CN108520918B - Preparation method of organic-inorganic perovskite semiconductor material - Google Patents

Preparation method of organic-inorganic perovskite semiconductor material Download PDF

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CN108520918B
CN108520918B CN201810198345.0A CN201810198345A CN108520918B CN 108520918 B CN108520918 B CN 108520918B CN 201810198345 A CN201810198345 A CN 201810198345A CN 108520918 B CN108520918 B CN 108520918B
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perovskite
semiconductor material
stirring
linear substrate
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CN108520918A (en
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熊杰
孙浩轩
晏超贻
邬春阳
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University of Electronic Science and Technology of China
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    • H—ELECTRICITY
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    • 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
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    • 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
    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
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    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Abstract

The invention provides a preparation method of a novel organic-inorganic perovskite semiconductor material, which comprises the steps of firstly, vertically immersing a linear substrate into perovskite precursor liquid, adjusting the perovskite to be in a saturated state in a mixed liquid phase through the temperature and the amount of an anti-solvent, and disturbing the liquid phase mixture through a magnetic stirrer to enable the linear substrate to be positioned in a disturbance center; then, continuously dripping the anti-solvent to ensure that the liquid phase is supersaturated and crystal precipitation occurs, and depositing on the surface of the linear substrate to form a film under the action of solution disturbance. According to the invention, the linear substrate is vertically immersed into the precursor liquid and is positioned at the liquid phase disturbance center in combination with magnetic stirring, so that the influence of gravity on precipitated crystals is greatly reduced, and the uniform and compact perovskite thin film is obtained.

Description

Preparation method of organic-inorganic perovskite semiconductor material
Technical Field
The invention relates to a preparation method of a novel organic-inorganic perovskite semiconductor material.
Background
With the rapid development of the photoelectric science and technology, higher requirements are put forward on the performances of photoelectric materials, particularly photoelectric semiconductor materials. For optoelectronic semiconductor materials, two properties are of primary interest: first, energy conversion, such as solar cells, photodetectors, light emitting diodes, etc.; and the other is the modulation and transmission of signals, such as optical waveguide, antenna modulation, etc. In 2009, the japanese scientist Miyasaka first proposed an organic-inorganic composite halide perovskite material (CH)3NH3PbX3X ═ Cl, Br, I) and their use in the field of optoelectronics, since then the new class of optoelectric materials has received increasing attention from researchers. Especially, the efficiency of the solar cell based on perovskite material can reach 22.1% in 2017, which is enough to compare with the current monocrystalline silicon-based solar cell, and is praised as the solar cell with the fastest development speed so far. Perovskite photovoltaic materials can achieve such brilliant achievements due to their extremely excellent photovoltaic characteristics: such as a perovskite material pairThe sensing and light emitting ranges of light cover all visible wavelengths and a part of infrared wavelengths, and convenience is provided for the preparation of various photoelectric devices; the long carrier free path and the lower exciton binding energy of the material enable the photoelectric energy conversion to be easier; and the extremely high carrier mobility of the perovskite material also reduces the loss of energy in the transmission of the perovskite material.
At present, the preparation method of the perovskite semiconductor material mainly comprises the following steps: a vapor phase method typified by double source co-evaporation, a liquid phase method typified by spin coating, and a solid phase method in which mixed powders react to form perovskite. Among them, the liquid phase method (solution method) is the most widely studied and applied method at present due to its advantages of low cost, simple process, easy control, etc. The liquid phase method mainly comprises a spin coating method and a soaking method, and the spin coating method is limited by a spin coating instrument, can only realize preparation on a planar substrate, and is hardly suitable for substrates with other shapes such as a linear substrate, and the like, so that the wide application of the method is greatly limited. Especially for the emerging wearable electronics industry, flexible, linear substrates are the direction of future development for better space utilization. Therefore, at present, a dipping method or a method of improving the formation of the perovskite material by the dipping method is mostly adopted for preparing the perovskite material on the substrate with other shapes such as a linear shape. For example, Li Qingwen et al (r.li, x.xiang, x.tong, j.zou, q.li, adv.mater.2015,27,3831) use self-made equipment to reciprocate the perovskite precursor droplets on the carbon fibers, which are dried to obtain a uniform and dense perovskite thin film. Li Liang et al (h.sun, t.lei, w.tian, f.cao, j.xiong, l.li, Small2017,13,1701042) successfully produced dense mixed layers of perovskite-hole transporting material on rough carbon cloth surfaces by soaking carbon cloth in a mixed solution of perovskite precursor solution and a solution of Spiro-OMeTAD in chlorobenzene, by controlling the crystallization temperature. However, in the above method, the components of the precursor liquid contacting the upper and lower surfaces of the line substrate are different due to the influence of gravity, resulting in non-uniformity of the upper and lower surfaces of the material formed on the line substrate.
Disclosure of Invention
The invention aims to provide a novel preparation method of an organic-inorganic perovskite semiconductor material, aiming at the problem of nonuniformity of a perovskite material grown on a linear substrate in the background technology. The perovskite semiconductor material obtained by the method has uniform and compact ring surface, the grain size can reach the micron level, and the perovskite semiconductor material is beneficial to the application in the photoelectric field.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a preparation method of an organic-inorganic perovskite semiconductor material comprises the following steps:
step 1, cleaning a linear substrate, and drying for later use;
step 2, preparing a perovskite precursor solution, and stirring for 8-12 hours at 50-70 ℃ to obtain a uniform perovskite precursor solution;
step 3, vertically immersing the line-shaped substrate cleaned in the step 1 into the perovskite precursor liquid obtained in the step 2, as shown in fig. 1, then placing the perovskite precursor liquid on a heating and stirring table, and heating to 90-120 ℃ under the stirring condition; wherein the rotation center of the stirring table and the center of the magnetic rotor are positioned on the straight line of the linear substrate, and the stirring speed is 200-500 rpm;
step 4, under the condition of stirring, adding an anti-solvent dropwise into the perovskite precursor solution treated in the step 3, and precipitating crystals to form a perovskite thin film on the linear substrate; wherein the volume ratio of the dropwise added anti-solvent to the perovskite precursor liquid is (1-2): 1, the larger the amount of the anti-solvent to be added, the thicker the thickness of the formed perovskite thin film.
Further, steps 2 to 4 were performed in a glove box under a nitrogen atmosphere.
Further, the linear substrate in step 1 is carbon fiber or the like.
Further, the antisolvent in the step 4 is chlorobenzene, dichlorobenzene, diethyl ether and the like.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the invention, the linear substrate is vertically immersed into the precursor liquid and is positioned at the liquid phase disturbance center in combination with magnetic stirring, so that the influence of gravity on the precipitated crystal is greatly reduced, the ring surface of the obtained perovskite film is uniform and compact, no difference exists in the vertical direction, and the difference in the vertical direction caused by the action of gravity in the traditional method is effectively avoided.
2. The perovskite semiconductor material obtained by the method is uniform and compact without pinholes, the grain size can reach the micron level, and the perovskite semiconductor material is beneficial to the application in the photoelectric field.
3. The preparation method of the novel organic-inorganic perovskite semiconductor material provided by the invention is simple to operate, low in cost, free of complex equipment and operation, and easy to realize industrial large-scale production.
Drawings
FIG. 1 is a schematic view of a jig for preparing an organic-inorganic perovskite semiconductor material according to an embodiment of the present invention;
FIG. 2 is a scanning electron microscope image of a perovskite semiconductor material obtained in an embodiment of the present invention;
FIG. 3 is an X-ray diffraction pattern of the perovskite semiconductor material obtained in the embodiment of the invention.
Detailed Description
The technical scheme of the invention is detailed below by combining the accompanying drawings and the embodiment.
A preparation method of an organic-inorganic perovskite semiconductor material comprises the following steps:
step 1, ultrasonically cleaning a linear substrate in acetone, ethanol and deionized water in sequence, and then placing the linear substrate in a vacuum drying oven to be dried for later use;
step 2, preparing a perovskite precursor solution, and stirring for 8-12 hours at 50-70 ℃ to obtain a uniform perovskite precursor solution;
step 3, vertically immersing the line-shaped substrate cleaned in the step 1 into the perovskite precursor liquid obtained in the step 2, as shown in fig. 1, then placing the perovskite precursor liquid on a heating and stirring table, and heating to 90-120 ℃ under the stirring condition; wherein the rotation center of the stirring table and the center of the magnetic rotor are positioned on the straight line of the linear substrate, and the stirring speed is 200-500 rpm;
step 4, dropwise adding an anti-solvent into the perovskite precursor solution treated in the step 3 under the stirring condition until crystals are separated out, and forming a perovskite thin film on a linear substrate; wherein the volume ratio of the dropwise added anti-solvent to the perovskite precursor liquid is (1-2): 1, the larger the amount of the anti-solvent to be added, the thicker the thickness of the formed perovskite thin film.
Further, steps 2 to 4 were performed in a glove box under a nitrogen atmosphere.
Further, the linear substrate in step 1 is carbon fiber or the like.
Further, the antisolvent in the step 4 is chlorobenzene, dichlorobenzene, diethyl ether and the like.
Examples
A preparation method of an organic-inorganic perovskite semiconductor material comprises the following steps:
step 1, ultrasonically cleaning carbon fibers in acetone, ethanol and deionized water respectively for 20min in sequence, then placing the carbon fibers in a vacuum drying oven, and drying the carbon fibers for later use;
step 2, preparing the perovskite semiconductor material by adopting the structure shown in figure 1, wherein the following steps are all completed in a glove box in a nitrogen atmosphere; firstly, preparing perovskite precursor liquid, weighing 0.347g of lead iodide and 0.238g of methyl amine iodide, adding the lead iodide and the methyl amine iodide into 2ml of gamma-butyrolactone (GBL), and stirring for 12 hours at 60 ℃ to obtain uniform perovskite precursor liquid;
step 3, washing the carbon fibers cleaned in the step 1 for 20min by ultraviolet-ozone, vertically immersing the carbon fibers into the perovskite precursor liquid obtained in the step 2, as shown in figure 1, then placing the perovskite precursor liquid on a heating and stirring table, and heating the perovskite precursor liquid to 110 ℃ under the stirring condition; wherein the rotation center of the stirring table and the center of the magnetic rotor are positioned on the straight line of the carbon fiber, and the stirring speed is 400 rpm;
step 4, dropwise adding Dichlorobenzene (DCB) into the perovskite precursor liquid by using an injector shown in the figure 1 under the stirring condition of 400rpm as an anti-solvent, and precipitating crystals to form a perovskite thin film on the carbon fibers; wherein the volume ratio of the dropwise added anti-solvent to the perovskite precursor liquid is 1: 1, the larger the amount of the anti-solvent to be added, the thicker the thickness of the formed perovskite thin film.
FIG. 1 is a schematic view of a jig for preparing an organic-inorganic perovskite semiconductor material according to an embodiment of the present invention; mainly comprises a reaction bottle with a cover, an injector for adding an anti-solvent and a sample hole for vertically inserting carbon fibers. FIG. 2 is a scanning electron microscope image of a perovskite semiconductor material obtained in an embodiment of the present invention; as can be seen from FIG. 2, the perovskite semiconductor material obtained in the example has a uniform and dense surface without pinholes, and the grain size can reach the micron level. FIG. 3 is an X-ray diffraction pattern of a perovskite semiconductor material obtained by an embodiment of the invention; as is clear from fig. 3, the perovskite semiconductor thin film obtained in the example had a pure phase perovskite structure and had no impurities such as lead iodide left.
In the preparation method of the novel organic-inorganic perovskite semiconductor material, gamma-butyrolactone (GBL) is used as a solvent of a perovskite precursor solution, the solubility of perovskite in the GBL is gradually reduced along with the rise of temperature, chlorobenzene, dichlorobenzene, ether and the like are used as anti-solvents, and the anti-solvents are mutually soluble with the GBL solvent but are insoluble in the perovskite material. Firstly, vertically inserting a linear substrate into a perovskite precursor liquid, regulating a target solute (perovskite) to be in a saturated state in a mixed liquid phase through the temperature and the amount of an anti-solvent, and disturbing the liquid phase mixture through a magnetic stirrer to enable the linear substrate to be positioned in a disturbance center; then, continuously dripping the anti-solvent to ensure that the liquid phase is supersaturated and crystal precipitation occurs, and depositing on the surface of the linear substrate to form a film under the action of solution disturbance. According to the invention, the linear substrate is vertically inserted into the precursor liquid and is positioned at the liquid phase disturbance center in combination with magnetic stirring, so that the influence of gravity on the precipitated crystal is greatly reduced, and the uniform and compact perovskite thin film is obtained.

Claims (4)

1. A preparation method of an organic-inorganic perovskite semiconductor material comprises the following steps:
step 1, cleaning a linear substrate, and drying for later use;
step 2, preparing a perovskite precursor solution, and stirring for 8-12 hours at 50-70 ℃ to obtain a uniform perovskite precursor solution;
step 3, vertically immersing the line-shaped substrate cleaned in the step 1 into the perovskite precursor liquid obtained in the step 2, then placing the perovskite precursor liquid on a heating and stirring table, and heating to 90-120 ℃ under the condition of stirring; wherein the rotation center of the stirring table and the center of the magnetic rotor are positioned on the straight line of the linear substrate, and the stirring speed is 200-500 rpm;
step 4, under the condition of stirring, adding an anti-solvent dropwise into the perovskite precursor liquid obtained in the step 3, and separating out crystals to form a perovskite thin film on the linear substrate; wherein the volume ratio of the dropwise added anti-solvent to the perovskite precursor liquid is (1-2): 1.
2. the method for producing an organic-inorganic perovskite semiconductor material as claimed in claim 1, wherein the steps 2 to 4 are carried out in a glove box under a nitrogen atmosphere.
3. The method for producing an organic-inorganic perovskite semiconductor material as claimed in claim 1, wherein the linear substrate in step 1 is a carbon fiber.
4. The method for producing an organic-inorganic perovskite semiconductor material as claimed in claim 1, wherein the antisolvent in step 4 is chlorobenzene, dichlorobenzene or diethyl ether.
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