CN115715137A - Method for constructing surface patterning of organic-inorganic hybrid perovskite single crystal film - Google Patents

Method for constructing surface patterning of organic-inorganic hybrid perovskite single crystal film Download PDF

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CN115715137A
CN115715137A CN202211520008.1A CN202211520008A CN115715137A CN 115715137 A CN115715137 A CN 115715137A CN 202211520008 A CN202211520008 A CN 202211520008A CN 115715137 A CN115715137 A CN 115715137A
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single crystal
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inorganic hybrid
hybrid perovskite
perovskite single
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邹友生
何泽人
陆星宇
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Nanjing University of Science and Technology
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Abstract

The invention discloses a method for constructing surface patterning of an organic-inorganic hybrid perovskite single crystal film. The invention takes the optical disk track recording layer as a mother set, takes PDMS as a pattern transfer stamp and adopts a liquid phase limited domain growth mode to realize patterning construction on the surface of the perovskite single crystal film. The finally prepared patterned perovskite single crystal thin film has the advantages of good material crystallinity, controllable pattern size and shape and the like, and the method is simple in process, low in cost and generally suitable for various materials. In addition, the prepared patterned organic-inorganic hybrid perovskite single crystal film can be applied to a polarization photoelectric detector.

Description

Method for constructing surface patterning of organic-inorganic hybrid perovskite single crystal film
Technical Field
The invention belongs to the technical field of patterned film preparation, and particularly relates to a method for constructing surface patterning of an organic-inorganic hybrid perovskite single crystal film.
Background
As a new semiconductor material, the organic-electrodeless hybrid perovskite material has the advantages of strong light absorption capacity, adjustable band gap, long carrier life, high mobility and the like, and is widely researched in the field of functional devices such as photoelectric detection, solar cells, lasers and the like. Despite continuous development and optimization, a large number of grain boundaries and defects inside the perovskite polycrystalline thin film inevitably bring about problems of unnecessary recombination and scattering of carriers, I-V curve hysteresis effect, internal ion migration and the like. Compared with the perovskite single crystal thin film, the perovskite single crystal thin film has higher carrier mobility due to fewer internal crystal boundaries and defects, and the prepared device also has excellent photoelectric performance and higher stability. The perovskite monocrystal film based surface array patterning construction is very important for promoting the application of perovskite materials in the aspects of polarization detection, physical anti-counterfeiting, micro-nano photoelectric device integration and the like.
The commonly used perovskite single crystal thin film preparation methods include a space limitation method (Nature Communications,2017,8 (1): 1890-1896) and a wire cutting method (Journal of materials Chemistry C2018,6 (16): 4464-4470). The spatial confinement method is to limit the growth space of the perovskite material so that the perovskite material grows into a specific target shape. The wire cutting method is to perform physical cutting, etching and other steps on the basis of three-dimensional block single crystals, and prepare the perovskite material into single crystal slices.
Currently used surface patterning construction techniques are photolithography (Nano Letters 202020 (5): 3710-3717), laser direct writing (Nanoscale, 2021,13 14450-14459), and stencil transfer (Physical Chemistry Chemical Physics,2017,19 (10): 7204-7214). The photoetching method adopts selective photoresist to prepare an etching mask plate, and the target is patterned, so that the photoetching method is a micro-nano processing means which is widely applied at present. The laser direct writing method utilizes laser to directly act on the surface of a material, and realizes patterning construction through photochemical reaction, directional ablation and other means. The template transfer printing method is to press a target pattern on the surface of a thin film material by a template stamp by utilizing the principle of a nano-imprinting technology. Most of the existing perovskite material surface patterning processes need precise instruments for pattern construction and are directed at perovskite polycrystalline materials, so that the processing process is complex, the cost is high, and the perovskite materials are poor in crystallization performance and stability. However, patterning of a single crystal thin film has not been found.
Disclosure of Invention
The invention aims to provide a method for constructing surface patterning of an organic-inorganic hybrid perovskite single crystal film aiming at the problems in the prior art.
The technical solution for realizing the purpose of the invention is as follows: a method for constructing surface patterning of an organic-inorganic hybrid perovskite single crystal thin film, comprising the following steps:
step 1, removing a protective layer of an optical disc, washing organic dye on the surface of a light path recording layer by using ethanol, and putting the light path recording layer into isopropanol for ultrasonic cleaning to obtain a grating structure template;
step 2, fully stirring the mixed polydimethylsiloxane PDMS main agent and curing agent, coating the mixture on a grating structure template, putting the grating structure template into a hydrothermal oven, drying, and demolding to obtain a PDMS template with a grating structure;
step 3, adding equimolar metal halide and methylamine halide in a solvent under the nitrogen atmosphere, and fully stirring to obtain an inorganic-inorganic hybrid perovskite precursor solution;
step 4, respectively cleaning the hard substrate with deionized water, acetone and isopropanol, and drying in a nitrogen atmosphere;
step 5, soaking the clean hard substrate obtained in the step 4 in a hydrophobic solution, taking out the substrate, naturally drying the substrate, washing the substrate by absolute ethyl alcohol, and drying the substrate by blowing with nitrogen to obtain a hydrophobic hard substrate;
step 6, placing the hydrophobic hard substrate on a heating table, dropwise adding an organic-inorganic hybrid perovskite precursor solution, reversely covering the hydrophobic hard substrate with another hydrophobic hard substrate, pressurizing and preserving heat for a certain time, and growing an organic-inorganic hybrid perovskite single crystal film between the substrates;
step 7, removing the upper hydrophobic hard substrate to expose the metal halogen perovskite single crystal film, pressing the PDMS template on the single crystal film, and applying a certain pressure;
and 8, dripping a metal halogen perovskite precursor solution on the edge of the PDMS template, sucking the solution through capillary action, continuously preserving the temperature for a period of time, and obtaining the organic-inorganic hybrid perovskite single crystal film with the patterned surface after the growth is finished.
Furthermore, in the step 1, the CD-ROM and the DVD-ROM which are not erasable are selected as the optical disc, and the ultrasonic cleaning time of the track recording layer is 15 min-20 min.
Further, in the step 2, the mixing mass ratio of the polydimethylsiloxane PDMS main agent to the curing agent is 10:1, setting the temperature of the hydrothermal oven at 60 ℃, and keeping the temperature for 8 hours.
Further, in step 3, the metal halide is lead bromide or lead iodide, the methylamine halide is methylamine iodide or methylamine bromide, and the organic-inorganic hybrid perovskite is CH 3 NH 3 PbX 3 Wherein X is a halogen element I or Br; the solvent is N, N-dimethylformamide solution DMF, the concentration of the precursor solution is 0.8mol/L, the stirring temperature is 30 ℃, and the time is 3 hours.
Further, the hard substrate in the step 4 is an electronic grade glass sheet or ITO glass, and the hard substrate is subjected to ultrasonic treatment for 15-20 min through deionized water, acetone and isopropanol respectively.
Further, the hydrophobic solution in step 5 is obtained by adding 12mL of dimethyldimethoxysilane and 600. Mu.L of sulfuric acid into 200mL of isopropanol, stirring uniformly, and then standing for 30 min.
Furthermore, in the step 6, the hydrophobic hard substrate is pressurized to 0kPa to 6kPa, the temperature is set to 45 ℃ to 55 ℃, and the heat preservation time is 24h to 30h.
Further, the pressure applied between the PDMS template and the hydrophobic hard substrate in step 7 ranges from 4kPa to 14kPa.
Further, the heat preservation temperature in the step 8 is 45-55 ℃, and the heat preservation time is 12-18 h.
Compared with the prior art, the invention has the following remarkable advantages:
1) The invention adopts a method with simple process and low cost, takes the light path recording layer of a commercial optical disk as a master mask, realizes the patterning construction on the surface of the organic-inorganic hybrid perovskite single crystal film, avoids the complicated operation and expensive equipment of common methods such as photoetching and the like, perfectly re-etches the structure on the master mask by the obtained patterning, is simultaneously suitable for the construction of various perovskite materials and different patterning, and has universality.
2) The surface-patterned organic-inorganic hybrid perovskite single crystal film constructed by the invention inherits various excellent performances of the perovskite single crystal film, such as few crystal boundaries, low internal defects, good crystallinity and the like, and has good resistance to water-oxygen erosion.
3) The surface patterned organic-inorganic hybrid perovskite single crystal film constructed by the invention can be used for realizing a polarized photoelectric detector.
The present invention is described in further detail below with reference to the attached drawing figures.
Drawings
FIG. 1 is an AFM image of the surface pattern of a track recording layer of a CD-ROM disc and a cross-sectional height distribution diagram of a trench pattern in accordance with an embodiment 1 of the present invention, wherein FIG. 1 (a) is an AFM image and FIG. 1 (b) is a cross-sectional height distribution diagram of a trench pattern.
FIG. 2 is an AFM image and an SEM image of the surface of the PDMS-CD template in example 1 of the present invention, wherein FIG. 2 (a) is the AFM image and FIG. 2 (b) is the SEM image.
FIG. 3 shows CH after surface patterning by using PDMS-CD template in example 1 of the present invention 3 NH 3 PbBr 3 SEM image of the surface of the single crystal thin film.
Fig. 4 is an AFM image of the surface of the patterned perovskite single crystal thin film prepared in example 1 of the present invention and a channel pattern cross-sectional height distribution diagram thereof, fig. 4 (a) is an AFM image, and fig. 4 (b) is a channel pattern cross-sectional height distribution diagram.
FIG. 5 shows CH after surface patterning by using PDMS-CD template in embodiment 1 of the present invention 3 NH 3 PbBr 3 X-ray diffraction pattern of single crystal thin film.
Fig. 6 is an AFM image of the surface of the PDMS-DVD template and a profile of the cross-sectional height of the channel pattern according to embodiment 2 of the present invention, wherein fig. 6 (a) is the AFM image and fig. 6 (b) is the profile of the cross-sectional height of the channel pattern.
Fig. 7 is an AFM image and an SEM image of the surface of the PDMS-DVD template in example 2 of the present invention, wherein fig. 7 (a) is the AFM image and fig. 7 (b) is the SEM image.
FIG. 8 is a block diagram of a surface patterned by a PDMS-DVD template in example 2 of the present inventionH 3 NH 3 PbBr 3 SEM image of the surface of the single crystal thin film.
FIG. 9 shows a patterned CH prepared in example 2 of the present invention 3 NH 3 PbBr 3 The AFM image of the surface of the single crystal thin film and the profile of the channel pattern cross-section height thereof, wherein fig. 9 (a) is the AFM image and fig. 9 (b) is the profile of the channel pattern cross-section height.
FIG. 10 shows CH after surface patterning by using PDMS-CD template in embodiment 2 of the present invention 3 NH 3 PbBr 3 X-ray diffraction pattern of single crystal thin film.
FIG. 11 shows a patterned CH prepared in example 3 of the present invention 3 NH 3 PbI 3 The AFM image of the surface of the single crystal thin film and the profile of the channel pattern cross-section height thereof, wherein fig. 11 (a) is the AFM image and fig. 11 (b) is the profile of the channel pattern cross-section height.
FIG. 12 shows CH after surface patterning by using PDMS-CD template in embodiment 3 of the present invention 3 NH 3 PbI 3 SEM image of the surface of the single crystal thin film.
FIG. 13 shows CH after surface patterning by using PDMS-CD template in embodiment 3 of the present invention 3 NH 3 PbI 3 X-ray diffraction pattern of single crystal thin film.
FIG. 14 is a diagram of a patterned CH-based structure constructed in example 4 of the present invention 3 NH 3 PbBr 3 I-V curve of single crystal thin film photodetector.
FIG. 15 shows a patterned CH-based structure constructed in example 4 of the present invention 3 NH 3 PbBr 3 EQE diagram of single crystal thin film photodetector.
Detailed Description
In order to make the objects, technical solutions and advantages of the present application more clearly understood, the present application is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the present application and are not intended to limit the present application.
The invention provides a method for constructing surface patterning of an organic-inorganic hybrid perovskite single crystal film, which comprises the following steps:
step 1, removing a protective layer of an optical disc, washing organic dye on the surface of a light path recording layer by using ethanol, and putting the light path recording layer into isopropanol for ultrasonic cleaning to obtain a grating structure template;
step 2, fully stirring the mixed polydimethylsiloxane PDMS main agent and curing agent, coating the mixture on a grating structure template, putting the grating structure template into a hydrothermal oven, drying, and demolding to obtain a PDMS template with a grating structure;
step 3, adding metal halide and methylamine halide in equimolar amount in the nitrogen atmosphere, dissolving in a solvent, and fully stirring to obtain an inorganic-inorganic hybrid perovskite precursor solution;
step 4, respectively cleaning the hard substrate with deionized water, acetone and isopropanol, and drying in a nitrogen atmosphere;
step 5, soaking the clean hard substrate obtained in the step 4 in a hydrophobic solution, taking out the substrate, naturally drying the substrate, washing the substrate by absolute ethyl alcohol, and drying the substrate by blowing by nitrogen to obtain a hydrophobic hard substrate;
step 6, placing the hydrophobic hard substrate on a heating table, dropwise adding an organic-inorganic hybrid perovskite precursor solution, covering the hydrophobic hard substrate with another hydrophobic hard substrate in an inverted manner, pressurizing and preserving heat for a certain time, and growing an organic-inorganic hybrid perovskite single crystal film between the substrates;
step 7, removing the upper layer of the hydrophobic hard substrate, exposing the metal halogen perovskite single crystal film, pressing the PDMS template on the single crystal film, and applying a certain pressure;
and 8, dripping a metal halogen perovskite precursor solution on the edge of the PDMS template, sucking the solution through capillary action, continuously preserving the temperature for a period of time, and obtaining the organic-inorganic hybrid perovskite single crystal film with the patterned surface after the growth is finished.
The present invention will be described in further detail with reference to specific examples.
Example 1
This embodiment is a method of operating a mobile station in CH 3 NH 3 PbBr 3 The method for patterning the surface of the single crystal film comprisesThe following steps:
step 1, cutting a CD-ROM into a square with the size of 1cm multiplied by 1cm, sticking the CD-ROM by using a transparent adhesive tape, pulling off a protective layer of the CD, putting the exposed track recording layer into absolute ethyl alcohol to rinse away green organic dye on the surface, carrying out ultrasonic treatment for 15min, taking out, and drying by using nitrogen gas to obtain the grating structure master plate with the linear grooves.
And 2, weighing 10g of PDMS main agent, dripping 1g of curing agent, fully stirring, dripping on the optical track recording layer of the optical disc, putting the optical track recording layer into a hydrothermal oven, preserving heat at 60 ℃ for curing for 8 hours, and demoulding to obtain the PDMS-CD template printed with the linear groove structure of the optical track recording layer.
Step 3, in the nitrogen atmosphere, 0.08957g CH is taken 3 NH 3 Br and 0.2936g PbBr 2 Placing into a 4ml reagent bottle, adding 1ml DMF as solvent, stirring with magneton at 30 deg.C for 180min to obtain CH with concentration of 0.8mol/L 3 NH 3 PbBr 3 And (3) precursor solution.
And 4, adding 12ml of dimethyl dimethoxysilane and 600 mu L of sulfuric acid into 200ml of isopropanol, uniformly stirring, and standing for 30min to obtain a hydrophobic solution.
And 5, taking an electronic grade glass sheet of 5cm multiplied by 5cm, sequentially putting a cleaning agent, deionized water, acetone and isopropanol into the electronic grade glass sheet, performing ultrasonic treatment for 15min respectively, then soaking the electronic grade glass sheet in a hydrophobic solution, taking out the hydrophobic solution, naturally drying the hydrophobic solution, rinsing the substrate with ethanol, and drying the substrate in nitrogen to obtain the hydrophobic substrate.
Step 6, placing the hydrophobic substrate on a heating table, and dripping 125 mu L of CH 3 NH 3 PbBr 3 Inverting the precursor solution with another hydrophobic substrate, pressurizing to 6KPa, maintaining at 50 deg.C for 24 hr, and growing to obtain CH 3 NH 3 PbBr 3 A single crystal thin film.
Step 7, opening the upper hydrophobic substrate, and pressing the PDMS-CD template on the CH 3 NH 3 PbBr 3 And applying 14KPa pressure on the monocrystalline film.
Step 8, 5 μ L of CH 3 NH 3 PbBr 3 The precursor solution is dripped at the edge of the PDMS template and is sucked to the PDMS template through the capillary actionKeeping the temperature of the gap between the template and the single crystal at 50 ℃ for 12h, and taking out the gap after the growth is finished to obtain the patterned CH 3 NH 3 PbBr 3 A single crystal thin film.
The products produced were then analytically characterized as shown in fig. 1, fig. 2, fig. 3, fig. 4, fig. 5. The results show that the surface pattern of the track recording layer of the CD disc can be completely reproduced to CH by the method of example 1 3 NH 3 PbBr 3 The surface of the single crystal film is constructed to realize surface patterning, no obvious defect is generated, the surface patterning structure is a groove array structure with the height of 200nm and the periodic distribution of 1600nm spacing, and an XRD (X-ray diffraction) chart shows CH (carbon-oxygen) after the surface patterning 3 NH 3 PbBr 3 The single crystal film has high crystal quality.
Example 2
This embodiment is a method of operating a mobile station in CH 3 NH 3 PbBr 3 The method for patterning the surface of the single crystal film specifically comprises the following steps:
step 1, cutting the DVD-ROM disk into a square with the thickness of 1cm multiplied by 1cm, sticking the DVD-ROM disk by using a transparent adhesive tape, pulling off a disk protective layer, putting the exposed track recording layer into absolute ethyl alcohol to rinse out purple organic dye on the surface, carrying out ultrasonic treatment for 15min, taking out, and drying by using nitrogen gas to obtain the grating structure master plate with the linear grooves.
And 2, weighing 10g of PDMS main agent, dripping 1g of curing agent, fully stirring, dripping on the optical track recording layer of the optical disc, putting the optical track recording layer into a hydrothermal oven, preserving heat at 60 ℃ for curing for 8 hours, and demoulding to obtain the PDMS-DVD template printed with the linear groove structure of the optical track recording layer.
Step 3, in the nitrogen atmosphere, 0.08957g CH is taken 3 NH 3 Br and 0.2936g PbBr 2 Placing into a 4ml reagent bottle, adding 1ml DMF as solvent, stirring with magneton at 30 deg.C for 180min to obtain CH with concentration of 0.8mol/L 3 NH 3 PbBr 3 Precursor solution;
step 4, adding 12ml of dimethyl dimethoxy silane and 600 mu L of sulfuric acid into 200ml of isopropanol, uniformly stirring, and standing for 30min to obtain a hydrophobic solution;
step 5, taking an electronic grade glass sheet with the size of 5cm multiplied by 5cm, sequentially adding a cleaning agent, deionized water, acetone and isopropanol into the electronic grade glass sheet, performing ultrasonic treatment for 15min respectively, then soaking the electronic grade glass sheet into a hydrophobic solution, taking out the electronic grade glass sheet, naturally drying the electronic grade glass sheet, rinsing the substrate with ethanol, and then drying the substrate in nitrogen to obtain a hydrophobic substrate;
step 6, placing the hydrophobic substrate on a heating table, and dripping 125 mu L of CH 3 NH 3 PbBr 3 Precursor solution, inversion of the gland with another hydrophobic substrate, pressurizing at 6KPa, maintaining at 50 deg.C for 24 hr, and growing to obtain CH 3 NH 3 PbBr 3 A single crystal thin film.
Step 7, opening the upper hydrophobic substrate, and pressing the PDMS-DVD template on the CH 3 NH 3 PbBr 3 Applying 14KPa pressure on the monocrystalline film;
step 8, 5 μ L of CH 3 NH 3 PbBr 3 Dripping the precursor solution at the edge of the PDMS template, sucking the precursor solution into the gap between the template and the single crystal through capillary action, keeping the temperature at 50 ℃ for 12h, and taking out the precursor solution after growth is finished to obtain the patterned CH 3 NH 3 PbBr 3 A single crystal thin film.
The prepared products were then analytically characterized as shown in fig. 6, 7,8, 9, 10. As a result, it was found that the surface pattern of the track recording layer of the DVD disk was completely reproduced on CH by the method of example 2 3 NH 3 PbBr 3 The surface patterning structure of the surface of the single crystal film is a groove array structure with the height of 100nm and the periodic distribution at the interval of 750nm, and an XRD (X-ray diffraction) chart shows CH after the surface patterning 3 NH 3 PbBr 3 The crystalline quality of the single crystal thin film is still high.
Example 3
This embodiment is a method of operating a mobile station in CH 3 NH 3 PbI 3 The method for patterning the surface of the single crystal film specifically comprises the following steps:
step 1, cutting a CD-ROM into a square with the size of 1cm multiplied by 1cm, sticking the CD-ROM by using a transparent adhesive tape, pulling off a protective layer of the CD, putting the exposed track recording layer into absolute ethyl alcohol to rinse away green organic dye on the surface, carrying out ultrasonic treatment for 15min, taking out, and drying by using nitrogen gas to obtain the grating structure master plate with the linear grooves.
And 2, weighing 10g of PDMS main agent, dripping 1g of curing agent, fully stirring, dripping on the optical track recording layer of the optical disc, putting the optical track recording layer into a hydrothermal oven, preserving heat at 60 ℃ for curing for 8 hours, and demoulding to obtain the PDMS-CD template printed with the linear groove structure of the optical track recording layer.
Step 3, taking 0.1271g CH in nitrogen atmosphere 3 NH 3 I and 0.3688g PbI 2 Placing in a 4ml reagent bottle, adding 1ml DMF as solvent, and stirring with magneton at 30 deg.C for 180min to obtain CH with concentration of 0.8mol/L 3 NH 3 PbI 3 Precursor solution;
step 4, adding 12ml of dimethyl dimethoxy silane and 600 mu L of sulfuric acid into 200ml of isopropanol, uniformly stirring, and standing for 30min to obtain a hydrophobic solution;
step 5, taking an electronic grade glass sheet of 5cm multiplied by 5cm, sequentially putting a cleaning agent, deionized water, acetone and isopropanol into the electronic grade glass sheet, performing ultrasonic treatment for 15min respectively, then soaking the electronic grade glass sheet in a hydrophobic solution, taking out the electronic grade glass sheet, naturally drying the electronic grade glass sheet, rinsing the substrate with ethanol, and drying the substrate in nitrogen to obtain a hydrophobic substrate;
step 6, placing the hydrophobic substrate on a heating table, and dripping 125 mu L of CH 3 NH 3 PbI 3 Inverting the precursor solution with another hydrophobic substrate, pressurizing to 6KPa, maintaining at 50 deg.C for 24 hr, and growing to obtain CH 3 NH 3 PbBr 3 A single crystal thin film.
Step 7, opening the upper hydrophobic substrate, and pressing the PDMS-CD template on the CH 3 NH 3 PbI 3 Applying 14KPa pressure on the monocrystalline film;
step 8, 5 μ L of CH 3 NH 3 PbI 3 Dripping the precursor solution at the edge of the PDMS template, sucking the precursor solution into the gap between the template and the single crystal through capillary action, keeping the temperature at 50 ℃ for 12h, and taking out the precursor solution after growth to obtain the patterned CH 3 NH 3 PbI 3 A single crystal thin film.
The prepared product is then subjected to analytical characterization, as shown in FIG. 11,Fig. 12 and 13 show the drawings. The results show that in CH, according to the method of example 3, the effect is achieved 3 NH 3 PbI 3 The surface pattern of the CD optical disk track recording layer on the surface of the single crystal film is completely re-etched, no obvious defect is seen in an SEM image, and an XRD chart shows CH after the surface is patterned 3 NH 3 PbI 3 The single crystal thin film still retains a crystalline quality close to that of a single crystal.
Example 4
This embodiment is a method of operating a mobile station in CH 3 NH 3 PbBr 3 The method for patterning the surface of the single crystal film and further preparing the photoelectric detector comprises the following steps:
step 1, cutting a CD-ROM into a square with the size of 1cm multiplied by 1cm, sticking the CD-ROM by using a transparent adhesive tape, pulling off a protective layer of the CD, putting the exposed track recording layer into absolute ethyl alcohol to rinse away green organic dye on the surface, carrying out ultrasonic treatment for 15min, taking out, and drying by using nitrogen gas to obtain the grating structure master plate with the linear grooves.
And 2, weighing 10g of PDMS main agent, dripping 1g of curing agent, fully stirring, dripping on the optical track recording layer of the optical disc, putting into a hydrothermal oven, preserving heat at 60 ℃, curing for 8 hours, and demoulding to obtain the PDMS-CD template printed with the linear groove structure of the optical track recording layer.
Step 3, in the nitrogen atmosphere, 0.08957g CH is taken 3 NH 3 Br and 0.2936g PbBr 2 Placing into a 4ml reagent bottle, adding 1ml DMF as solvent, stirring with magneton at 30 deg.C for 180min to obtain CH with concentration of 0.8mol/L 3 NH 3 PbBr 3 Precursor solution;
step 4, adding 12ml of dimethyl dimethoxy silane and 600 mu L of sulfuric acid into 200ml of isopropanol, uniformly stirring, and standing for 30min to obtain a hydrophobic solution;
step 5, taking 3cm × 3cm ITO electrode glass with a channel, wherein the channel is 50 microns, sequentially putting a cleaning agent, deionized water, acetone and isopropanol into the ITO electrode glass, performing ultrasonic treatment for 15min respectively, then soaking the ITO electrode glass in a hydrophobic solution, taking out the ITO electrode glass, naturally drying the ITO electrode glass, rinsing the substrate with ethanol, and drying the substrate in nitrogen to obtain a hydrophobic ITO substrate;
step 6, placing the hydrophobic ITO substrate on a heating table, and dropwise adding 125 mu L of CH 3 NH 3 PbBr 3 The precursor solution is inverted and covered by another hydrophobic ITO substrate, pressurized at 6KPa and kept at 50 ℃ for 24h, and CH is obtained after growth 3 NH 3 PbBr 3 A single crystal thin film.
Step 7, opening the upper hydrophobic substrate, and selecting a CH which is simultaneously contacted with two ITO electrodes 3 NH 3 PbBr 3 A single crystal thin film on which a PDMS-CD template is pressed and to which a pressure of 14KPa is applied;
step 8, adding 5 mu L of CH 3 NH 3 PbBr 3 Dripping the precursor solution at the edge of the PDMS template, sucking the precursor solution into the gap between the template and the single crystal through capillary action, keeping the temperature at 50 ℃ for 12h, and taking out the precursor solution after growth is finished to obtain the patterned CH-based material 3 NH 3 PbBr 3 A photodetector of a single crystal thin film.
The prepared photodetector devices were then characterized by electrical analysis, as shown in fig. 14 and 15. The results show that the patterning based CH was successfully prepared according to the method of example 4 3 NH 3 PbBr 3 A photodetector of a single crystal thin film. As can be seen, the detector has obvious light response characteristics, and can generate response to light of 300nm-560nm, and the external quantum efficiency is as high as 42% under the condition of 3V bias voltage.
The patterned perovskite monocrystal film prepared by the method has the advantages of good material crystallinity, controllable pattern size and shape and the like, and the method is simple in process, low in cost and generally suitable for various materials. In addition, the prepared patterned organic-inorganic hybrid perovskite single crystal film can be applied to a polarization photoelectric detector.
The foregoing illustrates and describes the principles, general features, and advantages of the present invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and the embodiments and descriptions are only illustrative of the principles of the invention, and any modifications, equivalents, improvements and the like within the spirit and scope of the invention should be included in the protection scope of the invention.

Claims (9)

1. A method for constructing surface patterning of an organic-inorganic hybrid perovskite single crystal thin film is characterized by comprising the following steps:
step 1, removing a protective layer of an optical disc, washing organic dye on the surface of a light path recording layer by using ethanol, and putting the light path recording layer into isopropanol for ultrasonic cleaning to obtain a grating structure template;
step 2, fully stirring the mixed polydimethylsiloxane PDMS main agent and curing agent, coating the mixture on a grating structure template, putting the grating structure template into a hydrothermal oven, drying, and demolding to obtain a PDMS template with a grating structure;
step 3, adding equimolar metal halide and methylamine halide in a solvent under the nitrogen atmosphere, and fully stirring to obtain an inorganic-inorganic hybrid perovskite precursor solution;
step 4, respectively cleaning the hard substrate with deionized water, acetone and isopropanol, and drying in a nitrogen atmosphere;
step 5, soaking the clean hard substrate obtained in the step 4 in a hydrophobic solution, taking out the substrate, naturally drying the substrate, washing the substrate by absolute ethyl alcohol, and drying the substrate by blowing with nitrogen to obtain a hydrophobic hard substrate;
step 6, placing the hydrophobic hard substrate on a heating table, dropwise adding an organic-inorganic hybrid perovskite precursor solution, reversely covering the hydrophobic hard substrate with another hydrophobic hard substrate, pressurizing and preserving heat for a certain time, and growing an organic-inorganic hybrid perovskite single crystal film between the substrates;
step 7, removing the upper layer of the hydrophobic hard substrate, exposing the metal halogen perovskite single crystal film, pressing the PDMS template on the single crystal film, and applying a certain pressure;
and 8, dripping a metal halogen perovskite precursor solution on the edge of the PDMS template, sucking the solution through capillary action, continuously preserving the temperature for a period of time, and obtaining the organic-inorganic hybrid perovskite single crystal film with the patterned surface after the growth is finished.
2. The method for constructing the surface patterning of the organic-inorganic hybrid perovskite single crystal film according to claim 1, wherein in the step 1, the CD-ROM and the DVD-ROM which are not erasable are selected as the optical disc, and the ultrasonic cleaning time of the optical recording layer is 15min to 20min.
3. The method for constructing the surface patterning of the organic-inorganic hybrid perovskite single crystal film according to claim 1, wherein the mixing mass ratio of the polydimethylsiloxane PDMS main agent to the curing agent in the step 2 is 10:1, setting the temperature of the hydrothermal oven at 60 ℃, and keeping the temperature for 8 hours.
4. The method for constructing the surface patterning of the organic-inorganic hybrid perovskite single crystal thin film according to claim 1, wherein the metal halide in step 3 is lead bromide or lead iodide, the methylamine halide is methylamine iodide or methylamine bromide, and the organic-inorganic hybrid perovskite is CH 3 NH 3 PbX 3 Wherein X is a halogen element I or Br; the solvent is N, N-dimethylformamide solution DMF, the concentration of the precursor solution is 0.8mol/L, the stirring temperature is 30 ℃, and the time is 3 hours.
5. The method for constructing the surface patterning of the organic-inorganic hybrid perovskite single crystal film according to claim 1, wherein the hard substrate in the step 4 is an electronic grade glass sheet or ITO glass, and the hard substrate is subjected to ultrasonic treatment for 15-20 min by deionized water, acetone and isopropanol respectively.
6. The method for constructing the surface patterning of the organic-inorganic hybrid perovskite single crystal thin film as claimed in claim 1, wherein the hydrophobic solution in the step 5 is prepared by adding 12mL of dimethyldimethoxysilane and 600 μ L of sulfuric acid into 200mL of isopropanol, stirring uniformly and then standing for 30 min.
7. The method for constructing the surface patterning of the organic-inorganic hybrid perovskite single crystal thin film according to claim 1, wherein the hydrophobic hard substrate is pressurized to 0kPa to 6kPa in step 6, the temperature is set to 45 ℃ to 55 ℃, and the heat preservation time is 24h to 30h.
8. The method for constructing the surface patterning of the organic-inorganic hybrid perovskite single crystal thin film according to claim 1, wherein the pressure applied between the PDMS template and the hydrophobic hard substrate in step 7 is in a range of 4kPa to 14kPa.
9. The method for constructing the surface patterning of the organic-inorganic hybrid perovskite single crystal film according to claim 1, wherein the temperature in the step 8 is 45-55 ℃ and the time for the temperature is 12-18 h.
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