regulates and controls the carrier concentration in the materials, and finally plays a role in regulating and controlling the performance of the cells.
Description
Technical Field
The invention belongs to the technical field of solar cells, and particularly relates to a method for improving the performance of a cadmium telluride solar cell.
Background
Cadmium telluride (CdTe) is a II-VI family direct band gap semiconductor with energy gap of 1.45eV, and its film has absorption coefficient as high as 105cm-1. Based on these characteristics, cadmium telluride has become a photovoltaic material with great application prospect and is receiving wide attention. At present, the laboratory highest conversion efficiency of the CdTe thin film solar cell reaches 22.1%, and the component efficiency of the CdTe thin film solar cell also reaches 18.6%. However, the photoelectric conversion efficiency is far from the theoretical 31%, which is greatly limited by the open circuit voltage (V)oc) Is raised.
In principle, there are several ways to increase the open circuit voltage of cadmium telluride thin film solar cells: firstly, the P-type doping concentration of the cadmium telluride material is improved. At present, I group elements in the periodic table of elements are mainly used for replacing Cd bits or V group elements are used for replacing Te bits so as to realize acceptor doping, for example, the common elements such as Li, Na, Cu, N, P and the like are used for P-type doping. However, the doping is difficult or ineffective due to the strong "self-compensating" effect inherent in the CdTe material itself. And secondly, prolonging the minority carrier lifetime. The minority carrier lifetime in the CdTe thin film is about 1ns generally, and the minority carrier lifetime can be prolonged by increasing the grain size or reducing interface defects and the like. However, there are also reports in the literature that the improvement effect of only minority carrier lifetime on the open-circuit voltage is limited, and minority carrier lifetime exceeding 10ns has no significant effect on the improvement of the battery performance. And thirdly, optimizing a back contact electrode. Copper-containing back contacts, transition metal oxide buffer layers or narrow bandgap heavily doped layers are commonly used to obtain good ohmic contact at the back electrode. However, the work function of P-type CdTe up to 5.7eV remains a challenge to obtain a suitable and stable back contact. In addition, the methods for increasing the open circuit voltage are all implemented in the device manufacturing process, which increases the complexity of the manufacturing process and increases the time consumption of the manufacturing cycle.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a method for improving the performance of a cadmium telluride solar cell, which can regulate and control the microscopic defect state in the cadmium telluride solar cell material, improve the open-circuit voltage of the cadmium telluride thin film solar cell, and further improve the overall performance of the device.
The invention provides a method for improving the performance of a cadmium telluride solar cell, which is used for carrying out microwave treatment on the cadmium telluride solar cell without an outer metal packaging structure.
Referring to fig. 1, fig. 1 is a schematic diagram of a method for improving the performance of a cadmium telluride solar cell provided by the present invention. In fig. 1, 1-a microwave transmitting device; 2-a protective cavity; 3-photovoltaic devices (cadmium telluride solar cells); 4-a substrate tray; 5-microwave control system; 6-microwave.
Specifically, a sample, i.e., a cadmium telluride solar cell, was first prepared. In the present invention, the cadmium telluride solar cell can be a laboratory prepared or commercially available cadmium telluride solar cell device as a sample for microwave treatment. The metal encapsulation structure outside the sample is removed prior to microwave treatment.
The cadmium telluride solar cell with the outer metal packaging structure removed comprises:
TCO conductive glass;
a window layer compounded on the TCO conductive glass;
a CdTe absorption layer compounded on the window layer;
a back contact layer and a back electrode compounded on the CdTe absorption layer.
The back contact layer is a copper layer, and the back electrode is a metal electrode.
In some embodiments of the invention, the cadmium telluride solar cell with the outer Metal packaging structure removed is a photovoltaic device with FTO/CdS/CdTe/Cu: Metal structure;
in other embodiments of the invention, the cadmium telluride solar cell with the outer Metal packaging structure removed is a photovoltaic device with FTO/MZO/CdSe/CdTe/Cu structure; wherein MZO is MgZnO;
in other embodiments of the present invention, the cadmium telluride solar cell without the outer metal encapsulation structure is FTO/SnO2A photovoltaic device of Metal structure;
in other embodiments of the invention, the cadmium telluride solar cell with the outer Metal packaging structure removed is a photovoltaic device of FTO/MZO/CdTe/Cu: Metal structure.
And then, performing microwave treatment on the cadmium telluride solar cell with the outer metal packaging structure removed. Namely, the cadmium telluride solar cell with the outer metal packaging structure removed is placed in a microwave field, and the frequency of the microwave treatment is 0.3-30 GHz, preferably 2450 +/-50 MHz; the power is 50-450W, preferably 240-380W; the time is 5-60 min, preferably 15-30 min. The process is carried out at room temperature, which in the present invention is defined as 25 ± 5 ℃, under standard atmospheric conditions. The microwave is one of electromagnetic waves, and the wavelength range of the microwave is 1 m-1 mm, and the corresponding frequency range is 300 MHz-300 GHz. The application technology of the microwave photovoltaic device is quite mature in the fields of military affairs, communication, energy and the like, but the microwave technology is rarely applied to the preparation and optimization treatment of the photovoltaic device.
The microwave supply means utilized in the present invention includes, but is not limited to, a laboratory microwave oven.
And finally, naturally cooling the microwave-treated device in the air, and if necessary, packaging.
Compared with the prior art, the invention provides a method for improving the performance of a cadmium telluride solar cell, which is used for carrying out microwave treatment on the cadmium telluride solar cell without an outer metal packaging structure. The invention introduces the microwave technology into the field of preparation and performance improvement of solar cells, utilizes the penetrability of microwaves to penetrate into devices, changes the concentration and distribution of point defects in materials through the specific thermal effect and electromagnetic effect of the microwaves, further regulates and controls the carrier concentration in the materials, and finally plays a role in regulating and controlling the performance of the cells.
The invention has the following advantages:
1. the microwave treatment method utilizes the thermal effect and the electromagnetic effect of the microwave to regulate and control the point defects and the impurity ion distribution, improves the overall performance of the battery from the material level, and has extremely obvious effect. As shown in fig. 2, the output characteristics varied significantly before and after the microwave treatment.
2. The microwave treatment method can effectively improve the P-type doping concentration of cadmium telluride. The microwave promotes the copper ions of the back contact layer to diffuse and migrate into the CdTe thin film, and further effective acceptor defects are formed, such as copper substituted cadmium site defects, copper gaps, cadmium vacancy composite defects and the like, so that the doping concentration is improved. As shown in fig. 3, the carrier concentration in the absorption layer of the cell is increased by one order of magnitude. Along with the increase of the open-circuit voltage, the resistivity of the material is also reduced due to the higher carrier concentration, and the increase of the cell fill factor (fill factor) is also promoted, so that the conversion efficiency of the cadmium telluride solar cell is improved.
3. The microwave treatment method has simple process and higher feasibility. In the field of electromagnetic waves, the application of microwaves is one of the most active, widespread and mature parts. The method for treating the cadmium telluride solar cell by microwaves can be adapted to the existing microwave technology. The processing process only needs to carry out microwave radiation on the device with proper power and proper time, and the process complexity is low. Compared with other common ways of improving the open-circuit voltage, such as optimizing the back contact electrode, increasing the minority carrier concentration and prolonging the service life, the method greatly reduces the complexity of technical implementation, time consumption of the process period and the cost of materials, and is suitable for large-scale industrial production and manufacturing.
4. The microwave used in the microwave treatment method is a special electromagnetic wave which can go deep into the device to interact with materials on the basis of not damaging the structure of the battery. As a treatment method after the device is finished, compared with a series of optimized processes in the battery preparation process, the microwave treatment reduces the pollution of the external environment to the core semiconductor material and improves the performance and stability of the device.
Drawings
FIG. 1 is a schematic illustration of a method of improving the performance of a cadmium telluride solar cell provided by the present invention;
FIG. 2 shows cadmium telluride thin film solar cells before and after microwave treatment under standard test conditions (1000W/m) for solar cells2AM1.5) current-voltage (I-V) profile measured at 25 ℃;
FIG. 3 shows the doping concentration-depletion region width (N (X) -X) of cadmium telluride thin film solar cell before and after microwave treatmentD) Graph is shown.
Detailed Description
For further understanding of the present invention, the method for improving the performance of a cadmium telluride solar cell provided by the present invention is described below with reference to the following examples, and the scope of the present invention is not limited by the following examples.
Example 1:
and (5) preparing the cadmium telluride solar cell. The process for preparing the photovoltaic device with the FTO/CdS/CdTe/Cu Metal structure comprises the following steps: preparing a cadmium sulfide (CdS) film on commercial fluorine-doped tin dioxide (FTO) conductive glass by adopting a chemical water bath method or a magnetron sputtering method, wherein the thickness of the film is 100 nm; preparing a cadmium telluride thin film with the thickness of 4 mu m by adopting a close space sublimation method (CSS); cadmium chloride (CdCl) for CdTe film2) Etching with a phosphoric-nitric acid solution after heat treatment; a copper thin film about 5nm thick and a metal electrode about 200nm thick were prepared in sequence using a vacuum thermal evaporation method. After coating, the sample was subjected to vacuum annealing at 200 ℃ for 25 min. And finishing the device preparation process.
The prepared battery was treated with microwave. The above cell samples were placed in ceramic or glass containers and transferred with the containers to a laboratory-specific microwave oven. Setting the microwave power to 380W; the treatment time is 15 min; the microwave frequency used in the process is 2450 +/-50 MHz; the environment in the microwave oven is room temperature and standard atmospheric pressure. And after the microwave treatment process is finished, taking out the cell sample, placing the cell sample in air for natural cooling, and finishing the treatment process of the cadmium telluride thin-film solar cell by the microwave.
The performance of the solar cell before and after the microwave treatment was tested and the results are shown in Table 1
Table 1 performance test results of solar cells before and after microwave treatment one
The specific performance parameters are listed in table 1, the open-circuit voltage of the battery is increased from 758mV to 811mV, the fill factor is increased from 70.3% to 72.1%, the photoelectric conversion efficiency is increased from 13.4% to 14.6%, and the performance is greatly improved.
The output performance of the solar cell before and after microwave treatment is tested, the result is shown in FIG. 2, FIG. 2 shows cadmium telluride thin-film solar cell before and after microwave treatment under the standard test condition (1000W/m) of the solar cell2AM1.5), 25 ℃, current-voltage (I-V) profile. As can be seen from fig. 2, the improvement in the battery performance before and after the microwave treatment, particularly the improvement in the open circuit voltage, was significant.
The doping concentration-depletion region width of the solar cell before and after the microwave treatment is tested, and the result is shown in fig. 3, wherein fig. 3 is the doping concentration-depletion region width (N (X) -X) of the cadmium telluride thin film solar cell before and after the microwave treatmentD) Graph is shown. As shown in fig. 3, the carrier concentration in the absorber layer of the cell is increased by an order of magnitude, which is a significant breakthrough for cadmium telluride materials that have a strong "self-compensating" effect. Along with the increase of the open-circuit voltage, the resistivity of the material is also reduced by the higher carrier concentration, so that the filling factor of the cell is improved, and the conversion efficiency of the cadmium telluride cell is improved.
Example 2:
and (5) preparing the cadmium telluride solar cell. The process for preparing the photovoltaic device with the FTO/MZO/CdSe/CdTe/Cu Metal structure comprises the following steps: preparing a magnesium-doped zinc oxide (MZO) film on commercial fluorine-doped tin dioxide (FTO) conductive glass by adopting a magnetron sputtering method, wherein the thickness of the film is 20 nm; preparing a cadmium selenide (CdSe) film by a magnetron sputtering method, wherein the thickness of the cadmium selenide (CdSe) film is 80 nm; preparing a cadmium telluride thin film with the thickness of 4 mu m by adopting a close space sublimation method (CSS); cadmium chloride (CdCl) for CdTe film2) Etching with bromomethanol solution after heat treatment; preparing copper film with thickness of about 5nm and metal electrode with thickness of about 200nm by vacuum thermal evaporation methodAnd (4) a pole. After coating, the sample was subjected to vacuum annealing at 200 ℃ for 25 min. And finishing the device preparation process.
The battery prepared as described above was treated with microwaves, and a sample of the battery was placed in a ceramic or glass container, together with the container, and transferred to a microwave oven dedicated to a laboratory. Setting the microwave power to 240W; the treatment time is 30 min; the microwave frequency used in the process is 2450 +/-50 MHz; the environment in the microwave oven is room temperature and standard atmospheric pressure. And after the microwave treatment is finished, taking out the cell sample, placing the cell sample in air for natural cooling, and finishing the microwave treatment process of the cadmium telluride thin-film solar cell.
The performance of the solar cell before and after the microwave treatment was tested and the results are shown in Table 2
Table 2 performance test results of solar cells before and after microwave treatment
Example 3:
and (5) preparing the cadmium telluride solar cell. Preparation of FTO/SnO2The process of the photovoltaic device with a/CdS/CdTe/Cu Metal structure comprises the following steps: preparing stannic oxide (SnO) on commercial fluorine-doped stannic oxide (FTO) conductive glass by adopting magnetron sputtering method2) A film with the thickness of 20 nm; preparing a cadmium sulfide (CdS) film by adopting a chemical water bath method or a magnetron sputtering method, wherein the thickness of the film is 80 nm; preparing a cadmium telluride thin film with the thickness of 4 mu m by adopting a close space sublimation method (CSS); cadmium chloride (CdCl) for CdTe film2) Etching with a phosphoric-nitric acid solution after heat treatment; a copper thin film about 5nm thick and a metal electrode about 200nm thick were prepared in sequence using a vacuum thermal evaporation method. After coating, the sample was subjected to vacuum annealing at 200 ℃ for 25 min. And finishing the device preparation process.
The prepared cell was treated with microwaves, and the cell sample was placed in a ceramic or glass container, together with the container, and transferred to a microwave oven dedicated to the laboratory. Setting the microwave power to be 50W; the treatment time is 60 min; the microwave frequency used in the process is 2450 +/-50 MHz; the environment in the microwave oven is room temperature and standard atmospheric pressure. And after the microwave treatment is finished, taking out the cell sample, placing the cell sample in air for natural cooling, and finishing the microwave treatment process of the cadmium telluride thin-film solar cell.
The performance of the solar cell before and after the microwave treatment was tested and the results are shown in Table 3
Table 3 performance test results of solar cells before and after microwave treatment
Example 4:
and (5) preparing the cadmium telluride solar cell. The process for preparing the photovoltaic device with the FTO/MZO/CdTe/Cu Metal structure comprises the following steps: preparing a magnesium-doped zinc oxide (MZO) film on commercial fluorine-doped tin dioxide (FTO) conductive glass by adopting a magnetron sputtering method, wherein the thickness of the film is 100 nm; preparing a cadmium telluride thin film with the thickness of 4 mu m by adopting a close space sublimation method (CSS); cadmium chloride (CdCl) for CdTe film2) Etching with a phosphoric-nitric acid solution after heat treatment; a copper thin film about 5nm thick and a metal electrode about 200nm thick were prepared in sequence using a vacuum thermal evaporation method. After coating, the sample was subjected to vacuum annealing at 200 ℃ for 25 min. And finishing the device preparation process.
The prepared cell was treated with microwaves, and the cell sample was placed in a ceramic or glass container, together with the container, and transferred to a microwave oven dedicated to the laboratory. Setting the microwave power to 450W; the treatment time is 5 min; the microwave frequency used in the process is 2450 +/-50 MHz; the environment in the microwave oven is room temperature and standard atmospheric pressure. And after the microwave treatment is finished, taking out the cell sample, placing the cell sample in air for natural cooling, and finishing the microwave treatment process of the cadmium telluride thin-film solar cell.
The performance of the solar cell before and after the microwave treatment was tested and the results are shown in Table 4
Table 4 performance test results of solar cells before and after microwave treatment
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (4)
1. A method for improving the performance of a cadmium telluride solar cell is characterized in that the cadmium telluride solar cell with an outer metal packaging structure removed is subjected to microwave treatment; the frequency of the microwave treatment is 2450 +/-50 MHz; the power is 240-380W; the time is 15-30 min;
the cadmium telluride solar cell with the outer metal encapsulation structure removed comprises:
TCO conductive glass;
a window layer compounded on the TCO conductive glass;
a CdTe absorption layer compounded on the window layer;
the back contact layer and the back electrode are compounded on the CdTe absorption layer, and the back contact layer is a copper layer.
2. The method according to claim 1, further comprising cooling the microwave after the microwave treatment, wherein the cooling is performed under natural conditions.
3. The method of claim 1, wherein the back electrode is a metal electrode.
4. The method of claim 1, wherein the method is performed at room temperature, which is 25 ± 5 ℃, under standard atmospheric conditions.
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