CN115084290A - Polycrystalline selenium film, preparation method thereof and solar cell - Google Patents
Polycrystalline selenium film, preparation method thereof and solar cell Download PDFInfo
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- 239000011669 selenium Substances 0.000 title claims abstract description 176
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- 229910052711 selenium Inorganic materials 0.000 title claims abstract description 159
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
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- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
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- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
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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
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/0272—Selenium or tellurium
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- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/042—PV modules or arrays of single PV cells
- H01L31/0445—PV modules or arrays of single PV cells including thin film solar cells, e.g. single thin film a-Si, CIS or CdTe solar cells
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Abstract
The invention relates to a polycrystalline selenium film, wherein an XRD diffraction pattern of the polycrystalline selenium film has characteristic peaks at the following 2 theta: 23.5 degrees +/-0.3 degrees, 29.7 degrees +/-0.3 degrees, 41.3 degrees +/-0.3 degrees, 45.3 degrees +/-0.3 degrees, 51.7 degrees +/-0.3 degrees, 61.2 degrees +/-0.3 degrees, 61.6 degrees +/-0.3 degrees, 65.2 degrees +/-0.3 degrees and 68.2 degrees +/-0.3 degrees; and the fit forbidden band width of the polycrystalline selenium film is 1.7-1.8 eV. The invention also provides a polycrystalline selenium film and a preparation method thereof, which adopts a blade coating-based melting method, does not need complex large-scale equipment and a large amount of solvents by regulating and controlling the melting working temperature, solves the problems of high equipment requirement, high preparation cost and low material utilization rate at present, and is a method expected to industrially produce the polycrystalline selenium film.
Description
Technical Field
The invention belongs to the field of photoelectric material and thin-film solar cell preparation, and particularly relates to a polycrystalline selenium thin film, a preparation method thereof and a solar cell.
Background
A solar cell is a device for converting solar energy into electric energy, which can efficiently use the solar energy, wherein a thin film solar cell is more widely spotlighted because of its excellent performance. At present, most of light absorption materials of mainstream thin-film solar cells contain rare metal elements or toxic elements, or have the problems of complex process, poor stability and the like, and the development of the solar cells is greatly restricted by the problems.
Selenium (Se) as the earliest discovered photovoltaic material has the advantages of low price, greenness, no toxicity, good stability and the like, the band gap of the material is about 1.8eV, the spectral response covers most visible light, and the absorption coefficient is as high as 10 5 cm -1 . Therefore, the selenium thin-film solar cell has very large application potential as a new generation thin-film solar cell.
Although selenium is the oldest photovoltaic material, it has low theoretical efficiency because its band gap is too large, about 1.8eV, and as a single junction cell, it cannot effectively utilize the wavelengths of the solar spectrum; with the rapid development of silicon cells (with a band gap of 1.12eV, which can make full use of the solar spectrum), the interest in selenium solar cells is more limited. Until recently, with the rise of tandem solar cells, wide bandgap (1.7-1.9 eV) solar cells have attracted much attention as the top cell of tandem cells, and the old selenium solar cells have not come into the field of vision again.
Thin films of elemental selenium are typically prepared using vacuum thermal evaporation, electrochemical deposition, which is also based on solution systems, and solution processes. However, the above methods are uneconomical, or the processes are complicated and not environmentally friendly enough, and thus they are not suitable for mass production of high-quality polycrystalline selenium thin films for solar cells.
CN110863177A discloses a method for preparing a selenium semiconductor film, which comprises placing selenium powder and a substrate on a glass substrate or an ITO substrate in a quartz tube, and obtaining the selenium film by a vacuum thermal evaporation method. However, the vacuum thermal evaporation method requires a complicated vacuum system, requires professional evaporation equipment and is high in cost; high-temperature and high-vacuum preparation conditions are also needed, so that high energy consumption and low productivity are caused; in addition, the vacuum thermal evaporation method has low material utilization rate because the whole evaporation bin is filled with vapor in the evaporation process.
The solution method has the advantages of low-temperature preparation and low cost, but the solution method usually needs a toxic solvent, the volatilization of the solvent can cause poor surface appearance of the film, in addition, the grain size of the film prepared by the solution method is generally smaller, and the most important factor is that the solution method based on the spin coating process can not be prepared in a large scale, which is also one of the main reasons for limiting the development of the solution method.
Film-forming processes based on the molten state have not been extensively studied, since the light-absorbing materials of solar cells currently under extensive study all have relatively high melting points, such as Si (1410 deg.C), GaAs (1238 deg.C), CdTe (1093 deg.C), CIGS (1000 deg.C) and perovskite (476 deg.C).
Disclosure of Invention
The invention aims to solve the problem that no preparation method capable of reliably, stably, massively and inexpensively producing the polycrystalline selenium film suitable for solar photovoltaic materials exists in the prior art, and the invention aims to provide the high-quality polycrystalline selenium film and the preparation method thereof.
Selenium has a very low melting point (217 ℃), which is the lowest of all photovoltaic absorber layer materials, and the very low melting point enables selenium to have a lower processing temperature than other photovoltaic materials in a high-temperature film-making process, which also provides the possibility of melt-method film-making of selenium. However, the preparation of selenium films by the melt processing method has not been reported. This is because, first, selenium has a large band gap (1.8 eV) and cannot effectively use various wavelengths of the solar spectrum as a single junction cell, and thus selenium solar cells have not been widely studied; secondly, because the common photovoltaic material has a high melting point, a mature melting method process is not available; most importantly, the inorganic materials are evaporated when the inorganic materials are molten, so that the materials are lost, the production is not facilitated, and toxic steam can be generated to harm human health. The inventor finds that selenium has another important physical property and can be conveniently processed by a melting method, namely selenium does not evaporate in a temperature range (217-300 ℃) which is quite above the melting point, the property is based on lower saturated vapor pressure of molten selenium in the temperature range, the root of the property is that the selenium is not easy to evaporate due to a long-chain structure of the molten selenium, and the characteristic enables the selenium to have a larger process window in the process of melting and film making. However, tests show that the wettability of the molten selenium on a common electron transport layer such as titanium dioxide in a solar cell is poor, so that the temperature of the molten selenium is regulated and controlled, the surface tension of the molten selenium is reduced, and the wettability is improved by adopting the mesoporous titanium dioxide, so that a blade coating method is smoothly used for preparing a selenium film, and finally the obtained amorphous selenium film is annealed, and a high-performance polycrystalline selenium film is successfully developed. The method disclosed by the invention is low in cost, environment-friendly, simple to operate, free of large-scale complex equipment, stable in quality of the obtained polycrystalline selenium film, excellent in performance and suitable for being used as a photovoltaic material of a solar cell. The polycrystalline selenium film is used for an absorption layer of a solar cell; the prepared solar cell has excellent photovoltaic performance and is environment-friendly. When the polycrystalline selenium film is prepared by a melting method based on a blade coating method, the requirements on equipment are low, the manufacturing process is simple, the material utilization rate is high, the film forming quality is good, the manufacturing cost of the solar cell is greatly reduced, and a method with great development prospects is provided for the industrialization of the solar cell.
The invention achieves the purpose through the following technical scheme:
a polycrystalline selenium film having an XRD diffraction pattern with characteristic peaks at the following 2 theta: 23.5 degrees +/-0.3 degrees, 29.7 degrees +/-0.3 degrees, 41.3 degrees +/-0.3 degrees, 45.3 degrees +/-0.3 degrees, 51.7 degrees +/-0.3 degrees, 61.2 degrees +/-0.3 degrees, 61.6 degrees +/-0.3 degrees, 65.2 degrees +/-0.3 degrees and 68.2 degrees +/-0.3 degrees; and the fit forbidden band width of the polycrystalline selenium film is 1.7-1.8 eV.
Furthermore, the thickness of the polycrystalline selenium film is 2-8 μm, preferably 4-6 μm. .
The invention also provides a preparation method of the polycrystalline selenium film, which comprises the following steps:
(S1) placing a titanium dioxide substrate with a mesoporous structure on a hot table, placing a selenium raw material on the titanium dioxide substrate with the mesoporous structure, heating the hot table to 217-300 ℃ to melt selenium powder, blade-coating molten selenium to prepare a selenium film, and cooling to obtain an amorphous selenium film;
(S2) annealing the amorphous selenium film to obtain the polycrystalline selenium film.
The polycrystalline selenium film prepared by the invention is a high-quality polycrystalline film, and the high-quality polycrystalline film is continuous, compact, good in crystallinity and large in crystal grains.
Further, in the step (S1), the titanium dioxide substrate having a mesoporous structure on the surface is prepared by the following steps in the following order: the method comprises the following steps of surface cleaning of a blank substrate, preparation of a titanium dioxide dense layer and preparation of a titanium dioxide mesoporous layer.
Wherein the blank substrate is a transparent conductive substrate. Preferably, the transparent conductive substrate includes a transparent substrate (e.g., glass or flexible plastic) and a layer of transparent electrode material (e.g., Indium Tin Oxide (ITO), Fluorine Tin Oxide (FTO), etc.) overlying the transparent substrate. For example, FTO glass. The surface cleaning process comprises the following steps: ultrasonic cleaning with deionized water, acetone and isopropanol for 20-60 min, blowing with high purity nitrogen, and ultraviolet-ozone cleaning for 15-30 min.
The preparation method comprises the following steps of preparing a titanium dioxide compact layer, wherein a raw material used for preparing the titanium dioxide compact layer is bis (acetylacetonato) diisopropyl titanate or an ethanol solution of titanium tetrachloride, and the bis (acetylacetonato) diisopropyl titanate is selected as the raw material; preferably, the volume ratio of bis (acetylacetonate) diisopropyl titanate to absolute ethyl alcohol is 1: 10. the preparation of the titanium dioxide compact layer adopts a spin coating method; the spin coating method is well known in the art, and in one embodiment of the invention, a substrate is placed at the center of a spin coater, a proper amount of solution is sucked by a pipette gun to be uniformly coated on the substrate, and spin coating is carried out at a certain rotating speed. After spin coating, the substrate is transferred to a hot stage, preheated for 5-15min at the temperature of 150-.
Wherein, the raw material for preparing the titanium dioxide mesoporous layer is ethanol solution of titanium dioxide slurry (30 NR-D sold in the market), and the average particle size of the titanium dioxide is 30-40 nm; preferably, the mass ratio of the titanium dioxide paste to the absolute ethyl alcohol is 1: 2.5. The preparation of the titanium dioxide mesoporous layer adopts a spin-coating method; preferably, the rotation speed during spin coating is 3000-; after spin coating, transferring to a hot stage, preheating for 5-15min at the temperature of 150-.
The thickness of the blank substrate is 1-3mm, the thickness of the titanium dioxide dense layer is 50-100nm, and the thickness of the titanium dioxide mesoporous layer is 300-500 nm. The titanium dioxide compact layer and the titanium dioxide mesoporous layer are both anatase phases. The average pore diameter of the titanium dioxide mesoporous layer is 30-40 nm.
According to the present invention, in step (S1), the temperature of the hot stage is 250-280 ℃. According to the equation of the Poplar equation: gamma ray SG -γ SL ＝γ LG cos θ, wherein γ SG 、γ SL And gamma LG Is the interfacial tension of solid-gas, solid-liquid and liquid-gas interfaces, respectively, theta is the contact angle of the liquid on the substrate, the contact angle of the liquid is defined by gamma SG 、γ SL And gamma LG It was determined that the wettability of the substrate could be quantitatively evaluated by the contact angle (θ) of the liquid on the substrate. According to the invention, the surface tension gamma of the molten selenium is selected in a selected temperature range LG The contact angle of the film on a substrate is small, so that the wettability is improved, and the coverage and the density of the film are improved; the inventors have found that molten selenium starts to evaporate at 300c, and thus if the temperature is further increased above the selected temperature, the molten selenium is prone to evaporate, producing toxic selenium vapour, which is detrimental to production and human health. Therefore, the high-quality polycrystalline selenium film can be conveniently and efficiently prepared in the temperature range selected by the invention.
The selenium material is not particularly limited, and may be in the form of a solid, powder, or the like. As long as the selenium is simple substance, the purity is more than 99 percent.
According to the present invention, in the step (S2), the temperature of the annealing treatment is 170-220 ℃; preferably 200-210 ℃.
In the preparation method, the molten selenium has good wettability to the mesoporous titanium dioxide substrate, the film is easier to form, the uniformity of the film obtained by blade coating is good, and the polycrystalline selenium film obtained after annealing is compact, good in crystallinity and large in grain size. The inventor finds that a polycrystalline selenium film with excellent photoelectric properties can be obtained by film preparation through the melting process in the steps.
The invention provides a thin film solar cell containing the polycrystalline selenium film, which comprises an n-type window layer, a p-type absorption layer and a back electrode layer which are sequentially stacked, wherein the p-type absorption layer is the polycrystalline selenium film.
According to the invention, the thin film solar cell further comprises a substrate adjacent to the n-type window layer, namely the thin film solar cell comprises the substrate, the n-type window layer, the p-type absorption layer and the back electrode layer which are sequentially stacked.
According to the invention, the substrate is a transparent conductive substrate. Preferably, the transparent conductive substrate includes a transparent substrate (e.g., glass (which may be white glass, in particular), flexible plastic, or the like) and a transparent electrode material (e.g., Indium Tin Oxide (ITO), Fluorine Tin Oxide (FTO), or the like) layer covering the transparent substrate. For example, FTO glass.
According to the invention, the material of the back electrode layer can be one or more of Mo, Cu, Au, Ni, Ag and Al; the thickness of the back electrode layer may be 80-200 nm.
The invention also provides a preparation method of the thin film solar cell, which comprises the following steps: the preparation method comprises the steps of n-type window layer deposition, p-type absorption layer deposition and back electrode layer deposition, wherein the p-type absorption layer is formed by the polycrystalline selenium film, and the preparation method of the polycrystalline selenium film is adopted in the n-type window layer deposition step and the p-type absorption layer deposition step.
The method comprises the following steps:
a) depositing an n-type window layer: depositing an n-type window layer 2 on the surface of a substrate 1 by adopting the step (1) in the preparation method of the polycrystalline selenium film;
b) and (3) depositing a p-type absorption layer: depositing a p-type absorption layer 3 on the n-type window layer 2 prepared in the step a) by adopting the preparation method of the polycrystalline selenium film;
c) back electrode deposition: depositing a back electrode layer 4 on the p-type absorption layer 3 prepared in the step b), thereby preparing the thin-film solar cell with the p-n junction structure.
According to the present invention, in step c), the back electrode layer 4 can be prepared by magnetron sputtering, thermal evaporation, or the like.
The structure of the thin film solar cell with the p-n junction structure is shown as a schematic diagram in figure 1.
The invention has the beneficial effects that:
1. the invention provides a high-quality polycrystalline selenium film and a preparation method thereof, the thickness of the polycrystalline selenium film is 2-6 mu m, the polycrystalline selenium film is prepared by adopting a blade coating method-based fusion method, and when the polycrystalline selenium film is prepared, the equipment requirement is low, the manufacturing process is simple, the material utilization rate is high, and the film forming quality is good.
2. The invention also provides a solar cell containing the polycrystalline selenium film and a preparation method thereof, wherein the Se element in the p-type absorption layer material in the solar cell is an element with higher content in the crust, the p-type absorption layer material is a semiconductor photoelectric material with low price, stable performance and environmental friendliness, the direct forbidden bandwidth of the p-type absorption layer material is 1.78eV, most of visible light spectrums are covered, and the light absorption coefficient is as high as 10 5 cm -1 . In addition, due to the low melting point characteristic, the film can be quickly formed by a melting process based on a blade coating method, the method has low equipment requirement and high material utilization rate, and therefore, the thin film solar cell formed by taking the film as the absorption layer has the advantages of excellent photovoltaic performance, environmental friendliness and low-cost production hopefully.
Drawings
FIG. 1 is a schematic structural diagram of a polycrystalline selenium thin film solar cell prepared according to the present invention; wherein 1 is a substrate, and 2 is an n-type window layer (TiO) 2 Dense layerAnd TiO 2 A mesoporous layer), 3 is a p-type absorption layer, and 4 is an electrode layer;
FIG. 2 is a schematic view of a melt blade coating apparatus for preparing the polycrystalline selenium film according to the present invention, wherein, 5-hot stage; 6-a titanium dioxide substrate; 7-selenium raw material; 8-a scraper;
FIG. 3(a) is a thermogravimetric plot (TGA) of Se powder, and FIG. 3(b) is a relationship between vapor pressure and temperature of Se;
FIG. 4 is a graph showing the contact angles of molten selenium on a titanium dioxide substrate at different temperatures in preparation example 1 of the present invention;
FIG. 5 shows TiO in example 1 of the present invention 2 SEM photographs of the mesoporous layer;
FIG. 6 is a Raman spectrum of the polycrystalline selenium thin film prepared in example 1 of the present invention on a titanium dioxide substrate;
FIG. 7 is an X-ray diffraction pattern of a polycrystalline selenium film prepared in example 1 of the present invention on a titanium dioxide substrate;
FIG. 8 is an SEM image of a polycrystalline selenium film on a titania substrate in accordance with example 1 of the present invention;
FIG. 9 is a fitting graph of the forbidden band width of the poly-crystalline selenium film in example 1 of the present invention;
FIG. 10 is an I-V curve test chart of the poly-crystalline selenium thin film solar cell in example 1 of the present invention;
FIG. 11 is an I-V curve test chart of the polycrystalline selenium thin film solar cell in example 2 of the present invention;
FIG. 12 is an I-V curve test chart of the poly-crystalline selenium thin film solar cell in example 3 of the present invention;
FIG. 13 is a scanning electron microscope image of a polycrystalline selenium film on a titanium dioxide substrate according to example 2 of the present invention;
FIG. 14 is an electron scanning microscope image of a polycrystalline selenium film on a titanium dioxide substrate according to example 3 of the present invention;
FIG. 15 is an XPS energy spectrum and an EDS spectrum (energy dispersive X-ray spectroscopy) of a polycrystalline selenium thin film in example 5 of the present invention;
FIG. 16 is a graph of stability testing of a polycrystalline selenium film of the present invention;
FIG. 17 is an I-V curve test chart of the poly-crystalline selenium thin film solar cell in example 5 of the present invention;
FIG. 18 is an optical photograph of the selenium film of comparative example 1 of the present invention after annealing.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Furthermore, it should be understood that various changes or modifications can be made by those skilled in the art after reading the description of the present invention, and such equivalents also fall within the scope of the invention.
The thin film solar cell using the poly-crystal selenium film as the absorption layer prepared by the invention is shown in figure 1, and comprises a substrate 1 and an n-type window layer 2 (formed by TiO) sequentially deposited on the substrate 2 Dense layer and TiO 2 A mesoporous layer), a p-type absorption layer 3 (polycrystalline selenium film), and an electrode layer 4.
The melt blade coating device for preparing the polycrystalline selenium film comprises a heating table 5, a titanium dioxide substrate 6, a selenium raw material 7 and a scraper 8, as shown in figure 2.
Preparation example 1
In order to find the optimal melting processing temperature of Se, FIG. 3(a) is a thermogravimetric analysis (TGA) of Se powder to get a thorough understanding of the melting process of Se. Fig. 3 shows that the weight loss of Se starts at about 300℃, which is above the melting point of Se (217 ℃), indicating that when the heating temperature is in the range of 217 to 300 ℃, the molten Se is still present in liquid state, rather than evaporating as Se vapor. FIG. 3(b) is a graph showing the relationship between the vapor pressure and temperature of Se. Medium Se starts to exhibit a relatively high vapour pressure of 13Pa at 300 ℃. The above results can show that melt processing of Se at temperatures below 300 ℃ is feasible.
The invention adopts selenium melting blade coating to form a high-quality polycrystalline selenium film under the specific temperature range (217 ℃ C. -300 ℃ C., preferably 250 ℃ C. -280 ℃ C.). This is because selenium is in the melt processing temperature range of 217-300 c, which facilitates processing without vaporizing to the gaseous state. Another key parameter for the processing of molten selenium into a film is the wettability of the molten selenium on the substrate. To find the optimum melt working temperature for selenium processed films, we confirmed this for the contact angles of molten selenium at different temperatures.
With mesoporous TiO 2 Dense TiO 2 the/FTO glass was used as a substrate and the contact angle at 220 ℃ was measured. Fig. 4 is a contact angle of selenium on a substrate at different temperatures. It can be seen that as the temperature increases from 220 ℃ to 250 ℃ and 280 ℃, the contact angles gradually decrease, being 85.7 °, 63.1 °, 45.2 °, respectively.
Example 1
a) And (3) depositing an n-type window layer: depositing an n-type window layer 2 on a conductive glass substrate 1 by adopting a spin-coating method;
the substrate 1 comprises transparent glass (or white glass) and transparent FTO (SnO) 2 : f) The thickness of the plating layer (marked as FTO conductive glass or FTO glass) is 2 mm;
ultrasonically cleaning the substrate 1 by using deionized water, acetone and ethanol for 30 minutes respectively, then blowing clean by using high-purity nitrogen, and cleaning for 15 minutes by using ultraviolet-ozone;
the n-type window layer 2 is made of TiO 2 Is divided into TiO 2 Dense layer and TiO 2 The thickness of the mesoporous layer is 50nm and 400nm respectively;
depositing an n-type window layer 2 on the substrate 1 by adopting a spin-coating method, wherein the deposition steps are as follows: preparing 1mL of bis (acetylacetone) diisopropyl titanate and 10mL of absolute ethyl alcohol into a solution, and filtering the solution by using a filter head with the pore diameter of 0.22 mu m; placing the substrate 1 at the center of a spin coater, sucking a proper amount of the solution by a pipette gun, uniformly coating the solution on the substrate 1, and spin-coating for 30s at the rotating speed of 4000 rpm; transferring the spin-coated substrate 1 to a hot stage, heating the hot stage to 150 ℃ for 10min, raising the temperature of the hot stage to 500 ℃, covering a cover, keeping the temperature for 30min, cooling, and taking down the substrate 1 to obtain the TiO 2 A dense layer.
Weighing 3gTiO 2 The slurry (commercially available 30NR-D, average particle size 30nm) was dissolved in 7.5g of absolute ethanol to obtain a solution containing TiO 2 Placing the substrate 1 of the compact layer at the center of a spin coater, sucking a proper amount of the solution by a liquid-moving gun, uniformly coating the solution on the substrate 1, and spin-coating for 30s at the rotating speed of 4000 rpm; will be spin-coatedTransferring the substrate 1 to a heating table, wherein the temperature of the heating table is 150 ℃, after 10min, raising the temperature of the heating table to 500 ℃, covering a cover, preserving the heat for 30min, cooling and then taking down the substrate 1 to obtain the TiO 2 The mesoporous layer (SEM photograph see FIG. 5).
b) And (3) depositing a p-type absorption layer: depositing a p-type absorption layer 3 on the n-type window layer 2 by adopting a melt blade coating method; the p-type absorption layer 3 is made of selenium, and as can be seen from fig. 5, the thickness of the polycrystalline selenium film is 4 μm. A thickness of 4 μm is sufficient to absorb incident sunlight.
A melt-draw process was used to deposit a p-type absorber layer 3 on an n-type window layer 2, using the equipment shown schematically in figure 2, the deposition steps being: weighing 0.3g of selenium powder, and uniformly scattering the selenium powder on the titanium dioxide substrate 6 (selenium raw material 7) by using a 200-mesh sieve; heating the hot table 5 to 280 ℃, and transferring the titanium dioxide substrate to the hot table 5 after the temperature is stable; placing the scraper 8 on the hot table 5 for preheating for 10 min; after the selenium raw material 7 is completely melted, the selenium raw material 7 is blade-coated into a film by a preheated scraper 8, then the substrate 6 is immediately taken down from the hot table 5 for cooling, and an amorphous selenium film is obtained after cooling; and adjusting the temperature of the hot table 5 to 200 ℃, after the temperature is stable, placing the amorphous selenium film on the hot table 5, heating and annealing for 2min, then immediately taking down and cooling, and obtaining a polycrystalline selenium film after cooling, namely depositing the p-type absorption layer 3 on the n-type window layer 2.
Fig. 6 is a Raman diagram of the polycrystalline selenium-germanium film prepared in example 1 of the present invention on an FTO glass substrate. At 142cm -1 And 237cm -1 The characteristic peak of the method can be classified into Se-Se vibration, and further proves that the pure-phase polycrystalline selenium film is successfully obtained by a melting method.
FIG. 7 is an X-ray diffraction pattern of a polycrystalline selenium thin film prepared in example 1 of the present invention on an FTO glass substrate. It can be seen that all diffraction peaks of the polycrystalline selenium film obtained by the invention except the diffraction peak of the FTO substrate are consistent with JCPDS NO.06-0362, which shows that the polycrystalline selenium film prepared by the melting method has a photovoltaic phase and is suitable for being used as a photovoltaic material of a solar cell.
Fig. 8(a) is an electron scanning microscope image of the polycrystalline selenium film on an FTO glass substrate according to example 1 of the present invention, and it can be seen that the polycrystalline selenium film prepared by the fusion process of the present invention has very good uniformity and compactness, and has large grains of micron order; fig. 8(b) is an electron scanning microscope sectional image of the polycrystalline selenium thin film of example 1, and it can be seen that the polycrystalline selenium thin film of the present invention obtained by the melting method is very excellent in crystallinity.
Fig. 9 is a fitting graph of the forbidden band width of the poly-crystalline selenium film in example 1 of the present invention, wherein the band gap of the poly-crystalline selenium film prepared by the melting method of the present invention is 1.78eV, and the absorption spectrum of the poly-crystalline selenium film can cover most of visible light.
c) Back electrode layer deposition: depositing a back electrode layer 4 on the p-type absorption layer 3 by adopting a vacuum evaporation method;
the back electrode layer 4 is made of gold material and has a thickness of 80 nm.
The polycrystalline selenium thin-film solar cell with the p-n junction structure can be prepared through the steps.
Fig. 10 is an I-V curve test chart of the polycrystalline selenium thin film solar cell in example 1 of the present invention. The photoelectric conversion efficiency was 3.5%.
Example 2
Substantially the same as in example 1, except that: in the step b), the temperature of the heating table 5 is raised to 250 ℃, and the titanium dioxide substrate is transferred to the heating table 5 after the temperature is stable. Namely, the selenium raw material 7 is coated into a film at the temperature of 250 ℃.
The polycrystalline selenium thin film prepared in example 2 was assembled into a solar cell device in the same manner as in example 1, and the I-V curve thereof was tested, with the results shown in fig. 11. The photoelectric conversion efficiency is 2.4 percent
Example 3
Substantially the same as in example 1, except that: in the step b), the temperature of the heating table 5 is raised to 220 ℃, and the titanium dioxide substrate is transferred to the heating table 5 after the temperature is stable. Namely, the selenium raw material 7 is coated into a film at the temperature of 220 ℃.
The polycrystalline selenium thin film prepared in example 3 was assembled into a solar cell device in the same manner as in example 1, and the I-V graph thereof was tested, with the results shown in fig. 12. The photoelectric conversion efficiency was 1.0%.
It can be seen from examples 1-3 that when the working temperature of the selenium melt blade coating film is increased from 220 ℃ to 280 ℃, the coverage of the film on the substrate is improved, the quality of the polycrystalline selenium film is improved, and the photoelectric conversion efficiency of the prepared solar cell is improved. This is due to the increased temperature, which improves the wettability of the titanium dioxide substrate by the molten selenium, thereby making it easier to form a film on the titanium dioxide substrate. We also tested the morphology of the selenium polycrystalline film produced. Fig. 13 and 14 are scanning electron microscope images of the selenium polycrystalline thin films prepared at the operating temperatures of 250 ℃ (example 2) and 220 ℃ (example 3), respectively. As compared with fig. 8, it can be seen that the selenium polycrystalline thin film prepared at the 220 deg.c operating temperature exhibited poor surface coverage, and the selenium polycrystalline thin film prepared at the 220 deg.c operating temperature exhibited poor surface morphology and crystallinity. This is due to the fact that at relatively low temperatures, the molten selenium does not have good wettability for the substrate.
Example 4
We also performed stability tests on the polycrystalline selenium film obtained in example 1. Fig. 15 (a) is an XPS spectrum of a polycrystalline selenium thin film prepared by a melting method in air. It can be seen that characteristic peaks at 55.3eV and 56.16eV, corresponding to the elements, appear 0 3d of Se 5/2 And 3d 3/2 The binding energy of (4). No Se at 59.9eV was observed 4+ Oxidation peak of (2). FIG. 15 (b) is an enlarged XPS spectrum at 525 to 540eV, and it can be seen that Se is not oxidized in the polycrystalline selenium thin film according to the present invention, which is manufactured in the air using the melting method.
To further verify the air stability of the polycrystalline selenium film of the present invention, EDS spectroscopy (energy dispersive X-ray spectroscopy) was also performed. EDS has the advantage over XPS of being able to detect the micron level in thin films, whereas XPS has a probing degree of only around 10 nm. FIG. 15 (c) is an EDS energy spectrum of the polycrystalline selenium film of example 1 after air treatment, and no oxygen is observed. The polycrystalline selenium film prepared by the method has excellent air stability. Is suitable for being used as a photovoltaic material of a solar cell. Solar cells prepared from the polycrystalline selenium films obtained in the present invention were stored in air for 1000h without showing significant efficiency loss (fig. 16).
Example 5
Basically the same as in example 1, except that: in step b), the temperature of the heating table 5 is raised to 290 ℃, and the titanium dioxide substrate is transferred to the heating table 5 after the temperature is stabilized. Namely, the selenium raw material 7 is coated into a film at 290 ℃.
The polycrystalline selenium thin film prepared in example 6 was assembled into a solar cell device in the same manner as in example 1, and the I-V graph thereof was tested, and the photoelectric conversion efficiency thereof was 3.2% as shown in fig. 17. However, melting at this temperature may cause some selenium to evaporate, resulting in less photoelectrochemical efficiency than in example 1.
Comparative example 1
Substantially the same as in example 1, except that:
the n-type window layer 2 is made of TiO 2 The thickness of the dense layer was 50 nm.
Depositing an n-type window layer 2 on the substrate 1 by adopting a spin-coating method, wherein the deposition steps are as follows: preparing 1mL of bis (acetylacetone) diisopropyl titanate and 10mL of absolute ethyl alcohol into a solution, and filtering the solution by using a filter head with the aperture of 0.22 mu m; placing the substrate 1 at the center of a spin coater, sucking a proper amount of the solution by a liquid-transferring gun, uniformly coating the solution on the substrate 1, and spin-coating for 30s at the rotating speed of 4000 rpm; transferring the spin-coated substrate 1 to a hot stage, heating the hot stage to 150 ℃ for 10min, raising the temperature of the hot stage to 500 ℃, covering a cover, keeping the temperature for 30min, cooling, and taking down the substrate 1 to obtain the TiO 2 A dense layer. After the molten blade coating method is carried out on TiO 2 On a dense layer, not TiO 2 A mesoporous layer.
The amorphous selenium film prepared in comparative example 1 was delaminated after annealing (see fig. 18 for a photograph), indicating that the molten selenium had poor wettability to the dense layer of titanium dioxide under these conditions.
Claims (10)
1. A polycrystalline selenium film characterized by an XRD diffraction pattern having characteristic peaks at the following 2 theta: 23.5 degrees +/-0.3 degrees, 29.7 degrees +/-0.3 degrees, 41.3 degrees +/-0.3 degrees, 45.3 degrees +/-0.3 degrees, 51.7 degrees +/-0.3 degrees, 61.2 degrees +/-0.3 degrees, 61.6 degrees +/-0.3 degrees, 65.2 degrees +/-0.3 degrees and 68.2 degrees +/-0.3 degrees; and the fit forbidden band width of the polycrystalline selenium film is 1.7-1.8 eV.
2. The polycrystalline selenium film according to claim 1, wherein the thickness of the polycrystalline selenium film is 2-8 μm, preferably 4-6 μm.
3. The method for preparing a polycrystalline selenium film according to claim 1 or 2, comprising the steps of:
(S1) placing a titanium dioxide substrate with a mesoporous structure on the surface on a hot table, placing a selenium raw material on the titanium dioxide substrate with the mesoporous structure, heating the hot table to 217-300 ℃ to melt selenium powder, blade-coating molten selenium to prepare a selenium film, and cooling to obtain an amorphous selenium film;
(S2) annealing the amorphous selenium film to obtain the polycrystalline selenium film.
4. The method according to claim 3, wherein in the step (S1), the titanium dioxide substrate having a mesoporous structure on the surface is prepared by the following steps in the following order: cleaning the surface of a blank substrate, preparing a titanium dioxide compact layer and preparing a titanium dioxide mesoporous layer;
wherein, the raw material used for preparing the titanium dioxide mesoporous layer is ethanol solution of titanium dioxide slurry, and the average particle size of the titanium dioxide is 30-40 nm; preferably, the mass ratio of the titanium dioxide paste to the absolute ethyl alcohol is 1: 2.5; the preparation of the titanium dioxide mesoporous layer adopts a spin-coating method.
5. The method as claimed in claim 4, wherein the spin coating is performed at a rotation speed of 3000-5000rpm for 20-40 seconds; after spin coating, transferring to a hot stage, preheating for 5-15min at the temperature of 150-.
6. The method as claimed in claim 4, wherein the thickness of the blank substrate is 1-3mm, the thickness of the dense titanium dioxide layer is 50-100nm, the thickness of the mesoporous titanium dioxide layer is 300-500nm, and the average pore diameter is 30-40 nm; preferably, the titanium dioxide dense layer and the titanium dioxide mesoporous layer are both anatase phases.
7. The preparation method according to claim 4, wherein, in the step (S1), the temperature of the hot stage is 250-280 ℃.
8. The method as claimed in claim 4, wherein in the step (S2), the temperature of the annealing treatment is 170-220 ℃; preferably 200-210 ℃.
9. A solar cell, which comprises an n-type window layer, a p-type absorption layer and a back electrode layer which are sequentially stacked, wherein the p-type absorption layer is the polycrystalline selenium film of claim 1 or 2 or the polycrystalline selenium film prepared by the preparation method of any one of claims 3 to 8.
10. A method for manufacturing a solar cell according to claim 9, comprising the steps of:
a) and (3) depositing an n-type window layer: depositing an n-type window layer on the surface of the substrate;
b) and (3) depositing a p-type absorption layer: depositing a p-type absorption layer on the n-type window layer prepared in the step a) by adopting the preparation method of the polycrystalline selenium film;
c) back electrode deposition: depositing a back electrode layer on the p-type absorption layer prepared in the step b), thereby preparing and obtaining a thin film solar cell with a p-n junction structure;
preferably, in step c), the back electrode layer is formed by magnetron sputtering or thermal evaporation.
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