CN114242797A - Flexible photoelectric detector based on ultrathin single crystal perovskite thin film and preparation method thereof - Google Patents

Flexible photoelectric detector based on ultrathin single crystal perovskite thin film and preparation method thereof Download PDF

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CN114242797A
CN114242797A CN202010926997.9A CN202010926997A CN114242797A CN 114242797 A CN114242797 A CN 114242797A CN 202010926997 A CN202010926997 A CN 202010926997A CN 114242797 A CN114242797 A CN 114242797A
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彭茹雯
景灏
王牧
王嘉楠
李成尧
何捷
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Nanjing University
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Abstract

The invention discloses a flexible photoelectric detector based on an ultrathin monocrystal perovskite thin film, which comprises a supporting layer, a composite structure with a spacing layer and an active layer and an electrode layer which are sequentially arranged from bottom to top; the supporting layer is a flexible organic substrate; the composite structure is configured to include a flexible mica flake and a single crystal perovskite thin film grown on a surface of the flexible mica flake. The invention further discloses a preparation method of the flexible photoelectric detector, which comprises the steps of preparing the flexible mica sheet by adopting a mechanical stripping method, growing the single crystal perovskite thin film on the surface of the flexible mica sheet by adopting a low-temperature solution method, and annealing to obtain the composite structure. The invention can realize the high-performance flexible monocrystal perovskite thin film photoelectric detector by utilizing the composite structure with the spacing layer and the active layer and the flexibility of the organic supporting layer.

Description

Flexible photoelectric detector based on ultrathin single crystal perovskite thin film and preparation method thereof
Technical Field
The invention belongs to the technical field of photoelectric detectors, and particularly relates to a flexible perovskite photoelectric detector based on an ultrathin single crystal perovskite thin film and a preparation method thereof.
Background
In the last decade, perovskite materials have gained much attention in the field of optoelectronic devices such as solar cells, light emitting diodes, photodetectors, etc., due to their excellent optoelectronic properties, including high absorption coefficient, long carrier lifetime, high carrier mobility, low defect state density, tunable band gap, etc. Meanwhile, the material can be rapidly prepared by a low-temperature solution method, and the preparation cost is low, so that the large-scale preparation of the photoelectric device based on the perovskite material becomes possible. The perovskite material can be prepared on the flexible substrate due to the characteristic of the low-temperature solution method, and therefore efficient flexible photoelectric devices are achieved. Among the flexible photoelectric devices, the flexible photoelectric detector is expected to be used in the fields of bionic devices, wearable equipment and the like as a basic photoelectric device.
To date, perovskite thin films prepared on flexible substrates by a solution method are usually polycrystalline thin films, but the polycrystalline perovskite thin films have more crystal grain boundaries, so that the carrier life and mobility of the polycrystalline perovskite thin films are lower than those of single crystal perovskite thin films, which undoubtedly limits the performance of flexible perovskite photodetectors; it has also been shown that polycrystalline perovskite thin films are more susceptible to moisture in the environment than monocrystalline perovskite thin films, and are subsequently deliquesced, thereby reducing the stability of the detector. However, there are still major difficulties in preparing large-sized high-quality single-crystal perovskite thin films on flexible substrates and manufacturing high-performance flexible photoelectric detection devices based on the thin films. On one hand, because the compatibility of the single crystal perovskite thin film with the traditional flexible substrate is poor, the preparation of the large-size (the side length of a crystal grain is more than 10 μm) high-quality single crystal perovskite thin film on the traditional flexible substrate such as thermoplastic Polyester (PET), polymethyl methacrylate (PMMA) and the like by using a solution method such as a one-step method, a two-step method and the like is difficult; on the other hand, in the "support layer (conventional flexible substrate) -active layer-electrode layer" structural system employed in the conventional perovskite thin film-based photodetector, an ultra-thin single crystal perovskite thin film is difficult to be prepared due to the limitation of its cubic crystal system crystal structure. At present, although there are some literature reports on methods for preparing large-sized single crystal perovskite thin films, these preparation methods often use conventional rigid substrates, such as mica sheets, graphite sheets, silicon wafers, sapphire sheets, glass sheets, and the like, and these substrate materials cannot be bent, thus having no conditions for preparing flexible photodetectors. Therefore, the above difficulties have limited the development of high performance flexible photodetectors based on single crystal perovskite thin films.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: how to prepare a large-size and high-quality ultrathin single crystal perovskite thin film on a flexible substrate by a low-temperature solution method and prepare a high-performance flexible photoelectric detector based on the single crystal perovskite thin film.
In order to solve the problems, the invention provides a flexible photoelectric detector based on an ultrathin monocrystal perovskite thin film and a preparation method thereof, and the specific technical scheme comprises the following steps:
the first scheme is as follows: a flexible photoelectric detector based on an ultrathin monocrystal perovskite thin film comprises a supporting layer, a composite structure with a spacing layer and an active layer and an electrode layer which are sequentially arranged from bottom to top; the supporting layer is a flexible organic substrate; the composite structure comprises a flexible mica sheet and a single crystal perovskite thin film growing on the surface of the flexible mica sheet, wherein the flexible mica sheet serving as a spacing layer is prepared by a mechanical stripping method and has a thickness of 10-100 mu m, and the single crystal perovskite thin film serving as an active layer is grown on the surface of the flexible mica sheet by a low-temperature solution method and has a thickness of 20-800 nm.
Preferably, the chemical composition of the single crystal perovskite thin film is methylamine lead bromide (MAPbBr)3) Single crystal, methylamine lead chloride (MAPbCl)3) Single crystal, methylamine lead iodide (MAPbI)3) Single crystal, formamidine lead bromide (FAPBR)3) Single crystal, formamidine lead chloride (FAPbCl)3) Single crystal, formamidine lead iodide (FAPbI)3) Single crystal, cesium lead bromide (CsPbBr)3) Single crystal, cesium lead chloride (CsPbCl)3) Single crystal, cesium lead iodide (CsPbI)3) Any one of single crystals.
Preferably, the flexible mica sheet is prepared from artificially synthesized fluorophlogopite sheets by a mechanical stripping method.
As a preferable scheme, the supporting layer is a flexible transparent polymer with the thickness of 30-2000 mu m.
As a preferred approach, the flexible transparent polymer includes, but is not limited to, one or more of thermoplastic polyesters including polyethylene terephthalate (PET) and polybutylene terephthalate (PBT), polymethyl methacrylate (PMMA), polyethylene, polycarbonate, polyurethane, epichlorohydrin resin, polyethylene naphthalate, polyimide, and polyacrylate.
As a preferable scheme, the thickness of the electrode layer is 30-100 nm; the electrode layer is made of a metal conductor, a nonmetal conductor or a composite material formed by any metal conductor and/or nonmetal conductor particles.
Preferably, the electrode layer is one of gold, silver, copper, aluminum, Indium Tin Oxide (ITO), or a combination thereof.
Scheme II: a method for making the flexible photodetector of scheme one, comprising:
processing rigid mica sheets with the thickness of more than 100 mu m into flexible mica sheets by adopting a mechanical stripping method; growing a single crystal perovskite thin film on the surface of a flexible mica sheet by adopting a low-temperature solution method, then annealing the flexible mica sheet to obtain a composite structure with a spacing layer and an active layer; preparing an electrode layer on the composite structure; fixing the flexible mica sheet with the prepared electrode layer on the cleaned support layer to obtain the flexible photoelectric detector;
alternatively, the first and second electrodes may be,
processing rigid mica sheets with the thickness of more than 100 mu m into flexible mica sheets by adopting a mechanical stripping method; securing the flexible mica flakes to the cleaned support layer; growing a single crystal perovskite thin film on the surface of a flexible mica sheet by adopting a low-temperature solution method, then annealing the flexible mica sheet to obtain a composite structure with a spacing layer and an active layer; preparing an electrode layer on the composite structure to obtain the flexible photoelectric detector;
alternatively, the first and second electrodes may be,
processing rigid mica sheets with the thickness of more than 100 mu m into flexible mica sheets by adopting a mechanical stripping method; growing a single crystal perovskite thin film on the surface of a flexible mica sheet by adopting a low-temperature solution method, then annealing the flexible mica sheet to obtain a composite structure with a spacing layer and an active layer; fixing the prepared flexible mica sheet with the composite structure on the cleaned supporting layer; preparing an electrode layer on the composite structure to obtain the flexible photoelectric detector;
the annealing temperature is 25-35 ℃, and the annealing time is 10-30 hours.
As a preferred scheme, a low-temperature solution method is adopted to grow the single crystal perovskite thin film on the surface of the flexible mica sheet, and the method specifically comprises the following steps: firstly, covering a perovskite precursor solution on the surface of a flexible mica sheet, then tightly covering one surface of the flexible mica sheet covered with the perovskite precursor solution with a cover plate, then carrying out annealing treatment, and taking down the flexible mica sheet from the cover plate after annealing to obtain a composite structure with a spacing layer and an active layer; the cover plate is any one of a flexible mica sheet, a rigid mica sheet, a graphite sheet, a silicon wafer, a sapphire sheet and a glass sheet.
As a preferred embodiment, the perovskite is pre-perovskiteThe solute in the precursor solution is methylamine lead bromide (MAPbBr)3) Methylamine lead chloride (MAPbCl)3) Methylamine lead iodide (MAPbI)3) Lead formamidine bromide (FAPBR)3) Formamidine lead chloride (FAPBCl)3) Lead formamidine iodide (FAPBI)3) Cesium lead bromide (CsPbBr)3) Cesium lead chloride (CsPbCl)3) Cesium lead iodide (CsPbI)3) Any one of the above; the solvent is N, N-Dimethylformamide (DMF), bromic acid (HBrO)3) Any one of the above; the concentration of the solution is 0.4-1.0 mol/L.
As a preferred scheme, an electrode layer is prepared on the composite structure by combining a silicon mask technology and a coating technology, wherein the coating technology can be any one of electron beam evaporation coating, thermal evaporation coating, magnetron sputtering coating and Plasma Enhanced Chemical Vapor Deposition (PECVD) coating; the deposition rate of the coating film is
Figure BDA0002668768730000031
As a preferred scheme, at least two of the prepared electrode structures are in direct contact with the single crystal perovskite thin film; when the electrode structure is prepared, the central position of the hollow area of the silicon mask is adjusted to be aligned with the central position of the composite structure, so that the single crystal perovskite film is positioned under the silicon mask.
As a preferable scheme, the cleaning method of the supporting layer comprises the following steps: firstly, a clean wiping cloth is used for preliminarily cleaning a supporting layer; then immersing the supporting layer into deionized water cleaning liquid, and placing the supporting layer into an ultrasonic cleaning machine for ultrasonic cleaning for 10-30 minutes; the support layer was then removed and blown dry with clean nitrogen.
Preferably, the composite structure is fixedly connected to the support layer by means of an adhesive tape or an adhesive.
The invention has the following beneficial effects:
(1) compared with a structure system of a support layer (a traditional flexible substrate), an active layer and an electrode layer adopted by a traditional perovskite thin film-based photoelectric detector, the flexible mica thin sheet (the thickness is less than 100 mu m) is innovatively introduced to serve as a spacing layer between the flexible substrate and a single crystal perovskite thin film, and a structure system of the support layer (the traditional flexible substrate), a composite structure with the spacing layer and the active layer and the electrode layer is provided.
(2) According to the invention, the traditional rigid mica sheet substrate is prepared into the flexible mica sheet by adopting a mechanical stripping method, and the flexible mica sheet is used as the large-size high-quality ultrathin monocrystal perovskite film to prepare the excellent growth substrate, and the substrate has excellent wettability and an atomically flat surface, so that the difficulty that the large-size high-quality monocrystal perovskite film is difficult to prepare on the traditional flexible substrate is solved.
(3) The invention adopts a mechanical stripping method to process the traditional rigid mica sheet into the flexible mica sheet, the preparation process is simple and convenient, and the price is lower because the artificially synthesized fluorophlogopite sheet can be selected.
(4) The single crystal perovskite thin film is prepared on the flexible mica sheet growth substrate by a method of slowly heating and annealing a precursor solution, and the growth process is simple and convenient; the precursor solution used for preparing the single crystal perovskite film is an ionic material, and the raw material is rich; the annealing temperature is only about 30 ℃, the preparation cost is low, and the method is beneficial to large-scale production.
(5) The perovskite thin film prepared by the growth method is an ultrathin monocrystal perovskite thin film, has the characteristics of high crystal quality, large specific surface area and smooth surface, has excellent photoelectric conversion property, and is an excellent active layer which can be used as a high-performance flexible photoelectric detector.
Drawings
In fig. 1: (a) the flexible photoelectric detector provided by the embodiment of the invention has a schematic structural diagram in an unbent state (namely, a flat state); (b) the flexible photoelectric detector provided by the embodiment of the invention has a structural schematic diagram and an external circuit schematic diagram in a bending state; (c) optical micrographs of the device as a whole (scale bar in the figure represents 100 μm); (d) scanning electron micrographs (scale represents 10 μm in the figure) of the photodetecting sites of the device.
Note: in the flexible photoelectric detection device shown in fig. 1(c) and 1(d), the electrode structure provided on the ultrathin single-crystal perovskite thin film contains six conductive strips in total, and only two of them need to be selected to be connected to an external circuit when photoelectric detection is performed.
The attached drawings are marked as follows: 1-supporting layer, 2-flexible mica sheet, 3-single crystal perovskite thin film and 4-electrode.
In fig. 2: (a) is a flow chart of a manufacturing process of the flexible photoelectric detector; (b) another manufacturing process flow diagram of the flexible photoelectric detector; (c) still another process flow diagram for the fabrication of a flexible photodetector.
In fig. 3: (a) is a photograph of the sample with the flexible photodetector in an unbent state (i.e., flat state); (b) a photocurrent response volt-ampere characteristic curve of the photoelectric detector in a flat state is obtained; (c) a photocurrent response switch curve of the photoelectric detector in a flat state; (d) the picture of the sample when the flexible photoelectric detector is in a bending state; (e) a photocurrent response volt-ampere characteristic curve of the photoelectric detector in a bending state is obtained; (f) the switching curve is responded to the photocurrent of the photodetector in the bending state.
In fig. 4: (a) the flexible photoelectric detector composed of a single crystal perovskite thin film with the thickness of 20nm responds to a volt-ampere characteristic curve of photocurrent and dark current under a bending condition. (b) The flexible photoelectric detector composed of 200nm thick monocrystal perovskite thin film responds to the current-voltage characteristic curve of photocurrent and dark current under the bending condition. (c) The flexible photoelectric detector composed of the 800nm thick monocrystal perovskite thin film responds to a volt-ampere characteristic curve of photocurrent and dark current under a bending condition.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
Referring to fig. 1, the invention discloses a flexible photoelectric detector (referred to as "flexible photoelectric detector") based on a flexible mica sheet-ultrathin single crystal perovskite thin film composite structure. The flexible photoelectric detector sequentially comprises a supporting layer, a composite structure (called composite structure for short) with a spacing layer and an active layer and an electrode layer from bottom to top.
The support layer is a flexible organic substrate, which is also commonly called a "flexible organic material film" or an "organic support layer," and may be one or a combination of organic materials such as PET, PMMA, polyethylene, and the like, for example; the thickness is 30 to 2000 μm.
In the composite structure, the spacing layer is a flexible mica sheet with the thickness of 10-100 mu m, and a single crystal perovskite thin film serving as an active layer is prepared on the spacing layer and has the thickness of 20-800 nm.
The electrode layer is made of a conductive material with high conductivity, for example, the electrode layer can be made of any one or a combination of conductive materials with high conductivity such as gold, silver, copper, aluminum, Indium Tin Oxide (ITO), and the thickness of the conductive material is 30-100 nm. The central region of the electrode pattern is typically disposed directly above the composite structure, but is not so limited.
The flexible mica sheet is prepared by a mechanical stripping method, has an atomically flat surface and excellent wettability, solves the problem that a single crystal perovskite thin film is poor in compatibility with a traditional flexible substrate, and can be used as a large-size high-quality ultrathin single crystal perovskite thin film to prepare an excellent growth substrate. Furthermore, when the thickness of the mica flake is controlled to be between 10 and 100 mu m, the mica flake also has good flexibility and bending stability. Therefore, the mica sheet is used as a supporting layer and a spacing layer of the single crystal perovskite thin film, the problem that the compatibility of the single crystal perovskite thin film and the traditional flexible substrate is poor is solved, meanwhile, the good bending stability is kept, and the mica sheet can be used for preparing a high-performance flexible photoelectric detector. Preferably, the rigid mica plate used can be a synthetic fluorphlogopite mica plate, and the cost of the mica plate is lower.
Referring to fig. 2(a), the method for manufacturing a flexible photodetector disclosed by the present invention mainly includes the following steps:
step one, cleaning an organic supporting layer: firstly, cleaning an organic supporting layer by using clean wiping cloth such as non-woven fabric, dust-free paper, mirror wiping paper and the like; then immersing the organic supporting layer into deionized water cleaning liquid, and placing the organic supporting layer into an ultrasonic cleaning machine for ultrasonic cleaning for 10-30 minutes; the organic support layer was then removed and blown dry with clean nitrogen.
Here, the purpose of cleaning the organic supporting layer is mainly to remove large-sized impurities (e.g., dust, plastic particles, etc.) on the surface thereof, so that the composite structure of the spacer layer-active layer is more firmly fixed on the organic supporting layer, thereby improving the stability of the flexible photodetector during the bending process.
Step two, preparing the flexible mica sheet by adopting a mechanical stripping method: a rigid mica sheet (usually 100 to 1000 μm) having a thickness of more than 100 μm is processed into a flexible mica sheet by a mechanical peeling method and used as a growth substrate of a single crystal perovskite, and thus the flexible mica sheet is also called a "flexible mica substrate".
Based on the two-dimensional layered structure characteristic of the mica sheet, the mica sheet can be processed into a flexible mica sheet with the thickness of less than 100 mu m by adopting a mechanical stripping method. The scheme of preparing the flexible mica sheet by adopting a mechanical stripping method can be that the rigid mica sheet is repeatedly pasted and torn by using an adhesive tape; or a thin blade, a sharp-pointed forceps or a thin needle can be used for directly cutting from the side edge of the rigid mica sheet for stripping and the like. It should be noted that the preparation of the flexible mica flake is not limited to the above scheme, as long as the rigid mica flake is processed into a flake with a thickness of less than 100 μm by mechanical peeling, and the flake has good flexibility and bending stability.
Growing an ultrathin monocrystal perovskite thin film on the flexible mica sheet by using a low-temperature solution method: uniformly dripping a perovskite precursor solution with the concentration of 0.4-1.0 mol/L on a flexible mica substrate to enable the surface of the flexible mica substrate to be covered with a layer of perovskite precursor solution, tightly covering a cover plate on the flexible mica sheet dripped with the precursor solution, and then carrying out annealing treatment, wherein the annealing temperature is 25-35 ℃, and the annealing time is 10-30 hours. The perovskite thin film grown by the annealing process has good single crystal property and ultrathin property, and the thickness of the grown single crystal perovskite thin film is influenced by the selection of different annealing temperatures and annealing times. And after annealing, taking the flexible mica sheet down from the cover sheet to obtain the single crystal perovskite thin film with the thickness of 20-800 nm, and thus, preparing the composite structure with the spacing layer and the active layer.
Wherein the solute in the perovskite precursor solution can be methylamine lead bromide (MAPbBr)3) Methylamine lead chloride (MAPbCl)3) Methylamine lead iodide (MAPbI)3)、Formamidine lead bromide (FAPBR)3) Formamidine lead chloride (FAPBCl)3) Lead formamidine iodide (FAPBI)3) Cesium lead bromide (CsPbBr)3) Cesium lead chloride (CsPbCl)3) Cesium lead iodide (CsPbI)3) Any one of the above; the solvent is N, N-Dimethylformamide (DMF), bromic acid (HBrO)3) Any one of the above; the concentration of the solution is 0.4-1.0 mol/L. The chemical component of the ultrathin perovskite film grown based on the perovskite precursor solution is MAPbBr3Single crystal, MAPbCl3Single crystal, MAPbI3Single crystal, FAPBR3Single crystal, FAPbCl3Single crystal, FAPbI3Single crystal CsPbBr3Single crystal CsPbCl3Single crystal, CsPbI3Any one of single crystals.
The cover plate is a smooth flexible or rigid material with good wettability, and the cover plate can be a flexible mica sheet prepared by the method in the step two, or a rigid mica sheet, a graphite sheet, a silicon wafer, a sapphire sheet, a glass sheet and the like; however, the conventional flexible substrate material cannot be used as a cover sheet, such as PET, PMMA, etc., because of its poor wettability.
It should be noted that, compared with the annealing schemes of high temperature (110-130 ℃) and short time (12-18 min) reported in other documents, the annealing process of the invention adopts a lower temperature and a long time, and aims to ensure that the perovskite single crystal is always in a quasi-static growth process, so that the grown perovskite thin film has good single crystal property and ultrathin (thickness of 20-800 nm) property, thereby being beneficial to realizing a high-performance flexible photodetector.
Step four, preparing an electrode structure by combining a silicon mask technology with a coating technology: preparing an electrode structure on the composite structure obtained in the step three by utilizing a silicon mask technology and a coating technology, wherein the deposition rate is
Figure BDA0002668768730000071
The thickness is 30 to 100 nm.
The coating technology can be any one of electron beam evaporation coating, thermal evaporation coating, magnetron sputtering coating and Plasma Enhanced Chemical Vapor Deposition (PECVD) coating. When the electrode structure is prepared by combining the silicon mask technology with the film coating technology, the central position of the hollow area of the silicon mask plate and the central position of the composite structure are adjusted to be aligned, namely, the single crystal perovskite film is positioned right below the silicon mask plate. And setting the pattern of the hollow area of the silicon mask plate into the shape of the required electrode according to actual requirements. In the actual preparation process of the electrode structure, in order to reduce the influence of the position offset of the electrode structure caused by the positioning error of the silicon mask, the electrode structure with a plurality of conductive strips (as shown in fig. 1(c) and (d), a total of 6 electrode strips are arranged) can be prepared at one time, so as to ensure that at least 2 electrode strips are in direct contact with the composite structure obtained in the third step; when photoelectric detection is performed, it is generally only necessary to arbitrarily select 2 of the electrode strips in direct contact with the composite structure to be connected to an external circuit.
And fifthly, fixing the composite structure with the prepared electrode structure on an organic supporting layer to obtain the flexible single crystal perovskite photoelectric detector. The fixing method can be adhesive tape fixing or adhesive fixing. The adhesive tape can be cloth adhesive tape or plastic adhesive tape coated with adhesive rubber; the adhesive can be one or a combination of flexible organic adhesives such as acrylic resin, polyimide resin, epoxy resin and the like.
It should be noted that the above steps are not in a strict order. As shown in fig. 2(b), the flexible mica sheet may be fixed on the organic supporting layer, and then the growth of the single crystal perovskite thin film and the preparation of the electrode may be performed; as shown in fig. c, the flexible mica sheet with the single crystal perovskite thin film prepared may be fixed on the organic support layer, and then the electrode may be prepared. But is not limited thereto as long as the composite structure is finally fixed on the organic support layer and the electrode is disposed above the composite structure.
The following detailed description of the embodiments of the present invention is provided with reference to the drawings, and the embodiments are implemented on the premise of the technical solution of the present invention, and the detailed embodiments and the specific operation procedures are provided, but the protection scope of the present invention is not limited to the following embodiments.
As shown in FIG. 1, example 1 disclosesA flexible photoelectric detector is composed of flexible organic PET, flexible mica sheet spacer layer and single crystal perovskite MAPBBr3A composite structure composed of thin films, and a gold (Au) electrode layer above the thin films. The preparation method comprises the following specific steps:
the method comprises the following steps of firstly, repeatedly wiping a PET organic supporting layer by using non-woven fabric dipped with ethanol to remove large-size impurities on the surface of the PET organic supporting layer, such as dust, plastic particles and the like; then, the organic supporting layer is immersed in deionized water, and is taken out after ultrasonic cleaning is carried out for about 15 minutes; and finally blowing the glass fiber reinforced plastic film by using clean nitrogen.
And secondly, mechanically stripping the rigid mica sheet, wherein the specific process is as follows: fixing one surface of an artificially synthesized fluoraurum white mica sheet with the thickness of 0.1mm on an adhesive tape, sticking the other surface of the mica sheet by using another adhesive tape, and stripping; the flexible mica sheet is formed by repeatedly peeling until the thickness of the mica sheet is peeled to about 30 μm.
Third, 6 μ L of MAPbBr was dissolved3Dropwise adding an N, N-Dimethylformamide (DMF) precursor solution (with the concentration of 0.8mol/L) onto the stripped flexible mica sheet; then, covering a silicon chip above the flexible mica sheet dripped with the precursor solution; then placing the flexible mica sheet dripped with the precursor solution on a heating plate, heating to 30 ℃, and annealing for 15 hours to prepare single crystal MAPBBr with the thickness of about 20nm on the mica sheet3A perovskite thin film.
Fourthly, the flexible mica flake-single crystal MAPbBr is added3The composite structure of the perovskite film is fixed on a three-dimensional displacement table with a silicon mask, the hollow area of the silicon mask is set to be in the shape of an electrode shown in figure 1(c), and the composite structure is positioned right below the silicon mask; then, putting the film into a high vacuum electron beam evaporation coating system; then preparing Au electrode by electron beam evaporation, and controlling the evaporation rate
Figure BDA0002668768730000091
The vapor deposition time is about 1200 seconds, and the air pressure of the vacuum chamber is kept at 1 multiplied by 10 during the vapor deposition-6Near Torr(ii) a By adopting the method, the Au electrode with the thickness of about 60nm can be prepared above the composite structure.
And fifthly, fixing the composite structure with the prepared Au electrode above the PET supporting layer through an adhesive tape.
Fig. 3(a) shows a photograph of a sample when the flexible photodetector is in an unbent state (i.e., flat state). FIG. 3(b) shows the current-voltage characteristic curve of the photocurrent response of the flexible photodetector in the unbent condition, wherein the applied bias voltage is in the range of-2V to 2V, and the irradiated light is laser light with a wavelength of 514nm and a power density of 0.2mW/cm2. It can be seen that the detected current gradually increases with increasing bias voltage, which can be up to 10 at-2V or 2V-7A is above. FIG. 3(c) shows the photocurrent response switch curve of the flexible photoelectric detector under the unbent condition, the bias voltage is kept 2V, and the irradiated light has a power density of 0.2mW/cm2The modulation frequency of the laser light of 514nm is 5 Hz. It can be seen that with the periodic modulation of the incident light, the current output by the detector exhibits the characteristics of a periodic switch, which can reach 140nA in the case of illumination. The above results show the remarkable photodetection characteristics of the photodetector.
Fig. 3(d) shows a photograph of the sample with the flexible photodetector in a bent state. FIG. 3(e) shows the current-voltage characteristic curve of the photocurrent response of a flexible photodetector in a bent condition, wherein the curvature radius of the bend of the photodetector is about 12mm, the applied bias voltage is in the range of-2V to 2V, and the irradiated light is laser light having a wavelength of 514nm and a power density of 0.2mW/cm2. It can be seen that the photocurrent response of the photodetector in the bent condition shows substantially the same characteristics as the photocurrent response voltammogram in the unbent condition of fig. 3 (a). The above results show that the photocurrent response current-voltage characteristic of the flexible photodetector hardly changes with the bending of the detector. FIG. 3(f) shows the photocurrent response switch curve of the flexible photoelectric detector under bending condition, the bias voltage is kept 2V, and the irradiated light has power density of 0.2mW/cm2The modulation frequency of the laser light of 514nm is 5 Hz. Can see ifThe same bending condition is adopted, the current output by the detector also shows good periodic switching characteristics, and the current can still reach 140nA under the irradiation condition, and the result shows that the photocurrent response of the flexible photoelectric detector in the invention does not change along with the bending of the detector.
The experimental result of example 1 illustrates that the flexible photodetector of the present invention maintains substantially the same photodetection properties in both the non-bent state and the bent state, and proves that the flexible photodetector has good photodetection properties and bending stability.
Example 2 gives single crystal MAPbBr with 3 different thicknesses3The thicknesses of the flexible photodetectors of the perovskite thin film were 20nm, 200nm, and 800nm, respectively, and the other structures and parameters were the same as in example 1.
Based on the results of example 1, which demonstrates that the photocurrent response voltammetric characteristics of the flexible photodetector of the present invention hardly changed with the bending of the detector, the present example characterizes single crystal MAPbBr of different thickness3The flexible photodetector of perovskite film has the photoelectric detection performance in a bending state. FIG. 4(a) shows photocurrent and dark current response current-voltage characteristic curves of a flexible photodetector composed of a 20nm thick single crystal perovskite thin film under bending conditions; FIG. 4(b) shows the photocurrent and dark current response current-voltage characteristic curves of a flexible photodetector composed of a 200nm thick single crystal perovskite thin film under a bending condition; fig. 4(c) shows the photocurrent and dark current response current voltage characteristic curves of a flexible photodetector composed of a single crystal perovskite thin film with the thickness of 800nm under a bending condition. Wherein the applied bias voltage is fixed in the range of-1V to 1V, and the irradiated light is a broadband halogen lamp having a power density of 10.5mW/cm2. It can be seen that under the irradiation of the halogen lamp, single crystal MAPbBr with different thicknesses3The dark current response of the flexible photoelectric detector of the perovskite thin film is not greatly influenced by the thickness of the single crystal perovskite thin film, the photocurrent response is increased along with the increase of the thickness of the single crystal perovskite thin film, and when the thickness of the single crystal perovskite thin film is more than 200nm, the photocurrent response of the single crystal perovskite thin film tends to be saturated; that is, when the thickness of the single crystal perovskite thin film is in the range of 200nm to 800nmWhen the flexible photoelectric detector is used, under the illumination condition of the broadband halogen lamp, the photocurrent response of the flexible photoelectric detector is hardly influenced by the thickness of the single crystal perovskite thin film.
The results of example 2 demonstrate that the flexible photodetectors having different single crystal perovskite thin film thicknesses all exhibit significant photocurrent responses, and the photocurrent response voltammetry characteristics of the flexible photodetectors can change with changes in thickness of the perovskite thin film when the single crystal perovskite thin film thickness is between 20nm and 200 nm. When the thickness of the single crystal perovskite thin film is between 200nm and 800nm, under the illumination condition of a broadband halogen lamp, the photocurrent response volt-ampere characteristic of the flexible photoelectric detector shows a saturation property and is hardly influenced by the thickness of the single crystal perovskite thin film; meanwhile, the dark current response volt-ampere characteristic of the flexible photoelectric detector is not greatly influenced by the thickness of the single crystal perovskite thin film (the thickness of the single crystal perovskite thin film is in the range of 20 nm-800 nm).
In summary, the invention provides a flexible photoelectric detector based on a flexible mica sheet-ultrathin single crystal perovskite thin film composite structure, which has good flexibility and bending stability by utilizing the composite structure with a spacing layer and an active layer and the flexibility of an organic supporting layer, shows obvious photoelectric detection response in a non-bending state and a bending state, and can be widely used in the fields of wearable sensing devices, flexible intelligent equipment, optical communication, integrated photoelectric detection and the like.
Finally, it should be noted that the above-mentioned embodiments are only preferred embodiments of the present invention, and are not intended to limit the present invention, and those skilled in the art can make various modifications and changes. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (14)

1. A flexible photoelectric detector based on an ultrathin monocrystal perovskite thin film is characterized by comprising a supporting layer, a composite structure with a spacing layer and an active layer and an electrode layer which are sequentially arranged from bottom to top; the supporting layer is a flexible organic substrate; the composite structure comprises a flexible mica sheet and a single crystal perovskite thin film growing on the surface of the flexible mica sheet, wherein the flexible mica sheet serving as a spacing layer is prepared by a mechanical stripping method and has a thickness of 10-100 mu m, and the single crystal perovskite thin film serving as an active layer is grown on the surface of the flexible mica sheet by a low-temperature solution method and has a thickness of 20-800 nm.
2. The flexible photodetector of claim 1, wherein the chemical composition of the single crystal perovskite thin film is any one of methylamine lead bromide single crystal, methylamine lead chloride single crystal, methylamine lead iodide single crystal, formamidine lead bromide single crystal, formamidine lead chloride single crystal, formamidine lead iodide single crystal, cesium lead bromide single crystal, cesium lead chloride single crystal, and cesium lead iodide single crystal.
3. The flexible photodetector of claim 1, wherein the flexible mica flakes are fabricated from synthetic fluorphlogopite flakes by a mechanical exfoliation method.
4. The flexible photodetector of claim 1, wherein said support layer is a flexible transparent polymer; the thickness of the supporting layer is 30-2000 mu m.
5. The flexible photodetector of claim 4, wherein said flexible transparent polymer includes, but is not limited to, one or more of polyethylene terephthalate, polybutylene terephthalate, polymethyl methacrylate, polyethylene, polycarbonate, polyurethane, epichlorohydrin resins, polyethylene naphthalate, polyimide, and polyacrylate.
6. The flexible photodetector of claim 1, wherein the thickness of the electrode layer is 30 to 100 nm; the electrode layer is made of a metal conductor, a nonmetal conductor or a composite material formed by any metal conductor and/or nonmetal conductor particles.
7. The flexible photodetector of claim 6, wherein said electrode layer is one of gold, silver, copper, aluminum, indium tin oxide, or combinations thereof.
8. A method for preparing a flexible photodetector according to any one of claims 1 to 7, comprising:
processing rigid mica sheets with the thickness of more than 100 mu m into flexible mica sheets by adopting a mechanical stripping method; growing a single crystal perovskite thin film on the surface of a flexible mica sheet by adopting a low-temperature solution method, and annealing to obtain a composite structure with a spacing layer and an active layer; preparing an electrode layer on the composite structure; fixing the flexible mica sheet with the prepared electrode layer on the cleaned support layer to obtain the flexible photoelectric detector;
alternatively, the first and second electrodes may be,
processing rigid mica sheets with the thickness of more than 100 mu m into flexible mica sheets by adopting a mechanical stripping method; securing the flexible mica flakes to the cleaned support layer; growing a single crystal perovskite thin film on the surface of a flexible mica sheet by adopting a low-temperature solution method, and annealing to obtain a composite structure with a spacing layer and an active layer; preparing an electrode layer on the composite structure to obtain the flexible photoelectric detector;
alternatively, the first and second electrodes may be,
processing rigid mica sheets with the thickness of more than 100 mu m into flexible mica sheets by adopting a mechanical stripping method; growing a single crystal perovskite thin film on the surface of a flexible mica sheet by adopting a low-temperature solution method, and annealing to obtain a composite structure with a spacing layer and an active layer; fixing the prepared flexible mica sheet with the composite structure on the cleaned supporting layer;
preparing an electrode layer on the composite structure to obtain the flexible photoelectric detector;
the annealing temperature is 25-35 ℃, and the annealing time is 10-30 hours.
9. The method according to claim 8, wherein the growing of the single crystal perovskite thin film on the surface of the flexible mica thin sheet by using a low-temperature solution method comprises the following specific steps: firstly, covering a layer of perovskite precursor solution on the surface of a flexible mica sheet, covering the perovskite precursor solution with a cover plate, then carrying out annealing treatment, and taking down the flexible mica sheet from the cover plate after annealing to obtain a composite structure with a spacing layer and an active layer; the cover plate is any one of a flexible mica sheet, a rigid mica sheet, a graphite sheet, a silicon wafer, a sapphire sheet and a glass sheet.
10. The method of claim 9, wherein the solute in the perovskite precursor solution is any one of methylamine lead bromide, methylamine lead chloride, methylamine lead iodide, formamidine lead bromide, formamidine lead chloride, formamidine lead iodide, cesium lead bromide, cesium lead chloride, cesium lead iodide; the solvent is any one of N, N-dimethylformamide and bromic acid; the concentration of the solution is 0.4-1.0 mol/L.
11. The method of claim 8, wherein an electrode layer is prepared on the composite structure by combining a silicon mask technique and a coating technique, wherein the coating technique is any one of electron beam evaporation coating, thermal evaporation coating, magnetron sputtering coating, plasma enhanced chemical vapor deposition coating; the deposition rate of the coating film is
Figure FDA0002668768720000021
12. The method according to claim 8, wherein at least two electrode structures are prepared in contact with the single crystal perovskite thin film; when the electrode structure is prepared, the central position of the hollow area of the silicon mask is adjusted to be aligned with the central position of the composite structure, so that the single crystal perovskite film is positioned under the silicon mask.
13. The method of claim 8, wherein the cleaning of the support layer comprises: firstly, a clean wiping cloth is used for preliminarily cleaning a supporting layer; then immersing the supporting layer into deionized water cleaning liquid, and placing the supporting layer into an ultrasonic cleaning machine for ultrasonic cleaning for 10-30 minutes; the support layer was then removed and blown dry with clean nitrogen.
14. The method of claim 8, wherein the composite structure is fixedly attached to the support layer by an adhesive tape or an adhesive.
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