CN113594396B - Solvent atmosphere controlled perovskite in-situ film forming method and product and application thereof - Google Patents
Solvent atmosphere controlled perovskite in-situ film forming method and product and application thereof Download PDFInfo
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- CN113594396B CN113594396B CN202110772017.9A CN202110772017A CN113594396B CN 113594396 B CN113594396 B CN 113594396B CN 202110772017 A CN202110772017 A CN 202110772017A CN 113594396 B CN113594396 B CN 113594396B
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Abstract
The invention discloses a perovskite in-situ film forming method controlled by solvent atmosphere, which comprises the following steps: under the atmosphere with the partial pressure of solvent gas, spin-coating the perovskite precursor solution on a substrate, and heating, annealing and crystallizing to obtain a perovskite thin film; the solvent gas and the solvent in the perovskite precursor solution are the same substance. The invention also discloses a perovskite thin film prepared by the perovskite in-situ film forming method and application of the perovskite thin film in preparation of perovskite light-emitting diodes.
Description
Technical Field
The invention relates to the technical field of Perovskite thin film preparation, in particular to a solvent atmosphere controlled Perovskite (Perovskite) in-situ film forming method, a product and application thereof.
Background
Patent specification CN 111435707 a discloses a method for improving the film-forming quality of perovskite thin film, comprising the following steps:
step one, preparing a perovskite precursor solution;
depositing a perovskite precursor thin film layer on the surface of the transparent conductive substrate;
placing the perovskite precursor film in a variable gas pressure atmosphere for self-solvent annealing, and reacting the perovskite precursor to generate the perovskite film;
and step four, repeatedly cleaning by using inert gas to remove residual solvent in the atmosphere, and then carrying out heating annealing to complete the preparation of the perovskite film.
The technology of the patent improves the repeatability of the perovskite thin film preparation process by accurately regulating and controlling the crystallization process of the material so as to obtain the high-quality perovskite thin film. Wherein the atmosphere with variable gas pressure is inert gas.
Patent specification CN 111490168A discloses a preparation method of an inorganic perovskite solar cell based on atmosphere control, which comprises the following steps:
(1) cleaning transparent FTO conductive glass to obtain a transparent conductive substrate;
(2) preparing an electron transport layer on the transparent conductive substrate obtained in the step (1);
(3) dropwise adding an inorganic perovskite precursor solution onto the electron transport layer obtained in the step (2) in a specific atmosphere, spin-coating to form a film, and performing heat treatment in the specific atmosphere to obtain an electron transport layer/inorganic perovskite thin film;
(4) preparing a hole transport layer on the electron transport layer/inorganic perovskite thin film obtained in the step (3) under the specific atmosphere in the step (3) to obtain the electron transport layer/inorganic perovskite thin film/hole transport layer;
(5) and (4) depositing a counter electrode on the electron transport layer/inorganic perovskite thin film/hole transport layer obtained in the step (4) by an evaporation coating method to obtain the inorganic perovskite solar cell.
In the above patent technology, the specific atmosphere means that the oxygen content is 10% -30% and the water content is less than 8.8g/m 3 Air or an inert gas atmosphere.
Patent specification CN 109904322 a discloses a method for preparing an all-inorganic perovskite thin film, which comprises mixing inorganic perovskite components with organic amine salt, preparing a mixed thin film by spin coating, spray coating, slit coating, screen printing and other processes, then placing in an atmosphere of methylamine, ethylamine or butylamine gas, effectively repairing the defects of the perovskite thin film, reducing the surface roughness, and finally removing the organic amine salt through high-temperature treatment to achieve the purpose of repairing the inorganic perovskite thin film. The perovskite thin film prepared by the process has the advantages of uniform thickness, low roughness, good crystallinity, simple operation and low cost, and is suitable for preparing high-efficiency perovskite solar cells, high-performance light emitting diodes and laser devices in a large area.
The metal halide perovskite (metal halide perovskite) is a direct band gap semiconductor which can be used for solution process processing, has the advantages of high color purity, wide adjustable range of light-emitting wavelength, high fluorescence quantum yield and the like, is a star photoelectric material in recent years, has wide application in the fields of photovoltaics, light-emitting diodes, photoelectric detection and the like, and particularly has great application potential in the field of light-emitting diodes (LEDs).
However, compared with the Organic Light Emitting Diode (OLED) and the quantum dot light emitting diode (QLED) which have mature technologies, the research time of the perovskite light-emitting diode (PeLED) is still short, the device performance is greatly different from the former two, and the PeLED has poor neglect of the conditions such as spin coating atmosphere and the like in the preparation process, so the device efficiency is uneven and the repeatability is not high.
Disclosure of Invention
Aiming at the defects existing in the field, the invention provides a solvent atmosphere controlled perovskite in-situ film forming method, a perovskite precursor solution is subjected to in-situ film forming in the atmosphere containing solvent gas in a spin coating process to obtain a perovskite thin film with a specific morphology structure, a PeLED prepared on the basis of the perovskite thin film has higher device efficiency compared with the PeLED prepared on the basis of the perovskite thin film obtained by spin coating in a pure inert atmosphere, and the performance of the perovskite thin film obtained by spin coating in the atmosphere containing solvent gas is more repeatable compared with the pure inert atmosphere.
A solvent atmosphere controlled perovskite in-situ film forming method comprises the following steps: under the atmosphere with the partial pressure of solvent gas, spin-coating the perovskite precursor solution on a substrate, and heating, annealing and crystallizing to obtain a perovskite thin film;
the solvent gas and the solvent in the perovskite precursor solution are the same substance.
The inventor researches and discovers that the existence of the solvent gas in the atmosphere of the heating annealing crystallization process has little influence on the structure and the property of the obtained perovskite thin film. The key of the invention is the atmosphere control during the spin coating process.
Preferably, in the perovskite in-situ film forming method, the partial pressure of the solvent gas is 1-200 Pa.
Preferably, in the perovskite in-situ film forming method, the atmosphere is nitrogen and/or rare gas except solvent gas.
Preferably, in the perovskite in-situ film formation method, a solvent in the perovskite precursor solution is Dimethylformamide (DMF), dimethyl sulfoxide (DMSO), Chlorobenzene (CB), gamma-butyrolactone (GBL) or 1-methyl-2-pyrrolidone (NMP).
According to the perovskite in-situ film forming method, the substrate is made of quartz, PEDOT (PSS (poly 3, 4-ethylenedioxythiophene/polystyrene sulfonate)), PVK (poly [ 9-vinylcarbazole ]), and the like.
Preferably, in the perovskite in-situ film forming method, the composition of the perovskite thin film is expressed as a molecular formula L m A n-1 M n X 3n+1 Wherein:
m represents the valence of L and is 1 or 2;
l is monovalent or divalent organic cation, specifically monocyclic aromatic cation, aliphatic cation with carbon number not less than 2, etc.;
a is a monovalent cation selected from Methylammonium (MA) + ) Formamidine (FA) + ) Or Cs + ；
M is a divalent cation of main group IV, e.g. Pb 2+ 、Sn 2+ Etc.;
x is a monovalent halide anion, e.g. Cl - 、Br - 、I - Etc.;
n is a positive integer representing [ MX ] between the organic cations 6 ] 4- Number of octahedral layers.
The invention also provides the perovskite thin film prepared by the perovskite in-situ film forming method.
The invention also provides application of the perovskite thin film in preparation of perovskite light-emitting diodes.
As a general inventive concept, the present invention also provides a perovskite light emitting diode comprising an anode (e.g., indium tin oxide, etc.), a hole injection layer (e.g., NiO) disposed in sequence x Etc.), a hole transport layer (e.g., TFB (poly [9, 9-dioctylfluorene-CO-N- (4-butyl)Phenyl) diphenylamines]) PVK, etc.), perovskite light emitting layer, electron transporting layer (such as TPBi (1,3, 5-tris (1-phenyl-1H-benzimidazol-2-yl) benzene), etc.) and cathode (such as LiF/Al electrode, etc.);
the perovskite thin film is adopted in the perovskite light emitting layer.
The layers other than the perovskite light-emitting layer may be prepared by conventional methods.
Compared with the prior art, the invention has the main advantages that:
according to the perovskite in-situ film forming method controlled by the solvent atmosphere, the spin coating process is placed in the atmosphere containing the solvent gas, the perovskite precursor solution is subjected to in-situ film forming to obtain the perovskite thin film with the specific morphology structure, the PeLED prepared on the basis of the perovskite thin film has higher device efficiency compared with the PeLED prepared by the perovskite thin film obtained by spin coating in the pure inert atmosphere, and the performance of the perovskite thin film obtained by spin coating in the atmosphere containing the solvent gas is more repeatable compared with the pure inert atmosphere.
Drawings
FIG. 1 is a current density-voltage-luminance curve of a device in operation;
fig. 2 shows External Quantum Efficiencies (EQE) of the PeLED device at different operating voltages.
Detailed Description
The invention is further described with reference to the following drawings and specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The following examples are conducted under conditions not specified, usually according to conventional conditions, or according to conditions recommended by the manufacturer.
1. Preparing perovskite precursor solution
Accurately weighing 32.6mg of bromobutyronium bromide (PBABR), 19.2mg of cesium bromide, 4.8mg of FABr and 47.3mg of lead bromide by using a precision balance, pouring the weighed materials into a wash-free bottle filled with stirring magnetons, adding 2mL of DMSO, and continuously heating and stirring the materials on a heating table at 60 ℃ at a speed of 600rpm for more than 2 hours to fully dissolve the materials so as to obtain a perovskite precursor solution.
2. Preparation of perovskite thin films under different atmospheres
Preparing a perovskite thin film in a solvent-free gas atmosphere (pure nitrogen atmosphere): closing the nitrogen circulation function of the glove box, cleaning the glove box for 45min by using nitrogen, keeping the nitrogen circulation function of the glove box in an open state all the time when the perovskite is coated, and carrying out subsequent perovskite thin film preparation under the atmosphere of pure nitrogen (marked as DMSO-0-Pa) in the glove box.
Preparing the perovskite thin film under the atmosphere with the partial pressure of the solvent gas: and (2) cleaning the glove box by nitrogen, closing the nitrogen circulation function of the glove box, dropwise adding 600 mu L of DMSO (dimethyl sulfoxide) on a culture dish, placing the culture dish on a hot platform at 100 ℃ for heating, keeping the heating time for about 15min to ensure that the DMSO is completely volatilized, and after the DMSO is completely volatilized and the temperature of the hot platform is reduced to room temperature, taking the atmosphere in the glove box as nitrogen atmosphere (marked as DMSO-15-Pa) with 15Pa DMSO gas partial pressure to perform subsequent perovskite thin film preparation.
The preparation process of the perovskite thin film under different atmospheres is the same: and (3) placing the substrate on a spin coater and fixing, dropwise adding 40 mu L of the perovskite precursor liquid into a liquid transfer gun, uniformly smearing and spin-coating by using the gun head, setting spin-coating parameters to be 4000r/min and 120s of time, and then annealing for 30min on a hot bench at 100 ℃ to prepare the perovskite thin film under the corresponding atmosphere.
The device structure of the blue-light PeLED is ITO/NiO x /TFB/PVK/Perovskite/TPBi/LiF/Al. And when the perovskite luminescent layer is prepared, different spin coating atmospheres are controlled according to the method, and when the spin coating is carried out for 24s, 65 mu L of ethyl acetate anti-solvent is dripped on the substrate coated with the perovskite, and the dripped anti-solvent promotes the perovskite thin film to rapidly form a luminescent center similar to a quantum dot. After the perovskite luminescent layer is prepared, the preparation of the electron transport layer and the cathode can be carried out. Thereby obtaining the PeLED devices under different spin coating atmospheres respectively.
As shown in FIG. 1 and FIG. 2, the test results show that the EQE maximum value of the DMSO-0-Pa device is 9.1%, the EQE maximum value of the DMSO-15-Pa device is 14.4%, the dark current of the two devices is extremely small, no leakage current exists, the functional layers are uniformly formed into films and have no pin holes, and the brightness of the devices prepared in the pure nitrogen atmosphere and the atmosphere with the partial pressure of the solvent gas is 5VAre respectively 142cd/m 2 And 487cd/m 2 。
Furthermore, it should be understood that various changes and modifications can be made by one skilled in the art after reading the above description of the present invention, and equivalents also fall within the scope of the invention as defined by the appended claims.
Claims (8)
1. A solvent atmosphere controlled perovskite in-situ film forming method is characterized by comprising the following steps: evaporating a solvent in advance to enable the partial pressure of the solvent gas to be in an environment atmosphere, wherein the partial pressure of the solvent gas is 1-200 Pa, spin-coating a perovskite precursor solution on a substrate, and heating, annealing and crystallizing to obtain a perovskite thin film;
the solvent gas and the solvent in the perovskite precursor solution are the same substance.
2. The perovskite in-situ film formation method according to claim 1, wherein the ambient atmosphere is nitrogen and/or a rare gas other than the solvent gas.
3. The perovskite in-situ film forming method as claimed in claim 1, wherein the solvent in the perovskite precursor solution is dimethylformamide, dimethyl sulfoxide, chlorobenzene, gamma-butyrolactone or 1-methyl-2-pyrrolidone.
4. The perovskite in-situ film forming method as claimed in claim 1, wherein the substrate is made of quartz, PEDOT PSS, PVK.
5. The perovskite in-situ film formation method as claimed in claim 1, wherein the composition of the perovskite thin film is expressed as a molecular formula L m A n-1 M n X 3n+1 Wherein:
m represents the valence of L and is 1 or 2;
l is a monovalent or divalent organic cation;
a is a monovalent cation selected from the group consisting of methylammonium, formamidine and Cs + ；
M is a divalent cation of main group IV;
x is a negative monovalent halide ion;
n is a positive integer representing [ MX ] between the organic cations 6 ] 4- Number of octahedral layers.
6. The perovskite thin film prepared by the perovskite in-situ film forming method as claimed in any one of claims 1 to 5.
7. Use of the perovskite thin film as defined in claim 6 for the preparation of a perovskite light emitting diode.
8. A perovskite light-emitting diode is characterized by comprising an anode, a hole injection layer, a hole transport layer, a perovskite light-emitting layer, an electron transport layer and a cathode which are sequentially arranged;
the perovskite light-emitting layer uses the perovskite thin film described in claim 6.
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