CN111640868B - Preparation method of perovskite thin film photoelectric device based on electronic irradiation modification - Google Patents

Preparation method of perovskite thin film photoelectric device based on electronic irradiation modification Download PDF

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CN111640868B
CN111640868B CN202010400521.1A CN202010400521A CN111640868B CN 111640868 B CN111640868 B CN 111640868B CN 202010400521 A CN202010400521 A CN 202010400521A CN 111640868 B CN111640868 B CN 111640868B
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CN111640868A (en
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杨伟光
郭辉
陈伟
王聪
黄璐
崔星煜
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University of Shanghai for Science and Technology
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    • 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
    • H10K30/151—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2 the wide bandgap semiconductor comprising titanium oxide, e.g. TiO2
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    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
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Abstract

The invention discloses a preparation method of a perovskite thin film photoelectric device based on electron irradiation modification, and belongs to the field of photoelectric devices. The method comprises the steps of carrying out electron irradiation on lead halide precursor solution of the perovskite thin film, then carrying out spin coating to form a precursor thin film, dropwise adding methylamine iodine solution, reacting and annealing to obtain the modified perovskite thin film, and preparing the device. The perovskite thin film prepared by the method has large crystal grain size and flat and smooth surface, can passivate an interface, effectively reduce the crystal boundary effect, and promote the capability of transferring photons into electrons, thereby reducing the series resistance of a device and increasing the filling factor and the photoelectric conversion efficiency. The method disclosed by the invention is simple and convenient in process and good in repeatability, provides a feasible scheme for large-scale production of the high-performance perovskite thin film photoelectric device, and obviously improves the performance of the device.

Description

Preparation method of perovskite thin film photoelectric device based on electronic irradiation modification
Technical Field
The invention relates to a preparation method of a photoelectric device, in particular to application of an electron irradiation technology in modification of a perovskite thin film, and is suitable for the technical field of perovskite thin film photoelectric devices.
Background
The rapid development of the photoelectric conversion efficiency of perovskite solar cells from 3.9% in 2009 to now over 25% has been the focus of modern solar technology area with its surprising efficiency ramp-up speed and lower manufacturing costs. The electron irradiation technology is a novel oxidation-reduction technology which can be used for synthesizing or modifying nano materials, and shows excellent adaptability in the modification of various high-performance materials such as titanium oxide, carbon nano tubes, graphene and the like.
The optimization of the morphology of the lead halide precursor film, the promotion of the perovskite reaction process and the increase of the perovskite crystal grain size are the keys for preparing the perovskite material by adopting a two-step method and obtaining the effect of a smooth and compact film. The method for preparing the large-grain-size film and the high-efficiency solar cell device in the prior art is complex in process, unobvious in performance improvement, poor in stability and not beneficial to subsequent possible industrial production.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to overcome the defects in the prior art and provide a preparation method of a perovskite thin film photoelectric device based on electron irradiation modification. And introducing electron irradiation to modify the precursor solution for preparing the perovskite thin film by the two-step method, thereby promoting the film forming quality of the perovskite precursor thin film, promoting the reaction of the precursor solution and optimizing the effect of ion doping. The perovskite thin film prepared by electron irradiation modification has high crystallinity and large grain size, and can effectively reduce the crystal boundary effect, passivate the interface, reduce the series resistance of the battery, and increase the filling factor and the short-circuit current density. And the preparation process is simple and convenient, and the performance of the device is obviously improved.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of an electron irradiation modification-based perovskite thin film photoelectric device comprises the following steps:
etching and cleaning FTO conductive glass:
a-1, etching treatment is carried out on fluorine-doped tin oxide (FTO) conductive glass, an effective area and an electrode area of a device are protected by using an adhesive tape, then hydrochloric acid (HCl) diluted by zinc powder and deionized water is used for etching the part of an etching groove exposed by the adhesive tape, the width of the etching groove is 1.5mm, the etching time is 5-10s, then redundant zinc powder and hydrochloric acid are wiped off, the adhesive tape is torn off, and finally the isolation of a negative electrode and the effective area from a positive electrode area is completed;
the etching preferably includes: the area of the FTO conductive glass is 4cm multiplied by 2cm, effective areas of 3 devices are divided, and the area of each effective area is 10mm multiplied by 4 mm; the concentration of hydrochloric acid optimized in etching is not lower than 2 mol/L;
a-2, after the FTO conductive glass is etched in the step a-1, ultrasonically cleaning the etched FTO conductive glass by using deionized water for at least 3 times, wherein each time is not more than 20 minutes; then ultrasonically cleaning the FTO conductive glass by using ethanol for at least 3 times, wherein each time is not more than 20 minutes; ultrasonically cleaning the FTO conductive glass by using acetone for at least 3 times, wherein each time is not more than 20 minutes; after cleaning, blowing the conductive glass FTO by using argon to obtain a clean and dry FTO conductive glass substrate;
b. preparation of TiO2A dense layer:
b-1, measuring 4-9ml of absolute ethyl alcohol, 7-16 mu L of hydrochloric acid with the concentration not lower than 37 wt.%, magnetically stirring for at least 5 minutes to ensure that the solution is uniformly mixed to obtain a mixed solution;
b-2, weighing 0.42-0.68g of Tetrabutyl Titanate (TTIP) and adding the tetrabutyl titanate into the mixed solution prepared in the step b-1, and magnetically stirring for 30 minutes until the solution is uniform to obtain a dense layer solution;
b-3, protecting the clean and dry FTO conductive glass substrate obtained in the step a-2 by using an adhesive tape, placing the FTO conductive glass substrate on a spin coating instrument, and sucking the dense layer solution prepared in the step b-2 by using a dropper to drip and fill the area to be coated of the FTO conductive glass substrate; starting a spin coater, spin-coating at a low speed of 800rpm for 8 seconds, and spin-coating at a high speed of 2500rpm for 15 seconds; putting the coated FTO conductive glass substrate into a box-type resistance furnace, setting a heating curve to rise to 150 ℃ in 15 minutes, preserving heat for 30 minutes, then rising to 300 ℃ in 15 minutes, preserving heat for 30 minutes, finally rising to 500 ℃ in 15 minutes, preserving heat for 30-60 minutes, cooling to room temperature after annealing is finished, and obtaining uniform TiO in an effective area of the FTO conductive glass substrate2Dense layer to obtain bonded TiO2A substrate of a dense layer;
c. titanium tetrachloride treatment of TiO2A dense layer:
c-1, measuring 100ml of deionized water, putting the deionized water into a refrigerator to form an ice-water mixed bath, sucking 440 mu L of titanium tetrachloride solution with 400-;
c-2, combining the TiO prepared in the step b-32Putting the substrate of the dense layer into the titanium tetrachloride solution prepared in the step c-1, uniformly mixing, putting the substrate of the dense layer into a constant-temperature water bath heater at room temperature, heating to 75 ℃, keeping the temperature for 20-40 minutes, and carrying outCarrying out reaction; when the reaction is carried out, preferably, no more than 4 substrates are placed in each 100ml of the solution;
c-3, taking out the substrate completely reacted in the step c-2, washing the surface of the substrate by deionized water, removing redundant solution, then putting the substrate into a 70 ℃ drying oven for drying, putting the dried substrate into a box-type resistance furnace for annealing at 500 ℃; the preferred annealing heat treatment regime is as follows: the temperature rise curve of annealing in a box-type resistance furnace is from 15 minutes to 150 ℃, the temperature is preserved for 30 minutes, then the temperature rises to 300 ℃ after 15 minutes, the temperature is preserved for 30 minutes, and finally the temperature rises to 500 ℃ after 15 minutes, and the temperature is preserved for 30-60 minutes;
d. preparing the perovskite thin film by electron irradiation modification:
d-1 weighing lead iodide (PbI) at different molar ratios2) Lead chloride (PbCl)2) Dissolving the composite lead halide in a mixed solution of N, N-Dimethylformamide (DMF) and dimethyl sulfoxide (DMSO), standing and placing on a heating plate until no obvious precipitate exists in the solution; preference is given to PbI2And PbI2In a molar ratio of 9:1 to 7:3, preferably at a heating temperature of 30-40 ℃, preferably for a heating time of 30-60 minutes; preferably, PbI2The mass of the mixed solution is 0.322-0.498g and PbCl is contained in 1ml of the mixed solution2The mass of the mixed solution is 0.0278-0.1g per 1ml, and the volume ratio of DMF to DMSO is 4: 1;
d-2, performing electron irradiation treatment on the solution to be treated prepared in the step d-1 by using a linear electron accelerator, wherein the irradiation environment adopts normal temperature and normal pressure conditions, the irradiation mode adopts a back-and-forth scanning mode, and the preferable irradiation dose is 20-60 kGy; placing the irradiated precursor solution on a heating plate, stirring and dissolving for at least 12 hours until the solution is clear, and obtaining a precursor solution;
d-3, sticking the substrate prepared in the step c-3 with an adhesive tape, reserving an active area of the device, and putting the device into a glove box; fixing the substrate on a spin coater, dropwise adding the precursor solution in the step d-2 into a region to be coated, and spin-coating at a rotating speed of not less than 2500rpm for at least 25 seconds; drying the spin-coated substrate on a heating plate at 75-80 ℃ for 15-30 minutes, and cooling to room temperature for later use; the spin-coating rotation speed is preferably 2500-3000 rpm;
d-4, weighing 9-12mg of methylamine iodide (CH)3NH3I) Adding into 1ml Isopropanol (IPA), stirring and dissolving in glove box at room temperature in dark place to obtain CH3NH3I, solution; continuously dripping CH on the substrate treated in the step d-3 by using a liquid-transferring gun3NH3The color of the solution I is changed from yellow to reddish brown immediately, the solution I is kept stand until the precursor is completely reacted, a spin coating instrument is started to spin-coat for 20 to 40 seconds at the rotating speed of not less than 3000rpm to form a uniform and smooth film, and finally the film is placed on a heating plate to be annealed at the temperature of 100-; preferably, the suction capacity of the pipette gun is 90-150 mu L; the spin coating speed is preferably 3000-3500 rpm;
e. spin-coating a 2,2',7,7' -tetrakis [ N, N-bis (4-methoxyphenyl) amino ] -9,9' -spirobifluorene (Spiro-OMeTAD) hole transport layer:
e-1, weighing 1.7-1.9mol of lithium salt (Li-TFSI) and dissolving the lithium salt in 1ml of acetonitrile solution to obtain a lithium salt solution; weighing 0.05-0.07mol of Spiro-OMeTAD, dissolving in 1ml of chlorobenzene solution, and stirring until the solution is clear; dripping 15-20 μ L of the above lithium salt solution and 28-30 μ L of 4-tert-butylpyridine (TBP) with a pipette gun to improve the conductivity of Spiro-OMeTAD, and magnetically stirring until the solution is uniformly mixed;
e-2, continuously dropwise adding 40-50 mu L of the solution prepared in the step e-1 on the substrate obtained in the step d-4, starting a spin coater, and spin-coating at the rotating speed of not less than 5000rpm for 20-40 seconds; taking the spin-coated substrate out of the glove box, and drying the substrate in a drying dish for more than 12 hours to obtain a 2,2',7,7' -tetra [ N, N-di (4-methoxyphenyl) amino ] -9,9' -spirobifluorene (Spiro-OMeTAD) hole transport layer;
f. preparation of Metal electrodes
And e-2, continuously preparing a metal electrode on the hole transport layer prepared in the step e-2, thereby completing the preparation of the perovskite thin film photoelectric device. Preferably, the metal electrode is a gold electrode, and the thickness of the electrode is 100-110 nm; the metal electrode is preferably prepared by evaporation. The present invention has no special requirements for the specific conditions of the vapor deposition, as long as a metal electrode having a required thickness can be obtained.
Compared with the prior art, the invention has the following obvious substantive characteristics and remarkable advantages:
1. the perovskite thin film prepared by the method has large crystal grain size and smooth surface, can passivate an interface, effectively reduce the crystal boundary effect, and promote the capability of transferring photons into electrons, thereby improving the series resistance of a device and increasing the filling factor and the photoelectric conversion efficiency;
2. according to the method, an electron irradiation method is introduced, high-energy electron beams collide with substances in a target solution, although lead iodide and lead chloride are not easily affected by electron beam impact, the vibration frequency is increased by collision and solution temperature rise, and chemical bonds between oxygen and sulfur in an organic solvent are more easily formed into Lewis adducts with the lead iodide and the lead chloride under the action of the high-energy electron beams; meanwhile, the impact process of the high-energy electron beam is a high-heat cycle, so the process of electron irradiation is also a process of heating the solution at high temperature, and the two processes simultaneously act, so that insoluble lead chloride and insoluble lead iodide have more ideal dissolution states, and finally the preparation quality and the device performance of the perovskite film are improved;
3. the method has simple and convenient process and good repeatability, and is suitable for large-scale production.
Drawings
FIG. 1 is a SEM comparison of perovskite thin films prepared by the methods of the example of the present invention and the comparative example.
FIG. 2 is a comparison of the perovskite thin film IPCE prepared in the examples of the present invention and the comparative examples.
FIG. 3 is a graph comparing current-voltage (I-V) conversion efficiency of perovskite thin film photovoltaic devices fabricated according to examples one, two and comparative example one of the present invention.
FIG. 4 is a graph comparing the current-voltage (I-V) conversion efficiency of perovskite thin film photovoltaic devices fabricated according to examples three, four, and comparative example two of the present invention.
Detailed Description
The above-described scheme is further illustrated below with reference to specific embodiments, which are detailed below:
in this embodiment, referring to fig. 1 to 4, a method for preparing a perovskite thin-film solar cell device based on electron irradiation modification includes the following steps:
example one
Etching and cleaning FTO conductive glass:
a-1, etching treatment is carried out on fluorine-doped tin oxide (FTO) conductive glass, the area of the FTO conductive glass is 4cm multiplied by 2cm, effective areas of 3 devices are divided, and the area of each effective area is 10mm multiplied by 4 mm; firstly, protecting an effective area and an electrode area of a device by using an adhesive tape, and then etching the part of an etched groove exposed by the adhesive tape by using 2mol/L hydrochloric acid (HCl) diluted by zinc powder and deionized water, wherein the etching time is 5-10s, and the width of the etched groove is 1.5 mm; then wiping off redundant zinc powder and hydrochloric acid, tearing off the adhesive tape, and completing the isolation of the negative electrode and the effective area from the positive electrode area;
a-2, after etching, ultrasonically cleaning the etched FTO conductive glass by using deionized water for 3 times, wherein each time lasts for 20 minutes; then ultrasonically cleaning the FTO conductive glass with ethanol for 3 times, and each time for 20 minutes; ultrasonically cleaning the FTO conductive glass with acetone for 3 times, and each time for 20 minutes; after cleaning, blowing the conductive glass FTO by using argon to obtain a clean and dry FTO conductive glass substrate;
b. preparation of TiO2Dense layer
b-1, measuring 9ml of absolute ethyl alcohol and 16 mu L of hydrochloric acid with the concentration of 37 wt.%, and magnetically stirring for 5 minutes to ensure that the solution is uniformly mixed;
b-2, weighing 0.68g of Tetrabutyl Titanate (TTIP) and adding the Tetrabutyl Titanate (TTIP) into the solution in the b-1, and magnetically stirring for 30 minutes until the solution is uniform;
b-3, protecting the part except the active area of the FTO conductive glass in the step a by using an adhesive tape, placing the FTO conductive glass on a spin coater, and sucking the dense layer solution in the step b-2 by using a dropper to drip the solution to the area to be coated; starting a spin coater, spin-coating at a low speed of 800rpm for 8 seconds, and spin-coating at a high speed of 2500rpm for 15 seconds; putting the spin-coated glass substrate into a box-type resistance furnace, setting a heating curve to rise to 150 ℃ within 15 minutes, preserving heat for 30 minutes, then rising to 300 ℃ within 15 minutes, preserving heat for 30 minutes, finally rising to 500 ℃ within 15 minutes,keeping the temperature for 60min, cooling to room temperature after annealing is finished, and obtaining uniform TiO in the effective area of the FTO conductive film2Dense layer to obtain bonded TiO2A substrate of the dense layer;
c. titanium tetrachloride treatment of TiO2Dense layer
c-1, measuring 100ml of deionized water, putting the deionized water into a refrigerator to form an ice-water mixed bath, sucking 440 mu L of titanium tetrachloride solution by using a liquid transfer gun, slowly dripping the titanium tetrachloride solution into the ice-water mixed bath to prevent the titanium tetrachloride from being hydrolyzed too quickly, and then uniformly stirring by using a glass rod;
c-2, putting the 4 substrates prepared in the step b into the uniformly mixed solution in the step c-1, then putting the whole into a constant-temperature water bath heating instrument at room temperature, standing, heating to 75 ℃ at constant temperature, and preserving heat for 40 minutes;
c-3, taking out the substrate which is completely reacted, washing the surface with deionized water to remove redundant solution, and then putting the substrate into a 70 ℃ oven for drying; putting the dried substrate into a box-type resistance furnace, setting a heating curve to rise to 150 ℃ in 15 minutes, preserving heat for 30 minutes, then rising to 300 ℃ in 15 minutes, preserving heat for 30 minutes, and finally rising to 500 ℃ in 15 minutes, preserving heat for 30-60 minutes;
d. preparation of perovskite thin film by electron irradiation modification
d-1 weighing 0.3688g of lead iodide (PbI)2) 0.0556g of lead chloride (PbCl)2) Dissolving the mixture in a mixed solution of N, N-Dimethylformamide (DMF) and dimethyl sulfoxide (DMSO) in a volume ratio of 4:1 at a molar ratio of 8:2, standing on a heating plate at 30 ℃, and keeping the temperature for 60 minutes until no obvious precipitate exists in the solution;
d-2, performing electron irradiation treatment on the solution to be treated in the d-1 by using a linear electron accelerator, wherein the irradiation environment adopts normal temperature and normal pressure conditions, the irradiation mode adopts a back-and-forth scanning mode, and the irradiation dose is 20 kGy; placing the irradiated precursor solution on a heating plate, stirring and dissolving for more than 12 hours until the solution is clear, and obtaining a precursor solution;
d-3, sticking the substrate prepared in the step c with an adhesive tape, reserving an active area of the device, and putting the device into a glove box; fixing the substrate on a spin coater, dropwise adding the precursor solution in the d-2 in a region to be coated, spin-coating at the rotating speed of 2500rpm for 25 seconds, drying the spin-coated substrate on a heating plate at 75 ℃ for 20 minutes, and finally cooling to room temperature for later use;
d-4 weighing 12mg of methylamine iodine (CH)3NH3I) Adding into 1ml of Isopropanol (IPA), and stirring and dissolving in a glove box at room temperature in a dark place; 150 μ L of CH was added dropwise to the substrate in d-3 using a pipette3NH3The color of the solution I is changed from yellow to reddish brown immediately, the solution I is kept stand until the precursor completely reacts, a spin coating instrument is started to spin-coat for 35 seconds at the rotating speed of 3000rpm to form a uniform and smooth film, and finally the film is placed on a heating plate at 100 ℃ for annealing to obtain a crystallized perovskite film;
e. spin-coating 2,2',7,7' -tetrakis [ N, N-bis (4-methoxyphenyl) amino ] -9,9' -spirobifluorene (Spiro-OMeTAD) hole transport layer
e-1, weighing 1.81mol of lithium salt (Li-TFSI) and dissolving in 1ml of acetonitrile solution to obtain a lithium salt solution; weighing 0.07mol of Spiro-OMeTAD, dissolving in 1ml of chlorobenzene solution, and stirring until the solution is clear; dripping 18 mu L of the lithium salt solution and 29 mu L of 4-tert-butylpyridine (TBP) by using a liquid transfer gun to improve the conductivity of the Spiro-OMeTAD, and magnetically stirring until the solution is uniformly mixed;
e-2, dripping 45 mu L of the solution in the e-1 solution on the substrate in the step d, starting a spin coater, and spin-coating at the rotating speed of 5000rpm for 35 seconds; taking the spin-coated substrate out of the glove box, and drying the substrate in a drying dish for more than 12 hours;
f. preparation of Metal electrodes
And (4) evaporating a gold electrode on the Spiro-OMeTAD layer to finish the preparation of the whole perovskite photoelectric device.
Example two
The present embodiment is substantially the same as the first embodiment, and the special points are that:
in this embodiment, a method for preparing a perovskite thin-film solar cell device based on electron irradiation modification includes the following steps:
etching and cleaning of FTO conductive glass
a-1, etching treatment is carried out on fluorine-doped tin oxide (FTO) conductive glass, the area of the FTO conductive glass is 4cm multiplied by 2cm, effective areas of 3 devices are divided, and the area of each effective area is 10mm multiplied by 4 mm; firstly, protecting an effective area and an electrode area of a device by using an adhesive tape, and then etching the part of an etching groove exposed by the adhesive tape by using 2mol/L hydrochloric acid (HCl) diluted by zinc powder and deionized water, wherein the etching time is 5-10s, and the width of the etching groove is 1.5 mm; then wiping off redundant zinc powder and hydrochloric acid, tearing off the adhesive tape, and completing the isolation of the negative electrode and the effective area from the positive electrode area;
a-2, after etching, ultrasonically cleaning the etched FTO conductive glass by using deionized water for 3 times, wherein each time is 20 minutes; then ultrasonically cleaning the FTO conductive glass with ethanol for 3 times, and each time for 20 minutes; ultrasonically cleaning the FTO conductive glass with acetone for 3 times, and each time for 20 minutes; after cleaning, blowing the conductive glass FTO by using argon to obtain a clean and dry FTO conductive glass substrate;
b. preparation of TiO2Dense layer
b-1, measuring 9ml of absolute ethyl alcohol and 16 mu L of hydrochloric acid with the concentration of 37 wt.%, and magnetically stirring for 5 minutes to ensure that the solution is uniformly mixed;
b-2, weighing 0.68g of Tetrabutyl Titanate (TTIP) and adding the Tetrabutyl Titanate (TTIP) into the solution in the b-1, and magnetically stirring for 30 minutes until the solution is uniform;
b-3, protecting the part except the active area of the FTO conductive glass in the step a by using an adhesive tape, placing the FTO conductive glass on a spin coater, and sucking the dense layer solution in the step b-2 by using a dropper to drip the solution to the area to be coated; starting a spin coater, spin-coating at a low speed of 800rpm for 8 seconds, and spin-coating at a high speed of 2500rpm for 15 seconds; putting the spin-coated glass substrate into a box-type resistance furnace, setting a heating curve to be increased to 150 ℃ in 15 minutes, preserving heat for 30 minutes, increasing to 300 ℃ in 15 minutes, preserving heat for 30 minutes, increasing to 500 ℃ in 15 minutes, preserving heat for 60 minutes, cooling to room temperature after annealing is finished, and obtaining uniform TiO in an effective area of the FTO conductive film2Dense layer to obtain bonded TiO2A substrate of a dense layer;
c. titanium tetrachloride treatment of TiO2Dense layer
c-1, measuring 100ml of deionized water, putting the deionized water into a refrigerator to form an ice-water mixed bath, sucking 440 mu L of titanium tetrachloride solution by using a liquid transfer gun, slowly dripping the titanium tetrachloride solution into the ice-water mixed bath to prevent the titanium tetrachloride from being hydrolyzed too quickly, and then uniformly stirring by using a glass rod;
c-2, putting the 4 substrates prepared in the step b into the uniformly mixed solution in the step c-1, then putting the whole into a constant-temperature water bath heating instrument at room temperature, standing, heating to 75 ℃ at constant temperature, and preserving heat for 40 minutes;
c-3, taking out the substrate which is completely reacted, washing the surface with deionized water, removing redundant solution, and then putting the substrate into a 70 ℃ oven for drying; putting the dried substrate into a box-type resistance furnace, setting a temperature rise curve to be increased to 150 ℃ within 15 minutes, preserving heat for 30 minutes, then increasing to 300 ℃ within 15 minutes, preserving heat for 30 minutes, finally increasing to 500 ℃ within 15 minutes, and preserving heat for 30-60 minutes;
d. electronic irradiation modified perovskite film
d-1 weighing 0.3688g of lead iodide (PbI)2) 0.0556g of lead chloride (PbCl)2) Dissolving the mixture in a mixed solution of N, N-Dimethylformamide (DMF) and dimethyl sulfoxide (DMSO) in a volume ratio of 4:1 at a molar ratio of 8:2, standing on a heating plate at 30 ℃, and keeping the temperature for 60 minutes until no obvious precipitate exists in the solution;
d-2, performing electron irradiation treatment on the solution to be treated in the d-1 by using a linear electron accelerator, wherein the irradiation environment adopts normal temperature and normal pressure conditions, the irradiation mode adopts a back-and-forth scanning mode, and the irradiation dose is 60 kGy; placing the irradiated precursor solution on a heating plate, stirring and dissolving for more than 12 hours until the solution is clear, and obtaining a precursor solution;
d-3, sticking the substrate prepared in the step c with an adhesive tape, reserving an active area of the device, and putting the device into a glove box; fixing the substrate on a spin coater, dropwise adding the precursor solution in the d-2 in a region to be coated, spin-coating at the rotating speed of 2500rpm for 25 seconds, drying the spin-coated substrate on a heating plate at 75 ℃ for 20 minutes, and finally cooling to room temperature for later use;
d-4 weighing 12mg methylamine iodide (CH)3NH3I) Adding into 1ml of Isopropanol (IPA), and stirring and dissolving in a glove box at room temperature in a dark place; 150 μ L of CH was added dropwise to the substrate in d-3 using a pipette3NH3The color of the film of the solution I is changed from yellow to reddish brown immediately, the solution I is kept stand until the precursor is completely reacted, a spin coater is started, and the rotating speed is 3000rpmSpin-coating for 35 seconds to form a uniform and smooth film, and finally placing the film on a heating plate at 100 ℃ for annealing to obtain a crystallized perovskite film;
e. spin-coating 2,2',7,7' -tetrakis [ N, N-bis (4-methoxyphenyl) amino ] -9,9' -spirobifluorene (Spiro-OMeTAD) hole transport layer
e-1, weighing 1.81mol of lithium salt (Li-TFSI) and dissolving in 1ml of acetonitrile solution to obtain a lithium salt solution; weighing 0.07mol of Spiro-OMeTAD, dissolving in 1ml of chlorobenzene solution, and stirring until the solution is clear; dripping 18 mu L of the lithium salt solution and 29 mu L of 4-tert-butylpyridine (TBP) by using a liquid transfer gun to improve the conductivity of the Spiro-OMeTAD, and magnetically stirring until the solution is uniformly mixed;
e-2, dripping 45 mu L of the solution in the e-1 solution on the substrate in the step d, starting a spin coater, and spin-coating at the rotating speed of 5000rpm for 35 seconds; taking the spin-coated substrate out of the glove box, and drying the substrate in a drying dish for more than 12 hours;
f. preparation of Metal electrodes
And (4) evaporating a gold electrode on the Spiro-OMeTAD layer to finish the preparation of the whole perovskite photoelectric device.
Comparative example 1
This comparative example is essentially the same as the first example, with the particularity that:
in the comparative example, the preparation method of the perovskite thin film photoelectric device which is not modified by electron irradiation comprises the following steps:
etching and cleaning of FTO conductive glass
a-1, etching treatment is carried out on fluorine-doped tin oxide (FTO) conductive glass, the area of the FTO conductive glass is 4cm multiplied by 2cm, effective areas of 3 devices are divided, and the area of each effective area is 10mm multiplied by 4 mm; firstly, protecting an effective area and an electrode area of a device by using an adhesive tape, and then etching the part of an etching groove exposed by the adhesive tape by using 2mol/L hydrochloric acid (HCl) diluted by zinc powder and deionized water, wherein the etching time is 5-10s, and the width of the etching groove is 1.5 mm; then wiping off redundant zinc powder and hydrochloric acid, tearing off the adhesive tape, and completing the isolation of the negative electrode and the effective area from the positive electrode area;
a-2, after etching, ultrasonically cleaning the etched FTO conductive glass by using deionized water for 3 times, wherein each time lasts for 20 minutes; then ultrasonically cleaning the FTO conductive glass with ethanol for 3 times, and each time for 20 minutes; then acetone is used for ultrasonically cleaning the FTO conductive glass for 3 times, and each time lasts for 20 minutes; after cleaning, blowing the conductive glass FTO by using argon to obtain a clean and dry FTO conductive glass substrate;
b. preparation of TiO2Dense layer
b-1, measuring 9ml of absolute ethyl alcohol and 16 mu L of hydrochloric acid with the concentration of 37 wt.%, and magnetically stirring for 5 minutes to ensure that the solution is uniformly mixed;
b-2, weighing 0.68g of Tetrabutyl Titanate (TTIP) and adding into the solution in the b-1, and magnetically stirring for 30 minutes until the solution is uniform;
b-3, protecting the part except the active area of the FTO conductive glass in the step a by using an adhesive tape, placing the FTO conductive glass on a spin coating instrument, and sucking the dense layer solution in the step b-2 by using a dropper to drip the solution to the area to be coated; starting a spin coater, spin-coating at a low speed of 800rpm for 8 seconds, and spin-coating at a high speed of 2500rpm for 15 seconds; putting the spin-coated glass substrate into a box-type resistance furnace, setting a heating curve to be increased to 150 ℃ in 15 minutes, preserving heat for 30 minutes, increasing to 300 ℃ in 15 minutes, preserving heat for 30 minutes, increasing to 500 ℃ in 15 minutes, preserving heat for 60 minutes, cooling to room temperature after annealing is finished, and obtaining uniform TiO in an effective area of the FTO conductive film2Dense layer to obtain bonded TiO2A substrate of a dense layer;
c. titanium tetrachloride treatment of TiO2Dense layer
c-1, measuring 100ml of deionized water, putting the deionized water into a refrigerator to form an ice-water mixed bath, sucking 440 mu L of titanium tetrachloride solution by using a liquid transfer gun, slowly dropping the titanium tetrachloride solution into the ice-water mixed bath to prevent the titanium tetrachloride from being hydrolyzed too quickly, and then uniformly stirring by using a glass rod;
c-2, putting the 4 substrates prepared in the step b into the uniformly mixed solution in the step c-1, then integrally putting the substrates into a constant-temperature water bath heating instrument at room temperature, standing, heating to 75 ℃ at constant temperature, and keeping the temperature for 40 minutes;
c-3, taking out the substrate which is completely reacted, washing the surface with deionized water, removing redundant solution, and then putting the substrate into a 70 ℃ oven for drying; putting the dried substrate into a box-type resistance furnace, setting a temperature rise curve to be increased to 150 ℃ within 15 minutes, preserving heat for 30 minutes, then increasing to 300 ℃ within 15 minutes, preserving heat for 30 minutes, finally increasing to 500 ℃ within 15 minutes, and preserving heat for 30-60 minutes;
d. perovskite film preparation without electron irradiation modification
d-1 weighing 0.3688g of lead iodide (PbI)2) 0.0556g of lead chloride (PbCl)2) Dissolving the mixture in a mixed solution of N, N-Dimethylformamide (DMF) and dimethyl sulfoxide (DMSO) in a volume ratio of 4:1 at a molar ratio of 8:2, placing the mixture on a heating plate at 70 ℃, and stirring the mixture for 12 hours until no obvious precipitate exists in the solution;
d-2, sticking the substrate prepared in the step c by using an adhesive tape, reserving an active area of the device, and putting the device into a glove box; fixing a substrate on a spin coater, dropwise adding the precursor solution in the d-1 in a region to be coated, spin-coating at the rotating speed of 2500rpm for 25 seconds, drying the spin-coated substrate on a heating plate at the temperature of 75 ℃ for 20 minutes, and finally cooling to room temperature for later use;
d-4 weighing 12mg methylamine iodide (CH)3NH3I) Adding into 1ml Isopropanol (IPA), stirring and dissolving in a glove box at room temperature in dark place; 150 μ L of CH was added dropwise to the substrate in d-3 using a pipette3NH3The color of the solution I is changed from yellow to reddish brown immediately, the solution I is kept stand until the precursor completely reacts, a spin coating instrument is started to spin-coat for 35 seconds at the rotating speed of 3000rpm to form a uniform and smooth film, and finally the film is placed on a heating plate at 100 ℃ for annealing to obtain a crystallized perovskite film;
e. spin-coating 2,2',7,7' -tetrakis [ N, N-bis (4-methoxyphenyl) amino ] -9,9' -spirobifluorene (Spiro-OMeTAD) hole transport layer
e-1, weighing 1.81mol of lithium salt (Li-TFSI) and dissolving the lithium salt in 1ml of acetonitrile solution to obtain a lithium salt solution; weighing 0.07mol of Spiro-OMeTAD, dissolving in 1ml of chlorobenzene solution, and stirring until the solution is clear; dripping 18 mu L of the lithium salt solution and 29 mu L of 4-tert-butylpyridine (TBP) by using a liquid transfer gun to improve the conductivity of the Spiro-OMeTAD, and magnetically stirring until the solution is uniformly mixed;
e-2, dripping 45 mu L of e-1 solution on the substrate in the step d, starting a spin coater, and spin-coating at the rotating speed of 5000rpm for 35 seconds; taking the spin-coated substrate out of the glove box, and drying the substrate in a drying dish for more than 12 hours;
f. preparation of Metal electrodes
And (4) evaporating a gold electrode on the Spiro-OMeTAD layer to finish the preparation of the whole perovskite photoelectric device.
Scanning electron microscope, IPCE and I-V curve tests were performed on the perovskite thin films obtained in the above examples I and II and comparative example I. FIG. 1 SEM images of perovskite thin films prepared by electron irradiation modification and without electron irradiation modification; FIG. 2 is a diagram of a perovskite thin film IPCE prepared by electron irradiation modification and without electron irradiation modification; FIG. 3 shows the molar ratio PbI2:PbCl2And (2) when the ratio is 8:2, carrying out electron irradiation modification and carrying out I-V diagram of the perovskite thin film photoelectric device prepared without electron irradiation modification. As can be seen from figure 1, the perovskite thin film prepared by electron irradiation modification has obviously increased grain size which can reach more than 500nm, and the thin film is more smooth and compact. As can be seen from fig. 2, the electron irradiation modified perovskite thin film has higher efficiency of converting incident photons into electrons in the visible light band. As can be seen from FIG. 3, the performance of the electron irradiation modified perovskite thin film photoelectric device is obviously improved, and compared with a device which is not modified by electron irradiation, when the irradiation dose is 20kGy, the photoelectric conversion efficiency of the device is improved from 15.63% to 19.01%, and is improved by 21.63%; short-circuit current is from 26.41mA/cm2The lift is 27.50mA/cm2The fill factor increased from 0.54 to 0.62. When the irradiation dose is 60kGy, the photoelectric conversion efficiency of the device is improved from 15.63% to 17.99%, the photoelectric conversion efficiency is improved by 15.10%, and the filling factor is improved from 0.54 to 0.61. In the above embodiment, after performing electron irradiation on the lead halide precursor solution of the perovskite thin film, spin-coating the lead halide precursor solution to form a precursor thin film, after dropping methylamine iodine solution, performing reaction and annealing to obtain a modified perovskite thin film, and preparing a device. The perovskite thin film prepared by the method has large crystal grain size and smooth surface, can passivate an interface, effectively reduce the crystal boundary effect, and promote the capability of transferring photons into electrons, thereby reducing the series resistance of a device and increasing the filling factor and the photoelectric conversion efficiency. The method introduces an electron irradiation method, high-energy electron beams collide with substances in a target solution, and although lead iodide and lead chloride are not easily influenced by the impact of the electron beams, the vibration of the lead iodide and lead chloride is increased by the collision and the temperature rise of the solutionThe frequency and the chemical bond between oxygen and sulfur in the organic solvent are easier to form Lewis adduct with lead iodide and lead chloride under the action of high-energy electron beams. Meanwhile, the impact process of the high-energy electron beam is a high-heat cycle, so the process of electron irradiation is also a process of heating the solution at high temperature, and the two processes simultaneously act, so that the insoluble lead chloride and the insoluble lead iodide have more ideal dissolution states, and finally the preparation quality and the device performance of the perovskite film are improved. The method has simple and convenient process and good repeatability, and provides a feasible scheme for producing high-performance perovskite thin film photoelectric devices on a large scale.
EXAMPLE III
Etching and cleaning of FTO conductive glass
a-1, etching treatment is carried out on fluorine-doped tin oxide (FTO) conductive glass, the area of the FTO conductive glass is 4cm multiplied by 2cm, effective areas of 3 devices are divided, and the area of each effective area is 10mm multiplied by 4 mm; firstly, protecting an effective area and an electrode area of a device by using an adhesive tape, and then etching the part of an etched groove exposed by the adhesive tape by using 2mol/L hydrochloric acid (HCl) diluted by zinc powder and deionized water, wherein the etching time is 5-10s, and the width of the etched groove is 1.5 mm; then wiping off redundant zinc powder and hydrochloric acid, tearing off the adhesive tape, and completing the isolation of the negative electrode and the effective area from the positive electrode area;
a-2, after etching, ultrasonically cleaning the etched FTO conductive glass by using deionized water for 3 times, wherein each time lasts for 20 minutes; then, ultrasonically cleaning the FTO conductive glass by using ethanol for 3 times, wherein each time is 20 minutes; then acetone is used for ultrasonically cleaning the FTO conductive glass for 3 times, and each time lasts for 20 minutes; after cleaning, blowing the conductive glass FTO by using argon to obtain a clean and dry FTO conductive glass substrate;
b. preparation of TiO2Dense layer
b-1, measuring 9ml of absolute ethyl alcohol and 16 mu L of hydrochloric acid with the concentration of 37 wt.%, and magnetically stirring for 5 minutes to ensure that the solution is uniformly mixed;
b-2, weighing 0.68g of Tetrabutyl Titanate (TTIP) and adding into the solution in the b-1, and magnetically stirring for 30 minutes until the solution is uniform;
b-3, conducting the FTO in the step a with conductive glassProtecting the part except the active region by using the glass adhesive tape, placing the part on a spin coating instrument, and sucking the dense layer solution in the b-2 by using a dropper to drip the solution to the area to be coated; starting a spin coater, spin-coating at a low speed of 800rpm for 8 seconds, and spin-coating at a high speed of 2500rpm for 15 seconds; putting the spin-coated glass substrate into a box-type resistance furnace, setting a heating curve to be increased to 150 ℃ within 15 minutes, preserving heat for 30 minutes, then increasing to 300 ℃ within 15 minutes, preserving heat for 30 minutes, finally increasing to 500 ℃ within 15 minutes, preserving heat for 60 minutes, cooling to room temperature after annealing is finished, and obtaining uniform TiO in the effective area of the FTO conductive film2Dense layer to obtain bonded TiO2A substrate of the dense layer;
c. titanium tetrachloride treatment of TiO2Dense layer
c-1, measuring 100ml of deionized water, putting the deionized water into a refrigerator to form an ice-water mixed bath, sucking 440 mu L of titanium tetrachloride solution by using a liquid transfer gun, slowly dropping the titanium tetrachloride solution into the ice-water mixed bath to prevent the titanium tetrachloride from being hydrolyzed too quickly, and then uniformly stirring by using a glass rod;
c-2, putting the 4 substrates prepared in the step b into the uniformly mixed solution in the step c-1, then putting the whole into a constant-temperature water bath heating instrument at room temperature, standing, heating to 75 ℃ at constant temperature, and preserving heat for 40 minutes;
c-3, taking out the substrate which is completely reacted, washing the surface with deionized water, removing redundant solution, and then putting the substrate into a 70 ℃ oven for drying; putting the dried substrate into a box-type resistance furnace, setting a heating curve to rise to 150 ℃ in 15 minutes, preserving heat for 30 minutes, then rising to 300 ℃ in 15 minutes, preserving heat for 30 minutes, and finally rising to 500 ℃ in 15 minutes, preserving heat for 30-60 minutes;
d. electronic irradiation modified perovskite film
d-1 weighing 0.3227g of lead iodide (PbI)2) 0.0834g of lead chloride (PbCl)2) Dissolving the mixture in a mixed solution of N, N-Dimethylformamide (DMF) and dimethyl sulfoxide (DMSO) in a volume ratio of 4:1 at a molar ratio of 7:3, standing on a heating plate at 30 ℃, and keeping the temperature for 60 minutes until no obvious precipitate exists in the solution;
d-2, performing electron irradiation treatment on the solution to be treated in the d-1 by using a linear electron accelerator, wherein the irradiation environment adopts normal temperature and normal pressure conditions, the irradiation mode adopts a back-and-forth scanning mode, and the irradiation dose is 20 kGy; placing the irradiated precursor solution on a heating plate, stirring and dissolving for more than 12 hours until the solution is clear, and obtaining a precursor solution;
d-3, sticking the substrate prepared in the step c by using an adhesive tape, reserving an active area of the device, and putting the device into a glove box; fixing the substrate on a spin coater, dropwise adding the precursor solution in the d-2 in a region to be coated, spin-coating at the rotating speed of 2500rpm for 25 seconds, drying the spin-coated substrate on a heating plate at 75 ℃ for 20 minutes, and finally cooling to room temperature for later use;
d-4 weighing 12mg methylamine iodide (CH)3NH3I) Adding into 1ml of Isopropanol (IPA), and stirring and dissolving in a glove box at room temperature in a dark place; 150 μ L of CH was added dropwise to the substrate in d-3 using a pipette3NH3The color of the film in the solution I is changed from yellow to reddish brown immediately, the solution I is kept stand until the precursor completely reacts, a spin coating instrument is started, the film is spin-coated for 35 seconds at the rotating speed of 3000rpm to form a uniform and smooth film, and finally the film is placed on a heating plate at 100 ℃ for annealing to obtain a crystallized perovskite film;
e. spin-coating 2,2',7,7' -tetrakis [ N, N-bis (4-methoxyphenyl) amino ] -9,9' -spirobifluorene (Spiro-OMeTAD) hole transport layer
e-1, weighing 1.81mol of lithium salt (Li-TFSI) and dissolving in 1ml of acetonitrile solution to obtain a lithium salt solution; weighing 0.07mol of Spiro-OMeTAD, dissolving in 1ml of chlorobenzene solution, and stirring until the solution is clear; dripping 18 mu L of the lithium salt solution and 29 mu L of 4-tert-butylpyridine (TBP) by using a liquid transfer gun to improve the conductivity of the Spiro-OMeTAD, and magnetically stirring until the solution is uniformly mixed;
e-2, dripping 45 mu L of the solution in the e-1 solution on the substrate in the step d, starting a spin coater, and spin-coating at the rotating speed of 5000rpm for 35 seconds; taking the spin-coated substrate out of the glove box, and drying the substrate in a drying dish for more than 12 hours;
f. preparation of Metal electrodes
And (4) evaporating a gold electrode on the Spiro-OMeTAD layer to finish the preparation of the whole perovskite photoelectric device.
Example four
Etching and cleaning of FTO conductive glass
a-1, etching treatment is carried out on fluorine-doped tin oxide (FTO) conductive glass, the area of the FTO conductive glass is 4cm multiplied by 2cm, effective areas of 3 devices are divided, and the area of each effective area is 10mm multiplied by 4 mm; firstly, protecting an effective area and an electrode area of a device by using an adhesive tape, and then etching the part of an etching groove exposed by the adhesive tape by using 2mol/L hydrochloric acid (HCl) diluted by zinc powder and deionized water, wherein the etching time is 5-10s, and the width of the etching groove is 1.5 mm; then wiping off redundant zinc powder and hydrochloric acid, tearing off the adhesive tape, and completing the isolation of the negative electrode and the effective area from the positive electrode area;
a-2, after etching, ultrasonically cleaning the etched FTO conductive glass by using deionized water for 3 times, wherein each time is 20 minutes; then ultrasonically cleaning the FTO conductive glass with ethanol for 3 times, and each time for 20 minutes; then acetone is used for ultrasonically cleaning the FTO conductive glass for 3 times, and each time lasts for 20 minutes; after cleaning, blowing the conductive glass FTO by using argon to obtain a clean and dry FTO conductive glass substrate;
b. preparation of TiO2Dense layer
b-1, measuring 9ml of absolute ethyl alcohol and 16 mu L of hydrochloric acid with the concentration of 37 wt.%, and magnetically stirring for 5 minutes to ensure that the solution is uniformly mixed;
b-2, weighing 0.68g of Tetrabutyl Titanate (TTIP) and adding the Tetrabutyl Titanate (TTIP) into the solution in the b-1, and magnetically stirring for 30 minutes until the solution is uniform;
b-3, protecting the part except the active area of the FTO conductive glass in the step a by using an adhesive tape, placing the FTO conductive glass on a spin coating instrument, and sucking the dense layer solution in the step b-2 by using a dropper to drip the solution to the area to be coated; starting a spin coater, spin-coating at a low speed of 800rpm for 8 seconds, and spin-coating at a high speed of 2500rpm for 15 seconds; putting the spin-coated glass substrate into a box-type resistance furnace, setting a heating curve to be increased to 150 ℃ within 15 minutes, preserving heat for 30 minutes, then increasing to 300 ℃ within 15 minutes, preserving heat for 30 minutes, finally increasing to 500 ℃ within 15 minutes, preserving heat for 60 minutes, cooling to room temperature after annealing is finished, and obtaining uniform TiO in the effective area of the FTO conductive film2Dense layer to obtain bonded TiO2A substrate of the dense layer;
c. titanium tetrachloride treatment of TiO2Dense layer
c-1, measuring 100ml of deionized water, putting the deionized water into a refrigerator to form an ice-water mixed bath, sucking 440 mu L of titanium tetrachloride solution by using a liquid transfer gun, slowly dripping the titanium tetrachloride solution into the ice-water mixed bath to prevent the titanium tetrachloride from being hydrolyzed too quickly, and then uniformly stirring by using a glass rod;
c-2, putting the 4 substrates prepared in the step b into the uniformly mixed solution in the step c-1, then putting the whole into a constant-temperature water bath heating instrument at room temperature, standing, heating to 75 ℃ at constant temperature, and preserving heat for 40 minutes;
c-3, taking out the substrate which is completely reacted, washing the surface with deionized water to remove redundant solution, and then putting the substrate into a 70 ℃ oven for drying; putting the dried substrate into a box-type resistance furnace, setting a temperature rise curve to be increased to 150 ℃ within 15 minutes, preserving heat for 30 minutes, then increasing to 300 ℃ within 15 minutes, preserving heat for 30 minutes, finally increasing to 500 ℃ within 15 minutes, and preserving heat for 30-60 minutes;
d. preparation of perovskite thin film by electron irradiation modification
d-1 weighing 0.3688g of lead iodide (PbI)2) 0.0834g of lead chloride (PbCl)2) Dissolving the mixture in a mixed solution of N, N-Dimethylformamide (DMF) and dimethyl sulfoxide (DMSO) in a volume ratio of 4:1 at a molar ratio of 7:3, standing on a heating plate at 30 ℃, and keeping the temperature for 60 minutes until no obvious precipitate exists in the solution;
d-2, performing electron irradiation treatment on the solution to be treated in the d-1 by using a linear electron accelerator, wherein the irradiation environment adopts normal temperature and normal pressure conditions, the irradiation mode adopts a back-and-forth scanning mode, and the irradiation dose is 60 kGy; placing the irradiated precursor solution on a heating plate, stirring and dissolving for more than 12 hours until the solution is clear, and obtaining a precursor solution;
d-3, sticking the substrate prepared in the step c with an adhesive tape, reserving an active area of the device, and putting the device into a glove box; fixing the substrate on a spin coater, dropwise adding the precursor solution in the d-2 in a region to be coated, spin-coating at the rotating speed of 2500rpm for 25 seconds, drying the spin-coated substrate on a heating plate at 75 ℃ for 20 minutes, and finally cooling to room temperature for later use;
d-4 weighing 12mg methylamine iodide (CH)3NH3I) Adding into 1ml of Isopropanol (IPA), and stirring and dissolving in a glove box at room temperature in a dark place; using pipette on substrate in d-3150 μ L of CH was added dropwise3NH3The color of the film in the solution I is changed from yellow to reddish brown immediately, the solution I is kept stand until the precursor completely reacts, a spin coating instrument is started, the film is spin-coated for 35 seconds at the rotating speed of 3000rpm to form a uniform and smooth film, and finally the film is placed on a heating plate at 100 ℃ for annealing to obtain a crystallized perovskite film;
e. spin-coating 2,2',7,7' -tetrakis [ N, N-bis (4-methoxyphenyl) amino ] -9,9' -spirobifluorene (Spiro-OMeTAD) hole transport layer
e-1, weighing 1.81mol of lithium salt (Li-TFSI) and dissolving the lithium salt in 1ml of acetonitrile solution to obtain a lithium salt solution; weighing 0.07mol of Spiro-OMeTAD, dissolving in 1ml of chlorobenzene solution, and stirring until the solution is clear; dripping 18 mu L of the lithium salt solution and 29 mu L of 4-tert-butylpyridine (TBP) by using a liquid transfer gun to improve the conductivity of the Spiro-OMeTAD, and magnetically stirring until the solution is uniformly mixed;
e-2, dripping 45 mu L of the solution in the e-1 solution on the substrate in the step d, starting a spin coater, and spin-coating at the rotating speed of 5000rpm for 35 seconds; taking the spin-coated substrate out of the glove box, and drying the substrate in a drying dish for more than 12 hours;
f. preparation of Metal electrodes
And (4) evaporating a gold electrode on the Spiro-OMeTAD layer to complete the preparation of the whole perovskite photoelectric device.
Comparative example No. two
The comparative example is basically the same as the third example, and is characterized in that:
in the comparative example, the preparation method of the perovskite thin film photoelectric device which is not modified by electron irradiation comprises the following steps:
etching and cleaning of FTO conductive glass
a-1, etching treatment is carried out on fluorine-doped tin oxide (FTO) conductive glass, the area of the FTO conductive glass is 4cm multiplied by 2cm, effective areas of 3 devices are divided, and the area of each effective area is 10mm multiplied by 4 mm; firstly, protecting an effective area and an electrode area of a device by using an adhesive tape, and then etching the part of an etched groove exposed by the adhesive tape by using 2mol/L hydrochloric acid (HCl) diluted by zinc powder and deionized water, wherein the etching time is 5-10s, and the width of the etched groove is 1.5 mm; then wiping off redundant zinc powder and hydrochloric acid, tearing off the adhesive tape, and completing the isolation of the negative electrode and the effective area from the positive electrode area;
a-2, after etching, ultrasonically cleaning the etched FTO conductive glass by using deionized water for 3 times, wherein each time lasts for 20 minutes; then, ultrasonically cleaning the FTO conductive glass by using ethanol for 3 times, wherein each time is 20 minutes; then acetone is used for ultrasonically cleaning the FTO conductive glass for 3 times, and each time lasts for 20 minutes; after cleaning, blowing the conductive glass FTO by using argon to obtain a clean and dry FTO conductive glass substrate;
b. preparation of TiO2Dense layer
b-1, measuring 9ml of absolute ethyl alcohol and 16 mu L of hydrochloric acid with the concentration of 37 wt.%, and magnetically stirring for 5 minutes to ensure that the solution is uniformly mixed;
b-2, weighing 0.68g of Tetrabutyl Titanate (TTIP) and adding the Tetrabutyl Titanate (TTIP) into the solution in the b-1, and magnetically stirring for 30 minutes until the solution is uniform;
b-3, protecting the part except the active area of the FTO conductive glass in the step a by using an adhesive tape, placing the FTO conductive glass on a spin coater, and sucking the dense layer solution in the step b-2 by using a dropper to drip the solution to the area to be coated; starting a spin coater, spin-coating at a low speed of 800rpm for 8 seconds, and spin-coating at a high speed of 2500rpm for 15 seconds; putting the spin-coated glass substrate into a box-type resistance furnace, setting a heating curve to be increased to 150 ℃ within 15 minutes, preserving heat for 30 minutes, then increasing to 300 ℃ within 15 minutes, preserving heat for 30 minutes, finally increasing to 500 ℃ within 15 minutes, preserving heat for 60 minutes, cooling to room temperature after annealing is finished, and obtaining uniform TiO in the effective area of the FTO conductive film2Dense layer to obtain bonded TiO2A substrate of the dense layer;
c. titanium tetrachloride treatment of TiO2Dense layer
c-1, measuring 100ml of deionized water, putting the deionized water into a refrigerator to form an ice-water mixed bath, sucking 440 mu L of titanium tetrachloride solution by using a liquid transfer gun, slowly dropping the titanium tetrachloride solution into the ice-water mixed bath to prevent the titanium tetrachloride from being hydrolyzed too quickly, and then uniformly stirring by using a glass rod;
c-2, putting the 4 substrates prepared in the step b into the uniformly mixed solution in the step c-1, then putting the whole into a constant-temperature water bath heating instrument at room temperature, standing, heating to 75 ℃ at constant temperature, and preserving heat for 40 minutes;
c-3, taking out the substrate which is completely reacted, washing the surface with deionized water to remove redundant solution, and then putting the substrate into a 70 ℃ oven for drying; putting the dried substrate into a box-type resistance furnace, setting a heating curve to rise to 150 ℃ in 15 minutes, preserving heat for 30 minutes, then rising to 300 ℃ in 15 minutes, preserving heat for 30 minutes, and finally rising to 500 ℃ in 15 minutes, preserving heat for 30-60 minutes;
d. perovskite film preparation without electron irradiation modification
d-1 weighing 0.3227g of lead iodide (PbI)2) 0.0834g of lead chloride (PbCl)2) Dissolving in a mixed solution of N, N-Dimethylformamide (DMF) and dimethyl sulfoxide (DMSO) in a volume ratio of 4:1 at a molar ratio of 7:3, placing on a heating plate at 70 ℃, and stirring for 12 hours until no obvious precipitate exists in the solution;
d-2, sticking the substrate prepared in the step c with an adhesive tape, reserving an active area of the device, and putting the device into a glove box; fixing a substrate on a spin coater, dropwise adding the precursor solution in the d-1 in a region to be coated, spin-coating at the rotating speed of 2500rpm for 25 seconds, drying the spin-coated substrate on a heating plate at the temperature of 75 ℃ for 20 minutes, and finally cooling to room temperature for later use;
d-4 weighing 12mg methylamine iodide (CH)3NH3I) Adding into 1ml of Isopropanol (IPA), and stirring and dissolving in a glove box at room temperature in a dark place; 150 μ L of CH was added dropwise to the substrate in d-3 using a pipette3NH3The color of the solution I is changed from yellow to reddish brown immediately, the solution I is kept stand until the precursor completely reacts, a spin coating instrument is started to spin-coat for 35 seconds at the rotating speed of 3000rpm to form a uniform and smooth film, and finally the film is placed on a heating plate at 100 ℃ for annealing to obtain a crystallized perovskite film;
e. spin-coating 2,2',7,7' -tetrakis [ N, N-bis (4-methoxyphenyl) amino ] -9,9' -spirobifluorene (Spiro-OMeTAD) hole transport layer
e-1, weighing 1.81mol of lithium salt (Li-TFSI) and dissolving the lithium salt in 1ml of acetonitrile solution to obtain a lithium salt solution; weighing 0.07mol of Spiro-OMeTAD, dissolving in 1ml of chlorobenzene solution, and stirring until the solution is clear; dripping 18 mu L of the lithium salt solution and 29 mu L of 4-tert-butylpyridine (TBP) by using a liquid transfer gun to improve the conductivity of the Spiro-OMeTAD, and magnetically stirring until the solution is uniformly mixed;
e-2, dripping 45 mu L of e-1 solution on the substrate in the step d, starting a spin coater, and spin-coating at the rotating speed of 5000rpm for 35 seconds; taking the spin-coated substrate out of the glove box, and drying the substrate in a drying dish for more than 12 hours;
f. preparation of Metal electrodes
And (4) evaporating a gold electrode on the Spiro-OMeTAD layer to finish the preparation of the whole perovskite photoelectric device.
Scanning electron microscope, IPCE and I-V curve tests were performed on the perovskite thin films obtained in examples three and four and comparative example two. The SEM and IPCE results are similar to those shown in FIGS. 1 and 2. FIG. 4 shows the molar ratio PbI2:PbCl2And (3) when the ratio is 7:3, carrying out electron irradiation modification and carrying out I-V diagram of the perovskite thin film photoelectric device prepared without electron irradiation modification. As can be seen from FIG. 4, the performance of the electron irradiation modified perovskite thin film photoelectric device is obviously improved. Compared with a device which is not modified by electron irradiation, when the irradiation dose is 20kGy, the photoelectric conversion efficiency of the device is improved from 15.57% to 18.63%, and is improved by 19.65%; short-circuit current is from 26.03mA/cm2Lifting to 28.10mA/cm2The fill factor increased from 0.54 to 0.61. When the irradiation dose is 60kGy, the photoelectric conversion efficiency of the device is improved from 15.57% to 17.20%, the photoelectric conversion efficiency is improved by 10.47%, and the filling factor is improved from 0.54 to 0.60.
In conclusion, the perovskite thin film prepared by the embodiment of the invention has large crystal grain size and smooth surface, can passivate an interface, effectively reduce the crystal boundary effect, and promote the capability of transferring photons into electrons, thereby improving the series resistance of a device and increasing the filling factor and the photoelectric conversion efficiency. The electron irradiation method is introduced, high-energy electron beams collide with substances in a target solution, although lead iodide and lead chloride are not easily affected by electron beam impact, the vibration frequency is increased by the collision and the solution temperature rise, and chemical bonds between oxygen and sulfur in an organic solvent are more easily formed into Lewis adducts with the lead iodide and the lead chloride under the action of the high-energy electron beams. Meanwhile, the impact process of the high-energy electron beam is a high-heat cycle, so the process of electron irradiation is also a process of heating the solution at high temperature, and the two processes simultaneously act, so that insoluble lead chloride and insoluble lead iodide have more ideal dissolution states, and finally the preparation quality and the device performance of the perovskite film are improved. The method has simple and convenient process and good repeatability, and provides a feasible scheme for producing high-performance perovskite thin film photoelectric devices on a large scale.
While the embodiments of the present invention have been described with reference to the accompanying drawings, the present invention is not limited to the above embodiments, and various changes, modifications, substitutions, combinations or simplifications made according to the spirit and principle of the present invention should be made by equivalent substitution modes, so long as the objects of the present invention are met, and the present invention is within the protection scope of the present invention as long as the technical principles and inventive concepts of the present invention for modifying perovskite thin film by electron irradiation and the applications thereof are not departed.

Claims (8)

1. A preparation method of a perovskite thin film photoelectric device based on electron irradiation modification is characterized by comprising the following steps:
etching and cleaning FTO conductive glass:
a-1, etching treatment is carried out on fluorine-doped tin oxide (FTO) conductive glass, an effective area and an electrode area of a device are protected by using an adhesive tape, then a hydrochloric acid (HCl) diluted by zinc powder and deionized water is used for etching the part of an etched groove exposed by the adhesive tape, the width of the etched groove is 1.5mm, the etching time is 5-10s, then redundant zinc powder and hydrochloric acid are wiped off, the adhesive tape is torn off, and finally the isolation of a negative electrode and the effective area from a positive electrode area is completed;
a-2, after the FTO conductive glass is etched in the step a-1, ultrasonically cleaning the etched FTO conductive glass by using deionized water for at least 3 times, wherein each time is not more than 20 minutes; then ultrasonically cleaning the FTO conductive glass by using ethanol for at least 3 times, wherein each time is not more than 20 minutes; ultrasonically cleaning the FTO conductive glass by using acetone for at least 3 times, wherein each time is not more than 20 minutes; after cleaning, blowing the conductive glass FTO by using argon to obtain a clean and dry FTO conductive glass substrate;
b. preparation of TiO2A dense layer:
b-1, measuring 4-9ml of absolute ethyl alcohol, 7-16 mu L of hydrochloric acid with the concentration not lower than 37 wt.%, magnetically stirring for at least 5 minutes to ensure that the solution is uniformly mixed to obtain a mixed solution;
b-2, weighing 0.42-0.68g of Tetrabutyl Titanate (TTIP) and adding into the mixed solution prepared in the step b-1, and magnetically stirring for 30 minutes until the solution is uniform to obtain a dense layer solution;
b-3, protecting the parts of the clean and dry FTO conductive glass substrate obtained in the step a-2 except the active area by using an adhesive tape, placing the FTO conductive glass substrate on a spin coater, and sucking the dense layer solution prepared in the step b-2 by using a dropper to drip the area of the FTO conductive glass substrate to be coated; starting a spin coater, spin-coating at a low speed of 800rpm for 8 seconds, and spin-coating at a high speed of 2500rpm for 15 seconds; putting the coated FTO conductive glass substrate into a box-type resistance furnace, setting a heating curve to rise to 150 ℃ within 15 minutes, preserving heat for 30 minutes, then rising to 300 ℃ within 15 minutes, preserving heat for 30 minutes, finally rising to 500 ℃ within 15 minutes, preserving heat for 30-60 minutes, cooling to room temperature after annealing is finished, and obtaining uniform TiO in an effective area of the FTO conductive glass substrate2Dense layer to obtain bonded TiO2A substrate of a dense layer;
c. titanium tetrachloride treatment of TiO2A dense layer:
c-1, measuring 100ml of deionized water, putting the deionized water into a refrigerator to form an ice-water mixed bath, sucking 440 mu L of titanium tetrachloride solution with 400-;
c-2, combining the TiO prepared in the step b-32Putting the substrate of the compact layer into the titanium tetrachloride solution prepared in the step c-1, uniformly mixing, then putting the substrate of the compact layer into a constant-temperature water bath heater at room temperature, heating to 75 ℃, keeping the temperature constant for 20-40 minutes, and reacting;
c-3, taking out the substrate completely reacted in the step c-2, washing the surface of the substrate by deionized water, removing redundant solution, then putting the substrate into a 70 ℃ drying oven for drying, putting the dried substrate into a box-type resistance furnace for annealing at 500 ℃;
d. preparing the perovskite thin film by electron irradiation modification:
d-1 weighing lead iodide (PbI) at different molar ratios2) Lead chloride (PbCl)2) Dissolving the composite lead halide in a mixed solution of N, N-Dimethylformamide (DMF) and dimethyl sulfoxide (DMSO), standing and placing on a heating plate until no obvious precipitate exists in the solution;
d-2, performing electron irradiation treatment on the solution to be treated prepared in the step d-1 by using a linear electron accelerator, wherein the irradiation environment adopts normal temperature and normal pressure conditions, the irradiation mode adopts a back-and-forth scanning mode, and the preferable irradiation dose is 20-60 kGy; placing the irradiated precursor solution on a heating plate, stirring and dissolving for at least 12 hours until the solution is clear, and obtaining a precursor solution;
d-3, sticking an adhesive tape on the substrate prepared in the step c-3, reserving an active area of the device, and placing the device into a glove box; fixing the substrate on a spin coater, dripping the precursor solution in the step d-2 on a region to be coated, and spin-coating at a rotating speed of not less than 2500rpm for at least 25 seconds; drying the spin-coated substrate on a heating plate at 75-80 ℃ for 15-30 minutes, and cooling to room temperature for later use;
d-4, weighing 9-12mg of methylamine iodide (CH)3NH3I) Adding into 1ml Isopropanol (IPA), stirring and dissolving in glove box at room temperature in dark place to obtain CH3NH3I, solution; continuously dripping CH on the substrate treated in the step d-3 by using a liquid-transferring gun3NH3The color of the film in the solution I is immediately changed from yellow to reddish brown, the solution I is kept stand until the precursor completely reacts, a spin coating instrument is started to spin-coat for 20 to 40 seconds at the rotating speed of not less than 3000rpm to form a uniform and smooth film, and finally the film I is placed on a heating plate to be annealed at the temperature of 100 ℃ and 110 ℃ to obtain the crystallized perovskite film;
e. spin-coating a 2,2',7,7' -tetrakis [ N, N-bis (4-methoxyphenyl) amino ] -9,9' -spirobifluorene (Spiro-OMeTAD) hole transport layer:
e-1, weighing 1.7-1.9mol of lithium salt (Li-TFSI) and dissolving the lithium salt in 1ml of acetonitrile solution to obtain a lithium salt solution; weighing 0.05-0.07mol of Spiro-OMeTAD, dissolving in 1ml of chlorobenzene solution, and stirring until the solution is clear; dripping 15-20 mu L of the lithium salt solution and 28-30 mu L of 4-tert-butylpyridine (TBP) by using a pipette gun to improve the conductivity of the 2,2',7,7' -tetra [ N, N-bis (4-methoxyphenyl) amino ] -9,9' -spirobifluorene, and magnetically stirring until the solution is uniformly mixed;
e-2, continuously dropwise adding 40-50 mu L of the solution prepared in the step e-1 on the substrate obtained in the step d-4, starting a spin coater, and spin-coating at a rotating speed of not less than 5000rpm for 20-40 seconds; taking the spin-coated substrate out of the glove box, and drying the substrate in a drying dish for more than 12 hours to obtain a 2,2',7,7' -tetra [ N, N-di (4-methoxyphenyl) amino ] -9,9' -spirobifluorene (Spiro-OMeTAD) hole transport layer;
f. preparing a metal electrode:
and e-2, continuously preparing a metal electrode on the hole transport layer prepared in the step e-2, thereby completing the preparation of the perovskite thin film photoelectric device.
2. The method for preparing the perovskite thin film photoelectric device based on electron irradiation modification according to claim 1, wherein the method comprises the following steps: in the step a-1, the concentration of hydrochloric acid used for etching is not lower than 2 mol/L.
3. The method for preparing the perovskite thin film photoelectric device based on electron irradiation modification according to claim 1, wherein the method comprises the following steps: in said step c-2, the reaction is carried out with not more than 4 substrates per 100ml of the solution.
4. The method for preparing the perovskite thin film photoelectric device based on electron irradiation modification according to claim 1, wherein the method comprises the following steps: in the step c-3, the temperature rise curve of annealing in the box-type resistance furnace is increased to 150 ℃ in 15 minutes, the temperature is kept for 30 minutes, then the temperature is increased to 300 ℃ in 15 minutes, the temperature is kept for 30 minutes, and finally the temperature is increased to 500 ℃ in 15 minutes, and the temperature is kept for 30-60 minutes.
5. The method for preparing the perovskite thin film photoelectric device based on electron irradiation modification according to claim 1, wherein the method comprises the following steps: in said step d-1, PbI2And PbI2At a molar ratio of 9:1 to 7:3, at a heating temperature of 30-40 deg.C, during heatingThe time is 30-60 minutes.
6. The method for preparing the perovskite thin film photoelectric device based on electron irradiation modification according to claim 1, wherein the method comprises the following steps: in the step d-1, the mass of the lead iodide is 0.322-0.498g in each 1ml of the mixed solution, the mass of the lead chloride is 0.0278-0.1g in each 1ml of the mixed solution, and the volume ratio of the mixed solution is N, N-dimethylformamide: dimethyl sulfoxide was 4: 1.
7. The method for preparing the perovskite thin film photoelectric device based on electron irradiation modification according to claim 1, wherein the method comprises the following steps: in the step d-4, the suction volume of the pipette is 90-150 μ L; the spin coating speed was 3000-3500 rpm.
8. The method for preparing the perovskite thin film photoelectric device based on electron irradiation modification according to claim 1, wherein the method comprises the following steps: in the step f, the metal electrode is a gold electrode, and the thickness of the electrode is 100-110 nm; metal electrodes were prepared by evaporation.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1510818A (en) * 1975-12-18 1978-05-17 Inst Poluprovod Akad Nauk Ukra Composite sensitive to electromagnetic and corpuscular radiation
CN104157788A (en) * 2014-08-19 2014-11-19 武汉大学 Perovskite film photovoltaic cell based on SnO2 and preparation method thereof
CN105655490A (en) * 2016-04-15 2016-06-08 厦门大学 Preparation method of perovskite solar cell
CN106784341A (en) * 2017-01-20 2017-05-31 电子科技大学中山学院 Microwave annealing treatment method for perovskite solar cell photoactive layer
CN110352507A (en) * 2018-01-30 2019-10-18 南方科技大学 The preparation method and applications of perovskite thin film

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10514188B2 (en) * 2014-10-20 2019-12-24 Nanyang Technological University Laser cooling of organic-inorganic lead halide perovskites

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1510818A (en) * 1975-12-18 1978-05-17 Inst Poluprovod Akad Nauk Ukra Composite sensitive to electromagnetic and corpuscular radiation
CN104157788A (en) * 2014-08-19 2014-11-19 武汉大学 Perovskite film photovoltaic cell based on SnO2 and preparation method thereof
CN105655490A (en) * 2016-04-15 2016-06-08 厦门大学 Preparation method of perovskite solar cell
CN106784341A (en) * 2017-01-20 2017-05-31 电子科技大学中山学院 Microwave annealing treatment method for perovskite solar cell photoactive layer
CN110352507A (en) * 2018-01-30 2019-10-18 南方科技大学 The preparation method and applications of perovskite thin film

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