CN114242797B - Flexible photoelectric detector based on ultrathin monocrystalline perovskite film and preparation method thereof - Google Patents
Flexible photoelectric detector based on ultrathin monocrystalline perovskite film and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a flexible photoelectric detector based on an ultrathin monocrystal perovskite film, which comprises a supporting layer, a composite structure with a spacing layer and an active layer and an electrode layer, wherein the supporting layer, the composite structure with a spacing layer and an active layer and the electrode layer are sequentially arranged from bottom to top; the supporting layer is a flexible organic substrate; the composite structure is configured to include flexible mica platelets and a single crystal perovskite film grown on the surface of the flexible mica platelets. The invention further discloses a preparation method of the flexible photoelectric detector, a mechanical stripping method is adopted to prepare a flexible mica sheet, a low-temperature solution method is adopted to grow a single crystal perovskite film on the surface of the flexible mica sheet, and a composite structure is obtained after annealing treatment. The invention can realize the flexible single crystal perovskite film photoelectric detector with high performance by utilizing the composite structure with the spacing layer and the active layer and the flexibility of the organic supporting layer.
Description
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 film and a preparation method thereof.
Background
In the past decade, perovskite materials have gained attention in the field of photovoltaic devices such as solar cells, light emitting diodes, photodetectors, and the like, due to their excellent photovoltaic properties, including high absorption coefficient, long carrier lifetime, high carrier mobility, low defect state density, tunable band gap, and the like. Meanwhile, the material can be rapidly prepared by a low-temperature solution method, and the preparation cost is low, so that large-scale preparation of photoelectric devices based on perovskite materials becomes possible. The perovskite material can be prepared on the flexible substrate due to the characteristic of low-temperature solution preparation, so that an efficient flexible photoelectric device is realized. Among these flexible photoelectric devices, the flexible photoelectric detector is expected to be used in the fields of bionic devices, wearable devices and the like as a type of basic photoelectric device.
Heretofore, perovskite thin films prepared on flexible substrates by solution methods have been generally polycrystalline thin films, but these polycrystalline perovskite thin films have more grain boundaries, so that the polycrystalline perovskite thin films have lower carrier lives and mobilities than single crystal perovskite thin films, which undoubtedly limits the performance of flexible perovskite photodetectors; it has also been shown that polycrystalline perovskite films are more susceptible to environmental moisture than single crystal perovskite films and are therefore deliquesced, thereby reducing the stability of the detector. However, there are still great difficulties in preparing high-quality single crystal perovskite thin films of large size on flexible substrates, and fabricating high-performance flexible photodetector devices based on the thin films. On the one hand, because the single crystal perovskite thin film is generally poor in compatibility with the traditional flexible substrate, the solution method such as a one-step method, a two-step method and the like is used for preparing the high-quality single crystal perovskite thin film with large size (the grain side length is longer than 10 mu m) on the traditional flexible substrate such as thermoplastic polyester (Polyethylene terephthalate, PET), polymethyl methacrylate (polymethyl methacrylate, PMMA) and the like; on the other hand, in the "support layer (conventional flexible substrate) -active layer-electrode layer" structure system employed in the conventional perovskite thin film-based photodetector, the ultrathin single crystal perovskite thin film is difficult to be prepared due to the limitation of its cubic crystal structure. At present, although there are some reports about large-size single crystal perovskite thin film preparation methods, these preparation methods often use conventional rigid substrates, such as mica sheets, graphite sheets, silicon sheets, sapphire sheets, glass sheets, etc., which cannot be bent, and thus do not have the conditions for preparing flexible photodetectors. Thus, the above-described difficulties limit the development of high-performance flexible photodetectors based on single crystal perovskite thin films.
Disclosure of Invention
The technical problems to be solved by the invention are as follows: how to prepare a large-size and high-quality ultrathin single crystal perovskite 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 film.
In order to solve the problems, the invention provides a flexible photoelectric detector based on an ultrathin single crystal perovskite film and a preparation method thereof, and the specific technical scheme comprises the following steps:
scheme one: a flexible photoelectric detector based on an ultrathin single crystal perovskite 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 is constructed to comprise a flexible mica sheet and a single crystal perovskite film grown on the surface of the flexible mica sheet, wherein the flexible mica sheet serving as a spacing layer is prepared by adopting a mechanical stripping method, the thickness of the flexible mica sheet is 10-100 mu m, and the single crystal perovskite film serving as an active layer is grown on the surface of the flexible mica sheet by adopting a low-temperature solution method, and the thickness of the single crystal perovskite film serving as the active layer is 20-800 nm.
As a preferable scheme, the chemical component of the single crystal perovskite film is lead methylamine bromide (MAPbBr) 3 ) Single crystal, methylamine lead chloride (MAPbCl) 3 ) Single crystal, methylamine lead iodide (MAPbI) 3 ) Single crystal, formamidine lead bromide (FAPbBr) 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 ) Monocrystal, cesium lead iodine (CsPbI) 3 ) Any one of single crystals.
As a preferable scheme, the flexible mica flake is prepared from artificially synthesized fluorophlogopite flakes by a mechanical stripping method.
Preferably, the supporting layer is a flexible transparent polymer with a thickness of 30-2000 μm.
As a preferred embodiment, 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, chloroether resin, polyethylene naphthalate, polyimide, and polyacrylate.
As a preferable mode, 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.
As a preferred embodiment, 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 the rigid mica sheet with the thickness of more than 100 mu m into a flexible mica sheet by adopting a mechanical stripping method; growing a monocrystalline perovskite film on the surface of a flexible mica sheet by adopting a low-temperature solution method, and 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 electrode layer prepared on the cleaned supporting layer to obtain the flexible photoelectric detector;
or,
processing the rigid mica sheet with the thickness of more than 100 mu m into a flexible mica sheet by adopting a mechanical stripping method; fixing the flexible mica flakes to a cleaned support layer; growing a monocrystalline perovskite film on the surface of a flexible mica sheet by adopting a low-temperature solution method, and 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;
or,
processing the rigid mica sheet with the thickness of more than 100 mu m into a flexible mica sheet by adopting a mechanical stripping method; growing a monocrystalline perovskite film on the surface of a flexible mica sheet by adopting a low-temperature solution method, and 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 preferable scheme, a low-temperature solution method is adopted to grow a single crystal perovskite film on the surface of the flexible mica flake, and the method specifically comprises the following steps: firstly, covering perovskite precursor solution on the surface of a flexible mica sheet, tightly covering the surface of the flexible mica sheet covered with the perovskite precursor solution by using a cover plate, then carrying out annealing treatment, and taking the flexible mica sheet off 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 sheet, a sapphire sheet and a glass sheet.
As a preferable scheme, the solute in the perovskite precursor solution is lead methylamine bromide (MAPbBr) 3 ) Methylamine lead chloride (MAPbCl) 3 ) Lead methyl iodide (MAPbI) 3 ) Lead bromide formamidine (FAPbBr) 3 ) Lead formamidine 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 them; the solvent is N, N-Dimethylformamide (DMF), bromic acid (HBrO) 3 ) Any one of them; 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
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 center position of the hollowed-out area of the silicon mask plate is aligned with the center position of the composite structure, so that the single crystal perovskite film is positioned right below the silicon mask plate.
As a preferred embodiment, the cleaning method of the support layer includes: firstly, primarily cleaning a supporting layer by using clean wiping cloth; then immersing the supporting layer into deionized water cleaning liquid, and placing the supporting layer in an ultrasonic cleaning machine for ultrasonic cleaning for 10-30 minutes; the support layer was then removed and blown dry with clean nitrogen.
As a preferred option, 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 the structural system of 'supporting layer (traditional flexible substrate) -active layer-electrode layer' adopted by the traditional perovskite film-based photoelectric detector, the invention innovatively introduces the flexible mica sheet (with the thickness of less than 100 μm) as a spacing layer between the flexible substrate and the single crystal perovskite film, and provides the structural system of 'supporting layer (traditional flexible substrate) -composite structure-electrode layer with spacing layer and active layer'.
(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 a large-size high-quality ultrathin single crystal perovskite film to prepare an excellent growth substrate, so that the substrate has excellent wettability and an atomically flat surface, and the difficulty that the large-size high-quality single crystal perovskite film is difficult to prepare on the traditional flexible substrate is solved.
(3) The invention adopts a mechanical stripping method to process and prepare the traditional rigid mica sheet into the flexible mica sheet, the preparation process is simple and convenient, and the artificially synthesized fluorophlogopite sheet can be selected, so that the price is low.
(4) The monocrystalline perovskite film is prepared on a flexible mica flake 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 materials are rich; the annealing temperature is only about 30 ℃, the preparation cost is low, and the method is favorable for mass production.
(5) The perovskite film prepared by the growth method is an ultrathin single crystal perovskite film, has the characteristics of high crystal quality, large specific surface area and flat 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 structure schematic diagram of the flexible photoelectric detector provided by the embodiment of the invention in an unbent state (namely a flat state); (b) The structure schematic diagram and the external circuit schematic diagram of the flexible photoelectric detector in the bending state are provided for the embodiment of the invention; (c) Optical photomicrographs of the device as a whole (scale in the figure represents 100 μm); (d) Scanning electron micrographs of photodetection sites of devices (scale in the figure represents 10 μm).
Note that: in the flexible photodetection 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 photodetection is performed.
The drawings are marked: 1-supporting layer, 2-flexible mica flake, 3-single crystal perovskite film, 4-electrode.
In fig. 2: (a) Is a manufacturing process flow chart of the flexible photoelectric detector; (b) Another manufacturing process flow chart of the flexible photoelectric detector; (c) Yet another fabrication process flow diagram for a flexible photodetector.
In fig. 3: (a) A photograph of the sample of the flexible photodetector in an unbent state (i.e., a flat state); (b) The characteristic curve of photocurrent response volt-ampere of the photoelectric detector in a flat state; (c) The photoelectric detector is a photoelectric current response switching curve in a flat state; (d) A photograph of the sample of the flexible photodetector in a flexed state; (e) The characteristic curve of photocurrent response volt-ampere of the photoelectric detector in a bending state; (f) Is a photocurrent response switching curve of the photodetector in a curved state.
In fig. 4: (a) Is the response volt-ampere characteristic curve of photocurrent and dark current of a flexible photoelectric detector consisting of a 20nm thick single crystal perovskite film under a bending condition. (b) Is the response volt-ampere characteristic curve of photocurrent and dark current of a flexible photoelectric detector consisting of 200nm thick single crystal perovskite film under the bending condition. (c) Is the response volt-ampere characteristic curve of photocurrent and dark current of a flexible photoelectric detector consisting of an 800nm thick single crystal perovskite film under a bending condition.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
Referring to fig. 1, the invention discloses a flexible photoelectric detector (called a flexible photoelectric detector for short) based on a flexible mica sheet-ultrathin single crystal perovskite film composite structure. The flexible photoelectric detector sequentially comprises a supporting layer, a composite structure (simply called a composite structure) 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, for example, the support layer can be one or a combination of organic materials such as PET, PMMA, polyethylene and the like; the thickness is 30-2000 mu m.
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 film serving as an active layer is prepared on the spacing layer with the thickness of 20-800 nm.
The electrode layer is made of conductive material with high conductivity, for example, any one or combination of conductive materials with high conductivity such as gold, silver, copper, aluminum, indium Tin Oxide (ITO) and the like, and the thickness is 30-100 nm. The central region of the electrode pattern is generally disposed directly above the composite structure, but is not limited thereto.
The flexible mica sheet is prepared by adopting a mechanical stripping method, has an atomically flat surface and excellent wettability, solves the problem that a single crystal perovskite film is generally poor in compatibility with a traditional flexible substrate, and can be used as a large-size high-quality ultrathin single crystal perovskite film to prepare an excellent growth substrate. Further, when the thickness of the mica flake is controlled between 10 and 100 mu m, the mica flake 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 film, so that the problem that the single crystal perovskite film is generally poor in compatibility with a traditional flexible substrate is solved, and meanwhile, good bending stability is maintained, and the mica sheet can be used for preparing a high-performance flexible photoelectric detector. Preferably, the rigid mica flakes used may be synthetic fluorophlogopite mica flakes, which are also less costly.
Referring to fig. 2 (a), the preparation method of the flexible photoelectric detector disclosed by the invention mainly comprises 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 fabrics, dust-free paper, mirror wiping paper and the like; then immersing the organic supporting layer into deionized water cleaning solution, 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 support layer is mainly to remove large-sized impurities (e.g., dust, plastic particles, etc.) on the surface thereof, so that the fixation of the spacer layer-active layer composite structure on the organic support layer is more secure, thereby improving the stability of the flexible photodetector during bending.
Preparing a flexible mica sheet by adopting a mechanical stripping method: rigid mica flakes (typically 100-1000 μm) having a thickness of greater than 100 μm are processed into flexible mica flakes by mechanical exfoliation and used as a growth substrate for single crystal perovskite, and are therefore also referred to as "flexible mica substrates".
Based on the two-dimensional lamellar structure characteristic of the mica sheet, the mica sheet can be processed into a flexible mica sheet with the thickness smaller than 100 mu m by adopting a mechanical stripping method. The scheme of adopting the mechanical stripping method to prepare the flexible mica sheet can be that the adhesive tape is used for repeatedly pasting and tearing the rigid mica sheet; the cutting and the direct peeling from the side edge of the rigid mica sheet can be performed by using a tool such as a thin blade, a pointed tweezer or a thin needle. It should be noted that the preparation of the flexible mica flakes is not limited to the above scheme, as long as the rigid mica flakes are processed into flakes with a thickness of less than 100 μm by a mechanical peeling method, and at this time, the flexible mica flakes have good flexibility and bending stability.
Thirdly, growing an ultrathin single crystal perovskite film on the flexible mica sheet by using a low-temperature solution method: uniformly dripping 0.4-1.0 mol/L perovskite precursor solution on a flexible mica substrate to cover a layer of perovskite precursor solution on the surface of the flexible mica substrate, tightly covering a cover plate above the flexible mica sheet dripped with the precursor solution, and then carrying out annealing treatment at the annealing temperature of 25-35 ℃ for 10-30 hours. The perovskite film grown by the annealing process has good monocrystal property and ultrathin property, and the thickness of the grown monocrystal perovskite film can be influenced by the selection of different annealing temperatures and annealing times. And after annealing, the flexible mica sheet is taken off from the cover plate to obtain a single crystal perovskite film with the thickness of 20-800 nm, so that the composite structure with the spacing layer and the active layer is also prepared.
Wherein the solute in the perovskite precursor solution may be lead methylamine bromide (MAPbBr) 3 ) Methylamine lead chloride (MAPbCl) 3 ) Lead methyl iodide (MAPbI) 3 ) Lead bromide formamidine (FAPbBr) 3 ) Lead formamidine 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 them; the solvent is N, N-Dimethylformamide (DMF), bromic acid (HBrO) 3 ) Any one of them; the concentration of the solution is 0.4-1.0 mol/L. The chemical components of the ultrathin perovskite film grown based on the perovskite precursor solution are MAPbBr 3 Single crystal, MAPbCl 3 Single crystal, MAPbI 3 Single crystal, FAPbBr 3 Single crystal, FAPbCl 3 Single crystal, FAPbI 3 Single crystal, csPbBr 3 Single crystal, csPbCl 3 Single crystal, csPbI 3 Any one of single crystals.
The cover plate is made of a smooth flexible or rigid material with good wettability, and the cover plate can be selected from flexible mica sheets prepared by the method in the second step, rigid mica sheets, graphite sheets, silicon wafers, sapphire sheets, glass sheets and the like; however, conventional flexible substrate materials cannot be used as a cover sheet due to their poor wettability, such as PET, PMMA, etc.
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 invention adopts the annealing process of lower temperature and 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 property (thickness is 20-800 nm), thereby being beneficial to realizing the flexible photoelectric detector with high performance.
Step four, adopting a silicon mask technology and a coating technology to prepare an electrode structure: preparing an electrode structure on the composite structure obtained in the third step by utilizing a silicon mask technology and a coating technology, wherein the deposition rate is as followsThe thickness is 30-100 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 a silicon mask technology with a coating technology, the center position of the hollowed-out area of the silicon mask plate is adjusted to be aligned with the center position of the composite structure, namely, the single crystal perovskite film is positioned right below the silicon mask plate. The pattern of the hollowed-out area of the silicon mask is set to be the shape of the needed electrode according to actual requirements. In the actual preparation process of the electrode structure, in order to reduce the influence of the positional deviation 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), 6 electrode strips are arranged in total) can be generally 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 step three; in the case of photoelectric detection, 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 tape fixing or adhesive fixing, etc. Wherein the adhesive tape can be selected from a cloth adhesive tape or a 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 steps are not strictly ordered. As shown in fig. 2 (b), the flexible mica flake may be fixed on the organic support layer, and then the growth of the single crystal perovskite film and the preparation of the electrode may be performed; as also shown in figure (c), the flexible mica flake with the prepared single crystal perovskite film can be fixed on an organic support layer, and then the electrode can be prepared. However, the present invention is not limited thereto, and the composite structure may be finally fixed to the organic support layer, and the electrode may be disposed above the composite structure.
The following describes embodiments of the present invention in detail with reference to the accompanying drawings, and the embodiments and specific operation procedures are given by the embodiments of the present invention under the premise of the technical solution of the present invention, but the scope of protection of the present invention is not limited to the following embodiments.
As shown in FIG. 1, example 1 discloses a flexible photodetector consisting essentially of a flexible organic PET, a flexible mica flake spacer layer, and a single crystal perovskite MAPbBr 3 A composite structure formed by the film and a gold (Au) electrode layer above the film. The preparation method comprises the following specific steps:
the first step, repeatedly wiping the PET organic supporting layer by using a non-woven fabric dipped with ethanol to remove large-size impurities such as dust, plastic particles and the like on the surface of the PET organic supporting layer; immersing the organic support layer in deionized water, and taking out the organic support layer after ultrasonic cleaning for about 15 minutes; finally, the mixture is dried by clean nitrogen.
The second step, mechanically stripping the rigid mica sheet, and the specific process is as follows: one surface of an artificially synthesized fluorophlogopite sheet with the thickness of 0.1mm is fixed on an adhesive tape, and the other surface of the mica sheet is adhered by using another adhesive tape to strip; the thickness of the mica sheet was peeled to about 30 μm by repeating the peeling, to thereby form a flexible mica sheet.
Third step, 6. Mu.L of the solution containing MAPbBr 3 N, N-Dimethylformamide (DMF) precursor solution (concentration of 0.8 mol/L) was added dropwise to the peeled flexible mica flakes; then, a piece of silicon wafer is covered on the flexible mica flake with the precursor solution; then placing the flexible mica sheet with the precursor solution on a heating plate, heating to 30 ℃, and annealing for 15 hours, namely preparing the single crystal MAPbBr with the thickness of about 20nm on the mica sheet 3 Perovskite thin films.
Fourth step, the flexible mica flake-single crystal MAPbBr 3 The composite structure of the perovskite thin film is fixed on a three-dimensional displacement table with a silicon mask, the hollowed-out area of the silicon mask is set to be in the shape of an electrode shown in fig. 1 (c), and the composite structure is positioned right below the silicon mask; then, putting the film into a high-vacuum electron beam evaporation film plating system; then preparing Au electrode by electron beam evaporation, evaporatingPlating rate is controlled toThe vapor deposition time is about 1200 seconds, and the pressure of the vacuum chamber is kept to be 1 multiplied by 10 during vapor deposition -6 Near Torr; 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 Au electrode prepared to the upper part of the PET supporting layer through an adhesive tape.
Fig. 3 (a) shows a photograph of a sample of the flexible photodetector in an unbent state (i.e., a flat state). FIG. 3 (b) shows the voltammetric response of a flexible photodetector in the unbent condition, wherein the applied bias voltage is in the range of-2V to 2V, the irradiated light is a laser light having a wavelength of 514nm and the power density is 0.2mW/cm 2 . It can be seen that with increasing bias, the detected current gradually increases, up to 10 at a bias of-2V or 2V -7 A is more than or equal to A. FIG. 3 (c) shows a photocurrent response switching curve of the flexible photodetector with no bending, the bias voltage was kept constant at 2V during detection, and the irradiated light was at a power density of 0.2mW/cm 2 Is modulated at a frequency of 5Hz. It can be seen that with a periodic modulation of the incident light, the current output by the detector exhibits a periodic switching behavior, which can reach 140nA in the case of illumination. The above results show that the photodetector has obvious photodetection characteristics.
Fig. 3 (d) shows a photograph of a sample of the flexible photodetector in a bent state. FIG. 3 (e) shows the voltammetric response of a flexible photodetector to a photocurrent in a bending regime, wherein the photodetector has a radius of curvature of about 12mm, a bias voltage in the range of-2V to 2V, and a laser with a wavelength of 514nm and a power density of 0.2mW/cm 2 . It can be seen that the photocurrent response of the photodetector in the bent condition and the photocurrent response voltammetric characteristic curve in the unbent condition of fig. 3 (a) exhibit substantially the same properties. The above results demonstrate that the photocurrent response voltammetric characteristics of the flexible photodetector hardly change with bending of the detector.FIG. 3 (f) shows a photocurrent response switching curve of a flexible photodetector with a deflection voltage of 2V, and the irradiated light having a power density of 0.2mW/cm 2 Is modulated at a frequency of 5Hz. It can be seen that the current output by the detector also exhibits good periodic switching characteristics as in the unbent case, and that the current can still reach 140nA under illumination, which indicates that the photocurrent response of the flexible photodetector of the present invention does not vary with detector bending.
The experimental results of example 1 demonstrate that the flexible photodetector of the present invention maintains substantially the same photodetection properties in both the non-bent state and the bent state, demonstrating that the flexible photodetector has good photodetection properties and bending stability.
Example 2 shows single crystal MAPbBr with 3 different thicknesses 3 The thickness of the flexible photodetectors of the perovskite thin film was 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, it has been demonstrated that the photocurrent response voltammetric characteristics of the flexible photodetectors of the present invention are hardly changed with bending of the detector, this example characterizes single crystals MAPbBr of different thickness 3 The flexible photoelectric detector of the perovskite film has photoelectric detection performance in a bending state. FIG. 4 (a) shows photocurrent and dark current response voltammetric characteristics of a flexible photodetector consisting of a 20nm thick single crystal perovskite thin film under bending conditions; FIG. 4 (b) shows photocurrent and dark current response voltammetric characteristics of a flexible photodetector consisting of a 200nm thick single crystal perovskite thin film under bending conditions; FIG. 4 (c) shows the photocurrent and dark current response voltammetric characteristic curves of a flexible photodetector consisting of an 800nm thick single crystal perovskite thin film under bending conditions. Wherein the applied bias voltage is fixed at-1V to 1V, and the irradiated light is a broadband halogen lamp with a power density of 10.5mW/cm 2 . It can be seen that under the irradiation of halogen lamps, single crystals of MAPbBr with different thickness 3 The dark current response of flexible photodetectors of perovskite thin films is affected by the thickness of the single crystal perovskite thin filmThe photocurrent response is not large and increases with the thickness of the single crystal perovskite film, and when the thickness of the single crystal perovskite film is larger than 200nm, the photocurrent response tends to be saturated; that is, when the thickness of the single crystal perovskite thin film is in the range of 200nm to 800nm, the photocurrent response of the flexible photodetector is hardly affected by the thickness of the single crystal perovskite thin film under the broadband halogen lamp illumination condition.
The results of example 2 demonstrate that the photocurrent response volt-ampere characteristics of flexible photodetectors having different single crystal perovskite film thicknesses can vary as the thickness of the perovskite film varies when the single crystal perovskite film thickness is between 20nm and 200 nm. When the thickness of the single crystal perovskite film is between 200nm and 800nm, under the condition of broadband halogen lamp illumination, the photocurrent response volt-ampere characteristic of the flexible photoelectric detector presents saturated property and is hardly influenced by the thickness of the single crystal perovskite film; meanwhile, the dark current response volt-ampere characteristic of the flexible photoelectric detector is not greatly influenced by the thickness of the monocrystalline perovskite film (the thickness of the monocrystalline perovskite film is in the range of 20-800 nm).
In summary, the invention provides the flexible photoelectric detector based on the flexible mica sheet-ultrathin monocrystal perovskite film composite structure, which has good flexibility and bending stability by utilizing the composite structure with the spacing layer and the active layer and the flexibility of the organic supporting layer, and shows obvious photoelectric detection response in both 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 understood that the above description is only of the preferred embodiments of the present invention and is not intended to limit the invention, but rather that various modifications and changes will be apparent to those skilled in the art. Any modification, equivalent replacement, improvement, etc. 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 single crystal perovskite film is characterized by comprising a supporting layer, a composite structure with a spacing layer and an active layer and an electrode layer, wherein the supporting layer, the composite structure with a spacing layer and an active layer and the electrode layer are sequentially arranged from bottom to top; the supporting layer is a flexible organic substrate; the composite structure is constructed to comprise a flexible mica sheet and a single crystal perovskite film grown on the surface of the flexible mica sheet, wherein the flexible mica sheet used as a spacing layer is prepared by adopting a mechanical stripping method, the thickness of the flexible mica sheet is 10-100 mu m, and the single crystal perovskite film used as an active layer is grown on the surface of the flexible mica sheet by adopting a low-temperature solution method, and the thickness of the single crystal perovskite film used as the active layer is 20-800 nm;
the low-temperature solution method comprises the steps of covering a layer of perovskite precursor solution on the surface of a flexible mica sheet, and carrying out annealing treatment on the perovskite precursor solution; the annealing treatment temperature is 25-35 ℃ and the annealing treatment time is 10-30 hours.
2. The flexible photodetector of claim 1 wherein the chemical composition of the single crystal perovskite thin film is any one of single crystal 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 cesium lead iodide.
3. The flexible photodetector of claim 1 wherein said flexible mica flakes are made from synthetic fluorophlogopite flakes by a mechanical stripping process.
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 comprises one or more of polyethylene terephthalate, polybutylene terephthalate, polymethyl methacrylate, polyethylene, polycarbonate, polyurethane, chloroether resin, polyethylene naphthalate, polyimide, and polyacrylate.
6. The flexible photodetector of claim 1 wherein said electrode layer has a thickness of 30 to 100nm; 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 or a combination of gold, silver, copper, aluminum, indium tin oxide.
8. A method for manufacturing a flexible photodetector as defined in any one of claims 1 to 7, characterized in that,
comprising the following steps:
processing the rigid mica sheet with the thickness of more than 100 mu m into a flexible mica sheet by adopting a mechanical stripping method; growing a monocrystalline perovskite film on the surface of the 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 electrode layer prepared on the cleaned supporting layer to obtain the flexible photoelectric detector;
or,
processing the rigid mica sheet with the thickness of more than 100 mu m into a flexible mica sheet by adopting a mechanical stripping method; fixing the flexible mica flakes to a cleaned support layer; growing a monocrystalline perovskite film on the surface of the 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;
or,
processing the rigid mica sheet with the thickness of more than 100 mu m into a flexible mica sheet by adopting a mechanical stripping method; growing a monocrystalline perovskite film on the surface of the 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 treatment temperature is 25-35 ℃ and the annealing treatment time is 10-30 hours.
9. The method of claim 8, wherein the growing of the single crystal perovskite thin film on the surface of the flexible mica flake by a low temperature solution method comprises: firstly, covering a layer of perovskite precursor solution on the surface of a flexible mica sheet, covering the perovskite precursor solution by using 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 sheet, 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 hydrobromic acid; the concentration of the solution is 0.4-1.0 mol/L.
11. The method of claim 10, wherein an electrode layer is prepared on the composite structure by combining a silicon masking technique and a plating technique, the plating technique being any one of electron beam evaporation plating, thermal evaporation plating, magnetron sputtering plating, and plasma enhanced chemical vapor deposition plating; the deposition rate of the coating film is
12. The method of claim 11, wherein at least two electrode structures are prepared in contact with the single crystal perovskite thin film; when the electrode structure is prepared, the center position of the hollowed-out area of the silicon mask plate is aligned with the center position of the composite structure, so that the single crystal perovskite film is positioned right below the silicon mask plate.
13. The method of claim 8, wherein the method of cleaning the support layer comprises: firstly, primarily cleaning a supporting layer by using clean wiping cloth; then immersing the supporting layer into deionized water cleaning liquid, and placing the supporting layer in 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 tape or adhesive.
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