CN113725366A - Perovskite solar cell device based on polyvinyl acetate passivation film surface/interface defects and preparation method thereof - Google Patents
Perovskite solar cell device based on polyvinyl acetate passivation film surface/interface defects and preparation method thereof Download PDFInfo
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- 239000010409 thin film Substances 0.000 claims abstract description 12
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- 238000000137 annealing Methods 0.000 claims description 14
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 5
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 4
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
- H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
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- H—ELECTRICITY
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- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/80—Constructional details
- H10K30/88—Passivation; Containers; Encapsulations
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- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
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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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
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- Y02E10/549—Organic PV cells
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Abstract
The invention provides a perovskite solar cell device based on surface/interface defects of a polyvinyl acetate passivation film and a preparation method thereof. The basic structure of the perovskite solar cell photovoltaic device comprises: the light-absorbing layer comprises a conductive substrate, an electron transport layer, an organic-inorganic hybrid metal halide perovskite light-absorbing layer, an interface defect passivation layer, a hole transport layer and a photo-anode. The perovskite thin-film solar photovoltaic device is simple in preparation method and low in cost, the PVA interface defect passivation layer greatly reduces interface non-radiative recombination loss, inhibits ion migration and performance degradation of the interface of the light absorption layer and the hole transmission layer, improves photoelectric conversion efficiency and long-term stability of the device, and provides important theoretical basis and technical support for practicality of high-efficiency stable perovskite solar cells.
Description
Technical Field
The invention relates to a semiconductor material photovoltaic technology, in particular to a perovskite solar cell device based on surface/interface defects of a polyvinyl acetate (PVA) passivation film and a preparation method thereof.
Background
The development of advanced photovoltaic technology is a great demand of national energy strategy. Novel Perovskite Solar Cells (PSCs for short) are different in military prominence and rapid in development in recent years, and are expected to break through the existing principle and technologyAnd the solar energy collection device is limited, provides a revolutionary technical support for the development and efficient utilization of clean solar energy, and is greatly concerned by academia and industry. As a direct band gap semiconductor material, the metal halide perovskite material has perovskite crystal form ABX3(A＝MA+(CH3NH3 +)、FA+(NH(CH3)2 +)、 Cs+Etc., B ═ Pb2+、Sn2+Etc., X ═ I-、Br-、Cl-) And a series of excellent photoelectric characteristics, such as high extinction coefficient, long carrier diffusion, adjustable band gap, high defect tolerance and the like, and can be grown by a simple and low-cost solution method, so that the film can be brightly developed in the field of photoelectric devices. Particularly in the photovoltaic field, the Photoelectric Conversion Efficiency (PCE) of small-area single-junction PSCs has been recorded as high as 25.5%.
Currently, PSCs have become the leaders and the most promising next generation photovoltaic technology for low cost, high efficiency solar cells. However, the device stability still varies greatly from commercial application standards, which seriously hinders its large-scale industrial application. Like other semiconductor solar cells, the PCE loss and operational instability of PSCs are strongly related to non-radiative recombination of carriers. Reducing non-radiative recombination losses and suppressing interface degradation by reducing or passivating defects are the main strategies to improve the photoelectric performance and stability of PSCs. Therefore, it is important to understand the mechanism of the defect on the stability of the PSCs and to provide effective countermeasures to minimize the energy loss caused by non-radiative recombination.
In view of the negative effects of defects on the performance and stability of PSCs devices, many researchers have proposed many effective strategies. Such as: preparing micron-sized large-size perovskite crystal grains by an anti-solvent method so as to reduce the density of crystal boundary and vacancy defects in a light absorption layer; FA+/MA+Mixed cation, I-/Br-The mixed halogen ion perovskite is used as a light absorption layer of PSCs to increase the crystallization quality and phase stability of the film. In recent years, researchers have developed a number of passivation approaches to improve the PCE and stability of PSCs devices. Can be largeThe result is classified into the following three major categories: (i) anions or metal cations are doped to passivate point defects in the perovskite film so as to enhance the stability of the perovskite layer under the working condition; (ii) the stability of a perovskite layer and the interface related to the perovskite layer is improved by introducing alkylammonium halide or Lewis acid-base passivation to the grain boundary or surface defect of the perovskite film; (iii) using PbI2Or introduce wide band gap materials to passivate interfacial defects between the perovskite thin film and the charge transport layer (ETL and HTL) to improve interfacial stability under operating conditions.
Disclosure of Invention
The invention aims to provide a perovskite solar cell device based on PVA (polyvinyl alcohol) passivation film surface/interface defects, aiming at the problems of carrier non-radiative coincidence loss and interface ion migration caused by the surface/interface defects of the conventional organic-inorganic metal halide perovskite film, and the solar cell device has excellent efficiency and stability.
The technical scheme adopted by the invention is as follows:
a perovskite solar cell device based on polyvinyl acetate passivation film surface/interface defects comprises a conductive substrate, an electron transmission layer, an organic-inorganic hybrid metal halide perovskite light absorption layer, an interface defect passivation layer, a hole transmission layer and a photo-anode which are sequentially prepared; the conductive substrate is indium tin oxide conductive glass; the electron transport layer is SnO2A nanoparticle layer with a thickness of 10-20 nm; the light absorption layer of the organic-inorganic hybrid metal halide perovskite is FAxMA1- xPbIyCl3-yThe thickness of the perovskite thin film layer is 700-900 nm, wherein 0.8<x<1，2.4<y<3; the interface defect passivation layer is a PVA thin layer, and the thickness of the interface defect passivation layer is 3-10 nm; the hole transport layer is a solid electrolyte Spiro-OMeTAD layer, and the thickness of the hole transport layer is 220-250 nm; the photo-anode is a metal thin film layer, and the thickness of the photo-anode is 60-80 nm.
A preparation method of a perovskite solar cell device based on surface/interface defects of a polyvinyl acetate passivation film comprises the following steps: an electron transport layer, an organic-inorganic hybrid metal halide perovskite light absorption layer, an interface defect passivation layer and a hole transport layer are sequentially grown on a conductive substrate by adopting an all-solution method, and a photo-anode is evaporated on the hole transport layer to prepare the perovskite solar cell device based on the polyvinyl acetate passivation film surface/interface defect;
the preparation method of the electron transport layer comprises the following steps: mixing 15 wt% of SnO2The volume ratio of the aqueous solution of the nano particles to water is 1: 3 mixing, and obtaining transparent and uniform SnO under the room temperature condition2A solution; preparing by adopting a single-step spin coating method, starting a spin coater, setting 3000 revolutions for 30s, placing the conductive substrate after ozone treatment on a rotary bracket of the spin coater, fixing the conductive substrate by vacuum adsorption, and carrying out SnO treatment2Dropping the solution in the center of the conductive substrate, starting a spin coater, moving the sample to a hot plate at 145-165 ℃ after the spin coater stops rotating, annealing for 30-60 min, and cooling to room temperature to obtain SnO2An ITO sample; wherein each 60 μ L of SnO2The solution corresponds to the area of the conductive substrate of 1.5 × 1.5cm2；
The preparation method of the organic-inorganic hybrid metal halide perovskite light absorption layer comprises the following steps: first, 1.5mM of PbI is prepared2A solution, namely a mixed solution of DMF and DMSO with the volume ratio of 90-94: 10-6, is stirred at the temperature of 120-150 ℃ for 0.3-0.5 h to obtain a precursor solution I; then preparing 1.5mM mixed organic salt solution, wherein the solute comprises 140: 10: 14, stirring the mixture of FAI, MAI and MACl for 0.3 to 0.5 hour at room temperature to obtain a precursor solution II, wherein the solvent is isopropanol; the preparation method adopts a two-step spin coating method: firstly, uniformly coating a precursor solution I on SnO treated by ozone for 10-15 min2Starting a spin coater on the ITO sample, wherein the spin coating setting is 1500-30 s; after the spin coater stops rotating, moving the sample to a hot plate at 65-75 ℃, and annealing for 15-20 s; then the sample is moved into a vessel to be naturally cooled to room temperature, and PbI is obtained2/SnO2An ITO sample; wherein, the area relation between the first precursor solution and the conductive substrate is as follows: 20 to 30 μ L for 1.5X 1.5cm2A conductive substrate; and secondly, starting a spin coater, wherein the spin coating setting is 2000-25 s, and dropping the precursor solution II on the PbI stably at a constant speed within 14-16 s after the rotation is finished2/SnO2On ITO samples, spin coater stoppedThen, moving the sample to a hot plate at 85-95 ℃, annealing for 25-35 s, and then moving the sample to a vessel to naturally cool to room temperature; then transferring the sample to a hot plate at 145-155 ℃, annealing for 10-12 min, and controlling the humidity at 35-45% to obtain perovskite/SnO2An ITO sample; and the area relation between the precursor solution II and the conductive substrate is as follows: 60 μ L for 1.5X 1.5cm2A conductive substrate;
the preparation method of the interface defect passivation layer comprises the following steps: dissolving PVA in chlorobenzene to obtain a chlorobenzene solution with the concentration of 5mg/mL, stirring for 20-30 h at 70-100 ℃, and standing for 8-10 h at room temperature to obtain a transparent and uniform solution; the preparation method adopts a single-step spin coating method, a spin coating machine is started, 5000 turns are set for 30s, and perovskite/SnO is put2The ITO sample is placed on a rotary bracket of a spin coater to be fixed through vacuum adsorption, the spin coater is started, and the prepared PVA chlorobenzene solution is stably dripped on the rotating perovskite/SnO at a constant speed within 20-22 s from the end of rotation2On an ITO sample, after the spin coater stops rotating, the sample is moved to a hot plate at 70-80 ℃, annealing is carried out for 3-5 min, and PVA/perovskite/SnO is obtained2An ITO sample; wherein, the area relation between the PVA solution and the conductive substrate is as follows: 80 μ L for 1.5X 1.5cm2A conductive substrate;
the preparation method of the hole transport layer comprises the following steps: the mass-volume ratio of the hole transport material Spiro-OMeTAD to the chlorobenzene solution is 723 mg: 10mL of the solution is mixed, and then 4-tert-butylpyridine and a lithium bistrifluoromethanesulfonylimide solution are sequentially added; chlorobenzene solution: 4-tert-butylpyridine: the volume ratio of the lithium bistrifluoromethanesulfonylimide solution is 10000: 288: 175; the preparation method adopts a single-step spin coating method, a spin coating machine is started, 3000 revolutions are set for 30s, and PVA/perovskite/SnO is added2The ITO sample is placed on a rotary bracket of a spin coater and fixed through vacuum adsorption, the spin coater is started, and the prepared Spiro-OMeTAD solution is stably dripped on the rotating PVA/perovskite/SnO at a constant speed within 18-20 s from the end of rotation2On the ITO sample, after the spin coater stops rotating, the sample is moved to a culture dish; wherein, the relationship between the area of the Spiro-OMeTAD solution and the area of the conductive substrate is as follows: 15 μ L for 1.5X 1.5cm2A conductive substrate;
finally, the gold electrode is evaporated to obtain the structure of Au/Spiro-OMeTAD/PVA/perovskite/SnO2ITO/organic-inorganic hybrid metal halide perovskite solar cell device based on PVA passivation film surface/interface defects.
The invention has the beneficial effects that:
1) the invention discloses a perovskite solar cell device based on PVA (polyvinyl alcohol) passivation film surface/interface defects, which is characterized in that an electron injection layer (SnO) is sequentially grown on a conductive ITO (indium tin oxide) substrate by adopting a full low-temperature solution method2) Perovskite light absorption layers, passivation layers and hole injection layers (Spiro-OMeTAD). The carrier life of the PSCs prepared by the method is measured to be 1.16 mu s at room temperature; meanwhile, the PSCs show excellent photoelectric conversion characteristics, the interface between the PVA organic passivation layer and the mixed perovskite layer greatly contributes to the excellent light stability of the PSCs, and the photoelectric conversion efficiency can still keep more than 76% of the initial efficiency after 1000-hour continuous light irradiation. In view of the advantages of the PSCs, the excellent efficiency and stability will inevitably expand its application area.
2) The invention creatively introduces the cheap nontoxic polymer PVA, provides a passivation layer by utilizing the relationship between the molecular structure of the PVA and the steric hindrance and the interaction force of the surface defects of the perovskite thin film, and solves the stability problem of the perovskite device.
3) The perovskite solar cell device based on the surface/interface defects of the PVA passivation film is simple and feasible in preparation and passivation method and low in cost.
Drawings
FIG. 1 is a cross-sectional SEM image of a perovskite solar cell device based on PVA passivation film surface/interface defects;
in FIG. 2, a and b are respectively the partial charge distribution of PVA polymer obtained by Density Functional Theory (DFT) calculation and iodine vacancy (V) on the surface of polymer and perovskite crystalI) Interaction energy of defect interaction (E)int)；
In FIG. 3, a and b are Scanning Electron Microscope (SEM) images of the perovskite thin film before and after PVA passivation, respectively;
FIG. 4 is an X-ray diffraction (XRD) spectrum of a perovskite thin film before and after PVA passivation;
FIG. 5 is a time-resolved PL decay curve with carrier lifetimes of 0.24 and 1.16 μ s before and after PVA modification, respectively, as calculated by double-exponential fitting;
FIG. 6 is a current-voltage (J-V) curve with the solid and dashed lines being data obtained by reverse and forward scans, respectively;
FIG. 7 is a graph of stable output efficiency;
FIG. 8 shows the photoelectric conversion efficiency under continuous illumination (90. + -. 10 mWcm)-2) Evolution process in a hot environment (85 ℃, nitrogen atmosphere);
FIG. 9 shows trap density curves for PSCs devices before and after PVA modification.
Detailed Description
The following further describes a specific embodiment of the present invention with reference to the drawings and technical solutions.
Example 1
SnO2The preparation method of the electron transport layer comprises the following steps: SnO2Mixing the solution of the nano particles and high-purity water in a volume ratio of 1: 3, stirring for 10min at room temperature to obtain transparent and uniform SnO2And (3) solution.
The preparation method of the perovskite precursor liquid comprises the following steps: step 1, firstly, 691.5mg of PbI2Adding the mixture into a mixed solvent of DMF and DMSO with the volume ratio of 900-940: 60-100 mu L for dissolving, and stirring for 0.3-0.5 h at the temperature of 120-150 ℃ to obtain a precursor solution I; step 2: 271.5mg HC (NH)2)2I(FAI)、19.5mg CH3NH3I (MAI) and 27.3mg CH3NH3And dissolving Cl (MACl) in 3mL of isopropanol to obtain a mixed organic salt solution, and stirring at room temperature for 0.3-0.5 h to obtain a precursor solution II.
The preparation method of the PVA passivation layer comprises the following steps: PVA is dissolved in high-purity chlorobenzene to obtain a chlorobenzene solution with the PVA concentration of 5mg/1mL, the chlorobenzene solution is stirred for 24 hours at the temperature of 80 ℃, and the solution is kept stand for 8 hours at room temperature to obtain a transparent and uniform solution.
Preparation method of hole transport layer Spiro-OMeTAD solution: 72.3mg of the hole transport material, Spiro-OMeTAD, was added to 1mL of chlorobenzene solution, followed by 28.8. mu.L of 4-tert-butylpyridine and 17.5. mu.L of lithium bistrifluoromethanesulfonylimide solution.
For PVA/perovskite/SnO grown under the above conditions2The passivation effect of PVA on the surface of the perovskite thin film is determined from both theoretical and test results by performing theoretical calculation (see FIG. 2), XRD (see FIG. 3) of the surface of the thin film, surface morphology (see FIG. 4) and the like tests on ITO (see FIG. 1).
Example 2:
the embodiment discloses a perovskite solar cell device based on PVA passivation film surface/interface defects, which comprises the following preparation steps:
the substrate is made of ITO with electric conduction grown on glass. SnO prepared by example 12Solution, perovskite precursor solution, PVA solution and Spiro-OMeTAD solution.
(1) Before preparing the electron transport layer, the substrate was first cleaned, the substrate being 15X 15mm2Square glass with one side coated with 7.5X 15mm2ITO of (2). Ultrasonic cleaning with detergent, deionized water, ethanol and isopropanol for 30 min. N for washed substrate2Blowing by an air gun, placing into a watch glass, treating for 12min by using ultraviolet-ozone cleaning equipment, and storing in a dust-free environment for later use.
(2) SnO preparation method adopting single-step spin coating process2An electron transport layer. Starting the spin coater, setting 3000 r 30s, placing the ITO substrate treated by ozone on a rotary bracket of the spin coater, fixing by vacuum adsorption, and taking 75 μ L SnO2Dropping the solution in the center of the ITO substrate, starting a spin coater, moving the sample to a hot plate at 150 ℃ after the spin coater stops rotating, annealing for 40min, cooling to room temperature, and then adding ozone for treatment for 10-15 min;
(3) the perovskite light absorption layer is prepared by a two-step spin coating method; firstly, 20-25 mu L of PbI2The precursor solution is uniformly coated on the SnO treated by ozone2Starting a spin coater on the ITO sample, wherein the spin coating setting is 1500-30 s; after the spin coater stops rotating, moving the sample to a hot plate at 70 ℃, and annealing for 15-20 s; then moving the sample into a vessel and naturally cooling to room temperature; second oneStarting a spin coater, wherein the spin coating setting is 2000-25 s, and 70-75 mu L of mixed organic salt solution is stably dripped on the rotating PbI at a constant speed between 15-16 s after the rotation is finished2/SnO2On the ITO substrate, after the spin coater stops rotating, the sample is moved to a hot plate at 90 ℃, annealed for 25-35 s, and then moved to a vessel to be naturally cooled to room temperature; then the sample is transferred to a hot plate at 150 ℃ and annealed for 10min, and the humidity is controlled at 35-45%.
(4) Preparing a PVA passivation layer by adopting a single-step spin coating method, starting a spin coating machine, setting 5000 turns for 30s, and carrying out Perovskite/SnO2The ITO sample is placed on a rotary bracket of a spin coater to be fixed through vacuum adsorption, the spin coater is started, the prepared PVA chlorobenzene solution is dripped on the rotating perovskite/SnO in a stable and uniform speed within 20-22 s from the end of rotation2On the ITO sample, after the spin coater stops rotating, the sample is moved to a hot plate at 80 ℃ and annealed for 3 min;
(5) preparing a hole transport layer Spiro-OMeTAD by adopting a single-step dynamic spin coating method, namely setting a spin coater to rotate for 25s, placing a prepared semi-finished product, starting the spin coater, dropping 14uL of prepared Spiro-OMeTAD solution on a rotating sample at a constant speed within 15-18 s from the end of rotation, and stopping the spin coater to obtain the sample for steaming an electrode.
(6) And (4) evaporating the gold electrode by adopting a thermal evaporation method. And putting a sample of the hole transport layer Spiro-OMeTAD in a designed metal mold, and evaporating metal Au on the surface layer (with the thickness of about 60nm) of the hole transport layer Spiro-OMeTAD by using a vacuum coating instrument to obtain the perovskite solar cell device with a complete structure.
For Au/Spiro-OMeTAD/PVA/perovskite/SnO grown under the above conditions2the/ITO carries out the life test of the current carrier. Test results show that after PVA modification and passivation, the fluorescence intensity and the carrier lifetime of the perovskite thin film (see figure 5) are greatly increased.
Example 3:
the embodiment discloses a perovskite solar cell device based on PVA passivation film surface/interface defects, which comprises the following preparation steps:
the substrate is made of ITO with electric conduction grown on glass. SnO prepared by example 12Solution, perovskite precursor solution, PVA solution and Spiro-OMeTAD solution.
(1) Before preparing the electron transport layer, the substrate was first cleaned, the substrate being 15X 15mm2Square glass with one side coated with 7.5X 15mm2ITO of (2). Ultrasonic cleaning with detergent, deionized water, ethanol and isopropanol for 30 min. N for washed substrate2Blowing by an air gun, placing into a watch glass, treating for 12min by using ultraviolet-ozone cleaning equipment, and storing in a dust-free environment for later use.
(2) SnO preparation method adopting single-step spin coating process2An electron transport layer. Starting the spin coater, setting 3000 r 30s, placing the ITO substrate treated by ozone on a rotary bracket of the spin coater, fixing by vacuum adsorption, and taking 75 μ L SnO2Dropping the solution in the center of the ITO substrate, starting a spin coater, moving the sample to a hot plate at 150 ℃ after the spin coater stops rotating, annealing for 40min, cooling to room temperature, and then adding ozone for treatment for 10-15 min;
(3) the perovskite light absorption layer is prepared by a two-step spin coating method; firstly, 20-25 mu L of PbI2The precursor solution is uniformly coated on the SnO treated by ozone2Starting a spin coater on the ITO sample, wherein the spin coating setting is 1500-30 s; after the spin coater stops rotating, moving the sample to a hot plate at 70 ℃, and annealing for 15-20 s; then moving the sample into a vessel and naturally cooling to room temperature; and secondly, starting a spin coater, wherein the spin coating setting is 2000-25 s, and 70-75 mu L of mixed organic salt solution is stably dripped on the rotating PbI at a constant speed within 15-16 s from the end of the rotation2/SnO2On the ITO substrate, after the spin coater stops rotating, the sample is moved to a hot plate at 90 ℃, annealed for 25-35 s, and then moved to a vessel to be naturally cooled to room temperature; then the sample is transferred to a hot plate at 150 ℃ and annealed for 10min, and the humidity is controlled at 35-45%.
(4) Preparing a PVA passivation layer by adopting a single-step spin coating method, starting a spin coating machine, setting 5000 turns for 30s, and carrying out Perovskite/SnO2Putting the ITO sample on a rotary bracket of a spin coater and sucking the ITO sample by vacuumFixing, starting a spin coater, taking the prepared PVA chlorobenzene solution, and dripping the PVA chlorobenzene solution onto the rotating perovskite/SnO at a stable and uniform speed within 20-22 s from the end of rotation2On the ITO sample, after the spin coater stops rotating, the sample is moved to a hot plate at 80 ℃ and annealed for 3 min;
(5) preparing a hole transport layer Spiro-OMeTAD by adopting a single-step dynamic spin coating method, namely setting a spin coater to rotate for 25s, placing a prepared semi-finished product, starting the spin coater, dropping 14uL of prepared Spiro-OMeTAD solution on a rotating sample at a constant speed within 15-18 s from the end of rotation, and stopping the spin coater to obtain the sample for steaming an electrode.
(6) And (4) evaporating the gold electrode by adopting a thermal evaporation method. And putting a sample of the hole transport layer Spiro-OMeTAD in a designed metal mold, and evaporating metal Au on the surface layer (with the thickness of about 60nm) of the hole transport layer Spiro-OMeTAD by using a vacuum coating instrument to obtain the perovskite solar cell device with a complete structure.
For Au/Spiro-OMeTAD/PVA/perovskite/SnO grown under the above conditions2the/ITO was subjected to a current-voltage (J-V) test, a stability test and a trap state density test. Test results show that after PVA modification and passivation, the efficiency and the working stability of the device are greatly increased (see figures 6, 7 and 8); the defect state density decreases (see fig. 9).
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (2)
1. The perovskite solar cell device based on the surface/interface defects of the polyvinyl acetate passivation film is characterized by comprising a conductive substrate, an electron transport layer, a first conductive layer, a second conductive layer, a third conductive layer, a fourth conductive layer and a fourth conductive layer, wherein the electron transport layer, the third conductive layer and the fourth conductive layer are sequentially prepared,An organic-inorganic hybrid metal halide perovskite light absorption layer, an interface defect passivation layer, a hole transport layer and a photo-anode; the conductive substrate is indium tin oxide conductive glass; the electron transport layer is SnO2A nanoparticle layer with a thickness of 10-20 nm; the light absorption layer of the organic-inorganic hybrid metal halide perovskite is FAxMA1-xPbIyCl3-yThe thickness of the perovskite thin film layer is 700-900 nm, wherein 0.8<x<1，2.4<y<3; the interface defect passivation layer is a PVA thin layer, and the thickness of the interface defect passivation layer is 3-10 nm; the hole transport layer is a solid electrolyte Spiro-OMeTAD layer, and the thickness of the hole transport layer is 220-250 nm; the photo-anode is a metal thin film layer, and the thickness of the photo-anode is 60-80 nm.
2. A preparation method of a perovskite solar cell device based on surface/interface defects of a polyvinyl acetate passivation film is characterized by comprising the following steps: an electron transport layer, an organic-inorganic hybrid metal halide perovskite light absorption layer, an interface defect passivation layer and a hole transport layer are sequentially grown on a conductive substrate by adopting an all-solution method, and a photo-anode is evaporated on the hole transport layer to prepare the perovskite solar cell device based on the polyvinyl acetate passivation film surface/interface defect;
the preparation method of the electron transport layer comprises the following steps: mixing 15 wt% of SnO2The volume ratio of the aqueous solution of the nano particles to water is 1: 3 mixing, and obtaining transparent and uniform SnO under the room temperature condition2A solution; preparing by adopting a single-step spin coating method, starting a spin coater, setting 3000 revolutions for 30s, placing the conductive substrate after ozone treatment on a rotary bracket of the spin coater, fixing the conductive substrate by vacuum adsorption, and carrying out SnO treatment2Dropping the solution in the center of the conductive substrate, starting a spin coater, moving the sample to a hot plate at 145-165 ℃ after the spin coater stops rotating, annealing for 30-60 min, and cooling to room temperature to obtain SnO2An ITO sample; wherein each 60 μ L of SnO2The solution corresponds to the area of the conductive substrate of 1.5 × 1.5cm2；
The preparation method of the organic-inorganic hybrid metal halide perovskite light absorption layer comprises the following steps: first, 1.5mM of PbI is prepared2The volume ratio of the solvent to the solution is 90-94: 10-6 of a mixed solution of DMF and DMSO, and stirring for 0.3-0.5 h at 120-150 ℃ to obtain a precursor solution I; then preparing 1.5mM mixed organic salt solution, wherein the solute comprises 140: 10: 14, stirring the mixture of FAI, MAI and MACl for 0.3 to 0.5 hour at room temperature to obtain a precursor solution II, wherein the solvent is isopropanol; the preparation method adopts a two-step spin coating method: firstly, uniformly coating a precursor solution I on SnO treated by ozone for 10-15 min2Starting a spin coater on the ITO sample, wherein the spin coating setting is 1500-30 s; after the spin coater stops rotating, moving the sample to a hot plate at 65-75 ℃, and annealing for 15-20 s; then the sample is moved into a vessel to be naturally cooled to room temperature, and PbI is obtained2/SnO2An ITO sample; wherein, the area relation between the first precursor solution and the conductive substrate is as follows: 20 to 30 μ L for 1.5X 1.5cm2A conductive substrate; and secondly, starting a spin coater, wherein the spin coating setting is 2000-25 s, and dropping the precursor solution II on the PbI stably at a constant speed within 14-16 s after the rotation is finished2/SnO2On an ITO sample, after a spin coater stops rotating, moving the sample to a hot plate at 85-95 ℃, annealing for 25-35 s, and then moving the sample to a vessel to naturally cool to room temperature; then transferring the sample to a hot plate at 145-155 ℃, annealing for 10-12 min, and controlling the humidity at 35-45% to obtain perovskite/SnO2An ITO sample; and the area relation between the precursor solution II and the conductive substrate is as follows: 60 μ L for 1.5X 1.5cm2A conductive substrate;
the preparation method of the interface defect passivation layer comprises the following steps: dissolving PVA in chlorobenzene to obtain a chlorobenzene solution with the concentration of 5mg/mL, stirring for 20-30 h at 70-100 ℃, and standing for 8-10 h at room temperature to obtain a transparent and uniform solution; the preparation method adopts a single-step spin coating method, a spin coating machine is started, 5000 turns are set for 30s, and perovskite/SnO is put2The ITO sample is placed on a rotary bracket of a spin coater to be fixed through vacuum adsorption, the spin coater is started, and the prepared PVA chlorobenzene solution is stably dripped on the rotating perovskite/SnO at a constant speed within 20-22 s from the end of rotation2On an ITO sample, after the spin coater stops rotating, the sample is moved to a hot plate at 70-80 ℃, annealing is carried out for 3-5 min, and PVA/perovskite/SnO is obtained2An ITO sample; whereinThe area relationship between the PVA solution and the conductive substrate is as follows: 80 μ L for 1.5X 1.5cm2A conductive substrate;
the preparation method of the hole transport layer comprises the following steps: the mass-volume ratio of the hole transport material Spiro-OMeTAD to the chlorobenzene solution is 723 mg: 10mL of the solution is mixed, and then 4-tert-butylpyridine and a lithium bistrifluoromethanesulfonylimide solution are sequentially added; chlorobenzene solution: 4-tert-butylpyridine: the volume ratio of the lithium bistrifluoromethanesulfonylimide solution is 10000: 288: 175; the preparation method adopts a single-step spin coating method, a spin coating machine is started, 3000 revolutions are set for 30s, and PVA/perovskite/SnO is added2The ITO sample is placed on a rotary bracket of a spin coater and fixed through vacuum adsorption, the spin coater is started, and the prepared Spiro-OMeTAD solution is stably dripped on the rotating PVA/perovskite/SnO at a constant speed within 18-20 s from the end of rotation2On the ITO sample, after the spin coater stops rotating, the sample is moved to a culture dish; wherein, the relationship between the area of the Spiro-OMeTAD solution and the area of the conductive substrate is as follows: 15 μ L for 1.5X 1.5cm2A conductive substrate;
finally, the gold electrode is evaporated to obtain the structure of Au/Spiro-OMeTAD/PVA/perovskite/SnO2ITO/organic-inorganic hybrid metal halide perovskite solar cell device based on PVA passivation film surface/interface defects.
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| CN115000185A (en) * | 2022-05-17 | 2022-09-02 | 武汉大学 | Ammonium fluoride salt passivated carbon-based inorganic perovskite solar cell and preparation method thereof |
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