CN107887513B - Solar cell based on ternary inorganic flat heterojunction thin film and preparation method thereof - Google Patents

Solar cell based on ternary inorganic flat heterojunction thin film and preparation method thereof Download PDF

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CN107887513B
CN107887513B CN201710995180.5A CN201710995180A CN107887513B CN 107887513 B CN107887513 B CN 107887513B CN 201710995180 A CN201710995180 A CN 201710995180A CN 107887513 B CN107887513 B CN 107887513B
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CN107887513A (en
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陈王伟
王命泰
齐娟娟
董超
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Hefei Institutes of Physical Science of CAS
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
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    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/30—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains
    • H10K30/35—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains comprising inorganic nanostructures, e.g. CdSe nanoparticles
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    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
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    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
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    • Y02E10/00—Energy generation through renewable energy sources
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    • Y02E10/549—Organic PV cells

Abstract

The invention provides a solar cell based on a ternary inorganic flat heterojunction film.A positive electrode, the ternary inorganic flat heterojunction film, an organic hole transmission layer and a negative electrode are sequentially deposited on a glass substrate; the ternary inorganic flat heterojunction film is made of TiO2Nano thin film, CdS nano thin film and CuInS2Composition of nano-film, TiO2Nano thin film, CdS nano thin film and CuInS2And the nano films are sequentially deposited on the solar cell anode. The technical progress and innovation points of the invention are mainly embodied in the following aspects: (1) in terms of core material, the critical CuInS2The preparation method of the thin film layer is completely different from the prior art, and the preparation method is easier to realize large-area preparation; (2) in the aspects of battery structure and performance, an organic hole transport layer is used in the battery, so that the short circuit phenomenon generated in the Au atom deposition process is effectively avoided, and the battery has higher performanceV oc。

Description

Solar cell based on ternary inorganic flat heterojunction thin film and preparation method thereof
Technical Field
The invention relates to the field of solar cells, in particular to a solar cell based on a ternary inorganic flat heterojunction thin film.
Background
The solar energy is converted into electric energy to realize photovoltaic power generation, which is an important way for utilizing renewable energy sources. The most critical of photovoltaic power generation systems is the device that captures and converts solar energy, i.e., the solar cell. Solar cells in practical applications need to meet two basic requirements: higher efficiency (> 10%) and stable battery performance (> 20 years of service life). The photoactive layer of the solar cell is a light absorption and free charge generation region, generally consists of a heterogeneous film junction consisting of an n-type semiconductor and a p-type semiconductor, has a decisive role in the photoelectric conversion process of the cell, and is a key material part of the solar cell. The inorganic semiconductor material has the advantages of high charge mobility and good structure stability. At present, most solar cells with higher efficiency and stability are mainly devices based on inorganic heterojunction (prog. photo: res. appl.2016, 24, 3-11); among them, commercial solar cells are mainly single crystal silicon cells represented by a photoactive layer composed of a p/n junction film of single crystal silicon, and the energy conversion efficiency (η) thereof has reached 25%. Typically, inorganic heterojunction solar cells are prepared by physical vapor deposition and chemical vapor deposition techniques (prog. photo: res. appl.2004, 12, 69-92; front. phys.2011, 6, 177-196). Although inorganic materials with good quality and higher crystallinity and efficient solar cell devices can be obtained, the vapor deposition preparation methods have the defects of complex technology and equipment, high energy consumption (high vacuum, 400-1400 ℃ high temperature is required), large material loss and the like, and the supply of high-purity raw materials is limited; these deficiencies, which result in high cell cost, are not conducive to large-scale applications. The establishment of a novel inorganic heterojunction thin film photoelectric conversion material system, the realization of low-cost preparation and the obtainment of high-efficiency solar cells are the main challenges in the development of inorganic thin film solar cells.
The solution method for preparing the thin film material is to deposit and assemble the thin film material by taking a certain solvent as a film forming medium. Commonly used solution processes mainly include chemical bath processes and precursor processes. The chemical bath method is mainly technically characterized in that: the substrate is put into the solution of reactants for preparing the film material, the reaction product in the solution is deposited on the substrate to obtain the film which is mainly amorphous or partially crystallized, and the amorphous film is generally annealed at a certain temperature (generally less than or equal to 500 ℃) under normal pressure to obtain the crystalline film material. The main technical characteristics of the precursor method are as follows: by solution processing techniques (e.g. spin coating, doctor-blading, screen-printing, ink-jet)Printing, dipping, etc.) at normal temperature and normal pressure, and then performing subsequent heat treatment at lower temperature (generally less than or equal to 500 ℃) under normal pressure to cause relevant chemical reactions and crystallization processes to occur in the precursor pre-deposited film, thus obtaining the crystalline film material. Crystalline CuInS2Having a narrow band gap (E)g1.5eV), wide light absorption range (300-900nm), environmental protection and the like, and is a potential solar cell light absorption material. In 2010 Li et al (J.Am.chem.Soc.2010, 132, 22-23) by the precursor method, CuInS was deposited sequentially on ITO conductive glass2And CdS nanoparticle thin film, made of CuInS2A binary flat heterojunction film comprising CdS and an open circuit voltage (V) of a solar cell based on the filmoc) Short-circuit current (J)sc) the Filling Factor (FF) and the energy conversion efficiency (η) reach 0.59V and 12.38mA/cm respectively254.80% and 3.99%. Cheshmekhavar et al (mater. chem. Phys.2017, 186, 446-455) in 2017 by the precursor method on TiO2In is deposited on the dense film In sequence2S3And CuInS2Nanoparticle film made of TiO2、In2S3And CuInS2Ternary flat heterojunction thin film formed, and V of thin film solar cell based on the heterojunctionoc、JscFF and η reach 0.52V and 10.90mA/cm respectively246% and 2.62%. In 2017, Golomostanfard et al (Sol. energy. Mater. Sol. cells2017, 164, 1-6) first treated with TiO2Depositing CdS nano-particle film on the compact film by a chemical bath method, and then carrying out electrophoresis process of nano-particles and H on the CdS film layer2Subsequent heat treatment in S atmosphere to prepare CuInS2Nanoparticle film made of TiO2CdS and CuInS2Ternary flat heterojunction thin film formed, and V of thin film solar cell based on the heterojunctionoc、JscFF and η reach 0.59V and 14.90mA/cm respectively261%, and 5.31%.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a solar cell based on a ternary inorganic flat heterojunction film and a solar cellA preparation method thereof. In the present invention, we use the chemical bath method and the precursor method respectively in TiO2CdS and CuInS are sequentially deposited on the compact film2Nanoparticle film prepared from TiO2CdS and CuInS2Ternary flat heterojunction film (TiO for short) composed of three nano-particle films2/CdS/CuInS2A heterojunction thin film); adding TiO into the mixture2/CdS/CuInS2The heterojunction film is compounded with an organic hole transport material to establish a solar cell (TiO for short) based on a ternary inorganic flat heterojunction film2/CdS/CuInS2solar cell) and a preparation method thereof, the efficiency of the solar cell reaches η -5.78%.
The invention is realized by the following technical scheme:
a solar cell based on a ternary inorganic flat heterojunction film is characterized in that an anode, the ternary inorganic flat heterojunction film, an organic hole transport layer and a cathode are sequentially deposited on a glass substrate; the ternary inorganic flat heterojunction film is made of TiO2Nano thin film, CdS nano thin film and CuInS2Composition of nano-film, TiO2Nano thin film, CdS nano thin film and CuInS2And the nano films are sequentially deposited on the solar cell anode.
The solar cell anode is an ITO layer or TiO layer2The nano film is made of 20-30nm TiO2The CdS nano-film is composed of CdS nano-particles of 10-20nm, CuInS2The nano film is made of CuInS with the thickness of 10-20nm2A nanoparticle composition; the organic hole transport layer is a Spiro-OMeTAD thin film, and the cathode is an Au thin film.
The thickness of the ITO layer is 100-300nm, and the thickness of the ITO layer is TiO2The thickness of the nano film is 50-150nm, the thickness of the CdS nano film is 50-100nm, and CuInS2The thickness of the nano film is 100-500nm, the thickness of the Spiro-OMeTAD film is 100-200nm, and the thickness of the Au film is 60-120 nm.
The Spiro-OMeTAD film is prepared from Spiro-OMeTAD, LiTFSI and TBP, and the molar ratio of Spiro-OMeTAD to LiTFSI to TBP is 1-3:1: 5-7.
The preparation method of the solar cell based on the inorganic flat heterojunction thin film comprises the following steps:
(1) etching the anode ITO conductive glass into thin strips by using concentrated hydrochloric acid and Zn powder, respectively ultrasonically cleaning the thin strips for 4-6 minutes by using acetone, isopropanol and ultrapure water, and drying to obtain etched ITO conductive glass; depositing TiO on the etched ITO conductive glass2Preparing a nano film for later use;
(2) preparing a cadmium sulfate aqueous solution with the concentration of 0.4-0.6g/L, adding ammonia water with the concentration of 25% -28% into the cadmium sulfate aqueous solution, and stirring and dissolving the cadmium sulfate aqueous solution in a water bath at the temperature of 60-70 ℃; preparing a thiourea aqueous solution with the concentration of 50-60 g/L; cadmium sulfate aqueous solution: ammonia water: the volume ratio of the thiourea aqueous solution is 340-360: 54-58: 43-47; will deposit TiO2Vertically suspending the ITO conductive glass of the film in the air, immersing the ITO conductive glass in a mixed aqueous solution of cadmium sulfate and ammonia water in a stirring state, adding a thiourea aqueous solution, and continuously carrying out reaction deposition in a water bath at 60-70 ℃ for 8-12min to obtain TiO2A binary flat heterojunction film consisting of two nano films of CdS;
(3) InCl is reacted at room temperature3Dissolving in N, N-dimethylformamide, stirring for 0.5-1.5 hr to obtain 145-147g/L solution, adding CuI, stirring for 0.5-1.5 hr, adding thiourea, and stirring at room temperature for 15-30 hr to obtain CuInS2Reaction precursor solution of InCl3The molar ratio of CuI to thiourea is 1:1: 6-10;
mixing CuInS2Dropwise adding the reactant precursor solution on the obtained binary flat-plate heterojunction thin film, performing spin coating to form a film, and repeating the spin coating for 2 times to obtain CuInS2Reacting the precursor film; drying the obtained reaction precursor film in a 65 ℃ vacuum drying oven, placing the film on a hot table under the protection of inert gas, raising the temperature of the hot table to 120-180 ℃ and keeping the temperature for 4-6 minutes, then continuously raising the temperature to 200-300 ℃ and carrying out heat treatment on the sample for 5-15 minutes at the temperature; after the heat treatment is finished, the sample is naturally cooled to room temperature to obtain crystalline CuInS2A embryonic membrane; repeat the operation to CuInS2The thickness of the nano film reaches the standard to obtain TiO2CdS and CuInS2A ternary flat heterojunction film consisting of three nano films;
(4) spin-coating a layer of mixture solution of Spiro-OMeTAD, LiTFSI and TBP with the concentration of 60-90mg/mL on the ternary flat heterojunction thin film obtained in the step (3), and carrying out heat treatment for 5-15 minutes at 50-150 ℃ in the air to obtain a Spiro-OMeTAD thin film hole transport layer;
(5) evaporating an Au film on the Spiro-OMeTAD thin film hole transport layer obtained in the step (4) by a thermal evaporation method to obtain a solar cell based on the ternary inorganic flat heterojunction thin film;
(6) and (5) packaging the solar cell prepared in the step (5) under the protection of inert gas to obtain a solar cell product.
The chemical bath method described in step (2) may be replaced by spin coating.
The solvent of the Spiro-OMeTAD solution in the step (4) is preferably chlorobenzene.
The spin coating operation described in steps (3) and (4) may be replaced by screen printing, doctor blading or ink jet printing.
The inert gas in the steps (3) and (6) is preferably nitrogen.
The invention has the beneficial effects that:
in the present invention, we are on TiO2On a/CdS heterogeneous thin film, by precursor solution (InCl)3A mixture of CuI, thiourea, N-dimethylformamide) to produce CuInS2Preparing TiO from the nano-particle film2/CdS/CuInS2A heterojunction thin film; in TiO2/CdS/CuInS2Respectively depositing a Spiro-OMeTAD organic hole transport film and an Au film electrode on the heterojunction film by a solution method and a thermal evaporation deposition method to obtain a film with a TiO structure2/CdS/CuInS2a/Spiro-OMeTAD/Au solar cell. Using CuInS2The nano light absorption performance realizes the absorption of solar photons by the solar cell in a wide spectral range of 300-900nm, the space position effect of the CdS nano film is used for fully separating photon-generated carriers in space, and TiO is used for fully separating photon-generated carriers2The nano film enables the solar cell to have a high-efficiency selective electron transmission channel; the solar cell efficiency reaches 5.78 percent (wherein, V)oc＝0.77V、Jsc＝11.60mA/cm2、FF＝64％)。
The technical progress and innovation points of the invention are mainly embodied in the following aspects: (1) in terms of core material, the critical CuInS2Compared with the prior art (Sol.energy.Mater.Sol.Cells2017, 164, 1-6), the preparation method of the thin film layer is completely different, and the preparation method is easier to realize large-area preparation; (2) in the aspects of battery structure and performance, an organic hole transport layer is used in the battery, so that the short circuit phenomenon generated in the Au atom deposition process is effectively avoided, and the battery has higher Voc. The preparation method of the key material of the cell and the cell device is simple and convenient, has low requirement on equipment, is suitable for large-scale preparation, and has great application value in the fields of photovoltaic materials, low-price solar cell devices and the like
Drawings
FIG. 1 is a schematic structural diagram of a ternary flat heterojunction-based thin-film solar cell according to the present invention; the reference numbers are as follows: (1) au film cathode, (2) Spiro-OMeTAD thin film, and (3) CuInS2Nano film, (4) CdS nano film, (5) TiO2Nano-film, (6) ITO anode, and (7) glass substrate.
FIG. 2 shows TiO according to the invention2And (5) XRD characterization results of the thin film.
FIG. 3 shows TiO according to the invention2SEM characterization results of the films.
FIG. 4 shows TiO according to the present invention2XRD characterization results of the/CdS heterojunction thin film.
FIG. 5 shows a TiO according to the invention2SEM characterization results of/CdS heterojunction thin films.
FIG. 6 shows TiO according to the present invention2And the UV-vis absorption spectrum characterization result of the/CdS heterojunction film.
FIG. 7 shows a TiO according to the invention2/CdS/CuInS2And (4) XRD characterization results of the heterojunction thin film.
FIG. 8 shows a TiO according to the invention2/CdS/CuInS2SEM characterization results of the heterojunction thin film.
FIG. 9 shows a TiO according to the invention2/CdS/CuInS2And (4) characterizing the result of the UV-vis absorption spectrum of the heterojunction film.
FIG. 10 shows a TiO according to the invention2/CdS/CuInS2IPCE characterization results of solar cells.
FIG. 11 shows a TiO according to the invention2/CdS/CuInS2And J-V performance characterization results of the solar cell.
Detailed Description
Examples
1、TiO2And (3) preparing a film.
(1-1) etching and cleaning of ITO conductive glass:
ITO conductive glass (size 3 × 3 cm)215 omega/□) etching an ITO film layer on the ITO conductive glass into 4 strips with the thickness of 16 × 4mm by using a concentrated HCl-water mixture and Zn powder with the volume ratio of 1:12Obtaining the etched ITO conductive glass substrate; and respectively ultrasonically cleaning the substrate by acetone, isopropanol and ultrapure water for 5 minutes to obtain a clean etched ITO conductive glass substrate, and drying the ITO conductive glass substrate for later use.
(1-2)TiO2Preparing a film:
mixing absolute ethyl alcohol, tetrabutyl titanate and glacial acetic acid according to the volume ratio of 4:1:0.1 to prepare uniform and colorless TiO2A sol precursor solution. 150 mu L of TiO2The sol precursor liquid drop is spin-coated on the etched ITO conductive glass (2000 r/min, 30 s), and the spin-coating is continuously carried out twice to obtain TiO2A sol film; adding TiO into the mixture2Storing the sol film in a humidity-maintaining device with a relative humidity of 50% at room temperature for 12 hours, placing the sol film in a muffle furnace with an air atmosphere, raising the temperature of the muffle furnace to 550 ℃ at a temperature raising rate of 1 ℃/min, and maintaining the temperature for 30 minutes to perform TiO2Sintering the sol film; after sintering, the muffle furnace is cooled to room temperature at the speed of 1 ℃/min to obtain TiO2And (3) a nano film. TiO 22The thickness of the nano-film is controlled by the spin-coating times.
(1-3) characterization of the product:
TiO2the nano-film is characterized in figures 2 and 3. The XRD results show that: the resulting TiO2The film layer belongs to an anatase crystal form (JCPDS 083-2243), and no other diffraction peaks except the diffraction peak of the ITO substrate are seenThe presence of impurity peaks, indicating the TiO obtained2The film purity and crystallinity are high. The SEM results show that: prepared TiO2The nano film is made of 20-30nm TiO2Nano particles, and the thickness of the film is 120 nm; TiO 22The film has smooth surface, no obvious pinhole or crack phenomenon in a large area range and high compactness.
2、TiO2And preparing the CdS heterojunction film.
(2-1) etching and cleaning of ITO conductive glass: and (1).
(2-2)TiO2Preparing a film: and (1).
(2-3)TiO2Preparation of a CdS heterojunction film:
two clean beakers were taken for use. CdSO with the concentration of 0.48g/L is prepared in a beaker 14·8/3H2350mL of O aqueous solution, then 56mL of ammonia water with the concentration of 25% -28% is added, and the mixed aqueous solution is continuously stirred in a water bath at 65 ℃. 45mL of a 55g/L aqueous solution of thiourea was placed in the beaker 2. Will deposit TiO2The ITO conductive glass of the film is vertically immersed in the CdSO in the beaker 1 in a stirring state4Mixing with ammonia water; after 1 minute, dropwise adding the thiourea aqueous solution in the beaker 2 into the beaker 1, and continuously stirring in a water bath at 65 ℃ for 10 minutes after dropwise adding for reaction and deposition; after the deposition is finished, the strip TiO is taken out2Leaching ITO conductive glass of the film with deionized water for several times, drying the leached ITO conductive glass with nitrogen, and then putting the leached ITO conductive glass into a vacuum drying oven at 65 ℃ for 3 hours to fully remove residual moisture to obtain the ITO conductive glass2Two-dimensional flat plate heterojunction thin film (i.e., TiO) composed of two kinds of nano-particle dense films of CdS2A CdS heterojunction thin film).
(2-4) characterization of the product:
TiO2the/CdS heterojunction thin film is characterized in the attached figures 4, 5 and 6. The XRD results show that: the CdS crystal form of the obtained film is a cubic phase (JCPDS 80-0019), and other impurity peaks do not exist, which indicates that the purity and the crystallinity of the obtained CdS film are very high; the SEM results show that: the resulting TiO2In the/CdS heterojunction film, the CdS film consists of CdS nano-particles of 10-20nm and the thickness of the CdS nano-particles is 80 nm; CdS film surface smoothingNo obvious pinhole or crack phenomenon exists in a large area, and the compactness is high. The absorption spectrum shows that: TiO 22The film layer mainly absorbs in the ultraviolet region<400nm) is substantially transparent in the visible spectral range, and TiO2the/CdS heterojunction film has CdS absorption in the spectral range of 400-550 nm.
3、TiO2/CdS/CuInS2And (3) preparing the heterojunction thin film.
(3-1) etching and cleaning of ITO conductive glass: and (1).
(3-2)TiO2Preparing a film: and (1).
(3-3)TiO2Preparation of a CdS heterojunction film: and 2. step 2.
(3-4)TiO2/CdS/CuInS2Preparing a heterojunction thin film:
to 10mL of N, N-dimethylformamide was added 1.46g of InCl3·4H2O and stirred at room temperature for 1 hour to give InCl3A solution; in InCl30.95g of CuI was added to the solution and stirring was continued at room temperature for 1 hour to give InCl3And a CuI mixture solution; to the resulting mixture solution was added 3.04g of thiourea, and the mixture was stirred at room temperature for 20 hours to obtain CuInS2Reaction precursor solution of InCl3,: and (2) CuI: the molar ratio of thiourea was 1:1: 8. The CuInS2The reaction precursor solution is colorless and transparent and is very stable.
150 mu L of CuInS2Dropwise addition of reactant precursor solution to TiO2Forming a film on the/CdS heterojunction film by spin coating (3000 r/min, 20 s), and repeating the spin coating for 2 times to obtain CuInS2Reacting the precursor film; drying the obtained reaction precursor film in a 65 ℃ vacuum drying oven for 15 minutes, then placing the film on a heating table under the protection of inert gas, raising the temperature of the heating table to 150 ℃ at the temperature raising rate of 20 ℃/minute and keeping the temperature for 5 minutes to promote the volatilization of the solvent, raising the temperature of the heating table to 250 ℃ at the temperature raising rate of 20 ℃/minute and carrying out heat treatment on the sample at the temperature for 10 minutes; after the heat treatment is finished, the sample is naturally cooled to room temperature to obtain the deposit on TiO2Junction on/CdS heterojunction thin filmCrystalline CuInS2And (5) a embryonic membrane. Once per completion of the crystalline CuInS2The preparation process of the embryonic membrane is CuInS2And (5) a growth process of the crystallized embryonic membrane. TiO 22CuInS on/CdS heterojunction thin film2The thickness of the thin film is determined by the crystalline CuInS2Controlling the times (n) of the growth process of the embryonic membrane. Crystalline CuInS repeated n times2After the growth process of the embryonic membrane, the CuInS with a certain thickness is finished2Film on TiO2In-situ growth on a CdS heterojunction film to obtain a CdS heterojunction film2、CdS、CuInS2Ternary flat heterojunction thin film (i.e., TiO) composed of three kinds of nanoparticle dense films2/CdS/CuInS2A heterojunction thin film). In this embodiment, control n is 2.
(3-5) characterization of the product:
TiO2/CdS/CuInS2the heterojunction film is characterized as shown in figures 7, 8 and 9, and XRD results show that: removing ITO and TiO2And outside the diffraction peak of CdS, TiO2/CdS/CuInS2The heterojunction film shows chalcopyrite crystal form CuInS2(JCPDS 85-1575) but no other hetero-peaks, and the obtained CuInS2The purity of the film is high. The SEM results show that: when n is 2, the resulting TiO2/CdS/CuInS2CuInS in heterojunction thin film2The thickness of the film is about 210nm, and CuInS2The film consists of CuInS with the thickness of 10-20nm2A nanoparticle composition; although CuInS2The surface of the film has certain fluctuation, but no obvious pinhole or crack phenomenon exists in a large area range, and the compactness is higher. UV-vis absorption spectrum shows: TiO 22/CdS/CuInS2The heterojunction film has good absorption in the spectral range of 300-900 nm.
4、TiO2/CdS/CuInS2And (4) preparing the solar cell.
(4-1) cleaning and etching of ITO conductive glass: and (1).
(4-2)TiO2Preparing a film: and (1).
(4-3)TiO2Preparation of a CdS heterojunction film: and 2. step 2.
(4-4)TiO2/CdS/CuInS2Preparing a heterojunction thin film: step 3
(4-5) preparation of Spiro-OMeTAD chlorobenzene solution:
73mg of Spiro-OMeTAD powder was added to 1mL of chlorobenzene, and stirred at room temperature for 2 hours to give a pale yellow solution of Spiro-OMeTAD chlorobenzene. To a solution of Spiro-OMeTAD in chlorobenzene, 19. mu.L of a LiTFSI acetonitrile solution (520mg/mL) and 29. mu.L of tert-butylpyridine (TBP) were added in this order and stirred at room temperature for 1 hour to give a clear pale yellow chlorobenzene solution of a mixture of Spiro-OMeTAD, LiTFSI and TBP in a molar ratio of Spiro-OMeTAD/LiTFSI/TBP of about 1.88/1/6.25.
(4-6)TiO2/CdS/CuInS2Preparing the solar cell:
65 μ L of a Spiro-OMeTAD chlorobenzene solution was added dropwise to the TiO2/CdS/CuInS2Spin coating (3000 r/min, 30 s) on the ternary heterojunction film; and (3) carrying out heat treatment in air at 100 ℃ for 10 minutes to obtain a Spiro-OMeTAD thin film hole transport layer with the thickness of about 100 nm.
depositing an Au film with the thickness of 100nm on the Spiro-OMeTAD film by a vacuum thermal evaporation method to be used as a cathode of the solar cell, wherein the position of the Au film is positioned right above the ITO layer, and the size of the Au electrode is controlled to be 1 × 4mm by a template2and the pressure in the evaporation chamber is 5 × 10-4Pa, evaporation rate of 0.5 angstroms/second (first 50nm) and 1 angstroms/second (last 50 nm). Packaging the cell in a glove box protected by nitrogen to obtain a solar cell (namely, TiO) based on the ternary flat heterojunction film2/CdS/CuInS2Solar cell), the cell structure is shown in figure 1.
(4-7) characterization of solar cell performance:
the performance of the solar cell is characterized by IPCE spectra and current-voltage (J-V) curves, see fig. 10 and 11. Both J-V and IPCE tests were performed at ambient and room temperature. IPCE spectrum shows that TiO is in the spectral range of 300-900nm2/CdS/CuInS2The solar cell has good photocurrent generation performance, which is similar to TiO2/CdS/CuInS2The absorption spectrum performance of the heterojunction film is consistent. J-V testing of batteries, usingIs AM 1.5 simulated sunlight (light intensity P)in＝100mW/cm2) the energy conversion efficiency η of the battery is determined by the open circuit voltage (V)oc) Short-circuit current (J)sc) and a Fill Factor (FF), i.e. η ═ Jsc·Voc·FF/Pin. In the J-V test process, the illumination area of the battery is controlled by the shielding window and is consistent with the size of the Au electrode. The J-V results show that the energy conversion efficiency of the battery reaches 5.78%.

Claims (8)

1. A solar cell based on a ternary inorganic flat heterojunction thin film is characterized in that: an anode, a ternary inorganic flat heterojunction film, an organic hole transport layer and a cathode are sequentially deposited on the glass substrate; the solar cell anode is an ITO layer; the ternary inorganic flat heterojunction film is made of TiO2Nano thin film, CdS nano thin film and CuInS2Composition of nano-film, TiO2Nano thin film, CdS nano thin film and CuInS2The nano films are sequentially deposited on the solar cell anode; the organic hole transport layer is a Spiro-OMeTAD film; the cathode is an Au thin film;
the preparation method of the solar cell based on the ternary inorganic flat heterojunction film comprises the following steps:
(1) etching the anode ITO conductive glass into thin strips by using concentrated hydrochloric acid and Zn powder, respectively ultrasonically cleaning the thin strips for 4-6 minutes by using acetone, isopropanol and ultrapure water, and drying to obtain etched ITO conductive glass; depositing TiO on the etched ITO conductive glass2Preparing a nano film for later use;
(2) preparing a cadmium sulfate aqueous solution with the concentration of 0.4-0.6g/L, adding ammonia water with the concentration of 25% -28% into the cadmium sulfate aqueous solution, and stirring and dissolving the cadmium sulfate aqueous solution in a water bath at the temperature of 60-70 ℃; preparing a thiourea aqueous solution with the concentration of 50-60 g/L; cadmium sulfate aqueous solution: ammonia water: the volume ratio of the thiourea aqueous solution is 340-360: 54-58: 43-47; will deposit TiO2Vertically suspending the ITO conductive glass of the film in the air, immersing the ITO conductive glass in a mixed aqueous solution of cadmium sulfate and ammonia water in a stirring state, adding a thiourea aqueous solution, and continuously carrying out reaction deposition in a water bath at 60-70 ℃ for 8-12min to obtain TiO2And CdS two kinds of nanometer film to form a binary plate type heterojunction film;
(3) InCl is reacted at room temperature3Dissolving in N, N-dimethylformamide, stirring for 0.5-1.5 hr to obtain 145-147g/L solution, adding CuI, stirring for 0.5-1.5 hr, adding thiourea, and stirring at room temperature for 15-30 hr to obtain CuInS2Reaction precursor solution of InCl3The molar ratio of CuI to thiourea is 1:1: 6-10;
mixing CuInS2Dropwise adding the reactant precursor solution on the obtained binary flat-plate heterojunction thin film, performing spin coating to form a film, and repeating the spin coating for 2 times to obtain CuInS2Reacting the precursor film; drying the obtained reaction precursor film in a 65 ℃ vacuum drying oven, placing the film on a hot table under the protection of inert gas, raising the temperature of the hot table to 120-180 ℃ and keeping the temperature for 4-6 minutes, then continuously raising the temperature to 200-300 ℃ and carrying out heat treatment on the sample for 5-15 minutes at the temperature; after the heat treatment is finished, the sample is naturally cooled to room temperature to obtain crystalline CuInS2A embryonic membrane; repeat the operation to CuInS2The thickness of the nano film reaches the standard to obtain TiO2CdS and CuInS2A ternary flat heterojunction film consisting of three nano films;
(4) spin-coating a layer of mixture solution of Spiro-OMeTAD, LiTFSI and TBP with the concentration of 60-90mg/mL on the ternary flat heterojunction thin film obtained in the step (3), and carrying out heat treatment for 5-15 minutes at 50-150 ℃ in the air to obtain a Spiro-OMeTAD thin film hole transport layer;
(5) evaporating an Au film on the Spiro-OMeTAD film hole transport layer obtained in the step (4) by a thermal evaporation method to obtain a solar cell based on the ternary inorganic flat heterojunction film;
(6) and (5) packaging the solar cell prepared in the step (5) under the protection of inert gas to obtain a solar cell product.
2. The solar cell based on a ternary inorganic flat heterojunction thin film according to claim 1, wherein: TiO 22The nano film is made of 20-30nm TiO2The CdS nano-film consists of 10-20nmCdS nanoparticles composition, CuInS2The nano film is made of CuInS with the thickness of 10-20nm2And (4) nano particles.
3. The solar cell based on a ternary inorganic flat heterojunction thin film according to claim 1, wherein: the thickness of the ITO layer is 100-300nm, and the thickness of the ITO layer is TiO2The thickness of the nano film is 50-150nm, the thickness of the CdS nano film is 50-100nm, and CuInS2The thickness of the nano film is 100-500nm, the thickness of the Spiro-OMeTAD film is 100-200nm, and the thickness of the Au film is 60-120 nm.
4. The solar cell based on a ternary inorganic flat heterojunction thin film according to claim 1, wherein: the Spiro-OMeTAD film is prepared from Spiro-OMeTAD, LiTFSI and TBP, and the molar ratio of Spiro-OMeTAD to LiTFSI to TBP is 1-3:1: 5-7.
5. The method of claim 1, wherein the method comprises: the chemical bath method of step (2) may be replaced with a spin coating method.
6. The method of claim 1, wherein the method comprises: the solvent of the Spiro-OMeTAD solution in the step (4) is chlorobenzene.
7. The method of claim 1, wherein the method comprises: the spin coating operation described in steps (3) and (4) may be replaced by screen printing, doctor blading or ink jet printing.
8. The method of claim 1, wherein the method comprises: and (4) taking nitrogen as the inert gas in the steps (3) and (6).
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