CN114203842A - Wide-bandgap copper-gallium-selenium light absorption layer, preparation method thereof and solar cell - Google Patents

Wide-bandgap copper-gallium-selenium light absorption layer, preparation method thereof and solar cell Download PDF

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CN114203842A
CN114203842A CN202111537336.8A CN202111537336A CN114203842A CN 114203842 A CN114203842 A CN 114203842A CN 202111537336 A CN202111537336 A CN 202111537336A CN 114203842 A CN114203842 A CN 114203842A
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gallium
selenium
copper
substrate
temperature
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童佩斐
李文杰
李国啸
陈志勇
刘旭辉
杨春雷
冯叶
钟国华
邵龑
李伟民
陈明
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Shenzhen Institute of Advanced Technology of CAS
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Abstract

The invention provides a wide-bandgap copper-gallium-selenium light absorption layer and a preparation method thereof, wherein the wide-bandgap copper-gallium-selenium light absorption layer comprises a copper-gallium-selenium thin film layer and an indium-gallium thin film layer covered on the copper-gallium-selenium thin film layer, and an In is formed on the interface of the copper-gallium-selenium thin film layer and the indium-gallium thin film layer through an annealing processCuA flip defect. The preparation method comprises the following steps: heating the substrate to a first temperature, and co-evaporating gallium and selenium on the substrate; raising the temperature of the substrate to a second temperature, and co-evaporating copper and selenium on the substrate; keeping the temperature of the substrate at a second temperature, and co-evaporating indium, gallium and selenium on the substrate; and keeping the temperature of the substrate at the second temperature, and annealing the substrate in the selenium atmosphere to prepare the wide bandgap copper-gallium-selenium light absorption layer. The invention also provides a solar cell comprising the wide bandgap copper-gallium-selenium light absorption layer. Hair brushThe wide-bandgap copper-gallium-selenium light absorption layer can obtain a solar cell with higher efficiency on the basis of having a wide bandgap, and can be better suitable for a laminated solar cell.

Description

Wide-bandgap copper-gallium-selenium light absorption layer, preparation method thereof and solar cell
Technical Field
The invention belongs to the technical field of solar cells, and particularly relates to a wide-bandgap copper-gallium-selenium light absorption layer and a preparation method thereof, and a solar cell comprising the wide-bandgap copper-gallium-selenium light absorption layer.
Background
In recent years, with the rapid development of photovoltaic technology, the efficiency of various single-junction solar cells has gradually approached the theoretical limit of the efficiency of the system. Continuing to improve the efficiency of single junction cells through technological advances will become exceptionally difficult. The tandem solar cell can connect absorption layers matched with different spectral bands in series to increase the absorption width of the cell to the solar spectrum. Meanwhile, the absorption layers with different forbidden band widths of the laminated solar cell absorb photons with different energies, so that the thermal relaxation loss caused by the excess energy of high-energy photons exceeding the forbidden band width can be reduced, the optical energy is converted into electric energy to the maximum extent, and the photoelectric conversion efficiency is greatly improved.
The mainstream double-junction laminated cell in the laminated cell needs a bottom cell with a narrow forbidden band and a top cell with a wide forbidden band. However, top cell materials for wide bandgap are scarce. In order to match the bottom cell absorption layer material with narrow forbidden band width, such as p-type crystalline silicon with the forbidden band width of 1.1eV or p-type copper indium selenide with the forbidden band width of 1.0eV, the top cell material is required to be a p-type material with the forbidden band width of 1.6eV-1.7eV, and the expensive III-V group material is the only choice for a long time. The search for high-efficiency and low-cost p-type wide bandgap top cell materials is the key for the future development of the double-junction laminated cell.
The forbidden band width of CIGS (copper indium gallium selenide) can be flexibly regulated and controlled in the interval of 1.0-2.5 eV. At present, the CIGS solar cell with the highest efficiency has the forbidden band width of 1.15eV, and the corresponding Ga/Ga + In ratio is 0.3. To obtain higher forbidden bandwidth, the current mainstream international research direction is realized by cation and anion replacement. In the aspect of cation replacement, the content of Ga component is mainly increased to improve the absorption band gap of the CIGS material. CuInGaSe2If all In is replaced by Ga to form copper gallium selenium (CGSe), the forbidden bandwidth of the CGSe can reach 1.7 eV. However, several research unit experiments found that the efficiency of solar cells decreases with increasing Ga content.
Ordered defect reconstruction layers (ODC layers) exist on the surfaces and grain boundary surfaces of the traditional CIGS materials, and the structures have fixed lattice structures and energy band structures, so that the recombination probability of carriers on the grain boundary surfaces can be greatly reduced. The presence of a large amount of In such an ordered defect-reconstructed layerCuInversion defect, however, to obtain copper gallium selenium with high forbidden band width, CuInGaSe2In (b) is completely replaced by Ga, the ordered defect reconstruction layer as described above is difficult to form at the interface, electron-hole recombination at the surface and the crystal interface cannot be suppressed, and the cell efficiency is lowered.
Disclosure of Invention
In view of the defects in the prior art, the invention provides a wide-bandgap copper-gallium-selenium light absorption layer, a preparation method thereof and a solar cell, so as to solve the problem that the efficiency of the cell is reduced in order to obtain copper-gallium-selenium with high bandgap in the prior art.
In order to achieve the purpose, the invention adopts the following technical scheme:
a wide-bandgap CuGaSe light absorption layer comprises a CuGaSe thin film layer and an InGaN thin film layer covering the CuGaSe thin film layer, wherein an In is formed on the interface of the CuGaSe thin film layer and the InGaN thin film layer through an annealing processCuA flip defect.
Preferably, the atomic ratio of gallium to the sum of indium and gallium in the indium-gallium thin film layer is (0.3-0.7): 1.
preferably, the atomic ratio of gallium to the sum of indium and gallium in the indium-gallium thin film layer is (0.5-0.7): 1.
preferably, the wide bandgap copper gallium selenium light absorption layer has a thickness of 1.0 μm to 3.0 μm.
The invention also provides a preparation method of the wide bandgap copper-gallium-selenium light absorption layer, which comprises the following steps:
s10, heating the substrate to a first temperature, and co-evaporating gallium and selenium on the substrate;
s20, raising the temperature of the substrate to a second temperature, and co-evaporating copper and selenium on the substrate;
s30, keeping the temperature of the substrate at a second temperature, and co-evaporating indium, gallium and selenium on the substrate;
s40, keeping the temperature of the substrate at a second temperature, annealing the substrate in a selenium atmosphere, and preparing the wide bandgap copper-gallium-selenium light absorption layer on the substrate;
wherein, in the step S30, when the indium, the gallium and the selenium are co-evaporated, the atomic ratio of the gallium to the sum of the indium and the gallium is controlled to be (0.3-0.7): 1.
preferably, in step S30, when co-evaporating indium, gallium, and selenium, the atomic ratio of gallium to the sum of indium and gallium is controlled to be (0.5 to 0.7): 1.
preferably, the annealing time of the annealing treatment is 15min to 20 min.
Preferably, the first temperature is 340-380 ℃ and the second temperature is 500-600 ℃.
Preferably, the substrate includes a molybdenum metal layer, and when the step S10 co-evaporates gallium and selenium, the selenium vapor is firstly introduced to form a molybdenum selenide layer on the surface of the molybdenum metal layer, and then the gallium vapor is introduced to co-evaporate gallium and selenium on the molybdenum selenide layer.
The embodiment of the invention also provides a solar cell, which comprises the wide bandgap copper-gallium-selenium light absorption layer.
According to the wide-bandgap copper-gallium-selenium light absorption layer and the preparation method thereof provided by the embodiment of the invention, on the basis of the traditional process for preparing copper-indium-gallium-selenium by three-step co-evaporation, In is completely replaced by Ga during the first-step co-evaporation, so that a copper-gallium-selenium (CGSe) film is obtained after Cu is co-evaporated In the second step, and the forbidden bandwidth of the light absorption layer is increased; thirdly, co-evaporating and introducing In, covering an In-rich indium gallium thin film layer on the copper gallium selenium thin film layer, and then performing an annealing process to form In on the interface of the copper gallium selenium thin film layer and the indium gallium thin film layerCuThe inversion defect forms a reconstructed phase structure which is beneficial to charge separation and inhibits interface recombination on a crystal boundary surface, so that the obtained copper-gallium-selenium light absorption layer can obtain a solar cell with higher efficiency on the basis of having a wide forbidden band, and can be better suitable for a laminated solar cell.
Drawings
Fig. 1 is a schematic structural view of a thin film solar cell fabricated in an example of the present invention;
FIG. 2 is a flowchart illustrating a method for fabricating a wide bandgap CoSe light absorption layer according to an embodiment of the present invention;
FIG. 3 is a SEM cross-sectional view of a forbidden band Cu-Ga-Se light absorption layer prepared in an embodiment of the present invention;
fig. 4 is a voltammogram of a thin film solar cell prepared in an example of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, embodiments of the present invention are described in detail below with reference to the accompanying drawings. Examples of these preferred embodiments are illustrated in the accompanying drawings. The embodiments of the invention shown in the drawings and described in accordance with the drawings are exemplary only, and the invention is not limited to these embodiments.
It should be noted that, in order to avoid obscuring the present invention with unnecessary details, only the structures and/or processing steps closely related to the scheme according to the present invention are shown in the drawings, and other details not so relevant to the present invention are omitted.
The embodiment of the invention firstly provides a wide-bandgap copper-gallium-selenium light absorption layer, which comprises a copper-gallium-selenium thin film layer and an indium-gallium thin film layer covered on the copper-gallium-selenium thin film layer, wherein an In is formed on the interface of the copper-gallium-selenium thin film layer and the indium-gallium thin film layer through an annealing processCuThe inversion defect forms a reconstructed phase structure which is beneficial to charge separation and inhibits interface recombination on a grain boundary surface.
In a preferred embodiment, the atomic ratio of gallium to the sum of indium and gallium (Ga/Ga + In) In the indium-gallium thin film layer is (0.3-0.7): 1, more preferably (0.5 to 0.7): 1.
in a preferred embodiment, the wide bandgap copper-gallium-selenium light absorption layer has a thickness of 1.0 μm to 3.0 μm.
The embodiment of the invention also provides a preparation method of the wide bandgap copper-gallium-selenium light absorption layer, which comprises the following steps:
s10, heating the substrate to a first temperature, and co-evaporating gallium and selenium on the substrate.
And S20, raising the temperature of the substrate to a second temperature, and co-evaporating copper and selenium on the substrate.
And S30, keeping the temperature of the substrate at the second temperature, and co-evaporating indium, gallium and selenium on the substrate.
And S40, keeping the temperature of the substrate at the second temperature, annealing the substrate in a selenium atmosphere, and preparing the wide bandgap copper-gallium-selenium light absorption layer on the substrate.
Specifically, In step S30, when co-evaporating indium, gallium, and selenium, the atomic ratio of gallium to the sum of indium and gallium (Ga/Ga + In) is controlled to be (0.3 to 0.7): 1, more preferably (0.5 to 0.7): 1.
in a preferred embodiment, the annealing time of the annealing treatment is 15min to 20 min.
In a specific scheme, the first temperature is 340-380 ℃, and the second temperature is 500-600 ℃.
In a preferred embodiment, the substrate includes a molybdenum metal layer, and when co-evaporating gallium and selenium in step S10, firstly, selenium vapor is introduced to form a molybdenum selenide layer on the surface of the molybdenum metal layer, and then gallium vapor is introduced to co-evaporate gallium and selenium on the molybdenum selenide layer. The molybdenum metal layer is uniformly selenized, so that the copper-gallium-selenium light absorption layer prepared subsequently can be better combined on the molybdenum metal layer.
The embodiment of the invention also provides a solar cell, wherein the solar cell adopts the wide bandgap copper-gallium-selenium light absorption layer as the light absorption layer. Further, in a preferred aspect of the present invention, a tandem solar cell is further provided, where the tandem solar cell employs a solar cell including the wide bandgap copper-gallium-selenium light absorption layer provided in the embodiment of the present invention.
Based on the traditional process for preparing copper indium gallium selenide by three-step co-evaporation, In is completely replaced by Ga In the first step of co-evaporation, so that a copper gallium selenide (CGSe) film is obtained after Cu is co-evaporated In the second step, and the forbidden bandwidth of the light absorption layer is increased; thirdly, co-evaporating and introducing In, covering an In-rich indium gallium thin film layer on the copper gallium selenium thin film layer, and then performing an annealing process to form In on the interface of the copper gallium selenium thin film layer and the indium gallium thin film layerCuThe inversion defect forms a reconstructed phase structure which is beneficial to charge separation and inhibits interface recombination on a crystal boundary surface, so that the obtained copper-gallium-selenium light absorption layer can obtain a solar cell with higher efficiency on the basis of having a wide forbidden band, and can be better suitable for a laminated solar cell.
Example 1
The embodiment provides a thin film solar cell, wherein a light absorption layer in the thin film solar cell adopts the wide bandgap copper gallium selenium light absorption layer provided by the embodiment of the invention. The structure of the thin-film solar cell is shown in fig. 1, and with reference to fig. 1, the preparation process of the thin-film solar cell comprises the following steps:
step S1, providing a supporting substrate 1, and preparing and forming a bottom electrode layer 2 on the supporting substrate 1.
Specifically, a cleaned soda-lime glass substrate is taken as a supporting substrate 1, the supporting substrate is placed into a magnetron sputtering chamber, and a Mo bottom electrode layer 2 with the thickness of 500nm is sputtered and deposited by using a Mo target material.
Step S2 is to prepare a copper-gallium-selenium light absorption layer 3 on the bottom electrode layer 2.
Specifically, the copper-gallium-selenium light absorption layer 3 is a wide bandgap copper-gallium-selenium light absorption layer, and as shown in fig. 2, in this embodiment, a three-step co-evaporation method is adopted to prepare the wide bandgap copper-gallium-selenium thin film absorption layer, which includes the following steps:
s10, heating the substrate to a first temperature, and co-evaporating gallium and selenium on the substrate.
Namely, the first step of co-evaporation deposition specifically comprises the following steps: the substrate obtained in step S1 was heated to 360 ℃, the temperature of the Ga source was raised to the Ga vaporization temperature 965 ℃, so that Ga changed from the solid state to the gas state to Ga vapor, followed by incubation for 20 min. Opening a main valve of a Se source 1min in advance, introducing Se steam, opening the Se source furnace in advance to fully release Se in the furnace, and manually opening a main baffle plate 30s in advance to ensure that Se falls on a Mo metal layer to generate a layer of molybdenum selenide first so as to ensure that the Mo layer is uniformly selenized. Then opening a beam source furnace baffle plate of the Ga source, introducing Ga steam, and co-evaporating gallium and selenium on the Mo metal layer; as shown in FIG. 2, the time for vaporizing Ga and Se in this embodiment is 36 min.
And S20, raising the temperature of the substrate to a second temperature, and co-evaporating copper and selenium on the substrate.
Namely the second step of co-evaporation deposition, which specifically comprises the following steps: and closing the baffle of the beam source furnace of the gallium after the first-step deposition is finished. And raising the temperature of the Cu source to the evaporation temperature of 1200 ℃ of the Cu, so that the Cu is changed into a gas state from a solid state and is changed into Cu vapor, and introducing the Cu vapor into the furnace. And raising the temperature of the substrate from 360 ℃ to 600 ℃, and then maintaining the temperature of the substrate at 600 ℃ to deposit Cu to prepare and form the copper-gallium-selenium film. When the occurrence of 0.1 ℃ cooling point was observed during the deposition of Cu, the deposition of Cu was terminated. Namely, when the stoichiometric ratio of Cu to Ga reaches 1:1, continuing to evaporate copper, enabling selenium and copper to generate copper selenide, enabling the liquid-phase copper selenide to absorb heat to generate a transient cooling phenomenon, keeping the transient cooling phenomenon for about 6-10 s, and when the transient cooling phenomenon is observed, indicating that the growth of copper is finished, reducing the temperature of a copper source, closing the copper source and finishing the deposition of Cu. As shown in FIG. 2, the time for evaporating Cu and Se in this example is 18 min.
And S30, keeping the temperature of the substrate at the second temperature, and co-evaporating indium, gallium and selenium on the substrate.
The third step is co-evaporation and deposition: and closing the beam source furnace baffle of the copper after the second step of deposition is finished. And (3) respectively raising the temperature of the In source and the temperature of the Ga source to 820 ℃ of the evaporation temperature of In and 900 ℃ of the evaporation temperature of Ga, so that the In and the Ga are changed into gas from solid state to In vapor and Ga vapor, keeping the temperature of the substrate at 600 ℃, introducing the Ga vapor and the In vapor into the furnace, and co-evaporating the InGaSe thin film layer on the CuGaSe thin film layer. In this example, the ratio of Ga/Ga + In the third co-evaporation deposition is 0.5:1, and as shown In FIG. 2, the co-evaporation time is 14 min.
And S40, keeping the temperature of the substrate at the second temperature, annealing the substrate in a selenium atmosphere, and preparing the wide bandgap copper-gallium-selenium light absorption layer on the substrate.
Specifically, the temperature of the substrate is kept at 600 ℃, the substrate is annealed in the Se atmosphere, then the temperature of each source is reduced, when the temperature of the substrate is reduced to 300 ℃, the main baffle of the Se source is closed, and when the temperature of the substrate is reduced to below 200 ℃, the prepared and formed wide-bandgap copper-gallium-selenium light absorption layer can be taken out. As shown in FIG. 2, the annealing time was 15 min.
The whole process for preparing the wide band gap copper-gallium-selenium light absorption layer is carried out in a sufficient Se atmosphere, the evaporation temperature of Se in the whole process is 650-660 ℃, and solid Se can be changed into gaseous Se vapor at the temperature.
The SEM of the cross section of the wide bandgap cgsse light absorption layer prepared in the above manner is obtained as shown in fig. 3, and it is known that the microstructure of the cgsse light absorption layer obtained in this example is a large-area uniform polycrystalline thin film with a grain size of 200nm to 1 μm.
Step S3, referring to fig. 1, a cadmium sulfide buffer layer 4, a window layer 5, and a top electrode layer 6 are thus formed on the copper gallium selenium light absorption layer 3, and the thin film solar cell is obtained.
The specific preparation processes of the cadmium sulfide buffer layer 4, the window layer 5 and the top electrode layer 6 are carried out according to the prior art. For example, the cadmium sulfide buffer layer 4 may be deposited using a chemical water bath deposition process; the window layer 5 may be an Intrinsic Zinc Oxide (IZO) layer and an aluminum-doped zinc oxide (AZO) layer prepared using a magnetron sputtering process; the top electrode layer 6 may be a metal top electrode layer prepared using a magnetron sputtering process.
In this example, the thin film solar cell prepared in the above example was subjected to an electrical test, and fig. 4 is a current-voltage characteristic curve obtained by the test. From the voltammetry characteristics shown in FIG. 4, it can be calculated that the open-circuit voltage (Voc) of the thin-film solar cell prepared in the above example is 837mV and the short-circuit current (Isc) is 19.0mA/cm2The Fill Factor (FF) was 66.1% and the efficiency (Eff) was 10.5%, with good electrical properties.
In summary, based on the conventional three-step co-evaporation process for preparing copper-gallium-selenium, Ga is used to replace all In the first co-evaporation step, so that a copper-gallium-selenium (CGSe) thin film is obtained after Cu is co-evaporated In the second step, thereby increasing the forbidden bandwidth of the light absorption layer; thirdly, co-evaporating and introducing In, covering an In-rich indium gallium thin film layer on the copper gallium selenium thin film layer, and then performing an annealing process to form In on the interface of the copper gallium selenium thin film layer and the indium gallium thin film layerCuThe inversion defect forms a reconstruction phase structure which is beneficial to charge separation and inhibits interface recombination on a crystal boundary surface, ensures the forbidden bandwidth of the copper-gallium-selenium light absorption layer, ensures that the solar cell prepared by using the wide-forbidden-band copper-gallium-selenium light absorption layer has excellent efficiency, realizes the improvement of the efficiency of the wide-forbidden-band CGSe solar cell, and can be better suitable for being used in the CGSe solar cellAs the top cell of a tandem solar cell.
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 (10)

1. The wide-bandgap CuGaSe light absorption layer is characterized by comprising a CuGaSe thin film layer and an InGaN thin film layer covering the CuGaSe thin film layer, wherein In is formed on the interface of the CuGaSe thin film layer and the InGaN thin film layer through an annealing processCuA flip defect.
2. The wide bandgap copper-gallium-selenium light absorbing layer according to claim 1, wherein the atomic ratio of gallium to the sum of indium and gallium in the indium-gallium thin film layer is (0.3-0.7): 1.
3. the wide bandgap copper-gallium-selenium light absorbing layer according to claim 2, wherein the atomic ratio of gallium to the sum of indium and gallium in the indium-gallium thin film layer is (0.5-0.7): 1.
4. the wide bandgap copper gallium selenide light absorbing layer according to any one of claims 1 to 3, wherein the thickness of the wide bandgap copper gallium selenide light absorbing layer is 1.0 μm to 3.0 μm.
5. The method for preparing the wide bandgap copper gallium selenium light absorption layer according to any one of claims 1 to 4, comprising the steps of:
s10, heating the substrate to a first temperature, and co-evaporating gallium and selenium on the substrate;
s20, raising the temperature of the substrate to a second temperature, and co-evaporating copper and selenium on the substrate;
s30, keeping the temperature of the substrate at a second temperature, and co-evaporating indium, gallium and selenium on the substrate;
s40, keeping the temperature of the substrate at a second temperature, annealing the substrate in a selenium atmosphere, and preparing the wide bandgap copper-gallium-selenium light absorption layer on the substrate;
wherein, in the step S30, when the indium, the gallium and the selenium are co-evaporated, the atomic ratio of the gallium to the sum of the indium and the gallium is controlled to be (0.3-0.7): 1.
6. the method according to claim 5, wherein in step S30, the atomic ratio of gallium to the sum of indium and gallium is controlled to be (0.5 to 0.7): 1.
7. the production method according to claim 5, wherein the annealing time of the annealing treatment is 15 to 20 min.
8. The method of any one of claims 5-7, wherein the first temperature is 340 ℃ to 380 ℃ and the second temperature is 500 ℃ to 600 ℃.
9. The method as claimed in claim 8, wherein the substrate includes a molybdenum metal layer, and in the step S10, when co-evaporating gallium and selenium, the selenium vapor is introduced first to form a molybdenum selenide layer on the surface of the molybdenum metal layer, and then the gallium vapor is introduced to co-evaporate gallium and selenium on the molybdenum selenide layer.
10. A solar cell comprising the wide bandgap CuGaSe light absorption layer as claimed in any one of claims 1 to 4.
CN202111537336.8A 2021-12-15 2021-12-15 Wide-bandgap copper-gallium-selenium light absorption layer, preparation method thereof and solar cell Pending CN114203842A (en)

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