CN115084290B - 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 179
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 title claims abstract description 167
- 229910052711 selenium Inorganic materials 0.000 title claims abstract description 162
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 65
- 239000010408 film Substances 0.000 claims description 115
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 107
- 239000000758 substrate Substances 0.000 claims description 80
- 239000004408 titanium dioxide Substances 0.000 claims description 49
- 239000010409 thin film Substances 0.000 claims description 30
- 238000010521 absorption reaction Methods 0.000 claims description 25
- 238000000151 deposition Methods 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 238000004528 spin coating Methods 0.000 claims description 18
- 230000008021 deposition Effects 0.000 claims description 17
- 239000002994 raw material Substances 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 10
- 238000000137 annealing Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 238000004140 cleaning Methods 0.000 claims description 6
- 238000002207 thermal evaporation Methods 0.000 claims description 6
- 235000019441 ethanol Nutrition 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 4
- 238000007790 scraping Methods 0.000 claims description 4
- 239000002002 slurry Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 3
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 25
- 238000002844 melting Methods 0.000 abstract description 23
- 230000008018 melting Effects 0.000 abstract description 22
- 238000010345 tape casting Methods 0.000 abstract description 11
- 239000002904 solvent Substances 0.000 abstract description 3
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 230000001276 controlling effect Effects 0.000 abstract 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 16
- 239000011521 glass Substances 0.000 description 16
- 230000008569 process Effects 0.000 description 12
- 238000001704 evaporation Methods 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
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- 239000007788 liquid Substances 0.000 description 5
- 238000001000 micrograph Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- -1 diisopropyl titanate Chemical compound 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000010128 melt processing Methods 0.000 description 3
- 238000010309 melting process Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000002411 thermogravimetry Methods 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
- 230000002588 toxic effect Effects 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- NPNMHHNXCILFEF-UHFFFAOYSA-N [F].[Sn]=O Chemical compound [F].[Sn]=O NPNMHHNXCILFEF-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
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- 230000007613 environmental effect Effects 0.000 description 2
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- 229920002457 flexible plastic Polymers 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- HTRSGQGJZWBDSW-UHFFFAOYSA-N [Ge].[Se] Chemical compound [Ge].[Se] HTRSGQGJZWBDSW-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000005251 gamma ray Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 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
- 239000007787 solid Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 231100000701 toxic element Toxicity 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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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
- 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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- 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
- 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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- 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
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Sustainable Development (AREA)
- Life Sciences & Earth Sciences (AREA)
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- Inorganic Chemistry (AREA)
- Photovoltaic Devices (AREA)
Abstract
The invention relates to a polycrystalline selenium film, wherein the XRD diffraction pattern of the polycrystalline selenium film has characteristic peaks at the following 2 theta: 23.5 ° ± 0.3 °, 29.7 ° ± 0.3 °, 41.3 ° ± 0.3 °, 45.3 ° ± 0.3 °, 51.7 ° ± 0.3 °, 61.2 ° ± 0.3 °, 61.6 ° ± 0.3 °, 65.2 ° ± 0.3 °, 68.2 ° ± 0.3 °; and the fit forbidden band width of the polycrystalline selenium film is 1.7-1.8eV. The invention also provides the polycrystalline selenium film and the preparation method thereof, which are a method for industrially producing the polycrystalline selenium film by adopting a melting method based on knife coating, regulating and controlling the melting working temperature without complex large-scale equipment and a large amount of solvents, and solving the problems of high equipment requirement, high preparation cost and low material utilization rate at present.
Description
Technical Field
The invention belongs to the field of photoelectric materials 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 solar energy, and among them, a thin film solar cell is receiving more attention because of its excellent performance. At present, most of light absorption materials of the 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 problems limit the development of the solar cells to a great extent.
Selenium (Se) is used as the photovoltaic material discovered at the earliest time, has the advantages of low price, green and nontoxic properties, good stability and the like, has a band gap of about 1.8eV, has spectral response covering most of visible light, and has an absorbance coefficient as high as 10 5 cm -1 . Therefore, the selenium thin film solar cell has great application potential as a new generation of thin film solar cells。
Selenium, although the oldest photovoltaic material, has a lower theoretical efficiency because it has a band gap of about 1.8eV, and it cannot effectively utilize the wavelengths of the solar spectrum when used as a single junction cell; with the rapid development of silicon cells (band gap of 1.12eV, which can fully utilize solar spectrum), the interest in selenium solar cells is more limited. Until recently, with the advent of stacked solar cells, wide band gap (1.7-1.9 eV) solar cells have received much attention as top cells for stacked cells, and older selenium solar cells have not come into view again.
Films of elemental selenium are typically prepared by vacuum thermal evaporation, electrochemical deposition, and solution processes, where electrochemical deposition is also based on a solution system. However, the above methods are uneconomical or complex in process, not environment-friendly enough, and are not suitable for mass production of high-quality polycrystalline selenium thin films for solar cells.
CN110863177a discloses a preparation method of selenium semiconductor film, in which selenium powder and substrate are placed in quartz tube on glass substrate or ITO substrate, and the selenium film is obtained by vacuum thermal evaporation method. However, the vacuum thermal evaporation method requires a complex vacuum system, requires professional evaporation equipment and has high cost; high-temperature high-vacuum preparation conditions are also required, so that high energy consumption and low productivity are caused; in addition, the vacuum thermal evaporation method fills the whole evaporation bin with vapor in the evaporation process, and the utilization rate of materials is very low.
The solution method has the advantages of low-temperature preparation and low cost, but the solution method often needs a toxic solvent, the volatilization of the solvent can lead to poor surface morphology of the film, in addition, the grain size of the film prepared by the solution method is generally smaller, and the most critical is that the solution method based on the spin coating process cannot be prepared in a large scale, which is one of main reasons for limiting the development of the solution method.
Since solar cell light absorbing materials currently widely studied have high melting points such as Si (1410 ℃), gallium arsenide (1238 ℃), cdTe (1093 ℃), CIGS (1000 ℃) and perovskite (476 ℃), film forming methods based on the molten state have not been intensively studied.
Disclosure of Invention
In order to solve the problems that a preparation method for reliably and stably producing a polycrystalline selenium film suitable for a solar photovoltaic material in a large scale and at low cost does not exist in the prior art, the invention aims to provide a high-quality polycrystalline selenium film and a preparation method thereof.
Selenium has a very low melting point (217 ℃) which is the lowest of all photovoltaic absorber materials, and the very low melting point gives selenium a lower processing temperature in the high temperature film forming process than other photovoltaic materials, which also gives the possibility of melt film forming of selenium. However, the preparation of selenium film by the melt process has not been reported yet. This is because, first, selenium has a large band gap (about 1.8 eV) and cannot effectively use each wavelength of the solar spectrum when used as a single junction cell, and thus selenium solar cells have not been widely studied; secondly, because the melting point of the common photovoltaic material is higher, no mature melting method process exists; most importantly, the inorganic materials are evaporated in a molten state, so that the materials are not only lost and are not beneficial to production, but also toxic vapor can be generated, and the human health is endangered. The inventor finds that selenium has another important physical property, namely that selenium can be conveniently processed by a melting method, namely that selenium does not evaporate in a quite large temperature range (217-300 ℃) above a melting point, the property is based on the low saturated vapor pressure of molten selenium in the temperature range, the root point is that the selenium is not easy to evaporate due to a long-chain structure of the molten selenium, and the characteristic also enables the selenium to have a large process window in the melting film making process. However, experiments show that the wettability of molten selenium on electron transport layers such as titanium dioxide commonly used in solar cells is poor, so that the temperature of the molten selenium is regulated and controlled, the surface tension of the molten selenium is reduced, mesoporous titanium dioxide is adopted, the wettability is improved, a selenium film can be prepared smoothly by using a knife coating method, and finally the obtained amorphous selenium film is annealed, so that a high-performance polycrystalline selenium film is successfully developed. The method has the advantages of low cost, environmental friendliness, simple operation, no need of large-scale complex equipment, stable quality of the obtained polycrystalline selenium film and excellent performance, and is 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 knife coating method, the equipment requirement is low, the manufacturing process is simple, the material utilization rate is high, the film forming quality is good, the manufacturing cost of a solar cell is greatly reduced, and a method with a great development prospect is provided for the industrialization of the solar cell.
The invention achieves the aim through the following technical scheme:
a polycrystalline selenium film having an XRD diffractogram with characteristic peaks at the following 2Θ:23.5 ° ± 0.3 °, 29.7 ° ± 0.3 °, 41.3 ° ± 0.3 °, 45.3 ° ± 0.3 °, 51.7 ° ± 0.3 °, 61.2 ° ± 0.3 °, 61.6 ° ± 0.3 °, 65.2 ° ± 0.3 °, 68.2 ° ± 0.3 °; and the fit forbidden band width of the polycrystalline selenium film is 1.7-1.8eV.
Further, 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 the surface on a heat table, placing a selenium raw material on the titanium dioxide substrate with the mesoporous structure, heating the heat table to 217-300 ℃ to melt selenium powder, scraping molten selenium to prepare a selenium film, and cooling to obtain an amorphous selenium film;
and (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 refers to continuous and compact polycrystalline film, good crystallinity and large grains.
Further, in the step (S1), the titanium dioxide substrate with the mesoporous structure on the surface is prepared according to the following steps in order: cleaning the surface of a blank substrate, preparing a titanium dioxide compact layer and preparing a titanium dioxide mesoporous layer.
Wherein the blank substrate is a transparent conductive substrate. Preferably, the transparent conductive substrate comprises 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 flow is as follows: ultrasonic cleaning with deionized water, acetone and isopropanol for 20-60 min, blowing with high-purity nitrogen, and cleaning with ultraviolet-ozone for 15-30 min.
Wherein, the raw material used for preparing the titanium dioxide compact layer is ethanol solution of di (acetyl) diisopropyl titanate or titanium tetrachloride, and the di (acetyl) diisopropyl titanate is selected as the raw material in the invention; preferably, the volume ratio of the bis (acetylacetonate) diisopropyltitanate to the absolute ethanol 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, 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 to uniformly coat the substrate, and spin coating is performed at a certain rotating speed. After spin coating, the substrate is transferred to a heat table, preheated for 5-15min at 150-200 ℃, the thermal state temperature is increased to 400-500 ℃, and the temperature is kept for 20-30min, so as to obtain the titanium dioxide compact layer.
Wherein, the raw material used for preparing the titanium dioxide mesoporous layer is ethanol solution of titanium dioxide slurry (30 NR-D sold in market), and the average particle size of the titanium dioxide is 30-40nm; 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 rotating speed during spin coating is 3000-5000rpm, and the spin coating time is 20-40 seconds; after spin coating, transferring to a heat table, preheating for 5-15min at 150-200 ℃, heating to 450-550 ℃, preserving heat for 30-60min, and cooling to obtain the titanium dioxide mesoporous layer.
The thickness of the blank substrate is 1-3mm, the thickness of the titanium dioxide compact layer is 50-100nm, and the thickness of the titanium dioxide mesoporous layer is 300-500nm. 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 30-40nm.
According to the invention, in step (S1), the temperature of the hot stage is 250-280 ℃. According to the young equation: gamma ray SG -γ SL ＝γ LG cos θ, where γ SG 、γ SL And gamma LG The interfacial tension of the solid-gas, solid-liquid and liquid-gas interfaces respectively, theta is the contact angle of the liquid on the substrate, and the contact angle of the liquid is formed by gamma SG 、γ SL And gamma LG By determining the contact angle (θ) of the liquid on the substrate, the wettability thereof can be quantitatively evaluated. According to the invention, the surface tension gamma of the molten selenium is within a selected temperature range LG The contact angle of the film on the substrate is smaller, so that the wettability is improved, and the coverage and the compactness of the film are improved; the inventors have found that the molten selenium begins to evaporate at 300c, so if the temperature is further increased over the selected temperature, the molten selenium is prone to evaporation, producing toxic selenium vapor, which is detrimental to production and human health. Therefore, the high-quality polycrystalline selenium film can be conveniently and efficiently prepared in the selected temperature range.
The selenium raw material is not particularly limited, and may be in the form of solid, powder, or the like. The purity of the selenium is above 99 percent as long as the selenium is simple.
According to the invention, in step (S2), the annealing treatment is carried out at a temperature of 170-220 ℃; preferably 200-210 ℃.
In the preparation method, the wettability of molten selenium to the mesoporous titanium dioxide substrate is good, 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, has good crystallinity and has large grains. The inventors have found through a great deal of experiments that the polycrystalline selenium thin film with excellent photoelectric properties can be obtained by forming a film according to the melting process of the steps.
The invention provides a thin film solar cell containing the polycrystalline selenium thin 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 thin 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 a substrate, an n-type window layer, a p-type absorption layer and a back electrode layer which are sequentially stacked.
According to the invention, the substrate is a transparent conductive substrate. Preferably, the transparent conductive substrate comprises a transparent substrate (e.g., glass (which may be white glass in particular) or flexible plastic, etc.) 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.
According to the invention, the material of the back electrode layer can be one or more of Mo, cu, au, ni, ag, al; the thickness of the back electrode layer may be 80-200nm.
The invention also provides a preparation method of the thin film solar cell, which comprises the following steps: the method comprises an n-type window layer deposition step, a p-type absorption layer deposition step and a back electrode layer deposition step, wherein the p-type absorption layer is formed by the polycrystalline selenium film, and the n-type window layer deposition step and the p-type absorption layer deposition step adopt the preparation method of the polycrystalline selenium film.
The specific method comprises the following steps:
a) n-type window layer deposition: adopting the step (1) in the preparation method of the polycrystalline selenium film, depositing an n-type window layer 2 on the surface of the substrate 1;
b) A p-type absorption layer deposition step: by adopting the preparation method of the polycrystalline selenium film, a p-type absorption layer 3 is deposited on the n-type window layer 2 prepared in the step a);
c) A back electrode deposition step: and b) 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 may be prepared by magnetron sputtering, thermal evaporation, or the like.
The structure of the thin film solar cell of the p-n junction structure is illustrated in fig. 1.
The invention has the beneficial effects that:
1. the invention provides a high-quality polycrystalline selenium film and a preparation method thereof, wherein the thickness of the polycrystalline selenium film is 2-6 mu m, the polycrystalline selenium film is prepared by adopting a melting method based on a knife coating method, and when the polycrystalline selenium film is prepared, the equipment requirement is low, the preparation 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 of the p-type absorption layer material in the solar cell is an element with higher content in the crust, is a semiconductor photoelectric material with low price, stable performance and environmental friendliness, has a direct forbidden band width of 1.78eV, covers most of visible light spectrum, and has a light absorption coefficient as high as 10 5 cm -1 . In addition, because the low-melting point characteristic can be rapidly formed into a film by utilizing a melting process based on a knife coating method, the method has the advantages of low equipment requirement and high material utilization rate, and the thin film solar cell formed by taking the thin film solar cell as an absorption layer has excellent photovoltaic performance, is environment-friendly and is expected to realize low-cost production.
Drawings
FIG. 1 is a schematic diagram of a polycrystalline selenium thin film solar cell prepared by the invention; wherein 1 is a substrate, 2 is an n-type window layer (TiO 2 Dense layer and TiO 2 Mesoporous layer), 3 is p-type absorption layer, 4 is electrode layer;
FIG. 2 is a schematic view of a melt doctor blade apparatus for preparing the polycrystalline selenium film of the present invention, wherein the 5-stage; a 6-titanium dioxide substrate; 7-selenium raw material; 8-scraping knife;
fig. 3 (a) is a thermal weight loss (TGA) diagram of Se powder, and fig. 3 (b) is a relationship between vapor pressure and temperature of Se;
FIG. 4 shows contact angles of molten selenium to titania substrates at various temperatures in preparation example 1 according to the present invention;
FIG. 5 is a diagram showing the TiO composition in example 1 of the present invention 2 SEM photograph of the mesoporous layer;
FIG. 6 is a Raman spectrum of the polycrystalline selenium film prepared in example 1 of the present invention on a titanium dioxide substrate;
FIG. 7 is an X-ray diffraction pattern of the polycrystalline selenium film prepared in example 1 of the present invention on a titanium dioxide substrate;
FIG. 8 is an electron scanning microscope image of a polycrystalline selenium film on a titania substrate according to example 1 of the present invention;
FIG. 9 is a fitted graph of forbidden band width of the polycrystalline selenium film of example 1 of the present invention;
FIG. 10 is a graph showing I-V curve test of a polycrystalline selenium thin film solar cell according to example 1 of the present invention;
FIG. 11 is a graph showing I-V curve test of a polycrystalline selenium thin film solar cell according to example 2 of the present invention;
FIG. 12 is a graph showing I-V curve test of a polycrystalline selenium thin film solar cell according to example 3 of the present invention;
FIG. 13 is an electron scanning microscope image of a polycrystalline selenium film of example 2 of the present invention on a titanium dioxide substrate;
FIG. 14 is an electron scanning microscope image of a polycrystalline selenium film of example 3 of the present invention on a titanium dioxide substrate;
FIG. 15 is an XPS spectrum and EDS spectrum (energy dispersive X-ray spectrum) of the polycrystalline selenium film of example 5 of the present invention;
FIG. 16 is a graph showing the stability test of a polycrystalline selenium film of the present invention;
FIG. 17 is a graph showing I-V curve test of a polycrystalline selenium thin film solar cell according to example 5 of the present invention;
FIG. 18 is an optical photograph of a selenium film of comparative example 1 of the present invention after annealing.
Detailed Description
The invention will be further illustrated with reference to specific examples. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. Further, it is understood that various changes and modifications of the invention will become apparent to those skilled in the art upon reading the description herein, and such equivalents are intended to fall within the scope of the invention as defined by the appended claims.
The thin film solar cell prepared by the invention and taking the polycrystalline selenium thin film as an absorption layer is shown in figure 1, and comprises a substrate 1 and n-type windows sequentially deposited on the substrateMouth layer 2 (made of TiO 2 Dense layer and TiO 2 A mesoporous layer), a p-type absorber layer 3 (polycrystalline selenium film) and an electrode layer 4.
The melting and knife coating equipment for preparing the polycrystalline selenium film comprises a heat 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 optimum melt processing temperature for Se, FIG. 3 (a) shows the Se powder subjected to thermogravimetric analysis (TGA) to gain insight into the Se melting process. Fig. 3 shows that the weight loss of Se starts at about 300℃, which is higher than the melting point of Se (217 ℃) indicating that when the heating temperature is in the range of 217 to 300 ℃, molten Se is still present in liquid state, rather than evaporating as Se vapor. Fig. 3 (b) is a graph of vapor pressure and temperature of Se. Se in (c) starts to exhibit a relatively high vapor pressure of 13Pa at 300 ℃. The above results indicate that melt processing of Se at a temperature of 300℃or lower is possible.
The invention adopts a specific temperature range (217-300 ℃, preferably 250-280 ℃) to prepare the high-quality polycrystalline selenium film by melting and knife coating the selenium film. This is because selenium is in the melt processing temperature range of 217-300 c, and molten selenium is easy to process without evaporating to a gaseous state. Another key parameter in the processing of molten selenium into a film is the wettability of the molten selenium on the substrate. To find the optimal melt working temperature of the selenium processed film, we demonstrate this for the contact angle of molten selenium at different temperatures.
With mesoporous TiO 2 Compact TiO 2 FTO glass was used as a substrate and tested for contact angle at 220 ℃. Fig. 4 is a graph of the contact angle of selenium on a substrate at different temperatures. It can be seen that as the temperature increases from 220 ℃ to 250 ℃,280 ℃, the contact angle gradually decreases, 85.7 °,63.1 °,45.2 °, respectively.
Example 1
a) n-type window layer deposition: depositing an n-type window layer 2 on the conductive glass substrate 1 by adopting a spin coating method;
the substrate 1 comprises transparent glass (or white glass) and transparent FTO (SnO) coated on the transparent glass 2 : f) Coating (denoted asFTO conductive glass or FTO glass) with a thickness of 2mm;
respectively ultrasonically cleaning the substrate 1 by deionized water, acetone and ethanol for 30 minutes, then blowing out the substrate by high-purity nitrogen, and cleaning the substrate by ultraviolet-ozone for 15 minutes;
the n-type window layer 2 material is TiO 2 Divided into TiO 2 Dense layer and TiO 2 The thickness of the mesoporous layer is respectively 50nm and 400nm;
an n-type window layer 2 is deposited on the substrate 1 by adopting a spin coating method, and the deposition steps are as follows: 1mL of bis (acetylacetonate) diisopropyl titanate and 10mL of absolute ethyl alcohol are prepared into a solution, and the solution is filtered by a filter head with the pore diameter of 0.22 mu m; placing the substrate 1 in the center of a spin coater, sucking a proper amount of the solution by a liquid-transfering gun, uniformly coating the solution on the substrate 1, and spin-coating the solution at a rotating speed of 4000rpm for 30s; transferring the spin-coated substrate 1 to a heat stage, wherein the temperature of the heat stage is 150deg.C, heating to 500deg.C after 10min, covering with a cover, maintaining the temperature for 30min, cooling, and removing the substrate 1 to obtain TiO 2 A dense layer.
Weigh 3g TiO 2 The slurry (commercially available 30NR-D, average particle diameter 30 nm) was prepared into a solution with 7.5g of absolute ethanol, and the above-mentioned solution having TiO was prepared 2 Placing the substrate 1 with the compact layer in 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 the solution at a rotating speed of 4000rpm for 30s; transferring the spin-coated substrate 1 to a heat stage, wherein the temperature of the heat stage is 150deg.C, heating to 500deg.C after 10min, covering with a cover, maintaining the temperature for 30min, cooling, and removing the substrate 1 to obtain TiO 2 Mesoporous layer (SEM photograph thereof is shown in fig. 5).
b) A p-type absorption layer deposition step: a melt knife coating method is adopted to deposit a p-type absorption layer 3 on the n-type window layer 2; the p-type absorption layer 3 is made of selenium, and as can be seen in fig. 5, the thickness of the polycrystalline selenium film is 4 μm. A thickness of 4 μm is sufficient to absorb incident sunlight.
A p-type absorption layer 3 is deposited on the n-type window layer 2 by a melt-knife coating method, and the adopted equipment schematic diagram is shown in fig. 2, wherein the deposition steps are as follows: 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 heat table 5 to 280 ℃, and transferring the titanium dioxide substrate to the heat table 5 after the temperature is stable; placing the scraper 8 on a heat table 5 for preheating for 10min; after the selenium raw material 7 is completely melted, a preheated scraper 8 is used for scraping the selenium raw material 7 into a film, then the substrate 6 is immediately taken off from the heat table 5 and cooled, and an amorphous selenium film is obtained after cooling; and (3) adjusting the temperature of the heat table 5 to 200 ℃, placing the amorphous selenium film on the heat table 5 after the temperature is stable, heating and annealing for 2min, immediately taking down and cooling, and obtaining the 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 a 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 (B) can be attributed to Se-Se vibration, and further verifies that the pure-phase polycrystalline selenium film is obtained by a melting method.
FIG. 7 is an X-ray diffraction pattern of the polycrystalline selenium film prepared in example 1 of the present invention on an FTO glass substrate. It can be seen that the polycrystalline selenium film obtained by the method is identical to JCPDS No.06-0362 except the diffraction peak of the FTO substrate, which shows that the polycrystalline selenium film prepared by the method has three phases of photovoltaic phases and is suitable for being used as a photovoltaic material of a solar cell.
FIG. 8 (a) is an electron scanning microscope image of a 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 melting method of the present invention has very good uniformity and compactness, and has large grains in the micrometer scale; fig. 8 (b) is an electron scanning microscope cross-sectional image of the polycrystalline selenium film of example 1, and it can be seen that the polycrystalline selenium film prepared by the melt process of the present invention has very good crystallinity.
Fig. 9 is a fitted graph of the forbidden band width of the polycrystalline selenium film in example 1 of the present invention, wherein the band gap of the polycrystalline selenium film prepared by the melting method is 1.78eV, and the absorption spectrum of the polycrystalline selenium film can cover most of visible light.
c) And a back electrode layer deposition step: 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 80nm.
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 of 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 step b), the temperature of the heat table 5 is raised to 250 ℃, and the titanium dioxide substrate is transferred onto the heat table 5 after the temperature is stabilized. I.e. selenium raw material 7 is knife coated to form a film at 250 ℃.
The polycrystalline selenium film prepared in example 2 was assembled into a solar cell device in the same manner as in example 1, and tested for I-V graph, and the results are shown in fig. 11. The photoelectric conversion efficiency is 2.4%
Example 3
Substantially the same as in example 1, except that: in step b), the temperature of the heat table 5 is raised to 220 ℃, and the titanium dioxide substrate is transferred onto the heat table 5 after the temperature is stabilized. Namely selenium raw material 7 is coated into a film at 220 ℃.
The polycrystalline selenium film prepared in example 3 was assembled into a solar cell device in the same manner as in example 1, and tested in an I-V graph, and the results are 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 knife 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 manufactured solar cell is improved. This is due to the increased temperature, the wettability of the melted selenium to the titanium dioxide substrate improves, thereby making selenium more likely to form a film on the titanium dioxide substrate. The morphology of the prepared selenium polycrystalline film is also tested. Fig. 13 and 14 are electron scanning microscope images of the selenium polycrystalline films produced at operating temperatures of 250 ℃ (example 2) and 220 ℃ (example 3), respectively. As can be seen by comparing with fig. 8, the selenium polycrystalline thin film prepared at 220 ℃ operating temperature shows poor surface coverage, and the selenium polycrystalline thin film prepared at 220 ℃ operating temperature shows poor surface morphology and crystallinity. This is due to the poor wettability of the substrate by molten selenium at relatively low temperatures.
Example 4
We also performed stability tests on the polycrystalline selenium film produced in example 1. Fig. 15 (a) is an XPS spectrum of a polycrystalline selenium film prepared by a melting method in air. It can be seen that characteristic peaks at 55.3eV and 56.16eV appear, corresponding to the elements 0 3d of Se 5/2 And 3d 3/2 Is a combination of the binding energy of the above-mentioned materials. Se at 59.9eV was not observed 4+ Is a peak of oxidation of (a). Fig. 15 (b) is an enlarged XPS spectrum from 525 to 540eV, and it can be seen that Se is not oxidized in the polycrystalline selenium film prepared in air using the melting method of the present invention.
To further verify the air stability of the polycrystalline selenium films of the present invention, EDS spectra (energy dispersive X-ray spectra) were also tested. EDS has the advantage over XPS that it is able to detect micron scale within the film, whereas the detection level of XPS is only around 10 nm. Fig. 15 (c) is an EDS spectrum of the polycrystalline selenium film of example 1 after air treatment, with no oxygen present being observed. The polycrystalline selenium film prepared by the method has excellent air stability. The material is suitable for being used as a photovoltaic material of a solar cell. The solar cell prepared by the polycrystalline selenium film obtained by the invention is stored for 1000 hours in the air, and has no obvious efficiency loss (figure 16).
Example 5
Substantially the same as in example 1, except that: in step b), the temperature of the heat table 5 is raised to 290 ℃, and the titanium dioxide substrate is transferred onto the heat table 5 after the temperature is stabilized. Namely selenium raw material 7 is knife coated into a film at 290 ℃.
A solar cell device was assembled by the same method as in example 1, and tested for I-V curve graph, as shown in fig. 17, with a photoelectric conversion efficiency of 3.2% by the polycrystalline selenium film prepared in example 6. However, conducting the melting operation at this temperature may have some selenium evaporated, 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 material is TiO 2 The dense layer thickness was 50nm.
An n-type window layer 2 is deposited on the substrate 1 by adopting a spin coating method, and the deposition steps are as follows: 1mL of bis (acetylacetonate) diisopropyl titanate and 10mL of absolute ethyl alcohol are prepared into a solution, and the solution is filtered by a filter head with the pore diameter of 0.22 mu m; placing the substrate 1 in the center of a spin coater, sucking a proper amount of the solution by a liquid-transfering gun, uniformly coating the solution on the substrate 1, and spin-coating the solution at a rotating speed of 4000rpm for 30s; transferring the spin-coated substrate 1 to a heat stage, wherein the temperature of the heat stage is 150deg.C, heating to 500deg.C after 10min, covering with a cover, maintaining the temperature for 30min, cooling, and removing the substrate 1 to obtain TiO 2 A dense layer. After that, the melting and knife coating method is to make the TiO 2 On dense layers other than TiO 2 And a mesoporous layer.
The amorphous selenium film prepared in comparative example 1, after annealing, was subject to film release (see fig. 18 for a photograph thereof), demonstrating that the wettability of the dense layer of titanium dioxide by molten selenium was poor under this condition.
Claims (13)
1. The preparation method of the polycrystalline selenium film is characterized by comprising the following steps:
(S1) placing a titanium dioxide substrate with a mesoporous structure on the surface on a heat table, placing a selenium raw material on the titanium dioxide substrate with the mesoporous structure, heating the heat table to 217-300 ℃ to melt selenium powder, scraping molten selenium to prepare a selenium film, and cooling to obtain an amorphous selenium film;
(S2) annealing the amorphous selenium film to obtain a polycrystalline selenium film;
the XRD diffraction pattern of the polycrystalline selenium film is as follows2θCharacteristic peaks appear: 23.5 ° ± 0.3 °, 29.7 ° ± 0.3 °, 41.3 ° ± 0.3 °, 45.3 ° ± 0.3 °, 51.7 ° ± 0.3 °, 61.2 ° ± 0.3 °, 61.6 ° ± 0.3 °, 65.2 ° ± 0.3 °, 68.2 ° ± 0.3 °; and the fit forbidden band width of the polycrystalline selenium film is 1.7-1.8eV.
2. The preparation method according to claim 1, wherein the thickness of the polycrystalline selenium film is 2-8 μm.
3. The method of claim 1, wherein the polycrystalline selenium film has a thickness of 4-6 μm.
4. The method according to claim 1, wherein in the step (S1), the titanium dioxide substrate having a mesoporous structure on the surface is prepared by the 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 30-40nm.
5. The preparation method according to claim 4, wherein the mass ratio of the titanium dioxide slurry to the absolute ethyl alcohol is 1:2.5; the preparation of the titanium dioxide mesoporous layer adopts a spin coating method.
6. The method according to claim 5, wherein the spin-coating is carried out at a rotation speed of 3000 to 5000rpm for 20 to 40 seconds; after spin coating, transferring to a heat table, preheating for 5-15min at 150-200 ℃, raising the temperature of the heat table to 450-550 ℃, preserving heat for 30-60min, and cooling to obtain the titanium dioxide mesoporous layer.
7. The method according to claim 4, wherein the thickness of the blank substrate is 1-3mm, the thickness of the dense layer of titanium dioxide is 50-100nm, the thickness of the mesoporous layer of titanium dioxide is 300-500nm, and the average pore diameter is 30-40nm.
8. The method of claim 7, wherein the dense titania layer and the mesoporous titania layer are both anatase phases.
9. The method according to claim 1, wherein in the step (S1), the temperature of the hot stage is 250 to 280 ℃.
10. The method according to claim 1, wherein in the step (S2), the annealing treatment is performed at a temperature of 170 to 220 ℃.
11. The method according to claim 10, wherein in the step (S2), the annealing treatment is performed at a temperature of 200 to 210 ℃.
12. A method of manufacturing a solar cell, comprising the steps of:
a) n-type window layer deposition: depositing an n-type window layer on the surface of the substrate;
b) A p-type absorption layer deposition step: by adopting the preparation method of the polycrystalline selenium film, a p-type absorption layer is deposited on the n-type window layer prepared in the step a);
c) A back electrode deposition step: depositing a back electrode layer on the p-type absorption layer prepared in the step b), thereby preparing a thin film solar cell with a p-n junction structure;
the solar cell 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 any one of claims 1-11.
13. The method of claim 12, wherein in step c), the back electrode layer is formed by magnetron sputtering or thermal evaporation.
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