CN114678472A - FAPBI3Perovskite thin film and method for efficient perovskite solar cell by using same - Google Patents

FAPBI3Perovskite thin film and method for efficient perovskite solar cell by using same Download PDF

Info

Publication number
CN114678472A
CN114678472A CN202210284744.5A CN202210284744A CN114678472A CN 114678472 A CN114678472 A CN 114678472A CN 202210284744 A CN202210284744 A CN 202210284744A CN 114678472 A CN114678472 A CN 114678472A
Authority
CN
China
Prior art keywords
perovskite
fapbi
solar cell
solution
thin film
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202210284744.5A
Other languages
Chinese (zh)
Inventor
陈永华
王殿曦
杜晓琴
夏英东
黄维
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nanjing Tech University
Original Assignee
Nanjing Tech University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nanjing Tech University filed Critical Nanjing Tech University
Priority to CN202210284744.5A priority Critical patent/CN114678472A/en
Publication of CN114678472A publication Critical patent/CN114678472A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
    • H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • H10K71/15—Deposition of organic active material using liquid deposition, e.g. spin coating characterised by the solvent used
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/16—Deposition of organic active material using physical vapour deposition [PVD], e.g. vacuum deposition or sputtering
    • H10K71/164—Deposition of organic active material using physical vapour deposition [PVD], e.g. vacuum deposition or sputtering using vacuum deposition
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Abstract

The invention relates to a method for preparing FAPBI3A perovskite thin film and a method for a high-efficiency perovskite solar cell thereof belong to the field of photoelectron materials and devices. The pure phase FAPBI in the invention3The preparation of the film adopts a one-step method to dissolve ammonium acetate as an additive and perovskite components in N, N-dimethylformamide as a precursor solution to be coated on an FTO conductive substrate with an electron transport layer, and the uniform and compact perovskite film is prepared by annealing, and the whole process is carried out in an anhydrous and oxygen-free glove box. Then carrying out subsequent treatment on the film and using a Spiro-OMeTAD as a hole transport layer, and then evaporating MoO by using a vacuum evaporation technology3And finishing the preparation of the device by the modification layer and the metal electrode. Pure-phase FAPBI prepared by the method3The perovskite solar cell has excellent photoelectric conversion efficiency, and the invention adopts ammonium acetate as an additive to enable a one-step methodAnd preparing the pure-phase formamidine perovskite solar cell.

Description

FAPBI3Perovskite thin film and method for efficient perovskite solar cell by using same
Technical Field
The invention relates to a method based on The pure-phase FAPbI is prepared by one-step method by using ammonium sulfate as a precursor solution additive and adjusting the mass of ammonium acetate3A perovskite film and a method for preparing a high-efficiency perovskite solar cell by using the same, in particular to a method for preparing a high-efficiency pure-phase formamidino perovskite film by using an additive through a one-step method, belonging to the field of photoelectron materials and technologies.
Background
With the continuous development of society, environmental problems caused by traditional fossil energy are more and more concerned by people, and the development of clean energy is urgent. Along with the continuous improvement of the requirement of human beings on clean energy, solar power generation is more and more taken attention by people. To date, most solar cells have been made of silicon because this material is very good at absorbing light. However, the manufacturing cost of the silicon panel is very expensive, and the crystalline silicon solar cell needs thousands of high temperature sintering during the preparation process, which not only wastes much financial resources and material resources, but also is not good for sustainable development strategy.
The novel solar cell comprises a perovskite solar cell, a dye-sensitized solar cell, an organic solar cell, a quantum dot solar cell and the like, and accordingly, the perovskite solar cell is concerned internationally due to the characteristics of low cost, simplicity in preparation, excellent photoelectric conversion performance and the like. Therefore, compared with the existing mature crystalline silicon solar cell technology, the method has the advantages and brings optimistic prospects for the commercial application of perovskite solar cells. While in perovskite materials FAPbI 3Perovskites (where FA is formamidine) have proven to be ideal candidates for the fabrication of highly efficient, stable perovskite solar cells. However, FAPBI3Can be transformed from the alpha phase with optical activity into delta phase without optical activity at the temperature of less than 150 ℃, thereby obtaining high-crystallization, stable and pure alpha phase FAPBI3Perovskite thin films are crucial for achieving a practical wide range of applications for perovskite solar cells. The previous studies have mainly been through doping MA+(methylamine), Cs+Or is Br-Plasma to obtain pure alpha-phase FAPBI3Perovskites, but doping these ionsThe photons blue-shift the uv-vis absorption peak of the perovskite material, resulting in a broadening of the band gap of this system. Although the open circuit voltage (V) of the device is improvedOC) But reduced short circuit current density (J)SC) And FAPBI3The band gap (about 1.48V) is the system which is the closest to the ideal band gap (1.3V-1.4V) in the known perovskite materials, and more importantly, the doping strategies influence the stability of the device to a certain extent, so that the pure alpha-phase FAPBI can be obtained by using the perovskite-type composite material3Particularly important are reagents or methods that do not change their band gap.
Disclosure of Invention
The invention aims at the FAPBI 3The perovskite is easy to be converted from an alpha phase with optical activity into a delta phase without optical activity at the temperature of less than 150 ℃, and uniform and compact FAPbI is difficult to prepare by a one-step method3Perovskite thin films and devices thereof.
In order to solve the problems, the technical scheme provided by the invention is as follows: ammonium acetate (NH) by regulating and controlling additive4Ac) in the precursor, and the method for preparing the high-efficiency pure-phase formamidine-based perovskite thin film and the perovskite solar cell thereof by a one-step method, comprises the following steps:
(1) lead iodide and formamidine iodide are mixed according to the mol ratio of 1.2:1, and an additive ammonium acetate is mixed with perovskite precursor material lead iodide and formamidine iodide according to the mass ratio of X, 15%<X<25 percent of FAPBI dissolved in N, N-dimethylformamide solvent to prepare the new FAPBI3Heating, stirring and dissolving the perovskite precursor solution at the temperature of below 50 ℃ for 0.5-1 hour;
(2) spin-coating and depositing an electron transport material on the cleaned and processed FTO transparent conductive glass sheet;
(3) coating the prepared perovskite precursor solution on an FTO conductive substrate with an electron transport layer in an anhydrous and oxygen-free glove box in a spinning way, and annealing at 170 ℃ for 10 minutes to obtain a flat and compact perovskite thin film;
(4) Spin-coating a mixed solution of iodoformamidine and chloroformamidine on the perovskite layer for post-treatment;
(5) spin coating a hole transport layer on the perovskite layer;
(6) vacuum evaporating an interface modification layer and a metal electrode on the hole transport layer;
the post-treatment layer formed by spin coating deposition in the step (4) is iodoformamidine FAI and chloroformamidine FACL; the method comprises the following specific steps:
(a) dissolving 10mg of iodoformamidine and 5mg of chloroformamidine in 1mL of an Isopropanol (IPA) solution;
(b) stirring the prepared mixed IPA solution of the FACL and the FAI for 3 hours at normal temperature and at the rotating speed of 300 rpm;
(c) and (3) taking 40uL of the solution obtained in the step (2) to spin on the perovskite, wherein the spin-coating condition is 4000-30 s.
Preferably, the mass ratio of the additive ammonium acetate to the perovskite precursor material lead iodide and formamidine iodide is 20%.
Preferably, the electron transport layer on the transparent conductive FTO glass in step (2) is SnO2The method comprises the following specific steps:
(1) the spin coating conditions were 4000 spin coating for 30 seconds,
(2) after the spin coating, the substrate was annealed at 150 ℃ for 30 minutes.
Preferably, the film preparation in the step (3) adopts a spin coating and annealing mode in a water-free and oxygen-free glove box, and comprises the following specific steps:
(1) the spin coating conditions were 4000 spin coating for 30 seconds.
(2) After the spin coating, annealing was performed on a hot stage at 170 ℃ for 10 minutes.
Preferably, the hole transport layer spin-coated and deposited in the step (5) is Spiro-OMeTAD; the method comprises the following specific steps:
(1) 73.2mg of Spiro-OMeTAD was dissolved in 1mL of chlorobenzene;
(2) 520mg of lithium bistrifluoromethylsulfonimide are dissolved in 1mL of acetonitrile solution.
(3) TBP solution was added to 28.8. mu.L of Spiro-OMeTAD solution;
(4) the lithium salt solution was added to 17.6. mu.L of the Spiro-OMeTAD solution;
(5) stirring the mixed solution for 2 hours at normal temperature;
(6) the spin coating conditions were 3000 rpm for 30 s.
Preferably, the interface modification layer in the step (6) is MoO3The metal electrode is Ag. The method comprises the following specific steps:
(1)MoO3evaporating on the hole transport layer to a thickness of 5 nm;
(2) the thickness of the metal Ag electrode is 100 nm.
In order to solve the above problems, another technical solution proposed by the present invention is: ammonium acetate (NH) by regulating additive4Ac) in the precursor solution to realize the one-step preparation of the high-efficiency pure-phase formamidine perovskite thin film and the perovskite solar cell thereof.
In order to solve the above problems, another technical solution proposed by the present invention is: the additive is ammonium acetate (NH) 4Ac) in the precursor solution to realize the one-step preparation of the high-efficiency pure-phase formamidine-based perovskite thin film and the perovskite solar cell thereof, and the application of the prepared perovskite solar cell in the photoelectric field.
The invention has the beneficial effects that:
(1) the previous studies have mainly been through doping MA+(methylamine ion), Cs+Or Br-Plasma to obtain pure alpha-phase FAPBI3Perovskite, but doping these ions can produce a blue shift of the ultraviolet-visible absorption peak of the perovskite material, resulting in a broadening of the band gap of this system, albeit increasing the open circuit voltage (V) of the deviceOC) But reduced short circuit current density (J)SC) And FAPBI3The band gap (about 1.48V) is the system which is the closest to the ideal band gap (1.3V-1.4V) in known perovskite materials, however, the pure-phase formamidine perovskite solar cell prepared by the invention uses ammonium acetate as an additive to obtain a uniform and compact perovskite thin film without influencing the band gap, so that the pure-phase FAPBI with excellent energy conversion efficiency can be prepared3Perovskite solar cell.
(2) The existing method for preparing the formamidine perovskite solar cell mainly comprises an anti-solvent method and a two-step method, wherein the anti-solvent method is used for dissolvingThe solvent method needs to use a solvent with low saturated vapor pressure, easily generates a large amount of harmful gas and has higher operation fineness, while the two-step method is more complicated, however, the invention adopts a one-step method to prepare the high-efficiency pure-phase formamidino FAPBI 3The perovskite solar cell is simple to operate and beneficial to realizing industrialization.
(3) The uniform and compact FAPBI can be prepared by regulating the dosage of the additive and subsequent treatment3A perovskite thin film. The invention determines that the dosage of the additive is 15-25% of the mass of the precursor material, the improvement of the crystallinity of the film is small when the mass ratio is less than 15%, and the additive is difficult to dissolve when the mass ratio is more than 25%.
(4) The perovskite thin film is subjected to post-treatment by using the isopropanol solution of the mixture of iodoformamidine and chlorformamidine, so that uncomplexed lead iodide can be effectively converted into formamidyl perovskite with optical activity, and the energy conversion efficiency of a device can be effectively improved.
Drawings
The invention is further described below with reference to the accompanying drawings.
FIG. 1 is a pure phase FAPbI prepared with ammonium acetate as additive in example 2 of the present invention3UV-vis absorption spectrum chart of the film;
FIG. 2 is a pure phase FAPbI prepared with ammonium acetate as additive in example 2 of the present invention3XRD pattern of film and no post-treatment in comparative example 3;
FIG. 3 is a pure phase FAPBI prepared according to example 2 of the present invention using ammonium acetate as an additive3SEM image of the film;
FIG. 4 is an SEM image of the additive-free perovskite thin film of comparative example 4;
FIG. 5 is a pure phase FAPBI prepared according to example 2 of the present invention using ammonium acetate as an additive3A device structure diagram of a perovskite solar cell;
FIG. 6 is a J-V curve of ammonium acetate perovskite solar cells added by mass ratio of 15%, 20%, 25% in example 1, example 2, and example 3, respectively, according to the present invention;
Detailed Description
Example 1
This example is ammonium acetate as FAPBI3Pure phase FAPBI with low defect state density and large grain size is prepared by adjusting and controlling the addition amount of ammonium acetate in perovskite precursor solution additive3Perovskite thin film and perovskite solar cell thereof, so as to be fully understood, the humidity condition of the laboratory is more than 70%. The method mainly comprises the following steps:
and step 1) sequentially carrying out ultrasonic treatment on the etched FTO conductive glass in ethanol, ultrapure water, a cleaning agent, ultrapure water and ethanol for 15 minutes respectively. And drying in an oven at 100 ℃ for 30 minutes after drying by nitrogen to obtain a clean FTO substrate.
Step 2) weighing 662.4mg of lead iodide, 206.6mg of iodoformamidine and 15% of ammonium acetate additive (130.4 mg) by mass ratio according to the proportion of 1.2:1, dissolving in 1mL of N, N-Dimethylformamide (DMF) solvent, and stirring at 48 ℃ for 1 hour until complete dissolution to prepare the perovskite precursor solution.
Step 3) dissolve 73.2mg of Spiro-OMeTAD in 1mL of chlorobenzene; 520mg of lithium bistrifluoromethylsulfinamide are dissolved in 1mL of acetonitrile solution; adding 28.8 mu L of TBP solution into the Spiro-OMeTAD solution, and adding 17.6 mu L of lithium salt solution into the Spiro-OMeTAD solution; stirring the mixed solution at normal temperature for 2 hours; the spin coating condition is 3000 r 30 s;
step 4) dissolving 10mg of iodoformamidine and 5mg of chloroformamidine in 1mL of isopropanol solution;
stirring the solution at 300 rotation speed for 3 hours at normal temperature; the spin coating condition is 3000 r 30 s;
and 5) carrying out ultraviolet ozone treatment on the FTO substrate cleaned in the step 1) for 15 minutes.
Step 6) getting electron transmission material SnO2Dripping 40 mu L of the solution on the FTO substrate processed in the step 4), spin-coating the solution by using a spin coater to form a film, wherein the spin speed is 4000 revolutions for 30 seconds, and then coating SnO on the film by spin coating2FTO (g) of (2) for 30 minutes at 150 ℃.
And 7) dripping 100 mu L of the perovskite precursor solution prepared in the step 2) on the FTO substrate in the step 6), spin-coating to form a film, and then annealing to form the perovskite thin film. The rotation speed of the perovskite precursor solution is 4000 revolutions for 30 seconds, and the perovskite precursor solution is annealed for 10 minutes at 170 ℃ in an anhydrous and oxygen-free glove box.
And 8) spin-coating the iodoformamidine and formamidine chloride post-treatment material obtained in the step 4) on the perovskite thin film obtained in the step 7), and spin-coating the iodoformamidine and formamidine chloride post-treatment material for 30 seconds by adopting 3000-turn spin coating.
And 9) spin-coating the hole transport material obtained in the step 3) on the perovskite thin film treated by the iodoformamidine and the formamidine chloride obtained in the step 8), and spin-coating the Spiro-OMeTAD for 30 seconds by adopting 3000-turn spin coating to form a hole transport layer.
Step 10) evaporating 5nm MoO on the hole transport layer in the step 9) by adopting a vacuum evaporation technology3And then evaporating 100nm metal electrode Ag to obtain the perovskite solar cell.
Step 11) under standard test conditions (am1.5g illumination), the optimal battery devices prepared in this example had energy conversion efficiencies of 14.68% respectively, open-circuit voltage of 1.01V, and short-circuit current of 23.35mA/cm2The fill factor is 61.97%;
example 2
This example is ammonium acetate as FAPBI3Pure phase FAPBI with low defect state density and large grain size is prepared by adjusting and controlling the addition amount of ammonium acetate in perovskite precursor solution additive3Perovskite thin film and perovskite solar cell thereof, so as to be fully understood, the humidity condition of the laboratory is more than 70%. The method mainly comprises the following steps:
and step 1) sequentially carrying out ultrasonic treatment on the etched FTO conductive glass in ethanol, ultrapure water, a cleaning agent, ultrapure water and ethanol for 15 minutes respectively. And drying the FTO substrate in an oven at 100 ℃ for 30 minutes after the nitrogen is dried to obtain a clean FTO substrate.
Step 2) weighing 662.4mg of lead iodide, 206.6mg of iodoformamidine and 20% ammonium acetate additive (173.8 mg) by mass ratio according to the proportion of 1.2:1, dissolving the weighed materials in 1mLN, N-Dimethylformamide (DMF) solvent, and stirring the solution at the temperature below 50 ℃ for 1 hour till complete dissolution to prepare perovskite precursor solution.
Step 3) dissolve 73.2mg of Spiro-OMeTAD in 1mL of chlorobenzene; 520mg of lithium bistrifluoromethylsulfinamide are dissolved in 1mL of acetonitrile solution; adding 28.8 mu L of TBP solution into the Spiro-OMeTAD solution, and adding 17.6 mu L of lithium salt solution into the Spiro-OMeTAD solution;
stirring the mixed solution at normal temperature for 2 hours; the spin coating condition is 3000 r 30 s;
step 4) dissolving 10mg of iodoformamidine and 5mg of chloroformamidine in 1mL of isopropanol solution;
stirring the solution at 300 rotation speed for 3 hours at normal temperature; the spin coating condition is 3000 r 30 s;
and 5) carrying out ultraviolet ozone treatment on the FTO substrate cleaned in the step 1) for 15 minutes.
Step 6) getting electron transmission material SnO2Dripping 40 mu L of the solution on the FTO substrate processed in the step 4), spin-coating the solution by using a spin coater to form a film, wherein the spin speed is 4000 revolutions for 30 seconds, and then coating SnO on the film by spin coating2FTO (g) of (2) for 30 minutes at 150 ℃.
And 7) dripping 100 mu L of the perovskite precursor solution prepared in the step 2) on the FTO substrate in the step 6), spin-coating to form a film, and then annealing to form the perovskite thin film. The rotation speed of the perovskite precursor solution is 4000 revolutions for 30 seconds, and the perovskite precursor solution is annealed at 170 ℃ for 10 minutes in an anhydrous and oxygen-free glove box.
And 8) spin-coating the iodoformamidine and chlorformamidine post-treatment material obtained in the step 4) on the perovskite thin film obtained in the step 7), and spin-coating the iodoformamidine and chlorformamidine post-treatment material for 30 seconds by adopting 3000-turn spin coating.
And 9) spin-coating the hole transport material obtained in the step 3) on the perovskite thin film treated by the iodoformamidine and the formamidine chloride in the step 8), and carrying out spin-coating on the Spiro-OMeTAD for 30 seconds by adopting 3000-turn spin coating to form a hole transport layer.
And step 10) evaporating 5nm of MoO3 on the hole transport layer in the step 9) by adopting a vacuum evaporation technology, and then evaporating 100nm of metal electrode Ag to obtain the perovskite solar cell.
Step 11) under standard test conditions (AM 1.5G illumination), the optimal battery device prepared in this example had an energy conversion efficiency of 20.49%, an open circuit voltage of 1.06V, and a short circuit current of 25.56mA/cm2The fill factor is 74.66%;
example 3
This example is ammonium acetate as FAPbI3Pure-phase FAPbI with low defect state density and large grain size is prepared by regulating and controlling the addition amount of ammonium acetate in perovskite precursor solution additive3Perovskite thin film and perovskite solar cell thereof, so as to be fully understood, the humidity condition of the laboratory is more than 70%. The method mainly comprises the following steps:
And step 1) sequentially carrying out ultrasonic treatment on the etched FTO conductive glass in ethanol, ultrapure water, cleaning agent, ultrapure water and ethanol for 15 minutes respectively. And drying the FTO substrate in an oven at 100 ℃ for 30 minutes after the nitrogen is dried to obtain a clean FTO substrate.
Step 2) weighing 662.4mg of lead iodide, 206.6mg of iodoformamidine and 25% of ammonium acetate additive (217.3 mg) according to the proportion of 1.2:1, dissolving in 1mL of N, N-Dimethylformamide (DMF) solvent, and stirring at the temperature below 50 ℃ for 1 hour until complete dissolution to prepare a perovskite precursor solution.
Step 3) dissolve 73.2mg of Spiro-OMeTAD in 1mL of chlorobenzene; 520mg of lithium bistrifluoromethylsulfonimide are dissolved in 1mL of acetonitrile solution; adding 28.8 mu L of TBP solution into the Spiro-OMeTAD solution, and adding 17.6 mu L of lithium salt solution into the Spiro-OMeTAD solution;
stirring the mixed solution for 2 hours at normal temperature; the spin coating condition is 3000 r 30 s;
step 4) dissolving 10mg of iodoformamidine and 5mg of formamidine chloride in 1mL of isopropanol solution;
stirring the solution at 300 rotation speed for 3 hours at normal temperature; the spin coating condition is 3000 r 30 s;
and 5) carrying out ultraviolet ozone treatment on the FTO substrate cleaned in the step 1) for 15 minutes.
Step 6) taking electron transport material SnO 240 mu L of the solution is dripped on the FTO substrate processed in the step 4), spin coating is carried out on the FTO substrate by using a spin coater to form a film, the spin coating speed is 4000 revolutions for 30 seconds, and then SnO is coated on the spin coating2FTO (0) for 30 minutes at 150 ℃.
And 7) dripping 100 mu L of the perovskite precursor solution prepared in the step 2) on the FTO substrate in the step 6), spin-coating to form a film, and then annealing to form the perovskite thin film. The rotation speed of the spin coating perovskite precursor solution is 4000 revolutions for 30 seconds, and annealing is carried out for 10 minutes at 170 ℃ in a water-free and oxygen-free glove box.
And 8) spin-coating the iodoformamidine and chlorformamidine post-treatment material obtained in the step 4) on the perovskite film obtained in the step 7), and spin-coating the iodoformamidine and chlorformamidine post-treatment material for 30 seconds by adopting 3000-rotation spin coating.
And 9) spin-coating the hole transport material obtained in the step 3) on the perovskite thin film treated by iodoformamidine and chlorformamidine in the step 8), and carrying out spin-coating on the hole transport material by adopting 3000-turn spin-coating for 30 seconds to form a hole transport layer.
Step 10) evaporating 5nm MoO on the hole transport layer in step 9) by adopting a vacuum evaporation technology3And then evaporating 100nm metal electrode Ag to obtain the perovskite solar cell.
Step 11) under standard test conditions (AM 1.5G illumination), the energy conversion efficiencies of the optimal battery devices prepared in this example were 17.04%, the open-circuit voltage was 1.04V, and the short-circuit current was 24.22mA/cm, respectively 2Fill factor 67.35%;
comparative example 1
Using other additives, e.g. ammonium chloride (NH)4Cl), methylamine acetate (MAAc) hydroxylamine acetate (HAAc), do not yield uniform and dense films and produce perovskite solar cells with low energy conversion efficiency.
Comparative example 2
Although the formamidine perovskite thin film prepared by using ammonium acetate with the mass ratio of 10% is improved to a certain extent compared with the thin film prepared by using no additive, the overall quality of the thin film is still poor, and the energy conversion efficiency of the prepared perovskite solar cell is only 7.07%. And when the mass ratio is more than 25%, the additive is difficult to dissolve in the precursor solution, so that the device preparation cannot be carried out.
Comparative example 3
If the film prepared by post-treatment without using the mixed isopropanol solution of iodoformamidine and chloroformamidine contains more uncoordinated lead iodide (as shown in figure 2), the performance of the device can be affected by the excessive lead iodide without optical activity, and the energy conversion efficiency of the device prepared by using the optimal additive mass ratio is only 15.91% if the device is not post-treated.
Comparative example 4
The pure-phase formamidine-based perovskite solar cell is prepared by a one-step method without adding an ammonium acetate additive, wherein the molar ratio of lead iodide to iodoformamidine is 1.2: 1, the prepared film has smaller grain size and a plurality of holes, the energy conversion efficiency of the device prepared by the method is only 3.89%, compared with the preparation method using ammonium acetate as an additive, the preparation method of the invention can prepare the film with larger grain size and no holes uniformly due to the auxiliary crystallization effect of the ammonium acetate, and the prepared perovskite solar cell has excellent energy conversion efficiency (as shown in figures 3 and 5)
In general, the invention is based on an ammonium acetate additive as pure-phase FAPBI3The perovskite precursor solution solvent is used for preparing the efficient FAPbI by controlling the mass ratio of the additive in the precursor solution to exert the auxiliary crystallization effect3The grain size of perovskite thin film crystal grains prepared by the perovskite thin film is micron-level, the appearance is compact and smooth, the prepared perovskite device has excellent device efficiency, and the pure-phase FAPBI prepared by the method3The perovskite solar cell method is simple to operate, high in photoelectric conversion efficiency and has rare industrialization advantages.
The invention is not limited to the specific technical solutions described in the above embodiments, and all technical solutions formed by equivalent substitutions are within the scope of the invention as claimed.

Claims (8)

1. Preparation of FAPBI3A perovskite thin film and a method for manufacturing the perovskite solar cell with high efficiency are characterized by comprising the following steps:
(1) adding 15 percent of lead iodide and formamidine iodide according to the molar ratio of 1.2:1 and the mass ratio X of additive ammonium acetate to perovskite precursor material lead iodide and formamidine iodide<X<25 percent of the compound is dissolved in N, N-dimethylformamide solvent to prepare novel FAPBI 3Perovskite precursor solution at a temperature below 50 deg.CHeating, stirring and dissolving for 0.5-1 hour;
(2) spin-coating and depositing an electron transport material on the cleaned and processed FTO transparent conductive glass sheet;
(3) coating the prepared perovskite precursor solution on an FTO conductive substrate with an electron transport layer in an anhydrous and oxygen-free glove box in a spinning way, and annealing at 170 ℃ for 10 minutes to obtain a flat and compact perovskite thin film;
(4) spin-coating a mixed solution of iodoformamidine and chloroformamidine on the perovskite layer for post-treatment;
(5) spin coating a hole transport layer on the perovskite layer;
(6) vacuum evaporating an interface modification layer and a metal electrode on the hole transport layer;
the post-treatment layer formed by spin coating deposition in the step (4) is iodoformamidine FAI and chloroformamidine FACL; the method comprises the following specific steps:
(a) dissolving 10mg of iodoformamidine and 5mg of chloroformamidine in 1mL of an Isopropanol (IPA) solution;
(b) stirring the prepared mixed IPA solution of the FACL and the FAI for 3 hours at normal temperature and at the rotating speed of 300 rpm;
(c) and (3) taking 40uL of the solution obtained in the step (b) to spin on the perovskite, wherein the spin-coating condition is 4000-30 s.
2. The manufacture FAPBI of claim 13A perovskite thin film and a method for manufacturing the perovskite solar cell with high efficiency are characterized in that: the mass ratio of the additive ammonium acetate to the perovskite precursor material lead iodide and formamidine iodide is 20%.
3. The preparation of FAPBI as in claim 13A perovskite thin film and a method for manufacturing the perovskite solar cell with high efficiency are characterized in that: the electronic transmission layer on the transparent conductive FTO glass in the step (2) is SnO2The method comprises the following steps:
(1) the spin coating conditions were 4000 spin coating for 30 seconds,
(2) after the spin coating, annealing was carried out at 150 ℃ for 30 minutes.
4. The preparation of FAPBI as in claim 13A perovskite thin film and a method for manufacturing the perovskite solar cell with high efficiency are characterized in that: the preparation of the film in the step (3) adopts a spin coating and annealing mode in an anhydrous and oxygen-free glove box, and comprises the following specific steps:
(1) the spin coating conditions were 4000 spin coating for 30 seconds.
(2) After the spin coating, annealing was performed on a hot stage at 170 ℃ for 10 minutes.
5. The manufacture FAPBI of claim 13A perovskite thin film and a method for manufacturing the perovskite solar cell with high efficiency are characterized in that: the hole transport layer deposited by spin coating in the step (5) is Spiro-OMeTAD; the method comprises the following specific steps:
(1) 73.2mg of Spiro-OMeTAD was dissolved in 1mL of chlorobenzene;
(2) 520mg of lithium bistrifluoromethylsulfonimide are dissolved in 1mL of acetonitrile solution.
(3) TBP solution was added to 28.8. mu.L of Spiro-OMeTAD solution;
(4) Adding 17.6 μ L of lithium salt solution to the Spiro-OMeTAD solution;
(5) stirring the mixed solution at normal temperature for 2 hours;
(6) the spin coating conditions were 3000 revolutions for 30 s.
6. The manufacture FAPBI of claim 13A perovskite thin film and a method for manufacturing the perovskite solar cell with high efficiency are characterized in that: the interface modification layer in the step (6) is MoO3The metal electrode is Ag. The method comprises the following specific steps:
(1)MoO3evaporating on the hole transport layer to a thickness of 5 nm;
(2) the thickness of the metal Ag electrode is 100 nm.
7. FAPBI prepared according to any one of claims 1 to 63Perovskite thin film and high-efficient perovskite solar cell thereof.
8. The preparation of FAPBI as in claim 73The perovskite thin film and the application of the high-efficiency perovskite solar cell thereof in the photoelectric field.
CN202210284744.5A 2022-03-22 2022-03-22 FAPBI3Perovskite thin film and method for efficient perovskite solar cell by using same Pending CN114678472A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210284744.5A CN114678472A (en) 2022-03-22 2022-03-22 FAPBI3Perovskite thin film and method for efficient perovskite solar cell by using same

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210284744.5A CN114678472A (en) 2022-03-22 2022-03-22 FAPBI3Perovskite thin film and method for efficient perovskite solar cell by using same

Publications (1)

Publication Number Publication Date
CN114678472A true CN114678472A (en) 2022-06-28

Family

ID=82074053

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210284744.5A Pending CN114678472A (en) 2022-03-22 2022-03-22 FAPBI3Perovskite thin film and method for efficient perovskite solar cell by using same

Country Status (1)

Country Link
CN (1) CN114678472A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115360309A (en) * 2022-10-21 2022-11-18 武汉大学 FAPBI 3 Preparation method of perovskite solar cell
CN116507185A (en) * 2023-06-30 2023-07-28 长江三峡集团实业发展(北京)有限公司 Formamidine perovskite solar cell and preparation method thereof

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115360309A (en) * 2022-10-21 2022-11-18 武汉大学 FAPBI 3 Preparation method of perovskite solar cell
CN115360309B (en) * 2022-10-21 2023-02-03 武汉大学 FAPBI 3 Preparation method of perovskite solar cell
CN116507185A (en) * 2023-06-30 2023-07-28 长江三峡集团实业发展(北京)有限公司 Formamidine perovskite solar cell and preparation method thereof
CN116507185B (en) * 2023-06-30 2023-10-20 长江三峡集团实业发展(北京)有限公司 Formamidine perovskite solar cell and preparation method thereof

Similar Documents

Publication Publication Date Title
CN108878554B (en) Lanthanide rare earth ion doping-based CsPbBr3All-inorganic perovskite solar cell and preparation method and application thereof
CN110246967B (en) Method for preparing flexible perovskite solar cell at low temperature
CN112802965B (en) Interface modification-based perovskite solar cell preparation method
CN108807694B (en) Flat perovskite solar cell with ultralow temperature stability and preparation method thereof
CN111092160B (en) Method for passivating lower interface of perovskite solar cell with inverse structure
CN109728169B (en) Perovskite solar cell doped with functional additive and preparation method thereof
CN108389969B (en) Green solvent system and mixed solution for preparing perovskite layer of perovskite solar cell
CN108807680B (en) Perovskite solar cell
CN114678472A (en) FAPBI3Perovskite thin film and method for efficient perovskite solar cell by using same
CN110335945B (en) Double-electron-transport-layer inorganic perovskite solar cell and manufacturing method and application thereof
CN112542549B (en) Wide-bandgap perovskite solar cell and preparation and application thereof
CN113903861B (en) Perovskite solar cell rapidly annealed in air and preparation method thereof
CN112490363B (en) Preparation method of perovskite solar cell based on magnetron sputtering zinc oxide/tin dioxide double electron transmission layer
CN105810831A (en) Lead-tin hybrid perovskite thin film, and preparation method and application therefor
CN115020596A (en) Double-layer electron transport layer, perovskite solar cell with double-layer electron transport layer, and preparation method and application of perovskite solar cell
CN113130762B (en) Light absorption layer material of solar cell, ternary cation perovskite solar cell and preparation method thereof
WO2023115870A1 (en) Pn heterojunction antimony selenide/perovskite solar cell, and preparation method therefor
CN113394343B (en) Back-incident p-i-n structure perovskite solar cell and preparation method thereof
CN114420853A (en) Method for modifying self-assembled hole transport layer by alkali metal acetate
CN114583061A (en) Lead-free tin-based perovskite thin film with three-dimensional structure and preparation method of solar cell thereof
CN110190192B (en) Preparation method of trans-organic-inorganic hybrid perovskite solar cell
CN114156414A (en) High-efficiency stable CsPbI3Preparation method of inorganic perovskite battery
CN114242824A (en) All-inorganic perovskite solar cell and preparation method thereof
CN111769197A (en) Perovskite solar cell and preparation method thereof
CN111211231A (en) Solar cell based on semitransparent quantum dots and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination