Semitransparent organic-inorganic hybrid perovskite solar cells based on conducting polymers

Abstract

A semi-transparent organic-inorganic hybrid perovskite solar cell based on a conductive polymer, when the conductive substrate is defined as the bottom layer, includes, from bottom to top: a conductive substrate layer; a tin dioxide electron transport layer; an organic-inorganic hybrid perovskite light absorption layer; a conductive polymer modified hole transport layer; and a counter electrode. The present invention proposes a novel semi-transparent perovskite solar cell structure, which improves the environmental stability of the device by doping the hole transport layer with an appropriate amount of polymer and utilizing the interaction between the polymer and the small molecule additive in the hole transport layer; in addition, it can improve the quality of the hole transport layer film, increase the oxidation degree of the hole transport material, reduce the defect state in the film, and improve the conductivity of the hole transport layer. At the same time, it can reduce the thickness of the metal counter electrode, reduce the device preparation cost, and construct a semi-transparent perovskite device to achieve the effect of double-sided light response.

Description

Technical Field

[0001] The invention relates to a semi-transparent perovskite solar cell, in particular to a semi-transparent organic-inorganic hybrid perovskite solar cell. Background Art

[0002] Semi-transparent perovskite solar cells (ST-PSCs) can convert solar energy from both the front and back sides into electrical energy, and the output power can exceed 50% by collecting the reflected radiation rate of the surrounding environment. With the development of semi-transparent perovskite solar cells, its application fields are becoming more and more extensive, especially in the fields of tandem solar cells, building integrated photovoltaics (BIPV) and wearable electronics. In actual production, the cost and stability of semi-transparent perovskite solar cells are particularly important. However, since semi-transparent solar cells need to comprehensively consider the photoelectric conversion efficiency and the transparency of the entire device, in other words, it is necessary to balance the relationship between the average visible light transparency (AVT) and the photoelectric conversion efficiency. Semi-transparent devices are limited by transparency. Compared with the photoelectric conversion efficiency of opaque devices, which has reached 25.8%, the efficiency of semi-transparent devices is far from this level. For semi-transparent devices, the key is to use highly transparent conductive electrodes to replace the opaque electrodes in perovskites, which allows sunlight to irradiate from both the front and back sides at the same time to transmit photons with energy lower than the perovskite band gap. Some early work has been carried out around the optimization of thin counter electrodes for semi-transparent devices. For example, Au, Ag nanowires, PEDOT:PSS, graphene, carbon nanotubes, mesh metals, ITO / FTO, and IZO have been proven to be transparent contact electrodes for semi-transparent devices, mainly to improve the photoelectric conversion efficiency. However, the environmental stability of semi-transparent perovskite solar cells still faces huge challenges.

[0003] The stability of semi-transparent perovskite solar cells is the main obstacle to their commercialization, and therefore has attracted the attention of many researchers. Common means of stabilizing PSCs include replacing methylamine ions with some rare metal elements (Rb and Cs, etc.) to improve the thermal stability of the device, and replacing commonly used organic small molecule hole transport materials with stable inorganic small molecules (NiO, CuI, etc.). In addition, there are many studies on the decomposition of the perovskite layer and the instability of the device caused by internal and external factors. Studies have also shown that when Au is used as the top counter electrode, it is beneficial to the stability of the device. The above methods are almost all based on opaque PSCs, and few studies have reported on ST-PSCs.

[0004] Improving the stability of ST-PSCs is essential for the practical application of ST-PSCs. The degradation of perovskite solar cells is mainly attributed to the external environment and its own preparation process, including 1) the degradation of hybrid perovskite materials caused by humidity, oxygen, and ultraviolet light; 2) the irreversible interface reaction between the perovskite layer and the additives LiTFSI and tBP in the hole transport layer; 3) the metal migration from the counter electrode to the hole transport layer, so the degradation of the device caused by the internal ion migration poses a great threat to the stability of the device.

[0005] Because of its low conductivity, the main components of the commonly used hole transport layer contain LiTFSI and tBP. The role of LiTFSI is to improve the conductivity of the hole transport layer, and tBP is to prevent its agglomeration. LiTFSI is very easy to absorb water, and tBP will dissolve the perovskite material. During the storage of the device, it may also form a coordinated complex PbI 2 -t-BP, causing instability in the perovskite layer and device. Summary of the invention

[0006] The technical problem to be solved by the present invention is to overcome the above-mentioned defects of the prior art and provide a semi-transparent organic-inorganic hybrid perovskite solar cell based on a conductive polymer with good stability.

[0007] The technical solution adopted by the present invention to solve the technical problem is: a semi-transparent organic-inorganic hybrid perovskite solar cell based on a conductive polymer, when the conductive substrate is defined as the bottom layer, from bottom to top, it includes: a conductive substrate layer; a tin dioxide electron transport layer; an organic-inorganic hybrid perovskite CH 3 NH 3 BX 3 A light absorbing layer, wherein B is Pb, Sn, In or Ge, and X is one or more of I, Br or Cl; a conductive polymer modified hole transport layer made of conductive polymer and hole transport material; and a counter electrode.

[0008] Preferably, the conductive substrate layer is transparent ITO conductive glass.

[0009] Preferably, the conductive polymer is one or more of polyaniline (PANI), polythiophene, polypyrrole (PVP), and poly (3,4-ethylenedioxythiophene:polystyrene sulfonate) (PEDOT:PSS).

[0010] Preferably, the hole transport material is a small molecule polymer, more preferably Spiro-OMeTAD and / or P3HT.

[0011] Preferably, the preparation method of the semi-transparent organic-inorganic hybrid perovskite solar cell based on conductive polymer comprises the following steps:

[0012] (1) Cleaning the transparent ITO conductive glass to obtain a transparent conductive substrate;

[0013] (2) preparing a tin dioxide electron transport layer on the surface of the conductive substrate;

[0014] (3) Preparing an organic-inorganic hybrid perovskite CH on the surface of the tin dioxide electron transport layer 3 NH 3 BX 3 Light absorbing layer;

[0015] (4) In the organic-inorganic hybrid perovskite CH 3 NH 3 BX 3 A conductive polymer-modified hole transport layer is prepared on the surface of the light-absorbing layer;

[0016] (5) Vapor-depositing a thin metal counter electrode on the surface of the conductive polymer modified hole transport layer.

[0017] More preferably, in step (1), the cleaning method is: placing the transparent ITO conductive glass in deionized water, anhydrous ethanol, and isopropanol, respectively, and ultrasonically vibrating for 10 to 20 minutes, baking at 80 to 120° C. for 5 to 15 minutes (for removing visible impurities on the surface), and treating with ultraviolet ozone for 20 to 30 minutes (for removing organic groups on the surface to reduce the water contact angle).

[0018] More preferably, in step (2), the preparation method of the tin dioxide electron transport layer is: dropwise adding a tin dioxide colloidal dispersion onto the surface of the conductive substrate, spin coating at 4000-6000 rpm for 20-30 s (to form a uniform film), and heating at 150-180 ° C for 30-40 min.

[0019] Further preferably, in step (2), the tin dioxide colloidal dispersion is prepared by mixing tin dioxide colloid and deionized water in a volume ratio of 1:1-4 and then ultrasonically dispersing the mixture.

[0020] More preferably, in step (3), the filtered organic-inorganic hybrid perovskite precursor is dripped onto the surface of the tin dioxide electron transport layer, spin-coated, heat-treated, and annealed to obtain an organic-inorganic hybrid perovskite CH 3 NH 3 BX 3 Light absorbing layer.

[0021] More preferably, in step (3), the preparation method of the organic-inorganic hybrid perovskite precursor solution is: mixing CH 3 NH 3 X and BX2 Dissolve in a mixture of dimethyl sulfoxide (DMSO) and N,N-dimethylformamide (DMF), heat and stir at 65-75 °C for 4-12 h.

[0022] Further preferably, in step (3), in the organic-inorganic hybrid perovskite precursor solution, CH 3 NH 3 The amount of X added is equivalent to 15~20% of the total mass of the precursor solution, BX 2 The amount of added is equivalent to 20%~30% of the total mass of the precursor solution, the amount of added dimethyl sulfoxide is equivalent to 40%~50% of the total mass of the precursor solution, and the amount of added N,N-dimethylformamide is equivalent to 10%~25% of the total mass of the precursor solution.

[0023] Further preferably, in step (3), the diameter of the filter head used for filtration is 0.22 to 0.45 m.

[0024] Further preferably, in step (3), the spin coating speed is 4000-7000 rpm and the time is 20-40 s.

[0025] Further preferably, in step (3), when the spin coating reaches the countdown of 19 to 24 s, 200 to 300 L Ethyl acetate or chlorobenzene solution (to help the perovskite crystallize quickly).

[0026] Further preferably, in step (3), the heat treatment temperature is 70-110° C. and the time is 10-20 min. After this heat treatment, a smooth perovskite film is obtained by annealing.

[0027] More preferably, in step (4), the conductive polymer / hole transport material mixed solution is added dropwise to the organic-inorganic hybrid perovskite CH 3 NH 3 BX 3 The surface of the light absorbing layer is spin coated to obtain a conductive polymer modified hole transport layer.

[0028] Further preferably, in step (4), in the conductive polymer / hole transport material mixed solution, the mass of the conductive polymer is less than 5wt% of the total mass of the solution, the mass of lithium bis(trifluoromethanesulfonyl)imide is 0.2-2% of the total mass of the solution, the mass of 4-tert-butylpyridine is 0.8-3% of the total mass of the solution, the mass of chlorobenzene is 60-80% of the total mass of the solution, and the mass of the hole transport material is 10%-30% of the total mass of the solution.

[0029] Further preferably, in step (4), the spin coating speed is 2000-4000 rpm and the time is 30-40 s.

[0030] More preferably, in step (5), a thin metal counter electrode is deposited by vacuum evaporation.

[0031] More preferably, in step (5), the vacuum evaporation rate is 0.1-0.6 nm / s, and the thickness of the thin metal counter electrode is 10-60 nm.

[0032] More preferably, gold is used as the plated metal.

[0033] The feature of the present invention is to propose a new type of semi-transparent perovskite solar cell structure, by doping the hole transport layer with an appropriate amount of polymer, utilizing the interaction between the polymer and the small molecule additive in the hole transport layer, inhibiting the hygroscopicity of the additive, and improving the environmental stability of the device. Polymer doping can also improve the quality of the hole transport layer film, increase the oxidation degree and charge extraction efficiency of the hole transport material, reduce the defect state in the film, and reduce the device cost by evaporating ultra-thin metal counter electrodes, and construct a semi-transparent perovskite device to achieve the effect of double-sided light response. The present invention controls the morphology and optical properties of the commonly used hole transport layer by developing an efficient modification method, improves the stability of the organic-inorganic hybrid perovskite solar cell; and constructs a semi-transparent perovskite solar cell of a new structure together with a thin metal counter electrode, optimizes the doping concentration and the thickness of the metal counter electrode, and further improves the photoelectric conversion efficiency of the semi-transparent perovskite solar cell with double-sided light response. In general, the present invention will provide a theoretical and technical basis for the development of highly stable and low-cost semi-transparent perovskite solar cells.

[0034] Compared with the prior art, the advantages of the present invention are:

[0035] (1) To overcome the problem of poor stability of semi-transparent perovskite solar cells based on commonly used hole transport layers due to the presence of additives in the prior art, a new semi-transparent perovskite solar cell structure is proposed. By doping the hole transport layer with an appropriate amount of polymer and utilizing the interaction between the polymer and the small molecule additives in the hole transport layer, the environmental stability of the device is improved;

[0036] (2) The polymer forms a mesh structure between the hole transport layer and the counter electrode to block the erosion of water in the air and the corrosion of the metal counter electrode, thereby maintaining the environmental stability of the hole transport layer, the perovskite layer and the device. The conductive polymer has good conductivity. The doped polymer improves the conductivity of the hole transport layer and can reduce the thickness of the metal counter electrode, thereby reducing the cost of device preparation.

[0037] (3) Polymer doping can also improve the quality of the hole transport layer film, increase the degree of oxidation of the hole transport material, and reduce the defect states in the film;

[0038] (4) The ultra-thin metal counter electrode is evaporated to reduce the device cost and construct a semi-transparent perovskite device to achieve a double-sided light response effect. DETAILED DESCRIPTION

[0039] In order to facilitate the understanding of the present invention, the present invention will be described more comprehensively and carefully in combination with preferred embodiments below, but the protection scope of the present invention is not limited to the following specific embodiments.

[0040] Unless otherwise defined, all the professional terms used below have the same meanings as those generally understood by those skilled in the art. The professional terms used herein are only for the purpose of describing specific embodiments and are not intended to limit the scope of protection of the present invention.

[0041] Unless otherwise specified, all reagents and raw materials used in the present invention are commercially available products or products that can be prepared by known methods.

[0042] Example 1

[0043] The semi-transparent organic-inorganic hybrid perovskite solar cell based on conductive polymer in this embodiment, when the conductive substrate is defined as the bottom layer, includes from bottom to top: a transparent ITO conductive glass substrate layer; a tin dioxide electron transport layer; an organic-inorganic hybrid perovskite CH 3 NH 3 SnClI 2 Light absorbing layer; conductive polymer modified hole transport layer made of PANI (conductive polymer) and P3HT (hole transport material) as raw materials; gold counter electrode.

[0044] The semi-transparent organic-inorganic hybrid perovskite solar cell based on conductive polymer in this embodiment has a preparation method comprising the following steps:

[0045] (1) Cleaning the transparent ITO conductive glass to obtain a transparent conductive substrate: Use deionized water, anhydrous ethanol, and isopropanol to clean the ITO conductive glass by ultrasonic oscillation for 10 min, then put it in an oven at 100 °C for 8 min to remove visible impurities on the surface, and then treat it in a UV ozone treatment machine for 25 min to remove organic groups on the surface to reduce the water contact angle;

[0046] (2) preparing a tin dioxide electron transport layer on the surface of the transparent conductive substrate obtained in step (1): dripping a tin dioxide colloidal dispersion onto the transparent conductive substrate treated with ozone, spinning it at 5000 rpm for 20 s to form a uniform film, and heating it on a heating table at 160° C. for 35 min to obtain a tin dioxide electron transport layer, wherein the tin dioxide colloidal dispersion is prepared by ultrasonically dispersing a tin dioxide colloidal dispersion and deionized water in a volume ratio of 1:4;

[0047] (3) Preparing an organic-inorganic hybrid perovskite CH on the surface of the tin dioxide electron transport layer obtained in step (2) 3 NH 3 SnClI 2 Light absorbing layer;

[0048] (3-I) CH 3 NH 3 Cl and SnI 2 , dissolved in a mixed solution of dimethyl sulfoxide (DMSO) and N,N-dimethylformamide (DMF) in a volume ratio of 1:4, heated and stirred at 65 °C for 4 h to obtain an organic-inorganic hybrid perovskite precursor solution, in which CH 3 NH 3 The amount of Cl added is equivalent to 18% of the total mass, SnI 2 The amount of solvent added is equivalent to 22% of the total mass, the amount of DMSO solvent added is equivalent to 45% of the total mass, and the amount of DMF solvent added is equivalent to 15% of the total mass;

[0049] (3-II) The organic-inorganic hybrid perovskite precursor solution obtained in step (3-I) is filtered through a filter head with a diameter of 0.22 μm, and then dripped onto the tin dioxide electron transport layer obtained in step (2), and an organic-inorganic hybrid perovskite CH is obtained by spin coating. 3 NH 3 BX 3 The light-absorbing layer was spin-coated at 5000 rpm for 30 s. When the spin-coating countdown reached 23 s, 300 μL of ethyl acetate or chlorobenzene solution was added. The film was heat-treated at 100 °C for 15 min and annealed to obtain a smooth perovskite film.

[0050] (4) The organic-inorganic hybrid perovskite CH obtained in step (3) 3 NH 3 BX 3 A conductive polymer modified hole transport layer is prepared on the surface of the light absorbing layer: in the conductive polymer / hole transport material mixed solution, the amount of PANI added accounts for 2% of the total solution mass, the amount of lithium bis(trifluoromethanesulfonyl)imide added accounts for 1.5% of the total solution mass, the amount of 4-tert-butylpyridine added accounts for 2.5% of the total solution mass, the amount of chlorobenzene added accounts for 64% of the total solution mass, and the amount of P3HT (hole transport material) added accounts for 30% of the total solution mass. The PANI / P3HT mixed solution is added dropwise to the organic-inorganic hybrid perovskite CH 3 NH 3 BX 3 The surface of the light absorbing layer is subjected to spin coating to obtain a conductive polymer modified hole transport layer, and the spin coating process is set to 4000 rpm for 30 s;

[0051] (5) Vapor-depositing a thin metal counter electrode on the surface of the conductive polymer modified hole transport layer: using a vacuum evaporation method, vacuum-depositing a 40 nm gold counter electrode at a rate of 0.4 nm / s.

[0052] The performance of the semi-transparent organic-inorganic hybrid perovskite solar cell based on conductive polymer obtained in this embodiment was tested: at room temperature, humidity less than 30%, a xenon lamp was used to simulate sunlight with a light intensity of 100 mW / cm 2 , the effective illumination area is 0.25 cm 2 The photoelectric conversion efficiency is 17%. After 290 days of stability testing, the photoelectric efficiency dropped to 97% of the initial value.

[0053] Example 2

[0054] The semi-transparent organic-inorganic hybrid perovskite solar cell based on conductive polymer in this embodiment, when the conductive substrate is defined as the bottom layer, includes from bottom to top: a transparent ITO conductive glass substrate layer; a tin dioxide electron transport layer; an organic-inorganic hybrid perovskite CH 3 NH 3 PbI 3 Light absorbing layer; conductive polymer modified hole transport layer made of polythiophene (conductive polymer) and Spiro-OMeTAD (hole transport material) as raw materials; gold counter electrode.

[0055] The semi-transparent organic-inorganic hybrid perovskite solar cell based on conductive polymer in this embodiment has a preparation method comprising the following steps:

[0056] The method for preparing a semi-transparent organic-inorganic hybrid perovskite solar cell based on a conductive polymer of this embodiment comprises the following steps:

[0057] (1) Cleaning the transparent ITO conductive glass to obtain a transparent conductive substrate: Use deionized water, anhydrous ethanol, and isopropanol to clean the ITO conductive glass by ultrasonic oscillation for 12 min, then put it in an oven at 80 °C for 15 min to remove visible impurities on the surface, and then treat it in a UV ozone treatment machine for 30 min to remove organic groups on the surface to reduce the water contact angle;

[0058] (2) preparing a tin dioxide electron transport layer on the surface of the transparent conductive substrate obtained in step (1): dripping a tin dioxide colloidal dispersion onto the transparent conductive substrate treated with ozone, spinning it at 6000 rpm for 20 s to form a uniform film, and heating it on a heating table at 155° C. for 25 min to obtain a tin dioxide electron transport layer, wherein the tin dioxide colloidal dispersion is prepared by ultrasonically dispersing a tin dioxide colloidal dispersion and deionized water in a volume ratio of 1:1;

[0059] (3) Preparing an organic-inorganic hybrid perovskite CH on the surface of the tin dioxide electron transport layer obtained in step (2) 3 NH 3 PbI 3 Light absorbing layer;

[0060] (3-I) CH 3 NH 3 I and PbI 2 It was dissolved in a mixed solution of dimethyl sulfoxide (DMSO) and N, N-dimethylformamide (DMF) with a volume ratio of 1:5, heated and stirred at 70 °C for 8 h to obtain an organic-inorganic hybrid perovskite precursor solution; CH 3 NH 3 The amount of I added is equivalent to 18% of the total mass, PbI 2 The amount of solvent added is equivalent to 22% of the total mass, the amount of DMSO solvent added is equivalent to 40% of the total mass, and the amount of DMF solvent added is equivalent to 20% of the total mass;

[0061] (3-II) The organic-inorganic hybrid perovskite precursor solution obtained in step (3-I) is filtered through a filter head with a diameter of 0.45 μm, and then dripped onto the tin dioxide electron transport layer obtained in step (2), and the organic-inorganic hybrid perovskite CH is obtained by spin coating. 3 NH 3 BX 3 The light-absorbing layer was spin-coated at 4000 rpm for 30 s. When the spin-coating countdown reached 23 s, 300 μL of ethyl acetate or chlorobenzene solution was added. The film was heat-treated at 95 °C for 20 min and annealed to obtain a smooth perovskite film.

[0062] (4) The organic-inorganic hybrid perovskite CH obtained in step (3) 3 NH 3 BX 3 A conductive polymer modified hole transport layer is prepared on the surface of the light absorbing layer: in the conductive polymer / hole transport material mixed solution, the amount of polythiophene added is 3% of the total solution mass, the amount of lithium bis(trifluoromethanesulfonyl)imide added is 2% of the total solution mass, the amount of 4-tert-butylpyridine added is 2.5% of the total solution mass, the amount of chlorobenzene added is 72.5% of the total solution mass, and the amount of Spiro-OMeTAD (hole transport material) added is 20% of the total solution mass. The polythiophene / Spiro-OMeTAD mixed solution is added dropwise to the organic-inorganic hybrid perovskite CH 3 NH 3 BX 3 The surface of the light absorbing layer is subjected to spin coating to obtain a conductive polymer modified hole transport layer, and the spin coating process is set to 3500 rpm for 35 s;

[0063] (5) Vapor-depositing a thin metal counter electrode on the surface of the conductive polymer modified hole transport layer: vacuum evaporation is performed at a rate of 0.5 nm / s to vacuum-deposit a 50 nm thick gold counter electrode.

[0064] The performance of the semi-transparent organic-inorganic hybrid perovskite solar cell based on conductive polymer obtained in this embodiment was tested: at room temperature, humidity less than 30%, a xenon lamp was used to simulate sunlight with a light intensity of 100 mW / cm 2 , the effective illumination area is 0.25 cm 2 The photoelectric conversion efficiency is 18%. After 250 days of stability testing, the photoelectric efficiency dropped to 95% of the initial value.

[0065] Example 3

[0066] The semi-transparent organic-inorganic hybrid perovskite solar cell based on conductive polymer in this embodiment, when the conductive substrate is defined as the bottom layer, includes from bottom to top: a transparent ITO conductive glass substrate layer; a tin dioxide electron transport layer; an organic-inorganic hybrid perovskite CH 3 NH 3 PbI 2 Light absorbing layer; conductive polymer modified hole transport layer made of PVP (conductive polymer) and Spiro-OMeTAD (hole transport material); gold counter electrode.

[0067] The semi-transparent organic-inorganic hybrid perovskite solar cell based on conductive polymer in this embodiment has a preparation method comprising the following steps:

[0068] (1) Cleaning the transparent ITO conductive glass to obtain a transparent conductive substrate: Use deionized water, anhydrous ethanol, and isopropanol to clean the ITO conductive glass by ultrasonic oscillation for 10 min, then put it in an oven at 100 °C for 8 min to remove visible impurities on the surface, and then treat it in a UV ozone treatment machine for 30 min to remove organic groups on the surface to reduce the water contact angle;

[0069] (2) preparing a tin dioxide electron transport layer on the surface of the transparent conductive substrate obtained in step (1): dripping a tin dioxide colloidal dispersion onto the transparent conductive substrate treated with ozone, spinning it at 4000 rpm for 30 s to form a uniform film, and heating it on a heating table at 180° C. for 30 min to obtain a tin dioxide electron transport layer, wherein the tin dioxide colloidal dispersion is prepared by ultrasonically dispersing a tin dioxide colloidal dispersion and deionized water in a volume ratio of 1:4;

[0070] (3) Preparing an organic-inorganic hybrid perovskite CH on the surface of the tin dioxide electron transport layer obtained in step (2) 3 NH3 PbI 2 Light absorbing layer;

[0071] (3-I) CH 3 NH 3 I and PbBr 2 It was dissolved in a mixed solution of dimethyl sulfoxide (DMSO) and N, N-dimethylformamide (DMF) with a volume ratio of 1:6, heated and stirred at 60 °C for 4 h to obtain an organic-inorganic hybrid perovskite precursor solution; CH 3 NH 3 The amount of I added is equivalent to 19% of the total mass, PbBr 2 The amount of solvent added is equivalent to 21% of the total mass, the amount of DMSO solvent added is equivalent to 45% of the total mass, and the amount of DMF solvent added is equivalent to 15% of the total mass;

[0072] (3-II) The organic-inorganic hybrid perovskite precursor solution obtained in step (3-I) is filtered through a filter head with a diameter of 0.36 μm, and then dripped onto the tin dioxide electron transport layer obtained in step (2), and an organic-inorganic hybrid perovskite CH is obtained by spin coating. 3 NH 3 BX 3 The light-absorbing layer was spin-coated at 7000 rpm for 20 s. When the spin-coating countdown reached 19 s, 300 μL of ethyl acetate or chlorobenzene solution was added. The film was heat-treated at 100 °C for 15 min and annealed to obtain a smooth perovskite film.

[0073] (4) The organic-inorganic hybrid perovskite CH obtained in step (3) 3 NH 3 BX 3 A conductive polymer modified hole transport layer is prepared on the surface of the light absorbing layer: in the conductive polymer / hole transport material mixed solution, the amount of PVP added accounts for 5% of the total solution mass, the amount of lithium bis(trifluoromethanesulfonyl)imide added accounts for 2% of the total solution mass, the amount of 4-tert-butylpyridine added accounts for 2% of the total solution mass, the amount of chlorobenzene added accounts for 75% of the total solution mass, and the amount of Spiro-OMeTAD (hole transport material) added accounts for 16% of the total solution mass. The PVP / Spiro-OMeTAD mixed solution is added dropwise to the organic-inorganic hybrid perovskite CH 3 NH 3 BX 3 The surface of the light absorbing layer is subjected to spin coating to obtain a conductive polymer-modified hole transport layer, and the spin coating process is set to 3000 rpm for 40 s;

[0074] (5) Vapor-depositing a thin metal counter electrode on the surface of the conductive polymer modified hole transport layer: vacuum evaporation is performed at a rate of 0.6 nm / s to vacuum-deposit a 60 nm gold counter electrode.

[0075] The performance of the semi-transparent organic-inorganic hybrid perovskite solar cell based on conductive polymer obtained in this embodiment was tested: at room temperature, humidity less than 30%, a xenon lamp was used to simulate sunlight with a light intensity of 100 mW / cm 2 , the effective illumination area is 0.25 cm 2 The photoelectric conversion efficiency is 18%. After 240 days of stability testing, the photoelectric efficiency dropped to 94% of the initial value.

[0076] Comparative Example

[0077] In this comparative example, a conductive polymer is not used to modify the hole transport layer. The semi-transparent organic-inorganic hybrid perovskite solar cell, when the conductive substrate is defined as the bottom layer, comprises, from bottom to top: a transparent ITO conductive glass substrate layer; a tin dioxide electron transport layer; an organic-inorganic hybrid perovskite CH 3 NH 3 PbI 3 Light absorbing layer; hole transport layer made of Spiro-OMeTAD (hole transport material); gold counter electrode.

[0078] The preparation method of the semi-transparent organic-inorganic hybrid perovskite solar cell of this comparative example comprises the following steps:

[0079] (1) Cleaning the transparent ITO conductive glass to obtain a transparent conductive substrate: Use deionized water, anhydrous ethanol, and isopropanol to clean the ITO conductive glass by ultrasonic oscillation for 15 min, then put it in an oven at 80 °C for 10 min to remove the visible impurities on the surface, and then treat it in a UV ozone treatment machine for 20 min to remove the organic groups on the surface to reduce the water contact angle;

[0080] (2) preparing a tin dioxide electron transport layer on the surface of the transparent conductive substrate obtained in step (1): dripping a tin dioxide colloidal dispersion onto the transparent conductive substrate treated with ozone, spinning it at 4000 rpm for 30 s to form a uniform film, and heating it on a heating table at 150° C. for 30 min to obtain a tin dioxide electron transport layer, wherein the tin dioxide colloidal dispersion is prepared by ultrasonically dispersing a tin dioxide colloidal dispersion and deionized water in a volume ratio of 1:3;

[0081] (3) Preparing an organic-inorganic hybrid perovskite CH on the surface of the tin dioxide electron transport layer obtained in step (2) 3 NH 3 PbI 3 Light absorbing layer:

[0082] (3-I) CH 3 NH 3 I and PbI 2 It was dissolved in a mixed solution of dimethyl sulfoxide (DMSO) and N, N-dimethylformamide (DMF) with a volume ratio of 1:5, heated and stirred at 70 °C for 4 h to obtain an organic-inorganic hybrid perovskite precursor solution; CH 3 NH 3 The amount of X added is equivalent to 15% of the total mass, PbI 2 The amount of solvent added is equivalent to 30% of the total mass, the amount of DMSO solvent added is equivalent to 40% of the total mass, and the amount of DMF solvent added is equivalent to 15% of the total mass;

[0083] (3-II) The organic-inorganic hybrid perovskite precursor solution obtained in step (3-I) is filtered through a filter head with a diameter of 0.22 μm, and then dripped onto the tin dioxide electron transport layer obtained in step (2), and an organic-inorganic hybrid perovskite CH is obtained by spin coating. 3 NH 3 BX 3 The light-absorbing layer was spin-coated at 6000 rpm for 30 s. When the spin-coating countdown reached 20 s, 250 μL of ethyl acetate or chlorobenzene solution was added. The film was heat-treated at 110 °C for 10 min and annealed to obtain a smooth perovskite film.

[0084] (4) The organic-inorganic hybrid perovskite CH obtained in step (3) 3 NH 3 BX 3 A hole transport layer is prepared on the surface of the light-absorbing layer: in the hole transport material mixed solution, the amount of lithium bis(trifluoromethanesulfonyl)imide added is 0.3% of the total solution mass, 4-tert-butylpyridine is 1.7% of the total solution mass, the amount of chlorobenzene added is 71% of the total solution mass, and the amount of Spiro-OMeTAD (hole transport material) added is 27% of the total solution mass. The Spiro-OMeTAD solution is added dropwise to the organic-inorganic hybrid perovskite CH 3 NH 3 BX 3 The hole transport layer was obtained by spin coating on the surface of the light absorbing layer, and the spin coating process was set to 3000 rpm for 30 seconds;

[0085] (5) Vapor-depositing a thin metal counter electrode on the surface of the hole transport layer: using a vacuum evaporation method, vacuum-deposit a 20 nm gold counter electrode at a rate of 0.3 nm / s.

[0086] The performance of the semi-transparent organic-inorganic hybrid perovskite solar cell obtained in this comparative example was tested: at room temperature, humidity less than 40%, a xenon lamp was used to simulate sunlight with a light intensity of 100 mW / cm 2 , the effective illumination area is 0.25 cm 2 The photoelectric conversion efficiency is 14%. After 290 days of stability testing, the photoelectric efficiency dropped to 30% of the initial value.

Claims

1. A semi-transparent organic-inorganic hybrid perovskite solar cell based on conductive polymer, It is characterized in that When the conductive substrate is defined as the bottom layer, it includes, from bottom to top: conductive substrate layer; tin dioxide electron transport layer; organic-inorganic hybrid perovskite CH 3 NH 3 BX 3 A light absorbing layer, wherein B is Pb, Sn, In or Ge, and X is one or more of I, Br or Cl; a conductive polymer modified hole transport layer made of conductive polymer and hole transport material; a counter electrode; The conductive polymer is one or more of polyaniline, polythiophene, polypyrrole, poly-3,4-ethylenedioxythiophene: polystyrene sulfonate; the hole transport material is small molecule polymer Spiro-OMeTAD and / or P3HT; The method for preparing the semi-transparent organic-inorganic hybrid perovskite solar cell comprises the following steps: (1) Cleaning the transparent ITO conductive glass to obtain a transparent conductive substrate; (2) preparing a tin dioxide electron transport layer on the surface of the conductive substrate; (3) Preparing an organic-inorganic hybrid perovskite CH on the surface of the tin dioxide electron transport layer 3 NH 3 BX 3 Light absorbing layer; (4) In the organic-inorganic hybrid perovskite CH 3 NH 3 BX 3 The conductive polymer modified hole transport layer is prepared on the surface of the light absorbing layer. The preparation operation method is: adding the conductive polymer / hole transport material mixed solution dropwise to the organic-inorganic hybrid perovskite CH 3 NH 3 BX 3 The surface of the light absorbing layer is spin-coated to obtain a conductive polymer-modified hole transport layer; (5) Vapor-depositing a thin metal counter electrode on the surface of the conductive polymer modified hole transport layer.

2. The semi-transparent organic-inorganic hybrid perovskite solar cell based on a conductive polymer according to claim 1, It is characterized in that The conductive substrate layer is transparent ITO conductive glass.

3. The semi-transparent organic-inorganic hybrid perovskite solar cell based on a conductive polymer according to claim 1 or 2, It is characterized in that In step (1), the cleaning method is as follows: placing the transparent ITO conductive glass in deionized water, anhydrous ethanol, and isopropanol, ultrasonically vibrating for 10 to 20 minutes, baking at 80 to 120° C. for 5 to 15 minutes, and treating with ultraviolet ozone for 20 to 30 minutes.

4. The semi-transparent organic-inorganic hybrid perovskite solar cell based on a conductive polymer according to claim 1 or 2, It is characterized in that In step (2), the preparation method of the tin dioxide electron transport layer is as follows: dropwise adding a tin dioxide colloidal dispersion onto the surface of the conductive substrate, spin coating at 4000-6000 rpm for 20-30 s, and heating at 150-180° C. for 30-40 min; the tin dioxide colloidal dispersion is prepared by mixing tin dioxide colloid and deionized water in a volume ratio of 1:1-4 and ultrasonically dispersing the mixture.

5. The semi-transparent organic-inorganic hybrid perovskite solar cell based on a conductive polymer according to claim 1 or 2, It is characterized in that In step (3), the filtered organic-inorganic hybrid perovskite precursor is dripped onto the surface of the tin dioxide electron transport layer, spin-coated, heat-treated, and annealed to obtain an organic-inorganic hybrid perovskite CH 3 NH 3 BX 3 The preparation method of the organic-inorganic hybrid perovskite precursor solution is: CH 3 NH 3 X and BX 2 Dissolve in a mixture of dimethyl sulfoxide and N,N-dimethylformamide, heat and stir at 65~75 ℃ for 4~12 h.

6. The semi-transparent organic-inorganic hybrid perovskite solar cell based on a conductive polymer according to claim 5, It is characterized in that In step (3), in the organic-inorganic hybrid perovskite precursor solution, CH 3 NH 3 The amount of X added is equivalent to 15~20% of the total mass of the precursor solution, BX 2 The amount of dimethyl sulfoxide added is equivalent to 20%~30% of the total mass of the precursor solution, the amount of N,N-dimethylformamide added is equivalent to 10%~25% of the total mass of the precursor solution; the diameter of the filter head used for filtration is 0.22~0.45 m; the spin coating speed is 4000~7000 rpm, the time is 20~40 s; when the spin coating countdown reaches 19~24 s, add 200~300 L ethyl acetate or chlorobenzene solution; the heat treatment temperature is 70-110°C and the time is 10-20 min.

7. The semi-transparent organic-inorganic hybrid perovskite solar cell based on a conductive polymer according to claim 1 or 2, It is characterized in that In step (4), in the conductive polymer / hole transport material mixed solution, the mass of the conductive polymer is less than 5wt% of the total mass of the solution, the mass of lithium bis(trifluoromethanesulfonyl)imide is 0.2-2% of the total mass of the solution, the mass of 4-tert-butylpyridine is 0.8-3% of the total mass of the solution, the mass of chlorobenzene is 60-80% of the total mass of the solution, and the mass of the hole transport material is 10%-30% of the total mass of the solution; the spin coating speed is 2000-4000 rpm, and the time is 30-40 s.

8. The semi-transparent organic-inorganic hybrid perovskite solar cell based on a conductive polymer according to claim 3, It is characterized in that In step (4), in the conductive polymer / hole transport material mixed solution, the mass of the conductive polymer is less than 5wt% of the total mass of the solution, the mass of lithium bis(trifluoromethanesulfonyl)imide is 0.2-2% of the total mass of the solution, the mass of 4-tert-butylpyridine is 0.8-3% of the total mass of the solution, the mass of chlorobenzene is 60-80% of the total mass of the solution, and the mass of the hole transport material is 10%-30% of the total mass of the solution; the spin coating speed is 2000-4000 rpm, and the time is 30-40 s.

9. The semi-transparent organic-inorganic hybrid perovskite solar cell based on a conductive polymer according to claim 4, It is characterized in that In step (4), in the conductive polymer / hole transport material mixed solution, the mass of the conductive polymer is less than 5wt% of the total mass of the solution, the mass of lithium bis(trifluoromethanesulfonyl)imide is 0.2-2% of the total mass of the solution, the mass of 4-tert-butylpyridine is 0.8-3% of the total mass of the solution, the mass of chlorobenzene is 60-80% of the total mass of the solution, and the mass of the hole transport material is 10%-30% of the total mass of the solution; the spin coating speed is 2000-4000 rpm, and the time is 30-40 s.

10. The semi-transparent organic-inorganic hybrid perovskite solar cell based on a conductive polymer according to any one of claims 1 or 2, It is characterized in that In step (5), a thin metal counter electrode is deposited by vacuum evaporation; the vacuum evaporation rate is 0.1-0.6 nm / s, and the thickness of the thin metal counter electrode is 10-60 nm.

11. The semi-transparent organic-inorganic hybrid perovskite solar cell based on a conductive polymer according to claim 9, It is characterized in that Gold is used as the plated metal.