CN117693271A - Perovskite film and preparation method and application thereof - Google Patents
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Abstract
The invention provides a perovskite film, a preparation method and application thereof. The preparation method comprises the following steps: coating a passivation solution containing a two-dimensional material on the non-mineralized perovskite film, and annealing to obtain the perovskite film. According to the invention, the passivation solution containing the two-dimensional material is coated on the surface of the non-mineralized perovskite film, the two-dimensional material is introduced to inhibit the generation of redundant lead iodide phases in the crystallization process, and meanwhile, the generation of a regular fibrous intermediate is promoted, the semiconductor performance of the film is improved by the regular fibrous intermediate, the photoelectric conversion efficiency is improved, the stability of a perovskite film layer is enhanced, and finally, the perovskite film with high quality is obtained.
Description
Technical Field
The invention belongs to the field of photovoltaic cells, and relates to a perovskite thin film, a preparation method and application thereof.
Background
In recent years, organic-inorganic metal halogenated three-dimensional perovskite have received attention because of its excellent photoelectric conversion efficiency and inexpensive material cost. However, its disordered crystallization process results in poor quality perovskite thin films and corresponding device stability is inadequate, becoming a tripping stone in its commercialization process. Ruddlesden-Popper quasi-two-dimensional perovskite has been found to have unique photoelectric properties and excellent stability, but its photoelectric conversion efficiency is low.
CN111640872a discloses a perovskite solar cell capable of regulating and controlling the growth of a lead iodide passivation layer and a preparation method thereof. The preparation method comprises the following steps: spin-coating an electron transport layer on the surface of a transparent conductive substrate to prepare lead iodide colloid, adding a ligand into the lead iodide colloid, stirring, spin-coating the prepared lead iodide colloid on the electron transport layer, annealing and crystallizing to form a lead iodide film on the electron transport layer, spin-coating halide ions on the lead iodide film to generate a perovskite light absorption layer, preparing a hole transport layer on the perovskite light absorption layer, and preparing an electrode on the composite hole transport layer. However, random crystallization of perovskite thin films makes it difficult to achieve high quality perovskite crystals with low defect state densities.
There are many effective passivation methods such as: lewis acid-base passivation defects, lewis acid-base passivation defect strategies, and the like. The passivation of defects by anions and cations has proven to be an effective strategy for improving the optoelectronic properties and stability of halide perovskite, and due to the ionic nature of metal halide perovskite, defects/trap state wide bandgap surface modifications in and on perovskite thin films can be repaired by electrostatic interactions, eliminating deep level defects at surfaces and grain boundaries. However, the passivation treatment is carried out on the perovskite film which is annealed to be ore, and the intermediate phase generated in the ore forming process of the perovskite film cannot be treated in the process, so that the passivation method of the perovskite film needs to be further improved to improve the stability of the perovskite film.
Therefore, how to improve the process method of the perovskite film and prepare the perovskite film with high stability is an important research method in the field.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide a perovskite film with high photoelectric conversion efficiency and high stability, and a preparation method and application thereof.
To achieve the purpose, the invention adopts the following technical scheme:
the invention aims at providing a preparation method of a perovskite thin film, which comprises the following steps: coating a passivation solution containing a two-dimensional material on the non-mineralized perovskite film, and annealing to obtain the perovskite film.
According to the non-annealed pre-crystallized perovskite film, the non-crystallized perovskite film is referred to as a non-annealed pre-crystallized perovskite film, more specifically, the non-crystallized or non-crystallized perovskite film is referred to as a non-crystallized perovskite film, at the moment, solvents in the non-crystallized perovskite film just start to volatilize or volatilize slightly, passivation solution containing two-dimensional materials is coated on the surface of the non-crystallized perovskite film, the two-dimensional materials are introduced to inhibit the generation of redundant lead iodide phases in the crystallization process, interface defects can be passivated, non-radiative recombination is effectively reduced, meanwhile, the generation of regular fibrous intermediates is promoted, the semiconductor performance of the film is improved, the photoelectric conversion efficiency is improved, the stability of a perovskite film layer is enhanced, and finally the high-quality perovskite film is obtained.
As a preferable technical scheme of the invention, a passivation solution containing a two-dimensional material is coated on a non-mineralized perovskite film, the two-dimensional material and the non-mineralized perovskite film generate an intermediate phase, and the generated intermediate phase precedes Pb in the perovskite film 2+ And bind as nucleation sites for perovskite crystals.
And annealing, wherein the non-mineralized perovskite film generates a perovskite crystal phase, and the intermediate phase generates a two-dimensional passivation layer at a grain boundary and/or a film surface to obtain the perovskite film with two-dimensional perovskite passivation.
Perovskite crystal is ABX 3 Wherein the A-site ion is typically FA + 、MA + 、Cs + And the ionic radius of the two-dimensional material is larger than that of the A-site ions in the perovskite crystal, and in the crystallization process, the perovskite crystal is firstly nucleated and separated out, and lead iodide of the A-site ions is deletedAnd combining the perovskite crystal with the two-dimensional material to form a middle, annealing to obtain a perovskite crystal and a two-dimensional passivation layer, and passivating the perovskite film through combining the two-dimensional material with excessive lead iodide to form the two-dimensional passivation layer.
The preparation method of the non-mineralized perovskite film comprises the following steps: and coating the perovskite precursor liquid on the substrate to obtain the non-mineralized perovskite film.
The coating method of the perovskite precursor liquid in the invention is not limited to the methods of knife coating, roll coating, spray coating, slit coating, and the like.
In the doctor blade method, redundant solvent is blown off by nitrogen, and the redundant solvent on the film surface is mainly removed.
Preferably, the perovskite precursor liquid comprises Cs 1-x FA x PbI 3 0.ltoreq.x.ltoreq.1, where the value of x may be 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9 or 1, etc., but is not limited to the values recited, other non-recited values within the range of values are equally applicable.
Preferably, the doctor blade is applied at a speed of 10 to 15mm/s, wherein the speed may be 10mm/s, 11mm/s, 12mm/s, 13mm/s, 14mm/s, 15mm/s, etc., and the coating speed is selected based on the formation of a uniform film layer, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the thickness of the non-mineralized perovskite thin film is 500 to 600nm, wherein the thickness may be 500nm, 510nm, 520nm, 530nm, 540nm, 550nm, 560nm, 570nm, 580nm, 590nm or 600nm, etc., but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
The thickness of the non-mineralized perovskite thin film is not too thick, if the thickness of the perovskite thin film obtained after annealing is too thick, separated electrons and holes cannot effectively pass through, the electron-hole pair recombination loss photons are more, and the charge collection of positive and negative electrodes is less; if the thickness of the perovskite thin film obtained after annealing is too thin, the perovskite coverage problem can occur, and meanwhile, the perovskite thin film layer cannot effectively absorb photons, so that the device performance is poor.
As a preferable technical scheme of the invention, the two-dimensional material comprises a large-volume aromatic amine compound and/or a long-chain alkylamine compound.
Preferably, the aromatic amine compound is a bulky aromatic amine compound with a tolerance factor of more than 1, and the tolerance factor may be 2, 3, 4, 5, 6, 7, 8 or 10, etc., but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
The bulky aromatic amine compound of the invention refers to the ionic radius of the bulky aromatic amine compound is larger than FA + The radius of the ions ensures that ions of the two-dimensional material do not enter the crystal lattice of the perovskite.
Preferably, the long-chain alkylamine compound is a linear or branched alkylamine compound having 2 to 20 carbon atoms, wherein the carbon atoms may be 2, 4, 6, 8, 10, 12, 14, 16, 18 or 20, etc., but not limited to the recited values, and other non-recited values within the range of the recited values are equally applicable.
Preferably, the two-dimensional material solute of the passivation solution containing the two-dimensional material comprises any one or a combination of at least two of 4-trifluoromethylphenyl ethylamine iodide, 4-trifluoromethylphenyl ethylamine chloride, 4-trifluoromethylphenyl ethylamine bromide, octyl iodinated amine, octyl chlorinated amine, octyl brominated amine, butyl chlorinated amine, butyl brominated amine, butyl iodinated amine, oleyl amine iodide, oleyl amine bromide or oleyl amine chloride, wherein typical but non-limiting examples of the combination are: a combination of 4-trifluoromethylphenylethylamine iodide and 4-trifluoromethylphenylethylamine bromide, a combination of 4-trifluoromethylphenylethylamine bromide and octyliodinated amine, a combination of octylamine chloride and octylamine bromide, a combination of butylamine chloride and butylamine bromide, or a combination of butylamine bromide and butyliodinated amine, etc.
Selection of 4-trifluoromethyl phenethylamine iodide (CF) in two-dimensional Material 3 -PEAI) and perovskite precursor liquid selection Cs 0.1 FA 0.9 PbI 3 The following are examples: spraying a layer of CF on the non-ore perovskite film 3 -PEAI solution for use with Pb 2+ Ion-generated interactionsForming an intermediate phase CF on the upper surface of the perovskite 3 -PEAI-PbI 2 Continuing as Cs x FA 1-x PbI 3 (0.ltoreq.x.ltoreq.1) heterogeneous nucleation sites. During annealing, FAI and CF 3 -PEAI-PbI 2 Mesophase reaction, CF during perovskite crystal growth 3 PEAI on the surface of perovskite with excess PbI 2 Reaction to form two-dimensional perovskite (CF) 3 -PEA) 2 PbI 4 Interface defects can be passivated, non-radiative recombination is effectively reduced, and the hydrophobic two-dimensional material can block moisture invasion to further improve the stability of perovskite.
Selection of octyl iodinated amine (OAI) and perovskite precursor fluids for Cs with two-dimensional materials 0.1 FA 0.9 PbI 3 The following are examples: spraying an OAI solution on the non-ore perovskite film to react with Pb 2+ Ion interactions to form mesophases OAI-PbI on the upper surface of perovskite 2 Continuing as Cs x FA 1-x PbI 3 (0.ltoreq.x.ltoreq.1) heterogeneous nucleation sites. During the growth of perovskite crystals, OAI is carried out on the surface of the perovskite with an excess of PbI 2 Reaction to form two-dimensional perovskite (OA) 2 PbI 4 Interface defects can be passivated, non-radiative recombination is effectively reduced, and the hydrophobic two-dimensional material can block moisture invasion to further improve the stability of perovskite.
Selection of butyl iodinated amine (BAI) and perovskite precursor fluids for Cs with two-dimensional materials 0.1 FA 0.9 PbI 3 The following are examples: spraying a BAI solution on the non-ore perovskite film for mixing with Pb 2+ Ion interactions to form mesophase BAI-PbI on the upper surface of perovskite 2 Continuing as Cs x FA 1-x PbI 3 (0.ltoreq.x.ltoreq.1) heterogeneous nucleation sites. During the growth of perovskite crystals, BAI is grown on the surface of perovskite with an excess of PbI 2 Reaction to form two-dimensional perovskite (BA) 2 PbI 4 Interface defects can be passivated, non-radiative recombination is effectively reduced, and the hydrophobic two-dimensional material can block moisture invasion to further improve the stability of perovskite.
As a preferred embodiment of the present invention, the solvent of the passivation solution includes isopropyl alcohol and dimethylformamide.
The method selects the combination of isopropyl alcohol and dimethylformamide as the solvent, so that shallow energy level defects on the surface of perovskite can be passivated more effectively, and a small amount of dimethylformamide can etch the surface of the perovskite film to be combined with a two-dimensional material more effectively to generate 2D perovskite, so that the defects are passivated effectively.
Preferably, the volume ratio of isopropyl alcohol and dimethylformamide is (150-250): 1, wherein the volume ratio may be 150:1, 160:1, 170:1, 180:1, 190:1, 200:1, 210:1, 220:1, 230:1, 240:1 or 250:1, etc., but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
As a preferred embodiment of the present invention, the concentration of the passivation solution is 0.5 to 2mg/ml, wherein the concentration may be 0.5mg/ml, 0.6mg/ml, 0.7mg/ml, 0.8mg/ml, 0.9mg/ml, 1.0mg/ml, 1.1mg/ml, 1.2mg/ml, 1.3mg/ml, 1.4mg/ml, 1.5mg/ml, 1.6mg/ml, 1.7mg/ml, 1.8mg/ml, 1.9mg/ml, 2mg/ml, etc., but is not limited to the recited values, and other non-recited values within the range of the values are equally applicable, preferably 0.8 to 1.2mg/ml.
The too high concentration of the passivation solution containing the two-dimensional material in the invention can affect the charge transfer because the interlayer spacing of the two-dimensional material is too large and the charge transfer is poor. Too low a concentration does not completely passivate the shallow level defects of the perovskite surface.
As a preferred embodiment of the present invention, the coating method includes spraying.
Preferably, the passivation solution has a coating thickness of 5 to 15nm, wherein the coating thickness may be 5mm, 6mm, 7mm, 8mm, 9mm, 10nm, 11nm, 12nm, 13nm, 14nm, 15nm, etc., but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
The coating thickness of the passivation solution containing the two-dimensional material is too thick, so that charge transmission can be influenced, and the charge transmission is poor; too thin a coating thickness of the passivation solution of the two-dimensional material cannot completely passivate the defects of the perovskite surface.
As a preferable technical scheme of the invention, the annealing comprises a first annealing and a second annealing which are sequentially carried out, wherein the first annealing temperature is lower than the second annealing temperature, and the first annealing temperature is lower than the perovskite phase forming temperature. The first anneal is used to remove solvent from the membrane face and the second anneal is used to produce the perovskite crystal phase.
Preferably, the temperature of the first annealing is 50 to 90 ℃, wherein the temperature may be 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, or 90 ℃, etc., but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
The invention adopts the first annealing at 50-90 ℃ to slow down the solvent volatilization speed, which is beneficial to regulating Cs x FA 1- x PbI 3 And (0.ltoreq.x.ltoreq.1) and can effectively planarize the film surface, increase the grain size and eliminate voids on the surface. Too fast solvent evaporation can lead to rapid crystal formation, often resulting in undersize of the formed grains and increased defects. By adopting low-temperature pre-annealing, the perovskite has larger crystal grains and more complete and pure structure.
The phase formation temperature of the perovskite is about 100-150 ℃ according to different components, the purpose of slowly crystallizing the perovskite firstly cannot be achieved due to the fact that the first annealing temperature is too high, and the perovskite crystallization is affected due to insufficient solvent volatilization caused by too low temperature.
Preferably, the time of the first annealing is 1 to 3 minutes, wherein the time may be 1 minute, 2 minutes, 3 minutes, or the like, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable. Too long a first annealing time can affect the subsequently formed three-dimensional perovskite crystal phase, and too short a time can not completely remove the solvent.
Preferably, the temperature of the second annealing is 100 to 120 ℃, wherein the temperature may be 100 ℃, 102 ℃, 104 ℃, 106 ℃, 108 ℃, 110 ℃, 112 ℃, 114 ℃, 116 ℃, 118 ℃, 120 ℃, or the like, but is not limited to the recited values, and other non-recited values within the range of the values are equally applicable.
Preferably, the second annealing time is 35-45 min, wherein the time may be 35min, 36min, 37min, 38min, 39min, 40min, 41min, 42min, 43min, 44min or 45min, etc., but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
The appropriate annealing temperature can repair defects in the perovskite film, optimize the crystal structure and further improve the photoelectric performance. However, an excessively high annealing temperature may cause the crystal structure of the perovskite thin film to be broken, and even induce phase transition of the crystallized phase. Annealing time is also an important factor affecting the annealing effect, too short annealing time may not adequately repair defects in the perovskite thin film, and too long annealing time may result in excessive growth of the material.
As a preferable technical scheme of the invention, the preparation method comprises the following steps:
coating a passivation solution containing a two-dimensional material with the concentration of 0.5-2 mg/ml on the non-mineralized perovskite film, and sequentially carrying out first annealing at the temperature of 50-90 ℃ and second annealing at the temperature of 100-120 ℃ to obtain the perovskite film.
The second object of the present invention is to provide a perovskite thin film, which is prepared by the preparation method of the perovskite thin film according to one of the objects, and the perovskite thin film comprises a perovskite thin film layer and a two-dimensional passivation layer arranged on the perovskite thin film layer.
The third object of the invention is to provide a perovskite solar cell, which comprises a substrate, a first carrier layer, a perovskite thin film as described in the second object, a second carrier layer and a metal electrode which are arranged in sequence from bottom to top.
It is a fourth object of the present invention to provide the use of a perovskite solar cell as defined in the third object, said perovskite solar cell being used in the field of photovoltaic cells.
The numerical ranges recited herein include not only the above-listed point values, but also any point values between the above-listed numerical ranges that are not listed, and are limited in space and for the sake of brevity, the present invention is not intended to be exhaustive of the specific point values that the stated ranges include.
Compared with the prior art, the invention has the beneficial effects that:
(1) According to the invention, the passivation solution containing the two-dimensional material is coated on the surface of the non-mineralized perovskite film, the two-dimensional material is introduced to inhibit the generation of redundant lead iodide phases in the crystallization process, and meanwhile, the generation of a regular fibrous intermediate is promoted, the semiconductor performance of the film is improved by the regular fibrous intermediate, the photoelectric conversion efficiency is improved, the stability of a perovskite film layer is enhanced, and finally, the perovskite film with high quality is obtained;
(2) The perovskite thin film prepared by the method is assembled into the perovskite solar cell, wherein the Isc of the perovskite solar cell can reach more than 24.87mA, the Voc can reach more than 1.10V, the PCE can reach more than 21.30 percent and the FF can reach more than 77.65 percent.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments.
Example 1
The embodiment provides a perovskite solar cell, perovskite solar cell from the bottom up has set gradually: a substrate, a hole transport layer, a perovskite thin film, an electron transport layer and a metal electrode;
the perovskite thin film includes a perovskite thin film layer disposed proximate to a hole transport layer, and a two-dimensional passivation layer disposed between the perovskite thin film layer and an electron transport layer.
The embodiment also provides a preparation method of the perovskite solar cell, which comprises the following steps:
(1) Ultrasonically cleaning the FTO conductive glass with 30cm multiplied by 30cm respectively with glass cleaning agent and deionized water in sequence, wherein the cleaning time of each solvent is 30min, and drying the FTO conductive glass with nitrogen after cleaning is completed to obtain a substrate FTO conductive glass layer;
(2) Plating a nickel oxide hole transport layer on the dried FTO conductive glass by using magnetron sputtering equipment;
(3) Taking 25ul of Cs on the nickel oxide hole transport layer in the step (2) 0.1 FA 0.9 PbI 3 (1.1M) a perovskite precursor solution, carrying out blade coating by using a scraping rod at a scraping speed of 12mm/s, and then blowing off excessive solvent by using nitrogen gas to form a non-mineralized perovskite film with a thickness of 550 nm;
(4) Spraying 1mg/ml CF on the non-mineralized perovskite film of the step (3) by using a spraying device 3 -PEAI solution, wherein CF 3 -a mixed solvent of pei in isopropanol and dimethylformamide (volume ratio of isopropanol to dimethylformamide 200:1), CF 3 The thickness of the PEAI solution sprayed is 10nm, after spraying, the perovskite film is obtained by annealing for 2min at 70 ℃ and then annealing for 40min at 110 ℃ on a heating table;
(5) Evaporating 25nm C60 and 5nm BCP on the surface of the perovskite film in the step (4) respectively to form an electron transport layer;
(6) And (3) depositing 80nm Cu on the surface of the electron transport layer in the step (5) by using a vacuum evaporation method.
Example 2
The embodiment provides a perovskite solar cell, perovskite solar cell from the bottom up has set gradually: a substrate, a hole transport layer, a perovskite thin film, an electron transport layer and a metal electrode;
the perovskite thin film includes a perovskite thin film layer disposed proximate to a hole transport layer, and a two-dimensional passivation layer disposed between the perovskite thin film layer and an electron transport layer.
The embodiment also provides a preparation method of the perovskite solar cell, which comprises the following steps:
(1) Ultrasonically cleaning the FTO conductive glass with 30cm multiplied by 30cm respectively with glass cleaning agent and deionized water in sequence, wherein the cleaning time of each solvent is 30min, and drying the FTO conductive glass with nitrogen after cleaning is completed to obtain a substrate FTO conductive glass layer;
(2) Plating a nickel oxide hole transport layer on the dried FTO conductive glass by using magnetron sputtering equipment;
(3) Taking 20ul of Cs on the nickel oxide hole transport layer in the step (2) 0.1 FA 0.9 PbI 3 (1.1M) a perovskite precursor solution, carrying out blade coating by using a scraping rod at the scraping speed of 10mm/s, and then blowing off redundant solvent by using nitrogen gas to form a non-mineralized perovskite film with the thickness of 500 nm;
(4) Spraying 1mg/ml of OAI solution on the non-mineralized perovskite film in the step (3) by using spraying equipment, wherein the OAI is dissolved in a mixed solvent of isopropyl alcohol and dimethylformamide (the volume ratio of the isopropyl alcohol to the dimethylformamide is 200:1), the thickness of the OAI solution sprayed is 10nm, and after the spraying is finished, annealing is carried out on a heating table at 70 ℃ for 2min, and then annealing is carried out at 110 ℃ for 40min, so that the perovskite film is obtained;
(5) Evaporating 25nm C60 and 5nm BCP on the surface of the perovskite film in the step (4) respectively to form an electron transport layer;
(6) And (3) depositing 80nm Cu on the surface of the electron transport layer in the step (5) by using a vacuum evaporation method.
Example 3
The embodiment provides a perovskite solar cell, perovskite solar cell from the bottom up has set gradually: a substrate, a hole transport film layer, a perovskite thin film, an electron transport layer and a metal electrode;
the perovskite thin film includes a perovskite thin film layer disposed proximate to a hole transport layer, and a two-dimensional passivation layer disposed between the perovskite thin film layer and an electron transport layer.
The embodiment also provides a preparation method of the perovskite solar cell, which comprises the following steps:
(1) Ultrasonically cleaning the FTO conductive glass with 30cm multiplied by 30cm respectively with glass cleaning agent and deionized water in sequence, wherein the cleaning time of each solvent is 30min, and drying the FTO conductive glass with nitrogen after cleaning is completed to obtain a substrate FTO conductive glass layer;
(2) Plating a nickel oxide hole transport layer on the dried FTO conductive glass by using magnetron sputtering equipment;
(3) Nickel oxide holes in step (2)Taking 25ul Cs above the transmission layer 0.1 FA 0.9 PbI 3 (1.1M) a perovskite precursor solution, carrying out blade coating by using a scraping rod at a scraping speed of 12mm/s, and then blowing off excessive solvent by using nitrogen gas to form a non-mineralized perovskite film with a thickness of 600 nm;
(4) Spraying 1mg/ml of BAI solution on the non-mineralized perovskite film in the step (3) by using spraying equipment, wherein the BAI is dissolved in a mixed solvent of isopropyl alcohol and dimethylformamide (the volume ratio of isopropyl alcohol to dimethylformamide is 200:1), the spraying thickness of the BAI solution is 10nm, and after spraying, annealing is carried out on a heating table at 70 ℃ for 2min, and then annealing is carried out at 110 ℃ for 40min, so that the perovskite film is obtained;
(5) Evaporating 25nm C60 and 5nm BCP on the surface of the perovskite film in the step (4) respectively to form an electron transport layer;
(6) And (3) depositing 80nm Cu on the surface of the electron transport layer in the step (5) by using a vacuum evaporation method.
Example 4
In this example, CF in step (4) is divided 3 The same conditions as in example 1 were followed except that the concentration of PEAI was replaced by 0.5 mg/ml.
Example 5
In this example, CF in step (4) is divided 3 The same conditions as in example 1 were followed except that the concentration of PEAI was replaced by 2mg/ml.
Example 6
This example is the same as example 2 except that the OAI concentration in step (4) is replaced with 0.5 mg/ml.
Example 7
This example is the same as example 2 except that the OAI concentration in step (4) is replaced with 2mg/ml.
Example 8
This example is identical to example 3 except that the BAI concentration in step (4) is replaced by 0.5 mg/ml.
Example 9
This example is identical to example 3 except that the BAI concentration in step (4) is replaced with 2mg/ml.
Example 10
In this example, step (4) CF is divided 3 The same conditions as in example 1 were followed except that the thickness of the spray coating of the PEAI solution was replaced by 5nm.
Example 11
In this example, step (4) CF is divided 3 The same conditions as in example 1 were followed except that the spray thickness of the PEAI solution was replaced by 20 nm.
Example 12
This example is identical to example 1 except that step (4) is annealed directly at 110℃for 40 min.
Example 13
Wherein CF is 3 -PEAI was dissolved in a mixed solvent of isopropanol and dimethylformamide, wherein the volume ratio of isopropanol to dimethylformamide was 150:1, with the other conditions being the same as in example 1.
Example 14
Wherein CF is 3 -PEAI was dissolved in a mixed solvent of isopropanol and dimethylformamide in a volume ratio of 250:1, with the other conditions being the same as in example 1.
Comparative example 1
The step (4) of this comparative example was modified as follows: placing the non-mineralized perovskite film of the step (3) on a heating table for annealing at 70 ℃ for 2min, then annealing at 110 ℃ for 40min, and spraying 1mg/ml CF on the step (3) by using a spraying device 3 -PEAI solution, wherein CF 3 Surface passivation was performed with a mixed solvent of pea dissolved in isopropyl alcohol and dimethylformamide (volume ratio of isopropyl alcohol to dimethylformamide 200:1), to obtain a perovskite thin film, and the other conditions were the same as in example 1.
Comparative example 2
Comparative example divides CF 3 The conditions were the same as in comparative example 1 except that the PEAI solution was replaced with an OAI solution.
Comparative example 3
Comparative example divides CF 3 The conditions were the same as in comparative example 1 except that the PEAI solution was replaced with the BAI solution.
Comparative example 4
Dividing the comparative example into the step (3) and the step(4) The modification is as follows: CF of the same quality as in example 1 3 -PEAI solution and Cs 0.1 FA 0.9 PbI 3 (1.1M) the perovskite precursor solution was mixed and then coated on the surface of the hole transport layer of nickel oxide of step (2), and the other conditions were the same as in example 1.
Comparative example 5
Comparative example divides CF 3 The conditions were the same as in comparative example 4 except that the PEAI solution was replaced with an OAI solution.
Comparative example 6
Comparative example divides CF 3 The conditions were the same as in comparative example 4 except that the PEAI solution was replaced with the BAI solution.
Comparative example 7
Comparative example was not sprayed with CF 3 The conditions were the same as in example 1 except for the PEAI solution.
The perovskite solar cells prepared in examples 1 to 12 and comparative examples 1 to 7 were subjected to tests of Isc (short-circuit current), voc (open circuit voltage), PCE (photoelectric conversion efficiency), FF (fill factor), rs (series resistance) and Rsh (parallel resistance), and the test results are shown in table 1.
The test method of PCE (photoelectric conversion efficiency) comprises the following steps: the solar simulator is used for emitting standard solar light (spectrum AM1.5G, incident power 100mW/cm 2 The test was carried out at a temperature of 25 ℃.
TABLE 1
The optimal concentration of the liquid film passivation in examples 1, 2 and 3 can be obtained through the table, and compared with the blank sample in comparative example 7, the efficiency of 19.21% is greatly improved, and the CF can be seen 3 The PEAI passivation effect is optimal, the efficiency is 21.72%, and the improvement of the relative surface efficiency by 2.5 points is mainly filling factor and openingThe path voltage is improved, which shows that the scheme obviously improves the crystal formation of perovskite and effectively passivates the defects of the perovskite film.
Examples 4-9 are the effects of different two-dimensional materials, different concentrations on cell performance, and it can be seen that a concentration range of 0.5-1 mg/ml has better cell performance because if the concentration of passivation material is too great, electron hole transport efficiency is affected.
Examples 10-11 are examples of different thicknesses, and too low a coating thickness results in too little two-dimensional material, which can not completely passivate perovskite crystals, and there is still a certain margin of lead iodide, and too high a coating thickness results in too much two-dimensional material, which affects the electron and hole transport efficiency.
Example 12 direct 110 ℃ anneal, the lower efficiency is mainly due to the fact that without pre-annealing, the solvent volatilizes too fast causing a large number of defects in the crystal growth.
Examples 13-14 are different from example 1 in terms of volume ratio of different isopropyl alcohol and dimethylformamide, because a small amount of dimethylformamide can etch the surface of the perovskite film to be combined with two-dimensional materials more effectively to generate 2D perovskite, and the three-dimensional perovskite is passivated, but if the content of dimethylformamide is too high, the perovskite film layer is damaged, so that the battery efficiency is affected. For example, example 13 mixed solvent 150:1 is relatively poor in effect mainly because of the high DMF content, and can erode perovskite films in large quantities.
Comparative examples 1, 2 and 3 are lower in efficiency than examples 1, 2 and 3, which shows that the passivation effect is better in the liquid film state, namely in the non-mineralized state, mainly because the two-dimensional material and the non-mineralized perovskite film form an intermediate phase, the intermediate phase can be screened, the perovskite crystallization in the annealing process is more facilitated, and defects of the perovskite in the forming process are reduced. Compared with the way of passivating after annealing to generate the perovskite film, the perovskite film with better performance and fewer defects can be obtained.
The battery obtained by bulk doping of comparative examples 4, 5, and 6 using a two-dimensional material as an additive is inferior in efficiency because, after the radius of the two-dimensional material is excessively large, vacancy defects are more likely to occur due to the excessively large a-site cations, thereby resulting in higher defect generation, and the carrier transport of the resulting perovskite thin film is hindered, resulting in the failure of efficient extraction of electrons and holes.
While the foregoing is directed to embodiments of the present invention, other and further details of the invention may be had by the present invention, it should be understood that the foregoing description is merely illustrative of the present invention and that no limitations are intended to the scope of the invention, except insofar as modifications, equivalents, improvements or modifications are within the spirit and principles of the invention.
Claims (10)
1. A method for producing a perovskite thin film, comprising: coating a passivation solution containing a two-dimensional material on the non-mineralized perovskite film, and annealing to obtain the perovskite film.
2. The method of claim 1, wherein a passivation solution containing a two-dimensional material is coated on the non-mineralized perovskite thin film, the two-dimensional material and the non-mineralized perovskite thin film forming a mesophase;
and annealing, wherein the perovskite film of the non-mineralized perovskite generates a perovskite crystal phase, and the intermediate phase generates a two-dimensional passivation layer at a grain boundary and/or a film surface to obtain the perovskite film.
3. The method of claim 1 or 2, wherein the two-dimensional material comprises bulky aromatic amine compounds and/or long chain alkylamine compounds;
preferably, the aromatic amine compound is a bulky aromatic amine compound with a tolerance factor of more than 1;
preferably, the long-chain alkylamine compound is a straight-chain or branched-chain alkylamine compound with 2-20 carbon atoms;
preferably, the two-dimensional material comprises any one or a combination of at least two of 4-trifluoromethyl phenethylamine iodide, 4-trifluoromethyl phenethylamine chloride, 4-trifluoromethyl phenethylamine bromide, octyl iodinated amine, octyl chlorinated amine, octyl brominated amine, butyl chlorinated amine, butyl brominated amine or butyl iodinated amine;
preferably, the solvent of the passivation solution comprises isopropyl alcohol and dimethylformamide;
preferably, the volume ratio of the isopropyl alcohol to the dimethylformamide is (150-250): 1.
4. A method according to any one of claims 1-3, characterized in that the concentration of the passivating solution is 0.5-2 mg/ml, preferably 0.8-1.2 mg/ml.
5. The method of any one of claims 1-4, wherein the method of coating comprises spraying;
preferably, the passivation solution is coated to a thickness of 5 to 15nm.
6. The method according to any one of claims 1 to 5, wherein the annealing comprises a first annealing and a second annealing performed sequentially;
preferably, the temperature of the first annealing is 50-90 ℃;
preferably, the time of the first annealing is 1-3 min;
preferably, the temperature of the second annealing is 100-120 ℃;
preferably, the second annealing time is 35-45 min.
7. The production method according to any one of claims 1 to 6, characterized in that the production method comprises:
coating a passivation solution containing a two-dimensional material with the concentration of 0.5-2 mg/ml on the non-mineralized perovskite film, and sequentially carrying out first annealing at the temperature of 50-90 ℃ and second annealing at the temperature of 100-120 ℃ to obtain the perovskite film.
8. A perovskite thin film, characterized in that the perovskite thin film is prepared by the preparation method of the perovskite thin film according to any one of claims 1 to 7, and the perovskite thin film comprises a perovskite thin film layer and a two-dimensional passivation layer arranged on the perovskite thin film layer.
9. A perovskite solar cell, comprising a substrate, a first carrier layer, the perovskite thin film according to claim 8, a second carrier layer and a metal electrode, which are arranged in sequence from bottom to top.
10. Use of a perovskite solar cell according to claim 9, wherein the perovskite solar cell is applied in the field of photovoltaic cells.
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