CN110875399B - Wide-spectrum absorption thin-film solar cell and photovoltaic power generation device - Google Patents
Wide-spectrum absorption thin-film solar cell and photovoltaic power generation device Download PDFInfo
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- 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
- H01L31/02—Details
- H01L31/0236—Special surface textures
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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
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- H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
- H01L31/022441—Electrode arrangements specially adapted for back-contact solar cells
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- H—ELECTRICITY
- H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
- H02S—GENERATION OF ELECTRIC POWER BY CONVERSION OF INFRARED RADIATION, VISIBLE LIGHT OR ULTRAVIOLET LIGHT, e.g. USING PHOTOVOLTAIC [PV] MODULES
- H02S40/00—Components or accessories in combination with PV modules, not provided for in groups H02S10/00 - H02S30/00
- H02S40/30—Electrical components
- H02S40/36—Electrical components characterised by special electrical interconnection means between two or more PV modules, e.g. electrical module-to-module connection
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
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Abstract
The invention relates to a thin film solar cell with wide spectrum absorption and a photovoltaic power generation device; the thin-film solar cell comprises a front electrode layer, a light absorption layer, a back electrode layer and a substrate layer, wherein micro-nanospheres made of non-metallic materials are dispersedly distributed on the surface of the front electrode layer away from the light absorption layer, and the radius of the micro-nanospheres is 15nm-150 nm; micro-nano hemispheres made of metal materials are dispersedly distributed in the back electrode layer, the radius of each micro-nano hemisphere is 25nm-250nm, and the distance between each micro-nano hemisphere and the light absorption layer is 10nm-100 nm. The photovoltaic power generation device comprises a solar cell module, a controller, a storage battery pack and a direct current-alternating current inverter, wherein the solar cell module comprises a plurality of thin film solar cells which are electrically connected. The invention adopts a composite light trapping structure, simultaneously realizes the absorption enhancement of short wave band and long wave band, and can obviously improve the photoelectric conversion efficiency of the thin-film solar cell and the photovoltaic power generation device.
Description
Technical Field
The invention relates to a photovoltaic power generation device, in particular to a thin film solar cell in the photovoltaic power generation device.
Background
Photovoltaic power generation devices convert absorbed light energy into electric energy by using the photovoltaic effect of solar cells, and are one of the most promising new energy sources. The light absorption efficiency of the solar cell is an important factor influencing the performance of the photovoltaic power generation device, most of absorption materials of the traditional solar cell are crystalline silicon, but the requirement on the purity of the silicon is extremely high, the processing technology is complex, so that the use cost of the crystalline silicon is high, and the absorption coefficient of the crystalline silicon is relatively low, so that the thickness of the commercial crystalline silicon solar cell is about 300 mu m generally, the large thickness causes the large consumption of materials, and the solar cell is also a main factor limiting the application of the crystalline silicon solar cell.
Compared with the traditional solar cell, the thin-film solar cell has the advantages that the thickness is remarkably reduced, and the use of materials is greatly saved. Due to the drastic reduction in thickness, thin film solar cells need to select materials with higher absorption coefficients. The method is characterized in that a light trapping structure with a micro-nano scale is arranged in a thin-film solar cell, and the positions of the micro-nano light trapping structure in the existing research are roughly divided into three types: (1) the solar cell is placed on the upper surface of the solar cell, and the mechanism of regulating and controlling the spectrum is to increase the scattering effect so that more light enters the absorption layer; (2) the structure is placed in the middle of a light absorption layer (namely a semiconductor material), and the mechanism of regulating the spectrum of the structure is that the near-field effect can increase the generation of electron-hole pairs; (3) the back structure is placed on the back of the solar cell, because the thickness required by the absorption of light is gradually increased along with the increase of the wavelength, but the thickness of the ultrathin solar cell cannot reach the required absorption optical path, the back structure improves the reflection of a long-wave band by a mechanism of increasing the reflection to regulate the spectrum. However, a single light trapping structure often only has an effect of improving the absorption efficiency of some bands, does not have an enhancement effect on the absorption of other bands, and even has a negative effect.
As an example of the prior art using a single light trapping structure, the application of silver nanoparticle plasma to amorphous silicon thin film solar cells (dao national peng, master academic thesis of shanxi university, 2016) discloses the application of silver nanoparticles to the back electrode of amorphous silicon thin film solar cells to enhance the efficiency of amorphous silicon thin film solar cells. The method comprises the steps of annealing a silver nano film in a nitrogen atmosphere to prepare silver nano particles, changing the size and the shape (ellipse/rod/sphere) of the silver nano particles by adjusting the annealing temperature, researching the influence of the annealing temperature on the light absorptivity and the battery efficiency, and only realizing the absorption enhancement in a long-wave band range.
Chinese patent document CN103094368A discloses a solar cell (non-thin film solar cell) comprising a substrate, and a reflective electrode layer, a light absorbing layer and a transparent electrode layer sequentially laminated on the substrate, the reflective electrode layer having therein metal nanoparticles spaced apart from the light absorbing layer, and each layer except the substrate having a rough surface; the metal nanoparticles in the reflective electrode layer enhance the absorption of the solar cell in the long wavelength band and the solar cell exhibits an extremely high light absorption efficiency, but the improvement of the light absorption efficiency is mainly due to the surface roughness of the layers, particularly the transparent electrode layer, and the formation of the surface roughness means a significant increase in the thickness of the layer, so that the structure is difficult to apply to the thin-film solar cell with strict requirements on the thickness.
There are also disclosures of using dual light trapping structures. For example, chinese patent document CN104064607A discloses a thin film silicon solar cell dual light trapping structure with anodic aluminum oxide nano-gratings on both the surface and the bottom; chinese patent document CN103811589A discloses a light trapping structure on the front and back surfaces of a semiconductor thin film solar cell, which includes a grating formed on the front surface of a light absorbing layer and a double-layer metal nanosphere on the back surface. The influence of diffraction gratings formed on the front and rear surfaces of the light absorption layer of a thin-film solar cell on light absorption was studied by Xianqin Meng et al (Xianqin Meng, et al, Combined front and back diffraction gratings for broadband light tracking in thin film solar cell,OPTICS EXPRESSseptember 2012, Vol. 20, number S5/A560-571). Although the light absorption can be enhanced by adopting the grating light trapping structure, the outstanding problems exist in that the grating is in surface contact with the absorption layer, so that the recombination probability of electron-hole pairs is remarkably increased, and the improvement of the cell efficiency is actually very limited.
Chinese patent document CN102646745A discloses a photovoltaic device and a solar cell including the same, the photovoltaic device includes three regions of a transparent electrode region, a window region and an absorption region, wherein such a dual light trapping structure is adopted: forming micro-nano spheres and/or nano wires on the light incident surface of the transparent electrode area and the back surface of the absorption area; the nano wire and the micro-nano ball are made of metal, nonmetal or composite material of metal and nonmetal. From the optical perspective, the micro-nano sphere on the back of the light incident surface and the back of the absorption region may play a certain role in improving the absorption spectrum, but in actual application, the micro-nano sphere is in direct contact with the absorption region, so that the recombination probability of the electron-hole pair is greatly increased, and the photoelectric conversion efficiency of the solar cell is seriously influenced. And the micro-nano structure that this patent provided is in order to arouse surface plasmon to increase the absorption of light, nevertheless because the absorption promotion that surface plasmon arouses and leads to mainly concentrate on micro-nano structure in, can not form the promotion of absorption layer effective absorption, it is very limited to final photoelectric conversion efficiency promotion effect.
The dual light trapping structure generally has better light absorption efficiency than the single light trapping structure, but the need to improve the light absorption efficiency well does not mean to simply superimpose two light trapping structures, because such simple superimposition is likely to cause a new series of problems, such as increased absorption in the long wavelength band accompanied by relative degradation in the absorption in other wavelength bands, while the prior art does not systematically disclose how to achieve effective matching between two light trapping structures. On the other hand, the increase in optical absorption is divided into an increase in effective absorption in the absorption region and an increase in ineffective absorption in the non-absorption region, and must be strictly defined. Moreover, in order to realize the final improvement of the photoelectric conversion efficiency, the introduction of the micro-nano structure can not damage the electrical characteristics of the original battery structure while improving the optical absorption, for example, the introduction of the micro-nano structure can greatly increase the electrode contact surface or new defects, so that the electron-hole recombination efficiency is greatly improved, and the photoelectric conversion efficiency is further reduced. The inventor carries out intensive research aiming at improving the effective absorption of the thin-film solar cell at the short wave band and the long wave band simultaneously under the condition of not influencing the electrical property of the cell, and further provides the invention.
Disclosure of Invention
The invention mainly aims to provide a thin-film solar cell with higher photoelectric conversion efficiency and a photovoltaic power generation device adopting the thin-film solar cell, wherein the double light trapping structures in the thin-film solar cell are well matched by integrally regulating and controlling the respective material, appearance, size and position of the double light trapping structures, and meanwhile, the effective absorption of short wave bands and long wave bands is enhanced, so that the higher photoelectric conversion efficiency is achieved.
In order to achieve the above main object, a first aspect of the present invention provides a broad spectrum absorption thin film solar cell, comprising a front electrode layer, a light absorbing layer, a back electrode layer and a substrate layer; wherein, the surface of the front electrode layer far from the light absorption layer is dispersed and distributed with micro-nano spheres made of non-metallic materials, and the radius of the micro-nano spheres is 15nm-150 nm; micro-nano hemispheres made of metal materials are dispersedly distributed in the back electrode layer, the radius of each micro-nano hemisphere is 25nm-250nm, and the distance between each micro-nano hemisphere and the light absorption layer is 10nm-100 nm.
According to a specific embodiment of the present invention, the nonmetal is one or more selected from the group consisting of silicon dioxide, titanium dioxide, silicon nitride, lithium fluoride, magnesium fluoride, and zinc oxide. That is to say, the surface of the front electrode layer away from the light absorption layer may be dispersedly distributed with non-metallic micro-nanospheres made of a single material, or may be dispersedly distributed with non-metallic micro-nanospheres made of a plurality of different materials.
According to a specific embodiment of the present invention, the metal is one or more selected from the group consisting of aluminum, silver and gold. That is to say, the back electrode layer can be internally provided with metal micro-nano hemispheres which are dispersedly distributed with a single material, and also can be internally provided with metal micro-nano hemispheres which are dispersedly distributed with a plurality of different materials.
In a preferred embodiment of the invention, the non-metal is silicon dioxide or silicon nitride and the metal is silver. The inventors have intensively studied and found that the combination of the silicon dioxide or silicon nitride micro/nanospheres and the light trapping structure of the silver nanospheres has relatively better effect in improving the light absorption and photoelectric conversion efficiency.
Preferably, the radius of the micro-nano sphere is 40nm to 90 nm.
Preferably, the radius of the micro-nano hemisphere is 80nm-120 nm.
Preferably, the radius of the micro-nano sphere is smaller than that of the micro-nano hemisphere.
In the embodiment of the invention, the distance between the micro-nano spheres can be 30nm-500nm, and the distance between the micro-nano hemispheres can be 10nm-400 nm. So set up, neither can influence the normal absorption of sunlight, can reach better light trapping effect again.
Preferably, the distance between the micro-nano spheres is 50nm-200nm, and the distance between the micro-nano hemispheres is 30nm-100 nm.
In order to achieve the above main object, a second aspect of the present invention provides a photovoltaic power generation apparatus, which includes a solar cell module, a controller, a battery pack, and a dc-ac inverter, wherein the solar cell module includes a plurality of any one of the above thin film solar cells, and the thin film solar cells are electrically connected to each other by a wire.
In the invention, the non-metal micro-nanospheres serving as light trapping structures are dispersedly distributed on the surface of the front electrode layer away from the light absorption layer, and the radius of the non-metal micro-nanospheres is 15nm-150nm, so that the light absorption at a short wave band is promoted; and metal micro-nano hemispheres which are also used as light trapping structures are dispersedly distributed in the back electrode layer, and the radius of each metal micro-nano hemisphere is 25nm-250nm, so that light absorption in a long wave band is promoted. The dual light trapping structures are mutually matched, so that the absorption enhancement of a short wave band and a long wave band can be realized simultaneously; in addition, the double light trapping structures are not in contact with the light absorbing layer, the electrical characteristics of the battery are not damaged, and the defect that the recombination probability of electron-hole pairs is increased due to the contact of the light trapping structures and the light absorbing layer in the prior art is overcome. Therefore, the invention can obviously improve the photoelectric conversion efficiency of the thin-film solar cell and the photovoltaic power generation device. In addition, the thin-film solar cell has all structures required by commercial solar cells, and the light trapping structure has mature technical processing and manufacturing, so that large-scale industrial production is realized conveniently.
To more clearly illustrate the objects, technical solutions and advantages of the present invention, the present invention will be further described in detail with reference to the accompanying drawings and detailed description.
Drawings
FIG. 1 is a block diagram of a photovoltaic power generation apparatus according to an embodiment of the present invention;
FIG. 2 is a schematic perspective view of an embodiment of a thin film solar cell of the present invention;
FIG. 3 is a schematic side view of an embodiment of a thin film solar cell of the present invention;
fig. 4a shows the absorption spectrum of the thin-film solar cell when micro-nanospheres made of different non-metallic materials are arranged on the surface of the front electrode layer;
fig. 4b shows the absorption spectrum of the thin-film solar cell when micro-nanospheres of different metal materials are arranged on the surface of the front electrode layer;
FIGS. 5a and 5b show absorption spectra of a thin-film solar cell when silica micro-nanospheres with different radii are arranged on the surface of a front electrode layer;
fig. 6 shows absorption spectrograms of the thin-film solar cell when micro-nano spheres of different materials and silver micro-nano hemispheres are arranged in the back electrode layer;
fig. 7 shows absorption spectrograms of the thin film solar cell when silver micro-nano hemispheres with different radii are arranged inside the back electrode layer;
FIG. 8 shows the combination of light trapping structures and the corresponding short-circuit current density enhancement ratio of thin-film solar cells of embodiments 1-6 of the present invention;
fig. 9a shows a light absorption spectrum of the thin film solar cell when the surface of the front electrode layer is provided with the silica micro-nano spheres and the inside of the back electrode layer is provided with the micro-nano hemispheres made of different metal materials;
fig. 9b shows a light absorption spectrum of the thin-film solar cell when the silicon nitride micro-nano spheres are arranged on the surface of the front electrode layer and the micro-nano hemispheres made of different metal materials are arranged in the back electrode layer;
fig. 10 shows a light absorption spectrum of the thin-film solar cell when the silicon dioxide micro-nanospheres are arranged on the surface of the front electrode layer, the silver micro-nano hemispheres are arranged in the back electrode layer, and the silicon dioxide micro-nanospheres are arranged on the surface of the front electrode layer and the silver micro-nano hemispheres are arranged in the back electrode layer;
fig. 11 shows a short-circuit current density-voltage curve of the thin-film solar cell when the silicon dioxide micro-nano spheres are arranged on the surface of the front electrode layer and the silver micro-nano hemispheres are arranged in the back electrode layer.
In the absorption spectrogram, the abscissa represents the Wavelength (Wavelength) and the ordinate represents the absorption (Aborption); in the Short-circuit current density-Voltage graph, the abscissa represents Voltage (Voltage) and the ordinate represents Short-circuit current density (Short-circuit current density).
Detailed Description
Photovoltaic Power Generation apparatus embodiments
Fig. 1 is a block diagram of a photovoltaic power generation apparatus according to an embodiment of the present invention. Referring to fig. 1, the photovoltaic power generation apparatus includes a solar cell array 10, a controller 20, a storage battery 30, and a dc-ac inverter 40; the solar cell array 10 is formed by connecting a plurality of solar cell modules 11 (only one is shown in fig. 1) in series and in parallel, and the plurality of solar cell modules 11 are connected in series to generate a desired voltage and connected in parallel to generate a desired current. The battery pack 30 is used for storing electric energy generated by the solar cell array 10, and the dc-ac inverter 40 converts the dc power stored in the battery pack 30 into ac power and outputs the ac power to the ac load 50. In addition, the electric energy generated by the solar cell array 10 may be directly output to the dc load 60.
The solar cell module 11 further includes a plurality of thin film solar cells (single cells) 12, and the thin film solar cells 12 are electrically connected to each other by a wire. The solar cell module 11 shown in fig. 1 includes 36 thin film solar cells 12, but the invention is not limited thereto, and for example, the solar cell module 11 may include 40 thin film solar cells 12.
Thin film solar cell embodiments
Fig. 2 and 3 schematically depict the structure of an embodiment of the thin film solar cell 12 of the present invention. It should be noted that, for clearly illustrating the structure to be expressed, the different structural parts in fig. 2 and 3 may not be drawn to the same scale, and therefore, unless explicitly stated otherwise, the content expressed in fig. 2 and 3 does not constitute a limitation on the size and scale relationship of the parts of the thin-film solar cell 12.
Referring to fig. 2 and 3, an embodiment of the thin film solar cell 12 includes a front electrode layer 121, a light absorbing layer 122, a back electrode layer 123, and a substrate layer 124. Micro-nano spheres 125 made of a non-metal material are dispersedly distributed on the surface of the front electrode layer 121 far away from the light absorption layer 122, and micro-nano hemispheres 126 made of a metal material are dispersedly distributed inside the back electrode layer 123.
The front electrode layer 121 is a transparent conductive oxide layer for collecting electrons and conducting electricity, and has a transparent and conductive characteristic. The material of the front electrode layer 121 may be, for example, AZO (Al: ZnO, aluminum-doped zinc oxide) and ITO (tin-doped indium oxide). The thickness of the front electrode layer 121 is preferably 70nm to 120nm, for example, about 100nm, from the viewpoint of reducing reflection of light, but the present invention is not limited thereto.
The material of the light absorption layer 122 is, for example, amorphous silicon, gallium arsenide, copper indium gallium selenide, or perovskite, which all have the characteristic of high light absorption coefficient, and only a few hundred nanometers of thickness is needed to realize the absorption of most visible light. In a specific embodiment of the present invention, the light absorbing layer is composed of a pin junction, the P layer is formed by doping intrinsic silicon with B (boron) element, the i layer is silicon not doped with any element, and the n layer is formed by doping intrinsic silicon with P (phosphorus) element. The p-n junction is used for forming a built-in electric field, so that electron-hole pairs generated in the intrinsic layer move towards the two poles and are collected by the electrode layers at the two ends.
The back electrode layer 123 is a transparent conductive oxide layer for collecting holes, and may also be made of, for example, AZO and ITO. The primary function of the base layer 124 is to increase the reflection of light incident on the back of the thin film solar cell and reduce the transmission of light; the base layer 124 is preferably made of a metal material having a high reflection coefficient, such as gold, silver, aluminum, or copper.
The micro-nano spheres 125 dispersedly distributed on the surface of the front electrode layer 121 far away from the light absorption layer 122 are used as a light trapping structure for increasing the light absorption of the thin film solar cell in a short wave band (380 nm-500 nm). The material of the micro-nano spheres 125 may be, for example, silicon nitride, silicon dioxide, titanium dioxide, zinc oxide, lithium fluoride, magnesium fluoride, etc., with silicon dioxide and silicon nitride being particularly preferred.
The inventor of the invention intensively researches and discovers that the micro-nano sphere made of the nonmetal material has a better effect than the micro-nano sphere made of the metal material in the aspect of improving the short-wave-band absorption of the thin-film solar cell. FIG. 4a shows that silicon nitride (Si) is respectively provided on the surfaces of the front electrode layers 1213N4) Silicon dioxide (SiO)2) And titanium dioxide (TiO)2) Absorption spectrum of micro-nano sphere and non-light-trapping structure (w/optical), and FIG. 4b shows that the front electrode layer 121 is respectively provided with a light-trapping layer on the surfaceWhen the micro-nanospheres made of silicon nitride, silicon dioxide and titanium dioxide are adopted, the thin-film solar cell has stronger absorption in short wave bands on the whole, and the silicon dioxide micro-nanospheres have the best effect.
The geometrical dimensions of the micro-nanospheres 125 also have a significant effect on the absorption spectrum. Radius R of the micro-nanosphere 1251(see fig. 3) should not be too large or too small, which would not only make it difficult to process but also reduce reflection and increase scattering, and too large which would block sunlight and affect absorption by light absorbing layer 122. In the embodiment of the present invention, the radius of the micro/nanosphere 125 may be 15nm to 150nm, preferably 30nm to 120nm, and more preferably 40nm to 90 nm. Fig. 5a and 5b show absorption spectra of thin film solar cells using silica micro-nanospheres with different radii r (in nm) and without light trapping structure (w/o particle), and it can be seen from fig. 5a and 5b that the silica micro-nanospheres with radii of 40nm-90nm can significantly improve the short wave absorption of the thin film solar cells, and most preferred is the silica micro-nanosphere with radius of 70 nm.
The spacing between the micro-nanospheres 125 (i.e., the separation distance between adjacent micro-nanospheres 125) also affects the absorption effect. Specifically, if the distance between the micro-nano spheres 125 is too large, the micro-nano spheres are too dispersed, and the best light trapping effect is not achieved, and if the distance is too small, the normal absorption of the solar cell is easily affected. In the embodiment of the present invention, the distance between the micro-nano spheres 125 may be 30nm to 500nm, preferably 50nm to 300nm, and more preferably 50nm to 200 nm. The micro-nanospheres 125 can be in a periodic or aperiodic dispersed distribution.
The micro-nano hemisphere 126 which is dispersedly distributed in the back electrode layer 123 serves as a light trapping structure, and the main functions of the light trapping structure include exciting surface plasma resonance and increasing reflection of a long wave band, so that absorption of the thin film solar cell in the long wave band (570 nm-780 nm) is enhanced. The micro-nano hemisphere 126 is in surface contact with the substrate layer 124, and has a distance with the light absorption layer 122. In the embodiment of the present invention, the distance between the micro-nano hemisphere 126 and the light absorption layer 122 may be 10nm to 100nm, preferably 10nm to 60nm, and more preferably 10nm to 30 nm.
The material of the micro-nano hemisphere 126 can be, for example, aluminum, silver, and gold, wherein silver is particularly preferred. FIG. 6 shows that silver (Ag), aluminum (Al), gold (Au), and silicon dioxide (SiO) are respectively disposed inside the back electrode layer 1262) Silicon nitride (Si)3N4) And titanium dioxide (TiO)2) The absorption spectra of the micro-nanospheres and the non-light-trapping structure (w/o particle) show that the silver and gold micro-nanospheres disposed inside the back electrode layer 126 have better effect than the silicon nitride, silicon dioxide and titanium dioxide micro-nanospheres, and the silver nanospheres disposed inside the back electrode layer 126 have relatively best effect in promoting the long-wave absorption.
Fig. 6 also shows a light absorption spectrum when silver micro-nano-spheres (Ag (Hemisphere) are disposed inside the back electrode layer 126, and it can be seen from comparison of absorption spectra when silver micro-nano-spheres (Ag) are disposed inside the back electrode layer 126 and silver micro-nano-spheres (Ag (Hemisphere)) are disposed, and the silver micro-nano-spheres disposed inside the back electrode layer 126 have a significantly higher long-wave absorption than the silver micro-nano-spheres. Specifically, fig. 6 shows that the aluminum micro-nano spheres (Al) disposed inside the back electrode layer 126 have no effect on promoting the long-wave absorption, but fig. 9a and 9b (described in detail later) show that the aluminum micro-nano spheres (Al) disposed inside the back electrode layer 126 have a significant effect on promoting the long-wave absorption. It can be seen that the geometry of the light trapping structure inside the back electrode layer 126 is critical to promote the effect of long-wave absorption.
The influence of the geometric dimension of the micro-nano hemisphere 126 on long-wave absorption is also large. In the embodiment of the invention, the radius R of the micro-nano hemisphere 1262(see FIG. 3) is 25nm to 250nm, preferably 50nm to 180nm, more preferably 80nm to 120 nm. Fig. 7 shows an absorption spectrum of the thin film solar cell when silver micro-nano hemispheres with different radii r and a light trapping free structure (w/o particle) are arranged in the back electrode layer 123, as can be seen from fig. 7, a radius of r is arranged in the back electrode layer 123The silver micro-nano hemisphere with the radius of 110nm can effectively improve the long wave absorption of the thin-film solar cell by 80-120 nm, and the silver micro-nano hemisphere with the radius of 110nm is the best. The micro-nano hemisphere 126 may have a radius larger than that of the micro-nano sphere 125 to facilitate processing, since a factor of blocking light is not considered.
The nanosphere hemispheres 126 can also be dispersed in a periodic or aperiodic distribution. The absorption effect is also affected by the distance between the micro-nano hemispheres 126 (i.e., the spacing distance between adjacent micro-nano hemispheres 126). In the embodiment of the present invention, the distance between the micro-nano hemispheres 126 may be 10nm to 400nm, preferably 30nm to 250nm, and more preferably 30nm to 100 nm. The spacing between the micro-nano hemispheres 126 may be smaller than the spacing between the micro-nano spheres 125.
Thin film solar cell embodiments 1-6
In embodiments 1-6 of the present invention, the micro-nanospheres 125 with a radius of 70nm are distributed in a two-dimensional periodic array on the surface of the front electrode layer 121 away from the light absorbing layer 122, and the periodic distance A is1250nm (corresponding to a spacing of 110nm between the micro-nanospheres 125); the micro-nano hemispheres 126 with the radius of 110nm are distributed in a two-dimensional periodic array in the back electrode layer 123, and the periodic interval A is2Is 250nm (corresponding to the distance between the micro-nano hemispheres 126 being 30 nm).
In the embodiments 1 to 6 of the present invention, light trapping structure combinations of micro-nano spheres 125 and micro-nano hemispheres 126 made of different materials are respectively adopted, as shown in fig. 8. Fig. 9a shows the absorption spectra of the thin film solar cell in the light trapping structure combination of embodiments 1-3 and without the light trapping structure (w/o particle), and fig. 9b shows the absorption spectra of the thin film solar cell in the light trapping structure combination of embodiments 4-6 and without the light trapping structure. As is clear from fig. 9a and 9b, each of the embodiments 1 to 6 of the present invention can achieve the light absorption enhancement of both the short wavelength band and the long wavelength band.
FIG. 10 shows a light trapping free structure (w/o particle), a silicon dioxide micro-nano Sphere (SiO) with a radius of 70nm is arranged on the surface of the front electrode layer2) The back electrode layer is internally provided with a radius of 110nm silver micro-nano Hemisphere (Ag (Hemisphere)), and specific example 1 (SiO)2Absorption spectrum of thin-film solar cell under + Ag (Hemisphere)). As can be seen from fig. 10, the silver micro-nano hemisphere disposed inside the back electrode layer does not substantially enhance the absorption of the degraded silica micro-nano sphere to the short wavelength band, and the silica micro-nano sphere disposed on the surface of the front electrode layer also does not substantially enhance the absorption of the degraded silver micro-nano sphere to the long wavelength band. In other words, the metal micro-nano hemisphere in the back electrode layer and the non-metal micro-nano sphere on the surface of the front electrode layer can be well matched, and meanwhile, the effective absorption of the short wave band and the long wave band is enhanced, so that the high photoelectric conversion efficiency is achieved.
The simulation results (see fig. 8) show that: compared with the thin-film solar cell without the light trapping structure, the short-circuit current density is improved by 21% when the light trapping structures of embodiment 1 are combined, the short-circuit current density is improved by 20% when the light trapping structures of embodiment 4 are combined, the short-circuit current density is improved by 15% when the light trapping structures of embodiments 2 and 5 are combined, and the short-circuit current density is improved by 12% when the light trapping structures of embodiments 3 and 6 are combined.
A great deal of research has been carried out on placing the spheres in the light absorption layer to prove that the absorption of the whole cell is improved, but the light trapping structure in the light absorption layer occupies a great deal of the volume of the light absorption layer, so that the generation of electrons and holes is inevitably reduced, and the micro-nano structure in the light absorption layer also generates a great deal of parasitic absorption. So, even though we see that the absorption of the overall structure does increase, the absorption in the light absorbing material may not increase much. In the past, when the absorption spectrum of the solar cell is calculated, the absorptivity of the solar cell is mostly calculated in a mode of 1-T (reflectivity) -R (transmissivity), the method can only calculate the absorptivity of the whole solar cell structure during calculation, and how much absorption occurs in an absorption material cannot be judged.
The invention uses a new calculation model to separately calculate the absorption spectrum of the whole cell, and only uses the effective spectrum absorption part, namely the part absorbed by the light absorption material to measure whether the designed structure can improve the photoelectric conversion efficiency of the solar cell. Specifically, the solar cell absorption rate is calculated by using a solar _ generation analysis group in the scientific FDTD software, and the absorption rate of a specific material or a specific area can be well calculated by the analysis group. By the calculation method, the effect of the light trapping structure is measured only by the absorption rate in the amorphous silicon absorption layer, and the absorbed photons can be converted into electron-hole pairs.
Fig. 11 shows a comparison of short-circuit current density-voltage curves of the light trapping structure combination and the light trapping structure without (w/o particle) of embodiment 1, and it can be seen that the short-circuit current density of embodiment 1 is significantly improved. The photoelectric conversion efficiency can be calculated and improved by 18 percent according to the calculation model of the invention.
The simulation method adopted in the invention is a time domain finite difference method (FDTD), and commercial software Lumerical FDTD can obtain the absorption spectrum of the solar cell at each wavelength by solving Maxwell equation of three-dimensional space and time domain by using the time domain finite difference method. The material optical constants of amorphous silicon in the simulation were taken from the Palik database, and other material constants included in the structure were selected from PV light source. The boundary condition of the light source direction is PML, and the boundary condition of the X and Y directions is a periodic boundary condition. In order to obtain the photoelectric conversion efficiency, the material surface recombination effect needs to be considered, the auger recombination and radiation recombination effects are mainly considered in the amorphous silicon in the simulation, and the carrier surface recombination speed of the amorphous silicon light absorption layer, the AZO back electrode layer and the ITO front electrode layer is assumed to be 1000 cm/s.
Although the invention has been described with reference to specific embodiments, it will be appreciated by those skilled in the art that equivalent modifications made in accordance with the present invention are intended to be included within the scope of the present invention without departing from the scope thereof.
Claims (10)
1. A thin film solar cell with wide spectrum absorption comprises a front electrode layer, a light absorption layer, a back electrode layer and a substrate layer; the method is characterized in that: micro-nanospheres made of non-metallic materials are dispersedly distributed on the surface of the front electrode layer, which is far away from the light absorption layer, and the radius of each micro-nanosphere is 15-150 nm; micro-nano hemispheres made of metal materials are dispersedly distributed in the back electrode layer, the radius of each micro-nano hemisphere is 25nm-250nm, and the distance between each micro-nano hemisphere and the light absorption layer is 10nm-100 nm; and flat surface contacts are formed between the front electrode layer and the light absorption layer and between the back electrode layer and the light absorption layer.
2. The broad spectrum absorbing thin film solar cell of claim 1, wherein: the nonmetal is one or more selected from silicon nitride, silicon dioxide, titanium dioxide, lithium fluoride, magnesium fluoride and zinc oxide.
3. The broad spectrum absorbing thin film solar cell of claim 1, wherein: the metal is one or more selected from aluminum, silver and gold.
4. The broad spectrum absorbing thin film solar cell of claim 1, wherein: the nonmetal is silicon dioxide or silicon nitride, and the metal is silver.
5. The broad spectrum absorbing thin film solar cell of claim 1, wherein: the radius of the micro-nano sphere is 40nm-90 nm.
6. The broad spectrum absorbing thin film solar cell of claim 1, wherein: the radius of the micro-nano hemisphere is 80nm-120 nm.
7. The broad spectrum absorbing thin film solar cell of claim 1, wherein: the radius of the micro-nano hemisphere is larger than that of the micro-nano sphere.
8. The broad spectrum absorbing thin film solar cell of claim 1, wherein: the space between the micro-nano spheres is 30nm-500nm, and the space between the micro-nano hemispheres is 10nm-400 nm.
9. The broad spectrum absorbing thin film solar cell of claim 8, wherein: the distance between the micro-nano spheres is 50nm-200nm, and the distance between the micro-nano hemispheres is 30nm-100 nm.
10. A photovoltaic power generation device comprises a solar cell module, a controller, a storage battery pack and a direct current-alternating current inverter, and is characterized in that: the solar cell module comprises a plurality of thin film solar cells according to any one of claims 1 to 9, which are electrically connected to each other by a wire.
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