CN114267791A - Semitransparent organic-inorganic hybrid perovskite solar cell based on conductive polymer - Google Patents

Semitransparent organic-inorganic hybrid perovskite solar cell based on conductive polymer Download PDF

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CN114267791A
CN114267791A CN202111561911.8A CN202111561911A CN114267791A CN 114267791 A CN114267791 A CN 114267791A CN 202111561911 A CN202111561911 A CN 202111561911A CN 114267791 A CN114267791 A CN 114267791A
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inorganic hybrid
organic
hybrid perovskite
conductive polymer
hole transport
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杨英
陈甜
郭学益
朱刘
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Central South University
First Rare Materials Co Ltd
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Central South University
First Rare Materials Co Ltd
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Abstract

A semitransparent organic-inorganic hybrid perovskite solar cell based on a conductive polymer comprises the following components in sequence from bottom to top when a conductive substrate is defined as the lowest layer: 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; a counter electrode. The invention provides a novel semitransparent perovskite solar cell structure, which improves the environmental stability of a device by doping a hole transport layer with a proper amount of polymer and utilizing the interaction between the polymer and small molecule additive molecules in the hole transport layer; in addition, the quality of a hole transport layer film can be improved, the oxidation degree of a hole transport material is improved, the defect states in the film are reduced, the conductivity of the hole transport layer is improved, meanwhile, the thickness of a metal counter electrode can be reduced, the preparation cost of the device is reduced, and a semitransparent perovskite type device is constructed to achieve the effect of double-sided photoresponse.

Description

Semitransparent organic-inorganic hybrid perovskite solar cell based on conductive polymer
Technical Field
The invention relates to a semitransparent perovskite solar cell, in particular to a semitransparent organic-inorganic hybrid perovskite solar cell.
Background
Translucent perovskite solar cells (ST-PSCs) can convert solar energy from the front and back into electrical energy simultaneously, and the output power can exceed 50% by collecting the ambient albedo radiance. With the development of the semitransparent perovskite solar cell, the application field of the semitransparent perovskite solar cell is more and more extensive, and the semitransparent perovskite solar cell is particularly applied to the fields of series solar cells, Building Integrated Photovoltaics (BIPV), wearable electronic products and the like. In practical production, the cost and stability of the semitransparent perovskite solar cell are important. However, since the translucent solar cell needs to comprehensively consider the photoelectric conversion efficiency and the transparency of the entire device, in other words, it is necessary to grasp the relationship between the average visible light transparency (AVT) and the photoelectric conversion efficiency. Semitransparent devices are limited in transparency, and the photoelectric conversion efficiency of the semitransparent devices currently reaches 25.8%, which is far from the same level as that of the opaque devices. For semi-transparent devices, it is critical to replace the opaque electrodes in the perovskite with highly transparent conductive electrodes, which allows sunlight to shine from both the front and back sides simultaneously to transmit photons with energies below the perovskite bandgap. Early work had centered around the optimized deployment of thin counter electrodes for semi-transparent devices, such as Au, Ag nanowires, PEDOT: PSS, graphene, carbon nanotubes, mesh metals, ITO/FTO, IZO have been demonstrated as transparent contact electrodes of semitransparent devices, mainly in improving photoelectric conversion efficiency, but the environmental stability of semitransparent perovskite solar cells still presents a great challenge.
The stability of the translucent perovskite solar cell is a major obstacle to its commercialization and has therefore attracted much attention from researchers. Common means for stabilizing PSCs include that some rare metal elements (Rb, Cs and the like) are used for replacing methylamine ions to improve the thermal stability of the device, and stable inorganic small molecules (NiO, CuI and the like) are used for replacing common organic small molecule hole transport materials. In addition, many researches on the decomposition of a perovskite layer and the instability of a device caused by internal and external factors exist, and the researches show that Au is favorable for the stability of the device when being used as a top counter electrode. The methods are almost all based on opaque PSCs, and ST-PSCs are reported in few researches.
Improving the stability of ST-PSCs is essential for the practical application of ST-PSCs. The degradation of the perovskite solar cell is mainly attributed to the external environment and the preparation process of the perovskite solar cell, and specifically comprises 1) the degradation of the hybrid perovskite material caused by humidity, oxygen and ultraviolet light; 2) irreversible interfacial reaction with the perovskite layer due to the additives LiTFSI and tBP of the hole transport layer; 3) the migration of metal from the counter electrode to the hole transport layer, and hence the degradation of the device induced by intrinsic ion migration poses a significant threat to the stability of the device.
Because of its low intrinsic conductivity, the main components of the conventional hole transport layer include LiTFSI, which serves to increase the conductivity of the hole transport layer, and tBP, which prevents agglomeration, which is very hygroscopic, which dissolves the perovskite material and may form a complex PbI during device storage2t-BP, which causes instability of the perovskite layer and the device.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects in the prior art and provide a semitransparent organic-inorganic hybrid perovskite solar cell based on a conductive polymer with good stability.
The technical scheme adopted by the invention for solving the technical problems is as follows: a semitransparent organic-inorganic hybrid perovskite solar cell based on a conductive polymer comprises the following components in sequence from bottom to top when a conductive substrate is defined as the lowest layer: a conductive substrate layer; a tin dioxide electron transport layer; organic-inorganic hybrid perovskite CH3NH3BX3The light absorption layer, wherein B is Pb, Sn, In or Ge, and X is I, Br or one or more of Cl; the conductive polymer modified hole transport layer is prepared by taking a conductive polymer and a hole transport material as raw materials; a counter electrode.
Preferably, the conductive substrate layer is transparent ITO conductive glass.
Preferably, the conductive polymer is Polyaniline (PANI), polythiophene, polypyrrole (PVP), poly 3, 4-ethylenedioxythiophene: one or more than two of polystyrene sulfonate (PEDOT: PSS).
Preferably, the hole transport material is a small molecule polymer, more preferably Spiro-OMeTAD and/or P3 HT.
Preferably, the preparation method of the semitransparent organic-inorganic hybrid perovskite solar cell based on the conducting polymer comprises the following steps:
(1) cleaning 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 organic-inorganic hybrid perovskite CH on the surface of the stannic oxide electron transport layer3NH3BX3A light absorbing layer;
(4) in the organic-inorganic hybrid perovskite CH3NH3BX3Preparing a conductive polymer modified hole transport layer on the surface of the light absorption layer;
(5) and (3) evaporating a thin metal counter electrode on the surface of the conductive polymer modified hole transport layer.
More preferably, in the step (1), the cleaning mode is as follows: and (3) placing the transparent ITO conductive glass in deionized water, absolute ethyl alcohol and isopropanol for 10-20 min by ultrasonic oscillation respectively, drying at 80-120 ℃ for 5-15 min (for removing visible impurities on the surface), and carrying out ultraviolet ozone treatment for 20-30 min (for removing organic groups on the surface to reduce the water contact angle).
More preferably, in the step (2), the preparation method of the tin dioxide electron transport layer comprises the following steps: and (3) dropwise adding a tin dioxide colloid dispersion liquid on the surface of the conductive substrate, spin-coating at 4000-6000 rpm for 20-30 s (so as to form a uniform film), and heating at 150-180 ℃ for 30-40 min to obtain the tin dioxide conductive film.
Further preferably, in the step (2), the tin dioxide colloid dispersion is prepared by mixing tin dioxide colloid and deionized water according to a volume ratio of 1: 1-4, and carrying out ultrasonic dispersion.
More preferably, in the step (3), the filtered organic-inorganic hybrid perovskite precursor solution is dripped on the surface of the tin dioxide electron transport layer, and the organic-inorganic hybrid perovskite CH is obtained through spin coating, heat treatment and annealing3NH3BX3A light absorbing layer.
More preferably, in the step (3), the preparation method of the organic-inorganic hybrid perovskite precursor solution comprises the following steps: mixing CH with the molar ratio of 1: 13NH3X and BX2Dissolving the mixture in a mixed solution of dimethyl sulfoxide (DMSO) and N, N-Dimethylformamide (DMF), and heating and stirring the mixture for 4 to 12 hours at the temperature of 65 to 75 ℃.
Further preferably, in the step (3), CH is contained in the organic-inorganic hybrid perovskite precursor solution3NH3The addition of X is equal to 15-20% of the total mass of the precursor liquid, and BX2The adding amount of the N, N-dimethylformamide is equal to 20-30% of the total mass of the precursor liquid, the adding amount of the dimethyl sulfoxide is equal to 40-50% of the total mass of the precursor liquid, and the adding amount of the N, N-dimethylformamide is equal to 10-25% of the total mass of the precursor liquid.
Further preferably, in the step (3), the diameter of the filter head used for filtering is 0.22 to 0.45 μm.
Further preferably, in the step (3), the spin coating speed is 4000-7000 rpm and the time is 20-40 s.
Further preferably, in the step (3), 200 to 300 μ L of ethyl acetate or chlorobenzene solution is added when the time for spin coating is 19 to 24 s (to assist rapid crystallization of the perovskite).
Further preferably, in the step (3), the temperature of the heat treatment is 70-110 ℃, and the time is 10-20 min; through the heat treatment in the mode, the smooth perovskite thin film is obtained through annealing.
More preferably, in step (4), the mixture is subjected toDropwise adding the mixed solution of the conducting polymer/the hole transport material to the organic-inorganic hybrid perovskite CH3NH3BX3And spin-coating the surface of the light absorption layer to obtain the conductive polymer modified hole transport layer.
Further preferably, in the step (4), in the mixed solution of the conductive polymer and the hole transport material, the mass of the conductive polymer is less than 5wt% of the total mass of the solution, the mass of lithium bis (trifluoromethanesulfonylimide) 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.
Further preferably, in the step (4), the spin coating speed is 2000-4000 rpm and the time is 30-40 s.
More preferably, in step (5), a thin metal counter electrode is evaporated by vacuum evaporation.
More preferably, in the 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.
Further preferably, the gold is metallized.
The invention is characterized in that a novel semitransparent perovskite solar cell structure is provided, a hole transport layer is doped with a proper amount of polymer, and the interaction between the polymer and small molecule additive molecules in the hole transport layer is utilized to inhibit the hygroscopicity of the additive and improve the environmental stability of a device. The doping of the polymer can also improve the film quality of a hole transport layer, improve the oxidation degree and the charge extraction efficiency of a hole transport material, reduce the defect state in the film, evaporate an ultrathin metal counter electrode to reduce the device cost, and construct a semitransparent perovskite type device to achieve the effect of double-sided photoresponse. The morphology and the optical property of a common hole transport layer are controlled by developing an efficient modification mode, and the stability of the organic-inorganic hybrid perovskite solar cell is improved; the semitransparent perovskite solar cell with a novel structure is constructed together with the thin metal counter electrode, the doping concentration and the thickness of the metal counter electrode are optimized, and the photoelectric conversion efficiency of the semitransparent perovskite solar cell with double-sided light response is further improved. Generally, the invention provides theoretical and technical basis for developing a high-stability low-cost semitransparent perovskite solar cell.
Compared with the prior art, the invention has the advantages that:
(1) the novel semitransparent perovskite solar cell structure is provided, and the environmental stability of a device is improved by doping a proper amount of polymer in the hole transport layer and utilizing the interaction between the polymer and small molecule additive molecules in the hole transport layer;
(2) the polymer forms a net structure between the hole transport layer and the counter electrode to block water erosion in the air and corrosion of metal to the electrode, so that the environmental stability of the hole transport layer, the perovskite layer and the device is maintained, the conductive polymer has good conductivity, the doped polymer improves the conductivity of the hole transport layer, and meanwhile, the thickness of the metal to the electrode can be reduced, and the preparation cost of the device is reduced;
(3) the doping of the polymer can also improve the quality of the hole transport layer film, improve the oxidation degree of the hole transport material and reduce the defect state in the film;
(4) and evaporating ultrathin metal counter electrodes to reduce the cost of the device, and constructing a semitransparent perovskite type device to achieve the effect of double-sided photoresponse.
Detailed Description
In order to facilitate an understanding of the present invention, the present invention will be described more fully and in detail with reference to the preferred embodiments, but the scope of the present invention is not limited to the specific embodiments described below.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specified, the reagents and materials used in the present invention are commercially available products or products obtained by a known method.
Example 1
The semitransparent organic-inorganic hybrid perovskite solar cell based on the conductive polymer in the embodiment defines the conductive substrate as the lowest layer, and sequentially comprises the following components from bottom to top: a transparent ITO conductive glass substrate layer; a tin dioxide electron transport layer; organic-inorganic hybrid perovskite CH3NH3SnClI2A light absorbing layer; the conductive polymer modified hole transport layer is prepared by taking PANI (conductive polymer) and P3HT (hole transport material) as raw materials; a gold counter electrode.
The preparation method of the semitransparent organic-inorganic hybrid perovskite solar cell based on the conducting polymer comprises the following steps:
(1) cleaning transparent ITO conductive glass to obtain a transparent conductive substrate: respectively adopting deionized water, absolute ethyl alcohol and isopropanol to ultrasonically vibrate for 10 min to clean the ITO conductive glass, placing the ITO conductive glass into an oven to be dried for 8 min at 100 ℃ after ultrasonic treatment to remove visible impurities on the surface, and then treating the ITO conductive glass on an ultraviolet ozone treatment machine for 25 min to remove organic groups on the surface so as to reduce a water contact angle;
(2) preparing a tin dioxide electron transport layer on the surface of the transparent conductive substrate obtained in the step (1): dropwise adding a tin dioxide colloid dispersion liquid on the transparent conductive substrate after ozone treatment, uniformly forming a film by spin coating at 5000 rpm for 20 s, heating at 160 ℃ for 35 min on a heating table to obtain a tin dioxide electronic transmission layer, wherein the tin dioxide colloid dispersion liquid is prepared by mixing tin dioxide colloid and deionized water according to a volume ratio of 1: 4, mixing and ultrasonically dispersing;
(3) preparing organic-inorganic hybrid perovskite CH on the surface of the stannic oxide electron transport layer obtained in the step (2)3NH3SnClI2A light absorbing layer;
(3-I) mixing a mixture of a molar ratio of 1: 1 CH3NH3Cl and SnI2Dissolved in a volume ratio of 1: 4, heating and stirring at 65 ℃ for 4 h to obtain the organic-inorganic hybrid perovskitePrecursor solution of CH3NH3Cl was added in an amount of 18% by mass, SnI2The amount of the added DMSO solvent is 22% of the total mass, the amount of the added DMSO solvent is 45% of the total mass, and the amount of the added DMF solvent is 15% of the total mass;
(3-II) filtering the organic-inorganic hybrid perovskite precursor solution obtained in the step (3-I) through a filter head with the diameter of 0.22 mu m, then dropwise adding the organic-inorganic hybrid perovskite precursor solution on the tin dioxide electron transport layer obtained in the step (2), and obtaining the organic-inorganic hybrid perovskite CH in a spin coating mode3NH3BX3A light absorption layer, wherein the spin coating process is set to be 5000 rpm for 30 s; adding 300 mu L of ethyl acetate or chlorobenzene solution when the coating is rotated until the countdown time is 23 s, carrying out heat treatment for 15 min at the temperature of 100 ℃, and annealing to obtain a smooth perovskite film;
(4) the organic-inorganic hybrid perovskite CH obtained in the step (3)3NH3BX3Preparing a conductive polymer modified hole transport layer on the surface of the light absorption layer: in the mixed solution of the conductive polymer and the hole transport material, the adding amount of PANI accounts for 2 percent of the total solution mass, the adding amount of lithium bis (trifluoromethanesulfonyl) imide accounts for 1.5 percent of the total solution mass, the adding amount of 4-tert-butylpyridine accounts for 2.5 percent of the total solution mass, the adding amount of chlorobenzene accounts for 64 percent of the total solution mass, the adding amount of P3HT (hole transport material) accounts for 30 percent of the total solution mass, and the mixed solution of PANI/P3HT is dripped into the organic-inorganic hybrid perovskite CH3NH3BX3Obtaining a conductive polymer modified hole transport layer on the surface of the light absorption layer in a spin coating mode, wherein the spin coating process is set to be 4000 rpm for 30 s;
(5) evaporating a thin metal counter electrode on the surface of the conductive polymer modified hole transport layer: vacuum evaporating at 0.4 nm/s rate for 40 nm gold counter electrode.
The performance of the conductive polymer semitransparent organic-inorganic hybrid perovskite-based solar cell obtained in the embodiment is tested: in a room temperature environment, the humidity is less than 30 percent, a xenon lamp is used for simulating sunlight, and the light intensity is 100 mW/cm2The effective illumination area is 0.25 cm2The photoelectric conversion efficiency is 17 percent, and the stability test lasts for 290 days, the photoelectric efficiency is reduced to97% of the initial value.
Example 2
The semitransparent organic-inorganic hybrid perovskite solar cell based on the conductive polymer in the embodiment defines the conductive substrate as the lowest layer, and sequentially comprises the following components from bottom to top: a transparent ITO conductive glass substrate layer; a tin dioxide electron transport layer; organic-inorganic hybrid perovskite CH3NH3PbI3A light absorbing layer; the hole transport layer is modified by a conductive polymer prepared by taking polythiophene (conductive polymer) and Spiro-OMeTAD (hole transport material) as raw materials; a gold counter electrode.
The preparation method of the semitransparent organic-inorganic hybrid perovskite solar cell based on the conducting polymer comprises the following steps:
the preparation method of the semitransparent organic-inorganic hybrid perovskite solar cell based on the conductive polymer comprises the following steps:
(1) cleaning transparent ITO conductive glass to obtain a transparent conductive substrate: respectively adopting deionized water, absolute ethyl alcohol and isopropanol to ultrasonically vibrate for 12 min to clean the ITO conductive glass, placing the ITO conductive glass into an oven to be dried for 15 min at 80 ℃ after ultrasonic treatment to remove visible impurities on the surface, and then treating the ITO conductive glass on an ultraviolet ozone treatment machine for 30 min to remove organic groups on the surface so as to reduce a water contact angle;
(2) preparing a tin dioxide electron transport layer on the surface of the transparent conductive substrate obtained in the step (1): dropwise adding tin dioxide colloid dispersion liquid on the transparent conductive substrate after ozone treatment, carrying out 6000 rpm spin coating through a spin coating method for 20 s to uniformly form a film, heating the film on a heating table at 155 ℃ for 25 min to obtain a tin dioxide electronic transmission layer, wherein the tin dioxide colloid dispersion liquid is prepared by mixing tin dioxide colloid and deionized water according to a volume ratio of 1: 1, mixing and ultrasonically dispersing;
(3) preparing organic-inorganic hybrid perovskite CH on the surface of the stannic oxide electron transport layer obtained in the step (2)3NH3PbI3A light absorbing layer;
(3-I) mixing a mixture of a molar ratio of 1: 1 CH3NH3I and PbI2Dissolving in a solvent with the volume ratio of 1: 5 dimethyl sulfoxide (DMSO) andheating and stirring the mixed solution of N, N-Dimethylformamide (DMF) for 8 hours at 70 ℃ to obtain organic-inorganic hybrid perovskite precursor solution; wherein CH3NH3The addition of I is 18% of the total mass, PbI2The amount of the added DMSO solvent is 22% of the total mass, the amount of the added DMSO solvent is 40% of the total mass, and the amount of the added DMF solvent is 20% of the total mass;
(3-II) filtering the organic-inorganic hybrid perovskite precursor solution obtained in the step (3-I) through a filter head with the diameter of 0.45 mu m, then dropwise adding the organic-inorganic hybrid perovskite precursor solution on the tin dioxide electron transport layer obtained in the step (2), and obtaining the organic-inorganic hybrid perovskite CH in a spin coating mode3NH3BX3The light absorption layer is provided with a spin coating process at 4000 rpm for 30 s; adding 300 mu L of ethyl acetate or chlorobenzene solution when the coating is rotated until the countdown time is 23 s, carrying out heat treatment at 95 ℃ for 20 min, and annealing to obtain a smooth perovskite film;
(4) the organic-inorganic hybrid perovskite CH obtained in the step (3)3NH3BX3Preparing a conductive polymer modified hole transport layer on the surface of the light absorption layer: in the mixed solution of the conductive polymer and the hole transport material, the adding amount of polythiophene accounts for 3% of the total solution mass, the adding amount of lithium bis (trifluoromethanesulfonylimide) accounts for 2% of the total solution mass, 4-tert-butylpyridine accounts for 2.5% of the total solution mass, the adding amount of chlorobenzene accounts for 72.5% of the total solution mass, the adding amount of Spiro-OMeTAD (hole transport material) accounts for 20% of the total solution mass, and the mixed solution of polythiophene/Spiro-OMeTAD is dripped into organic-inorganic hybrid perovskite CH3NH3BX3Obtaining a conductive polymer modified hole transport layer on the surface of the light absorption layer in a spin coating mode, wherein the spin coating process is set to 3500 rpm for 35 s;
(5) evaporating a thin metal counter electrode on the surface of the conductive polymer modified hole transport layer: vacuum evaporating at 0.5 nm/s rate to form 50 nm gold counter electrode.
The performance of the conductive polymer semitransparent organic-inorganic hybrid perovskite-based solar cell obtained in the embodiment is tested: in a room temperature environment, the humidity is less than 30%, a xenon lamp is used for simulating sunlight, and the light intensity is 100 mW/cm2The effective illumination area is 0.25 cm2The photoelectric conversion efficiency of the test piece is 18 percent, and the stability test lasts for 250 days, and the photoelectric efficiency is reduced to 95 percent of the initial value.
Example 3
The semitransparent organic-inorganic hybrid perovskite solar cell based on the conductive polymer in the embodiment defines the conductive substrate as the lowest layer, and sequentially comprises the following components from bottom to top: a transparent ITO conductive glass substrate layer; a tin dioxide electron transport layer; organic-inorganic hybrid perovskite CH3NH3PbIBr2A light absorbing layer; a conductive polymer modified hole transport layer prepared by taking PVP (conductive polymer) and Spiro-OMeTAD (hole transport material) as raw materials; a gold counter electrode.
The preparation method of the semitransparent organic-inorganic hybrid perovskite solar cell based on the conducting polymer comprises the following steps:
(1) cleaning transparent ITO conductive glass to obtain a transparent conductive substrate: respectively adopting deionized water, absolute ethyl alcohol and isopropanol to ultrasonically vibrate for 10 min to clean the ITO conductive glass, placing the ITO conductive glass into an oven to be dried for 8 min at 100 ℃ after ultrasonic treatment to remove visible impurities on the surface, and then treating the ITO conductive glass on an ultraviolet ozone treatment machine for 30 min to remove organic groups on the surface so as to reduce a water contact angle;
(2) preparing a tin dioxide electron transport layer on the surface of the transparent conductive substrate obtained in the step (1): dropwise adding a tin dioxide colloid dispersion liquid on the transparent conductive substrate after ozone treatment, carrying out spin coating for 30 s at 4000 rpm by a spin coating method to uniformly form a film, and heating the film on a heating table at 180 ℃ for 30 min to obtain a tin dioxide electronic transmission layer, wherein the tin dioxide colloid dispersion liquid is prepared by mixing tin dioxide colloid and deionized water according to a volume ratio of 1: 4, mixing and ultrasonically dispersing;
(3) preparing organic-inorganic hybrid perovskite CH on the surface of the stannic oxide electron transport layer obtained in the step (2)3NH3PbIBr2A light absorbing layer;
(3-I) mixing a mixture of a molar ratio of 1: 1 CH3NH3I and PbBr2Dissolving in a solvent with the volume ratio of 1: 6 dimethyl sulfoxide (DMSO) and N, N-Dimethylformamide (DMF)Heating and stirring the mixed solution at 60 ℃ for 4 h to obtain organic-inorganic hybrid perovskite precursor solution; wherein CH3NH3The amount of I added corresponds to 19% of the total mass, PbBr2The amount of the added component (A) is 21% of the total mass, the amount of the added component (B) is 45% of the total mass, and the amount of the added component (B) is 15% of the total mass;
(3-II) filtering the organic-inorganic hybrid perovskite precursor solution obtained in the step (3-I) through a filter head with the diameter of 0.36 μm, then dropwise adding the organic-inorganic hybrid perovskite precursor solution on the tin dioxide electron transport layer obtained in the step (2), and obtaining the organic-inorganic hybrid perovskite CH in a spin coating mode3NH3BX3The light absorption layer is provided with a spin coating process of 7000 rpm for 20 s; adding 300 mu L of ethyl acetate or chlorobenzene solution when the coating is rotated until the countdown time is 19 s, carrying out heat treatment for 15 min at the temperature of 100 ℃, and annealing to obtain a smooth perovskite film;
(4) the organic-inorganic hybrid perovskite CH obtained in the step (3)3NH3BX3Preparing a conductive polymer modified hole transport layer on the surface of the light absorption layer: in the mixed solution of the conductive polymer and the hole transport material, the addition amount of PVP accounts for 5% of the mass of the whole solution, the addition amount of lithium bis (trifluoromethanesulfonylimide) accounts for 2% of the mass of the total solution, 4-tert-butylpyridine accounts for 2% of the mass of the total solution, the addition amount of chlorobenzene accounts for 75% of the mass of the total solution, the addition amount of Spiro-OMeTAD (hole transport material) accounts for 16% of the mass of the total solution, and the mixed solution of the PVP/Spiro-OMeTAD is dripped into the organic-inorganic hybrid perovskite CH3NH3BX3Obtaining a conductive polymer modified hole transport layer on the surface of the light absorption layer in a spin coating mode, wherein the spin coating process is set to 3000 rpm for 40 s;
(5) evaporating a thin metal counter electrode on the surface of the conductive polymer modified hole transport layer: vacuum evaporating at 0.6 nm/s rate to form 60 nm gold counter electrode.
The performance of the conductive polymer semitransparent organic-inorganic hybrid perovskite-based solar cell obtained in the embodiment is tested: in a room temperature environment, the humidity is less than 30 percent, a xenon lamp is used for simulating sunlight, and the light intensity is 100 mW/cm2The effective illumination area is 0.25 cm2The photoelectric conversion efficiency of the light source is 18%, and the photoelectric efficiency is reduced to 94% of the initial value after 240 days of stability test.
Comparative example
This comparative example, which does not use a conductive polymer to modify the hole transport layer, includes, in order from bottom to top, when defining the conductive substrate as the lowermost layer: a transparent ITO conductive glass substrate layer; a tin dioxide electron transport layer; organic-inorganic hybrid perovskite CH3NH3PbI3A light absorbing layer; a hole transport layer made of a Spiro-OMeTAD (hole transport material) as a raw material; a gold counter electrode.
The preparation method of the semitransparent organic-inorganic hybrid perovskite solar cell of the comparative example comprises the following steps:
(1) cleaning transparent ITO conductive glass to obtain a transparent conductive substrate: respectively adopting deionized water, absolute ethyl alcohol and isopropanol to ultrasonically vibrate for 15 min to clean the ITO conductive glass, placing the ITO conductive glass into an oven to be dried for 10 min at 80 ℃ after ultrasonic treatment to remove visible impurities on the surface, and then treating the ITO conductive glass on an ultraviolet ozone treatment machine for 20 min to remove organic groups on the surface so as to reduce a water contact angle;
(2) preparing a tin dioxide electron transport layer on the surface of the transparent conductive substrate obtained in the step (1): dropwise adding a tin dioxide colloid dispersion liquid on the transparent conductive substrate after ozone treatment, carrying out spin coating for 30 s at 4000 rpm by a spin coating method to uniformly form a film, heating for 30 min at 150 ℃ on a heating table to obtain a tin dioxide electronic transmission layer, wherein the tin dioxide colloid dispersion liquid is prepared by mixing tin dioxide colloid and deionized water according to a volume ratio of 1: 3, mixing and ultrasonically dispersing;
(3) preparing organic-inorganic hybrid perovskite CH on the surface of the stannic oxide electron transport layer obtained in the step (2)3NH3PbI3Light absorbing layer:
(3-I) mixing a mixture of a molar ratio of 1: 1 CH3NH3I and PbI2Dissolving in a solvent with the volume ratio of 1: 5, heating and stirring the mixed solution of dimethyl sulfoxide (DMSO) and N, N-Dimethylformamide (DMF) at 70 ℃ for 4 hours to obtain an organic-inorganic hybrid perovskite precursor solution; wherein C isH3NH3The amount of X added is 15% of the total mass, PbI2The amount of the added DMSO solvent is 30 percent of the total mass, the amount of the added DMSO solvent is 40 percent of the total mass, and the amount of the added DMF solvent is 15 percent of the total mass;
(3-II) filtering the organic-inorganic hybrid perovskite precursor solution obtained in the step (3-I) through a filter head with the diameter of 0.22 mu m, then dropwise adding the organic-inorganic hybrid perovskite precursor solution on the tin dioxide electron transport layer obtained in the step (2), and obtaining the organic-inorganic hybrid perovskite CH in a spin coating mode3NH3BX3The light absorption layer is set to be 6000 rpm for 30 s by a spin coating process; spin coating until 20 s, adding 250 μ L ethyl acetate or chlorobenzene solution, heat treating at 110 deg.C for 10 min, and annealing to obtain smooth perovskite film;
(4) the organic-inorganic hybrid perovskite CH obtained in the step (3)3NH3BX3Preparing a hole transport layer on the surface of the light absorbing layer: in the hole transport material mixed solution, the adding amount of lithium bis (trifluoromethanesulfonylimide) accounts for 0.3 percent of the total solution mass, the adding amount of 4-tert-butylpyridine accounts for 1.7 percent of the total solution mass, the adding amount of chlorobenzene accounts for 71 percent of the total solution mass, the adding amount of Spiro-OMeTAD (hole transport material) accounts for 27 percent of the total solution mass, and the Spiro-OMeTAD solution is dropwise added to organic-inorganic hybrid perovskite CH3NH3BX3Obtaining a hole transport layer on the surface of the light absorption layer in a spin coating mode, wherein the spin coating process is set to be 3000 rpm for 30 s;
(5) and evaporating a thin metal counter electrode on the surface of the hole transport layer: and (3) performing vacuum evaporation on the 20 nm gold counter electrode at the speed of 0.3 nm/s by adopting a vacuum evaporation method to obtain the gold electrode.
The performance of the semitransparent organic-inorganic hybrid perovskite solar cell obtained in the comparative example was tested: in a room temperature environment, the humidity is less than 40 percent, a xenon lamp is used for simulating sunlight, and the light intensity is 100 mW/cm2The effective illumination area is 0.25 cm2The photoelectric conversion efficiency of the test piece is 14%, and the photoelectric efficiency is reduced to 30% of the initial value in 290 days of stability test.

Claims (10)

1. Semitransparent organic-inorganic material based on conductive polymerHybrid perovskite solar cell, its characterized in that, when defining electrically conductive substrate as the bottom layer, from the bottom up includes in proper order: a conductive substrate layer; a tin dioxide electron transport layer; organic-inorganic hybrid perovskite CH3NH3BX3The light absorption layer, wherein B is Pb, Sn, In or Ge, and X is I, Br or one or more of Cl; the conductive polymer modified hole transport layer is prepared by taking a conductive polymer and a hole transport material as raw materials; a counter electrode.
2. A semi-transparent organic-inorganic hybrid perovskite solar cell based on a conductive polymer as claimed in claim 1, characterized in that the conductive substrate layer is a transparent ITO conductive glass; the conductive polymer is polyaniline, polythiophene, polypyrrole, poly 3, 4-ethylenedioxythiophene: one or more than two of polystyrene sulfonate; the hole transport material is a small molecule polymer, preferably Spiro-OMeTAD and/or P3 HT.
3. A semi-transparent organic-inorganic hybrid perovskite solar cell based on conductive polymers according to claim 1 or 2, characterized in that the preparation method comprises the following steps:
(1) cleaning 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 organic-inorganic hybrid perovskite CH on the surface of the stannic oxide electron transport layer3NH3BX3A light absorbing layer;
(4) in the organic-inorganic hybrid perovskite CH3NH3BX3Preparing a conductive polymer modified hole transport layer on the surface of the light absorption layer;
(5) and (3) evaporating a thin metal counter electrode on the surface of the conductive polymer modified hole transport layer.
4. A semi-transparent organic-inorganic hybrid perovskite solar cell based on conductive polymer as claimed in claim 3, characterized in that in step (1) the cleaning is performed by: and (3) placing the transparent ITO conductive glass in deionized water, absolute ethyl alcohol and isopropanol for 10-20 min by ultrasonic oscillation respectively, drying at 80-120 ℃ for 5-15 min, and carrying out ultraviolet ozone treatment for 20-30 min.
5. A semitransparent organic-inorganic hybrid perovskite solar cell based on conductive polymer according to claim 3 or 4, characterized in that in the step (2), the preparation method of the tin dioxide electron transport layer comprises the following steps: dropwise adding tin dioxide colloid dispersion liquid on the surface of the conductive substrate, spin-coating at 4000-6000 rpm for 20-30 s by a spin-coating method, and heating at 150-180 ℃ for 30-40 min to obtain the conductive substrate; the tin dioxide colloid dispersion liquid is prepared from tin dioxide colloid and deionized water according to the volume ratio of 1: 1-4, and carrying out ultrasonic dispersion.
6. The semitransparent organic-inorganic hybrid perovskite solar cell based on conductive polymer as claimed in any one of claims 3 to 5, wherein in the step (3), the filtered organic-inorganic hybrid perovskite precursor solution is dripped on the surface of the tin dioxide electron transport layer, and the organic-inorganic hybrid perovskite CH is obtained through spin coating, heat treatment and annealing3NH3BX3A light absorbing layer; the preparation method of the organic-inorganic hybrid perovskite precursor solution comprises the following steps: mixing CH with the molar ratio of 1: 13NH3X and BX2Dissolving the mixture in a mixed solution of dimethyl sulfoxide and N, N-dimethylformamide, and heating and stirring the mixture for 4 to 12 hours at the temperature of 65 to 75 ℃.
7. Semi-transparent organic-inorganic hybrid perovskite solar cell based on conductive polymer as claimed in claim 5, characterized in that in step (3) in the organic-inorganic hybrid perovskite precursor liquid, CH3NH3The addition of X is equal to 15-20% of the total mass of the precursor liquid, and BX2The adding amount of the N, N-dimethylformamide is equal to 20-30% of the total mass of the precursor liquid, the adding amount of the dimethyl sulfoxide is equal to 40-50% of the total mass of the precursor liquid, and the adding amount of the N, N-dimethylformamide is equal to 10-25% of the total mass of the precursor liquid; filtrationThe diameter of the filter head is 0.22-0.45 μm; the spin coating speed is 4000-7000 rpm, and the time is 20-40 s; adding 200-300 mu L of ethyl acetate or chlorobenzene solution when the spin coating is carried out for 19-24 s; the temperature of the heat treatment is 70-110 ℃, and the time is 10-20 min.
8. A semi-transparent organic-inorganic hybrid perovskite solar cell based on a conductive polymer as claimed in any one of claims 3 to 7, wherein in the step (4), the conductive polymer/hole transport material mixed solution is dropwise added to the organic-inorganic hybrid perovskite CH3NH3BX3And spin-coating the surface of the light absorption layer to obtain the conductive polymer modified hole transport layer.
9. A semitransparent organic-inorganic hybrid perovskite solar cell based on a conductive polymer as claimed in claim 8, wherein in the 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 semitransparent organic-inorganic hybrid perovskite solar cell based on a conductive polymer as claimed in any one of claims 3 to 9, wherein in the step (5), a thin metal counter electrode is evaporated by a vacuum evaporation method; the vacuum evaporation rate is 0.1-0.6 nm/s, and the thickness of the thin metal counter electrode is 10-60 nm; the gold is preferably metallized.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117897029A (en) * 2024-01-17 2024-04-16 暨南大学 Organic-inorganic hybrid hole transport material and application thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117897029A (en) * 2024-01-17 2024-04-16 暨南大学 Organic-inorganic hybrid hole transport material and application thereof

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