CN113823740A - Perovskite-based X-ray detector with n-i structure and preparation method thereof - Google Patents

Perovskite-based X-ray detector with n-i structure and preparation method thereof Download PDF

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CN113823740A
CN113823740A CN202110897195.4A CN202110897195A CN113823740A CN 113823740 A CN113823740 A CN 113823740A CN 202110897195 A CN202110897195 A CN 202110897195A CN 113823740 A CN113823740 A CN 113823740A
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perovskite
functional layer
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ray detector
ammonium
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薛冬峰
李云龙
王晓明
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Shenzhen Institute of Advanced Technology of CAS
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Shenzhen Institute of Advanced Technology of CAS
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Abstract

The application belongs to the technical field of photoelectricity, and particularly relates to an n-i structure perovskite-based X-ray detector and a preparation method thereof. The n-i structure perovskite-based X-ray detector comprises an n-type perovskite functional layer and an i-type perovskite active layer which are laminated and attached; the n-type perovskite functional layer contains APbBr3A perovskite material, wherein the i-type perovskite active layer contains A' PbI3A perovskite material, wherein a and a' are each independently selected from alkali metal ions or organic ammonium ions. The n-i structure perovskite-based X-ray detector provided by the application has a simple device structure, and realizes high sensitivity, low detection limit and lower dark current.

Description

Perovskite-based X-ray detector with n-i structure and preparation method thereof
Technical Field
The application belongs to the technical field of photoelectricity, and particularly relates to an n-i structure perovskite-based X-ray detector and a preparation method thereof.
Background
An X-ray detector (X-ray detector) is a device that converts X-ray energy into electrical signals that can be recorded. In recent years, with the large-scale popularization and use of X-ray detectors, the X-ray detectors are increasingly used in the fields of small security inspection equipment, industrial part inspection, large container inspection, medical treatment and the like. At present, X-ray detectors are mostly applied to indirect conversion X-ray detectors using scintillators, and are generally formed by combining scintillators, detector chips and substrates; the working principle is that X photons enter a scintillator and are converted into visible light to be output, the visible light enters a detector chip, the detector chip performs photoelectric conversion to form an electric signal, and the electric signal is transmitted to a subsequent signal processing chip through the chip and a lead on a substrate, so that a final image is formed.
Compared with the prior art, the direct conversion X-ray detector can directly convert X-ray absorption into charge carriers, has the advantages of small required radiation dose, high spatial resolution, large contrast range, simple device structure and the like, and has wider application prospect in the aspect of high-end medical image application. The core of the direct conversion X-ray flat panel image detector is an X-ray active layer which is a material directly converting X-ray absorption into charge carriers. At present, the direct conversion X-ray active material with excellent performance can select a few kinds of amorphous selenium materials (a-Se: As) doped with arsenic As an X-ray active layer, which is the mainstream method. However, the device based on the material has harsh preparation conditions on one hand and extremely low detection efficiency on high-energy X-ray on the other hand. Therefore, finding alternative materials is of great significance for the development of the next generation of X-ray image detectors.
Currently, amorphous selenium (a-Se) -based direct conversion X-ray detectors employ a p-i-n structure, i.e., a very thick intrinsic-like a-Se sandwiched between a p-type and an n-type thin a-Se layer. Intrinsic a-Se can transfer both electrons and holes, p-type a-Se can transfer holes and inhibit electron transfer well, and n-type a-Se can transfer electrons and inhibit hole transfer well. However, the direct conversion X-ray detector based on the a-Se is high in cost and narrow in application field. Compared with an a-Se-based device, the perovskite material-based direct conversion X-ray detector has the advantages of low cost, easiness in preparation and high sensitivity, but the dark current of the existing perovskite-based direct conversion X-ray detector is very large.
Disclosure of Invention
The application aims to provide an n-i structure perovskite-based X-ray detector and a preparation method thereof, and aims to solve the technical problem of high dark current of the perovskite-based X-ray detector to a certain extent.
In order to achieve the purpose of the application, the technical scheme adopted by the application is as follows:
in a first aspect, the application provides an n-i structure perovskite-based X-ray detector, which comprises an n-type perovskite functional layer and an i-type perovskite active layer which are laminated and attached; the n-type perovskite functional layer contains APbBr3A perovskite material, wherein the i-type perovskite active layer contains A' PbI3A perovskite material, wherein a and a' are each independently selected from alkali metal ions or organic ammonium ions.
Further, the organic ammonium ions include: CH (CH)3NH3 +、CH2(NH3)2 +At least one of (1).
Further, the alkali metal ions include: cs+、Rb+At least one of (1).
Further, said a and said a' are each independently selected from: CH (CH)3NH3 +、CH2(NH3)2 +、Cs+Or Cs+And Rb+。
Furthermore, the thickness of the n-type perovskite functional layer is 15-25 mu m.
Furthermore, the thickness of the i-type perovskite active layer is 100-1000 mu m.
In a second aspect, the present application provides a method for manufacturing a perovskite-based X-ray detector with an n-i structure, comprising the following steps:
obtaining a conductive substrate, and preparing a first functional layer on the surface of the conductive substrate;
preparing a second functional layer on the surface of the first functional layer, which is far away from the conductive substrate;
preparing a back electrode on the surface of the second functional layer, which is far away from the first functional layer, so as to obtain the perovskite-based X-ray detector with the n-i structure;
wherein the first functional layer and the second functional layerThe energy layers are different and are respectively an n-type perovskite functional layer or an i-type perovskite active layer, and the n-type perovskite functional layer contains APbBr3A perovskite material, wherein the i-type perovskite active layer contains A' PbI3A perovskite material, wherein a and a' are each independently selected from alkali metal ions or organic ammonium ions.
Further, the first functional layer is the n-type perovskite functional layer, and the step of preparing the n-type perovskite functional layer includes: mixing ammonium bromide salt or alkali metal bromide salt with lead bromide, a surfactant and a first organic reagent to obtain a first perovskite solution;
and depositing the first perovskite solution on the surface of the conductive substrate, and carrying out primary drying annealing to form the n-type perovskite functional layer.
Further, the second functional layer is the i-type perovskite functional layer, and the step of preparing the i-type perovskite functional layer includes: mixing and processing ammonium iodide salt or alkali iodide salt, lead iodide, a conductive polymer adhesive and a second organic reagent to obtain second perovskite slurry;
and depositing the second perovskite slurry on the surface of the first functional layer, and carrying out secondary drying annealing to form the i-type perovskite functional layer.
Further, in the first perovskite solution, the ratio of the molar amount of the ammonium bromide salt or the alkali metal bromide salt to the molar amount of the lead bromide is 1: (1-1.10).
Further, in the first perovskite solution, a mass ratio of a total mass of the ammonium bromide salt, the alkali metal bromide salt and the lead bromide to the surfactant and the first organic reagent is 100: (0.5-1.5): (50-75).
Further, the surfactant is selected from quaternary ammonium salt surfactants.
Further, the first organic solvent includes: at least one of N, N-dimethylformamide, N-methylpyrrolidone and dimethyl sulfoxide.
Further, in the second perovskite slurry, a ratio of a molar amount of the ammonium iodide salt or the alkali metal iodide salt to a molar amount of the lead iodide is 1: (1-1.2).
Further, in the second perovskite slurry, a mass ratio of a total mass of the ammonium iodide salt, the alkali metal iodide salt, and the lead iodide to the conductive polymer binder and the second organic agent is 100: (0.5-2.5): (35-50).
Further, the conductive polymer binder is selected from: at least one of polythiophene, poly [ bis (4-phenyl) (2,4, 6-trimethylphenyl) amine ], poly [ bis (4-phenyl) (4-butylphenyl) amine ], and poly (p-phenylene ethylene).
Further, the second organic solvent includes: at least one of chlorobenzene, toluene, dimethyl sulfoxide and ethylene glycol.
Further, the step of depositing the first perovskite solution on the surface of the conductive substrate comprises: and spin-coating the first perovskite solution on the surface of the conductive substrate under the condition that the spin-coating revolution number is 5000-7000 rmp/s.
Further, under the conditions that the scraping speed is 10-15 mm/s and the height of a scraper is 30-50 mu m, the first perovskite solution is scraped on the surface of the conductive substrate.
Further, the conditions of the first drying annealing include: drying for 6-8 hours at 20-40 ℃, and then annealing for 25-30 minutes at 90-100 ℃.
Further, the step of depositing the second perovskite slurry on the surface of the first functional layer comprises: and scraping and coating the second perovskite slurry on the surface of the first functional layer under the conditions that the scraping and coating speed is 10-15 mm/s and the height of a scraper is 100-1500 mu m.
Further, the conditions of the second drying annealing include: drying the mixture for 12 to 14 hours at the temperature of 20 to 40 ℃, and then annealing the dried mixture for 45 to 60 minutes at the temperature of 90 to 100 ℃.
Further, the step of preparing the back electrode comprises: at vacuum degree of not less than 10-6mbar, evaporation rate of
Figure BDA0003198328610000041
And under the condition that the evaporation time is 100-150 s, evaporating and depositing a metal electrode on the surface of the second functional layer, which is far away from the first functional layer.
Further, the surfactant includes: at least one of cetyl trimethyl ammonium bromide, cetyl trimethyl ammonium chloride and didodecyl dimethyl ammonium bromide.
Further, the first organic solvent is (3-5) by volume: 1 of N, N-dimethylformamide and N-methylpyrrolidone.
Further, the second organic solvent is a mixture of 1: (0.33-2) a mixed solvent of ethylene glycol and chlorobenzene.
In the functional layer and the active layer of the n-i structure perovskite-based X-ray detector provided by the first aspect of the application, the lead bromide type perovskite and the lead iodide type perovskite are good in combination stability with the electrode, so that the interface impedance is favorably reduced, the carrier migration transmission efficiency is improved, and the detection sensitivity and stability of the device are improved. Moreover, these perovskite materials have high absorption efficiency for X-rays. In addition, lead bromide type APbBr is used3Perovskite material as n-type functional layer, lead iodide type A' PbI3The perovskite material is used as an i-type X-ray active layer, the energy level matching relation between the perovskite active layer and the electrode can be optimized, the migration efficiency of X-ray excited current carriers in the perovskite active layer is improved, and meanwhile, the n-type functional layer can prevent the current carriers from being injected into the perovskite active layer from the electrode, so that dark current in an X-ray detection device is inhibited. The n-i structure perovskite-based X-ray detector provided by the application has a simple device structure, and realizes high sensitivity, low detection limit and lower dark current.
The preparation method of the n-i structure perovskite-based X-ray detector provided by the second aspect of the application has a simple process, is suitable for industrial large-scale production and application, directly prepares the functional layer on the surface of the substrate, improves the combination tightness of the n-type perovskite functional layer and the i-type perovskite active layer with the electrode and the substrate, reduces interface defects, reduces interface resistance, and improves carrier migration efficiency, thereby obtaining high detection sensitivity; in addition, the prepared n-i structure perovskite-based X-ray detector can further improve the detection sensitivity of the device through the energy level matching of the n-type perovskite functional layer and the i-type perovskite active layer, and the n-type perovskite functional layer can inhibit electrode carriers from being injected into the i-type perovskite active layer, so that the dark current in the X-ray detector is reduced, and the stability and the safety of the device are improved.
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In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings needed to be used in the embodiments or the prior art descriptions will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
FIG. 1 is a schematic structural diagram of an n-i perovskite-based X-ray detector provided in example 1 of the present application;
FIG. 2 is a sectional SEM image of an n-type perovskite functional layer in an n-i structure perovskite-based X-ray detector provided in example 1 of the present application;
FIG. 3 is a sectional SEM image of an i-type perovskite functional layer in an n-i structure perovskite-based X-ray detector provided in example 1 of the present application;
FIG. 4 is a dark current i-t test chart of the X-ray detector provided in example 1 and comparative examples 1-2 of the present application;
FIG. 5 is a sensitivity test chart of the X-ray detector provided in example 1 and comparative examples 1 to 2 of the present application.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present application more clearly apparent, the present application is further described in detail below with reference to the 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.
In this application, the term "and/or" describes an association relationship of associated objects, meaning that there may be three relationships, e.g., a and/or B, which may mean: a is present alone, A and B are present simultaneously, and B is present alone. Wherein A and B can be singular or plural. The character "/" generally indicates that the former and latter associated objects are in an "or" relationship.
In the present application, "at least one" means one or more, "a plurality" means two or more. "at least one of the following" or similar expressions refer to any combination of these items, including any combination of the singular or plural items. For example, "at least one (one) of a, b, or c," or "at least one (one) of a, b, and c," may each represent: a, b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, wherein a, b, and c may be single or plural, respectively.
It should be understood that, in various embodiments of the present application, the sequence numbers of the above-mentioned processes do not mean the execution sequence, some or all of the steps may be executed in parallel or executed sequentially, and the execution sequence of each process should be determined by its function and inherent logic, and should not constitute any limitation to the implementation process of the embodiments of the present application.
The terminology used in the embodiments of the present application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in the examples of this application and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
The weight of the related components mentioned in the description of the embodiments of the present application may not only refer to the specific content of each component, but also represent the proportional relationship of the weight among the components, and therefore, the content of the related components is scaled up or down within the scope disclosed in the description of the embodiments of the present application as long as it is scaled up or down according to the description of the embodiments of the present application. Specifically, the mass in the description of the embodiments of the present application may be in units of mass known in the chemical industry, such as μ g, mg, g, and kg.
The terms "first" and "second" are used for descriptive purposes only and are used for distinguishing purposes such as substances from one another, and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. For example, a first XX may also be referred to as a second XX, and similarly, a second XX may also be referred to as a first XX, without departing from the scope of embodiments of the present application. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature.
The term "n-type" is an abbreviation for n-type semiconductor, and denotes a semiconductor that is predominantly electron conducting; the term "i-type" is an abbreviation for intrinsic semiconductor, intracsic semiconductor.
The embodiment of the application provides a perovskite-based X-ray detector with an n-i structure in a first aspect, which comprises an n-type perovskite functional layer and an i-type perovskite active layer which are laminated and attached; the n-type perovskite functional layer contains APbBr3Perovskite material, the i-type perovskite active layer contains A' PbI3A perovskite material, wherein a and a' are each independently selected from alkali metal ions or organic ammonium ions.
The perovskite-based X-ray detector with the n-i structure provided by the embodiment of the application comprises APbBr (active basic bromine compound) which is laminated and attached3N-type perovskite functional layer of perovskite material and composition containing A' PbI3The i-type perovskite active layer of the perovskite material forms an n-i structure full perovskite direct conversion X-ray detector. In the functional layer and the active layer of the n-i structure perovskite-based X-ray detector, the lead bromide type perovskite and the lead iodide type perovskite are good in combination stability with the electrode, so that the interface impedance is favorably reduced, the carrier migration transmission efficiency is improved, and the detection sensitivity and the stability of the device are improved. In addition, the perovskite materials have high absorption efficiency on X-ray, have the characteristics of high charge carrier mobility, long charge carrier diffusion length, very good bulk phase defect tolerance and the like, can directly absorb photons to generate electron and hole pairs, and then the electron and hole pairs are converted into free carriers under the action of an external electric field to migrate to electrodes and are finally collected by the respective electrodes, so that the detection sensitivity is high, and the detection lower limit value is low. In addition, lead bromide type APbBr is used3Perovskite material as n-type functional layer, lead iodide type A' PbI3Perovskite materials as i-type X photoactive layers, relative to A' PbI3A perovskite material,APbBr3the perovskite material has a deeper valence band energy level and a shallower conduction band energy level, the energy level matching relation between the titanium ore active layer and the electrode can be optimized, the migration efficiency of carriers excited by X-rays in the titanium ore active layer is improved, and meanwhile, the carriers can be prevented from being injected into the perovskite active layer from the electrode, so that dark current in the X-ray detection device is inhibited. The n-i structure perovskite-based X-ray detector provided by the embodiment of the application has a simple device structure, perovskite materials in n-type and i-type functional layers in the detector have the characteristics of high X-ray absorption efficiency, excellent carrier mobility, service life and the like, through the mutual cooperation of the n-type and i-type functional layers, the detector has high sensitivity, the interface defect is reduced, the dark current is reduced, and the n-i structure perovskite-based X-ray detector has a better low detection limit.
In some embodiments, the organic ammonium ions include: CH (CH)3NH3 +、CH2(NH3)2 +At least one of (1). In the perovskite-based X-ray detector of the n-i structure of the embodiment of the application, A' PbI3Perovskite material and APbBr3In the perovskite material, the preferred organic ammonium ions at the A and A' positions can effectively improve the film-forming property of the perovskite material.
In some embodiments, the alkali metal ions include: cs+、Rb+At least one of (1). In the perovskite-based X-ray detector of the n-i structure of the embodiment of the application, A' PbI3Perovskite material and APbBr3In the perovskite material, the alkali metal ions preferred for the A and A' sites can effectively improve the thermal stability of the perovskite material.
In some embodiments, a and a' are each independently selected from: CH (CH)3NH3 +、CH2(NH3)2 +、Cs+Or Cs+And Rb+. Namely, A' PbI3In the perovskite material, A' is CH3NH3 +、CH2(NH3)2 +、Cs+Or Cs+And Rb+；APbBr3A in the perovskite material is CH3NH3 +、CH2(NH3)2 +、Cs+Or Cs+And Rb+。
In some embodiments, the n-type perovskite functional layer has a thickness of 15 to 25 μm; the thickness not only ensures the uniform, flat and compact performance of the n-type perovskite functional layer film layer, but also ensures the inhibition effect of the n-type perovskite functional layer on dark current. If the thickness of the n-type perovskite functional layer is too high, the uniformity and compactness of the film layer are poor, and the transmission of current carriers is influenced; if the thickness of the n-type perovskite functional layer is too low, the adjustment of the energy levels of the i-type perovskite active layer and the electrode is not facilitated, and the effect of inhibiting the dark current of the device is not good. In some embodiments, the thickness of the n-type perovskite functional layer may be 15-20 μm, 20-23 μm, 23-25 μm, and the like.
In some embodiments, the thickness of the i-type perovskite active layer is 100-1000 μm, and the thickness ensures the absorption and conversion efficiency of the i-type perovskite active layer on X-ray, thereby ensuring the detection sensitivity of the X-ray detector. If the i-type perovskite active layer is too thin, the absorption to X-ray is weak; if the i-type perovskite active layer is too thick, recombination of carriers in the perovskite active layer may be severe. In some embodiments, the thickness of the i-type perovskite active layer may be 100 to 200 μm, 200 to 300 μm, 300 to 500 μm, 500 to 800 μm, 800 to 1000 μm, and the like.
In some embodiments, the n-type perovskite functional layer has a thickness of 15 to 25 μm; the thickness of the i-type perovskite active layer is 100-1000 microns, so that the n-type perovskite functional layer and the i-type perovskite active layer have a better energy level matching effect, the detection sensitivity of the n-i structure perovskite-based X-ray detector is improved, and the dark current is reduced.
The perovskite-based X-ray detector with the n-i structure in the embodiment of the application can be prepared by the following embodiment method.
A second aspect of the embodiments of the present application provides a method for manufacturing a perovskite-based X-ray detector with an n-i structure, including the following steps:
s10, obtaining a conductive substrate, and preparing a first functional layer on the surface of the conductive substrate;
s20, preparing a second functional layer on the surface of the first functional layer, which is far away from the conductive substrate;
s30, preparing a back electrode on the surface of the second functional layer, which is far away from the first functional layer, so as to obtain the perovskite-based X-ray detector with the n-i structure;
wherein, the first functional layer and the second functional layer are different and are respectively an n-type perovskite functional layer or an i-type perovskite active layer, and the n-type perovskite functional layer contains APbBr3Perovskite material, the i-type perovskite active layer contains A' PbI3A perovskite material, wherein a and a' are each independently selected from alkali metal ions or organic ammonium ions.
In the method for manufacturing the perovskite-based X-ray detector with the n-i structure provided by the second aspect of the embodiment of the application, APbBr is directly prepared on the surface of the conductive substrate3Or A' PbI3The first functional layer of the perovskite material is prepared, and then the A' PbI is contained on the surface of the first functional layer3Or APbBr3Then preparing a back electrode layer, and then preparing the n-i structure perovskite-based X-ray detector with the n-i structure. The preparation method of the n-i structure perovskite-based X-ray detector provided by the embodiment of the application has a simple process, is suitable for industrial large-scale production and application, directly prepares the functional layer on the surface of the substrate, improves the combination tightness of the n-type perovskite functional layer and the i-type perovskite active layer with the electrode and the substrate, reduces interface defects, reduces interface resistance, and improves carrier migration efficiency, thereby obtaining high detection sensitivity; in addition, the prepared n-i structure perovskite-based X-ray detector can further improve the detection sensitivity of the device through the energy level matching of the n-type perovskite functional layer and the i-type perovskite active layer, and the n-type perovskite functional layer can inhibit electrode carriers from being injected into the i-type perovskite active layer, so that the dark current in the X-ray detector is reduced, and the stability and the safety of the device are improved.
In some embodiments, in step S10, the conductive substrate is selected from a transparent glass with indium tin oxide. In some embodiments, the conductive substrate has dimensions of (1-3 inches) × (1-3 inches).
In some embodiments, a method of making an n-i structured perovskite-based X-ray detector includes the steps of:
s11, obtaining a conductive substrate, and preparing an n-type perovskite functional layer on the surface of the conductive substrate to serve as a first functional layer;
s21, preparing an i-type perovskite active layer on the surface of the first functional layer, which is far away from the conductive substrate, and using the i-type perovskite active layer as a second functional layer;
s31, preparing a back electrode on the surface of the second functional layer, which is far away from the first functional layer, so as to obtain the perovskite-based X-ray detector with the n-i structure; wherein the n-type perovskite functional layer contains APbBr3Perovskite material, the i-type perovskite active layer contains A' PbI3A perovskite material, wherein a and a' are each independently selected from alkali metal ions or organic ammonium ions. The examples of the present application consider A' PbI3Or APbBr3Dissolution characteristics of perovskite materials to avoid preparation of APbBr3In the case of functional layers of perovskite materials, the dissolution of the solvent destroys the A' PbI which has already been deposited and shaped3Perovskite material, preferably prepared on the surface of a conductive substrate and containing APbBr3Preparing an n-type perovskite functional layer of a perovskite material, and preparing a functional layer containing A' PbI3The i-type perovskite active layer and the back electrode of the perovskite material are beneficial to improving the stability of the perovskite-based X-ray detector with the n-i structure.
In some embodiments, in step S11, the first functional layer is an n-type perovskite functional layer, and the step of preparing the n-type perovskite functional layer includes:
s111, mixing ammonium bromide salt or alkali metal bromide salt with lead bromide, a surfactant and a first organic reagent to obtain a first perovskite solution;
and S112, depositing the first perovskite solution on the surface of the conductive substrate, and carrying out primary drying annealing to form an n-type perovskite functional layer.
In the preparation of the n-type perovskite functional layer in the embodiment of the application, ammonium bromide salt or alkali metal bromide salt and lead bromide are used as raw material components, and are mixed with a surfactant and a first organic reagent to prepare a perovskite solution; then depositing the first perovskite solution on the surface of the conductive substrate, and performing self-assembly of perovskite materials while drying the solution to form a filmAnd APbBr is generated in situ on the surface of the conductive substrate3A perovskite crystalline material. The embodiment of the application adopts the n-type perovskite functional layer prepared by the solution method, on one hand, the film forming performance of the n-type perovskite functional layer is improved, the film layer is more compact, the thickness is uniform, the surface is smooth, the defect of the film layer is reduced, the service life of the film layer is longer, the carrier diffusion length is improved, and therefore the mobility of the perovskite functional layer is improved; on the other hand, the n-type perovskite functional layer is high in combination tightness with the conductive substrate, and the n-type perovskite functional layer perovskite crystal can induce crystal growth in the i-type perovskite functional layer, so that interface defects are reduced, interface resistance is reduced, migration transmission efficiency of carriers is further improved, and detection sensitivity of the detector is improved.
In some embodiments, in step S111 above, the ratio of the molar amount of ammonium bromide salt or alkali metal bromide salt to the molar amount of lead bromide in the first perovskite solution is 1: (1-1.2); the molar ratio fully ensures the contact reaction among the raw material components. Preferably, lead bromide with slight excess is adopted, so that ammonium bromide salt or alkali metal bromide and lead bromide are in full contact reaction in the processes of slurry and drying film forming to generate APbBr3The perovskite crystal material improves the stability of perovskite crystals. In some embodiments, the ratio of the molar amount of ammonium bromide salt or alkali metal bromide salt to the molar amount of lead bromide may be 1:1, 1:1.1, 1:1.2, and the like.
In some embodiments, the mass ratio of the total mass of ammonium bromide salt, alkali metal bromide salt, and lead bromide to the surfactant and first organic agent in the first perovskite solution is 100: (0.5-1.5): (50-75), the mass ratio of the raw material components ensures that the first perovskite solution has proper viscosity, the dispersion stability of each component in the solution is good, the subsequent deposition film formation through modes of spin coating, blade coating and the like is facilitated, and the method is suitable for large-area preparation of an n-type perovskite functional layer. In addition, the mass ratio ensures APbBr in the functional layer3The content of perovskite material ensures the detection sensitivity of the n-type perovskite functional layer to an X-ray detector, the improvement of the absorption conversion efficiency of X-ray and the inhibition effect of dark current, and the formulaThe obtained n-type perovskite functional layer has a smooth surface appearance, and the perovskite crystalline thin film with high crystallinity can be obtained. If the content of the solvent is too low, the solubility of the solvent to the raw materials is poor, and the viscosity of the first perovskite solution is too high, so that the coating and deposition of the slurry are not facilitated; if the solvent content is too high, the viscosity of the first perovskite solution is too low, the solution is difficult to deposit and form, and the preparation of the film layer is also not facilitated. If the surfactant content is too high or too low, the film forming properties of the first perovskite solution may be reduced.
In some embodiments, the surfactant is selected from quaternary ammonium surfactants, which can more effectively adjust the surface tension of the solution and improve the film forming properties of the perovskite slurry. In some embodiments, the surfactant comprises: at least one of cetyl trimethyl ammonium bromide CTAB, cetyl trimethyl ammonium chloride CTAC and didodecyl dimethyl ammonium bromide DDAB.
In some embodiments, the first organic solvent comprises: at least one of N, N-dimethylformamide, N-methylpyrrolidone and dimethyl sulfoxide, and the organic solvents have good dissolubility for raw material components such as ammonium bromide salt or alkali metal bromide salt, lead bromide, surfactant and the like, and are favorable for full contact reaction of the raw material components. In some embodiments, the first organic solvent is a mixed solvent of N, N-dimethylformamide and N-methylpyrrolidone in a volume ratio of (3-5): 1; the dispersion stability of each raw material component in the solution can be better improved through the coordination of two solvents of N, N-dimethylformamide and N-methylpyrrolidone.
In some embodiments, in step S112, the step of depositing the first perovskite solution on the surface of the conductive substrate includes: and spin-coating the first perovskite solution on the surface of the conductive substrate under the condition that the spin-coating revolution number is 5000-7000 rmp/s. The first perovskite solution is deposited under the condition, so that the uniformity, stability and the like of the film layer can be improved, and the film layer is smooth and compact.
In other embodiments, the first perovskite solution is deposited on the surface of the conductive substrate by blade coating, and specifically, the first perovskite solution is blade coated on the surface of the conductive substrate under the conditions that the blade coating speed is 10-15 mm/s and the height of a scraper is 30-50 μm; the formed film layer is uniform, compact and smooth in surface.
In some embodiments, the conditions of the first dry anneal comprise: drying for 6-8 hours at the temperature of 20-40 ℃ to remove redundant solvent in the perovskite solution, and then annealing for 25-30 minutes at the temperature of 90-100 ℃; solidifying and molding the perovskite slurry and simultaneously enabling APbBr3The perovskite is self-assembled to improve APbBr in the n-type perovskite functional layer3The perovskite material has the characteristics of crystal form order, structural integrity, purity, performance stability and the like. If the annealing temperature is too low, the optimization effect on the perovskite crystal form, the purity and the like in the perovskite active layer is not good, and the photoelectric property and the stability of the perovskite active layer are not improved; if the annealing temperature is too high, the perovskite material itself is easily decomposed, and the stability of the perovskite active layer is deteriorated.
In some embodiments, in step S21, the second functional layer is an i-type perovskite functional layer, and the step of preparing the i-type perovskite functional layer includes:
s211, mixing ammonium iodide salt or alkali iodide salt with lead iodide, a conductive polymer adhesive and a second organic reagent to obtain second perovskite slurry;
s212, depositing the second perovskite slurry on the surface of the first functional layer, and performing secondary drying annealing to form the i-type perovskite functional layer.
In the preparation of the i-type perovskite functional layer in the embodiment of the application, ammonium iodide salt or alkali metal iodide salt and lead iodide are used as raw material components, and are mixed with a conductive high molecular adhesive and a second organic reagent to prepare perovskite slurry; then depositing the second perovskite slurry on the surface of the first functional layer, and inducing ordered self-assembly of perovskite materials through the first functional layer in the process of drying the slurry, thereby generating the A' PbI with matched crystal form on the surface of the first functional layer in situ3A perovskite crystalline material. The i-type perovskite functional layer prepared by the slurry method is beneficial to preparing a thicker i-type functional layer on one hand, so thatThe absorption and conversion efficiency of the detector to full-wave-band X-ray is ensured, on the other hand, through the induction of the first functional layer, the self-assembly effect of the perovskite material is improved, the film forming performance of the i-type perovskite functional layer is improved, the film layer is more compact, the thickness is uniform, the surface is smooth, the combination tightness of the i-type perovskite functional layer and the surface of the n-type first functional layer is improved, the interface defect is reduced, the interface resistance is reduced, the migration and transmission efficiency of carriers is improved, and therefore the detection sensitivity of the detector is improved.
In some embodiments, in the above step S211, the ratio of the molar amount of the ammonium iodide salt or the alkali metal iodide salt to the molar amount of the lead iodide in the second perovskite slurry is 1: (1-1.1); the proportion is favorable for full contact reaction of ammonium iodide salt andor alkali metal iodide and lead iodide in the processes of slurry and drying film formation to generate APbI3The perovskite crystal material improves the stability of perovskite crystals. In some preferred embodiments, the ratio of the molar amount of ammonium iodide salt or alkali metal iodide salt to the molar amount of lead iodide is 1: (1.05-1.1), lead iodide slightly in excess is more favorable for improving the crystallization and film-forming properties of the second perovskite slurry. In some embodiments, the ratio of the molar amount of ammonium iodide salt or alkali metal iodide salt to the molar amount of lead iodide in the second perovskite slurry may be 1:1.05, 1:1.08, 1:1.10, and the like.
In some embodiments, the ratio of the total mass of the ammonium iodide salt, the alkali metal iodide salt, and the lead iodide to the mass of the conductive polymer binder and the second organic agent in the second perovskite slurry is 100: (0.5-2.5): (35-50); the mass ratio of the raw material components ensures that the second perovskite slurry has proper viscosity and the components in the slurry have good dispersion stability, is beneficial to subsequent film deposition through blade coating and other modes, and is suitable for large-area preparation of the i-type perovskite functional layer. At the same time, the mass ratio ensures APbI in the functional layer3The content of the perovskite material ensures the detection sensitivity of the i-type perovskite functional layer to an X-ray detector and the improvement of the absorption conversion efficiency of the i-type perovskite functional layer to X-ray. If the content of the solvent is too low, the viscosity of the second perovskite slurry is too high, and the coating and deposition of the slurry are not facilitated; if the solvent content is too highAnd the viscosity of the second perovskite slurry is too low, and the slurry is difficult to deposit and form and is also not beneficial to film preparation. The conductive polymer adhesive can improve the viscosity of the second perovskite slurry and the conductivity of the functional layer, can enable perovskite crystals formed by self-assembly in the functional layer to be tightly combined, and plays a role in fixing perovskite microcrystals on a micro scale. If the content of the conductive polymer binder is too high or too low, the film forming property of the second perovskite slurry is reduced.
In some embodiments, the conductive polymeric binder is selected from: at least one of polythiophene, poly [ bis (4-phenyl) (2,4, 6-trimethylphenyl) amine ], poly [ bis (4-phenyl) (4-butylphenyl) amine ], and poly (p-phenylene vinylene); the conductive polymer adhesives have better conductivity, not only enable perovskite crystals in the functional layer to be tightly combined, but also form a conductive network through the combination of the perovskite crystals and the conductive polymers, and are beneficial to improving the migration and transmission performance of current carriers in the i-type perovskite functional layer; in addition, the conductive polymer adhesive can improve the viscosity of the perovskite slurry and improve the combination stability of the perovskite slurry and the first functional layer.
In some embodiments, the second organic solvent comprises: at least one of chlorobenzene, toluene, dimethyl sulfoxide and ethylene glycol has good dissolving effect on conductive high polymer materials, and has good uniform dispersion performance on perovskite raw materials such as ammonium iodide salt, alkali metal iodide salt and lead iodide and self-assembled perovskite, so that each component in the perovskite slurry is uniformly and stably dispersed in a solvent to form the perovskite slurry with proper viscosity, and the subsequent deposition and film formation are facilitated. In some embodiments, the second organic solvent is a mixture of 1: (0.33-2) and the dispersion stability of each raw material component in the slurry can be better improved by using the ethylene glycol and chlorobenzene mixed solvent in a compounding manner.
In some embodiments, the step of depositing the second perovskite slurry on the surface of the first functional layer in the step S212 includes: and scraping and coating the second perovskite slurry on the surface of the first functional layer under the conditions that the scraping and coating speed is 10-15 mm/s and the height of a scraper is 100-1500 mu m. The second perovskite slurry is deposited under the condition, so that the uniformity, stability and the like of the film layer can be improved, and the film layer is smooth and compact.
In some embodiments, the conditions of the second dry anneal comprise: drying at 20-40 ℃ for 12-14 hours to remove redundant solvent in the perovskite slurry, then annealing at 90-100 ℃ for 45-60 minutes to solidify and mold the perovskite slurry and make A' PbI3Self-assembly of perovskite is carried out to improve A' PbI in i-type perovskite functional layer3The perovskite material has the characteristics of crystal form order, structural integrity, purity, performance stability and the like. If the annealing temperature is too low, the optimization effect on the perovskite crystal form, the purity and the like in the perovskite active layer is not good, and the photoelectric property and the stability of the perovskite active layer are not improved; if the annealing temperature is too high, cracks are likely to occur in the perovskite active layer, and the material is decomposed, thereby deteriorating the stability of the perovskite active layer.
In some embodiments, in the step S30, the step of preparing the back electrode includes: at vacuum degree of not less than 10- 6mbar, evaporation rate of
Figure BDA0003198328610000151
And under the condition that the evaporation time is 100-150 s, evaporating and depositing a metal electrode on the surface of the second functional layer, which is far away from the first functional layer. If the degree of vacuum is too low, the electrode material is easily contaminated, and the deposition temperature is increased to decompose the perovskite material in the first functional layer and the second functional layer, thereby deteriorating the stability of the material and the functional layer. If the evaporation rate is too high, the surface of the perovskite active layer can be damaged; if the evaporation rate is too low, the deposition efficiency is low. In addition, the length of evaporation time can influence the stability of the deposited film layer on the one hand, and on the other hand, the length of deposition time can be determined according to the film layer thickness needing to be deposited, the stability of the deposited film layer is ensured by the evaporation time of 100-1500 s, and the application requirement of the X-ray detection device is met by the deposited electrode thickness. In some embodiments, the material of the back electrode comprises metals such as Al, Ag, Au, Cu, etcA material. In other embodiments, the back electrode may also be a carbon electrode prepared by a deposition process.
In order to make the above implementation details and operations of the present application clearly understood by those skilled in the art, and to make the advanced performance of the n-i structured perovskite-based X-ray detector and the manufacturing method thereof in the embodiments of the present application remarkably appear, the above technical solution is exemplified by a plurality of embodiments.
Example 1
An n-i structure perovskite-based X-ray detector is prepared by the following steps:
1. will CH3NH3Br, lead bromide, CTAB and a mixed solvent of DMF and NMP are mixed to prepare a first perovskite solution, wherein the volume ratio of DMF to NMP is 4:1, and CH is3NH3The mass ratio of the total mass of Br and lead bromide to CTAB and solvent is 100:0.75: 70; spin-coating the first perovskite solution on a conductive substrate of Indium Tin Oxide (ITO) transparent glass under the conditions of the spin-coating revolution number of 6000rmp/s and the spin time of 60s, drying the substrate at room temperature for 6 hours, and then annealing the substrate at 100 ℃ for 30 minutes to form CH3NH3PbBr3The thickness of the n-type perovskite functional layer is 7 mu m;
2. will CH3NH3I. Mixing lead iodide, polythiophene and a mixed solvent of ethylene glycol and chlorobenzene to prepare second perovskite slurry, wherein the volume ratio of the ethylene glycol to the chlorobenzene is 1:2, and CH3NH3The mass ratio of the total mass of I and lead iodide to the mass of the polythiophene and the solvent is 100:0.5: 50; under the conditions of blade coating speed of 10mm/s and blade height of 1200 mu m, the second perovskite slurry is coated on the surface of the n-type perovskite functional layer in a spinning way, dried for 6 hours at room temperature and annealed for 60 minutes at 100 ℃ to form CH3NH3PbI3The thickness of the i-type perovskite functional layer is 500 mu m;
3. at a vacuum degree of 10-6mbar, evaporation rate of
Figure BDA0003198328610000161
Under the condition that the evaporation time is 100s, the surface of the i-type perovskite functional layer is coated with the coating solutionVacuum evaporating Au to form Au metal back electrode to obtain n-i structure perovskite-based X-ray detector with n-i structure of ITO/CH3NH3PbBr3/CH3NH3PbI3The structure of Au is shown in figure 1.
Example 2
An n-i structure perovskite-based X-ray detector which is different from that of example 1 in that: step 1 is performed using CH2(NH3)2Br to obtain CH2(NH3)2PbBr3The n-type perovskite functional layer, the perovskite-based X-ray detector with the n-i structure is ITO/CH2(NH3)2Br/CH3NH3PbI3/Au。
Example 3
An n-i structure perovskite-based X-ray detector which is different from that of example 1 in that: step 2 is performed by CH2(NH3)2I, preparing CH2(NH3)2PbI3The structure of the i-type perovskite functional layer and the perovskite-based X-ray detector with the n-i structure is ITO/CH3NH3PbBr3/CH2(NH3)2I/Au。
Example 4
An n-i structure perovskite-based X-ray detector which is different from that of example 1 in that: CsBr is adopted in step 1 to prepare CsPbBr3The n-type perovskite functional layer, the perovskite-based X-ray detector with the n-i structure is ITO/CsPbBr3/CH3NH3PbI3/Au。
Example 5
An n-i structure perovskite-based X-ray detector which is different from that of example 1 in that: step 2, CsPbI is prepared by adopting CsI3The structure of the i-type perovskite functional layer and the perovskite-based X-ray detector with the n-i structure is ITO/CH3NH3PbBr3/CsPbI3/Au。
Example 6
An n-i structure perovskite-based X-ray detector which is different from that of example 1 in that: CsBr is adopted in step 1 to prepare CsPbBr3An n-type perovskite functional layer of (a); step 2, CsPbI is prepared by adopting CsI3The structure of the i-type perovskite functional layer and the perovskite-based X-ray detector with the n-i structure is ITO/CsPbBr3/CsPbI3/Au。
Comparative example 1
1. Will CH3NH3I. Mixing lead iodide, polythiophene and a mixed solvent of ethylene glycol and chlorobenzene to prepare second perovskite slurry, wherein the volume ratio of the ethylene glycol to the chlorobenzene is 1:2, and CH3NH3The mass ratio of the total mass of I and lead iodide to the mass of the polythiophene and the solvent is 100:0.5: 50; under the conditions that the blade coating speed is 10mm/s and the height of a scraper is 1200 mu m, the second perovskite slurry is spin-coated on the surface of the conductive substrate of the transparent glass of Indium Tin Oxide (ITO), after being dried for 6 hours at room temperature, the annealing treatment is carried out for 60 minutes at the temperature of 100 ℃, CH is formed3NH3PbI3The thickness of the i-type perovskite functional layer is 500 mu m;
2. at a vacuum degree of 10-6mbar, evaporation rate of
Figure BDA0003198328610000171
Under the condition that the evaporation time is 100s, carrying out vacuum evaporation on Au on the surface of the i-type perovskite functional layer to form Au metal back point gold to obtain the perovskite-based X-ray detector, wherein the perovskite-based X-ray detector is of an ITO/CH structure3NH3PbI3/Au。
Comparative example 2
An amorphous selenium-based X-ray detector from Canada analog was used as comparative example 2.
Further, to verify the advancement of the embodiments of the present application, the following performance tests were performed:
1. respectively observing the cross-sectional appearances of an n-type perovskite functional layer and an i-type perovskite functional layer in the n-i structure perovskite-based X-ray detector prepared in the embodiment 1 through a scanning electron microscope, wherein test charts are shown in attached drawings 2-3, wherein fig. 2 is a cross-sectional SEM (scanning electron microscope) chart of the n-type perovskite functional layer prepared by a solution method, and the compactness of a film layer is good; FIG. 3 is a sectional SEM image of an i-type perovskite functional layer prepared by a slurry method, and the crystals are uniform in size and tightly bonded.
2. Performing photocurrent tests, namely I-t tests, on the X-ray detectors prepared in the embodiments 1-6 and the comparative examples 1-2 respectively to obtain X-ray response electric quantity of the detectors under different doses, so as to obtain X-ray Sensitivity (S, Sensitivity) of the detectors respectively; and obtaining Dark Current density (Dark Current) of the detector under a Dark field respectively through I-t test, wherein Dark Current I-t test graphs of the embodiment 1 and the comparative examples 1-2 are shown in an attached figure 4, the abscissa is time, and the ordinate is Current density; the sensitivity test patterns of example 1 and comparative examples 1-2 are shown in fig. 5, with dose on the abscissa and charge on the ordinate. The test results are shown in table 1 below:
TABLE 1
Figure BDA0003198328610000181
Figure BDA0003198328610000191
According to the test results, the perovskite-based X-ray detector with the n-i structure prepared in the embodiments 1-4 of the application has higher detection sensitivity and lower dark current density. The perovskite-based X-ray detector with the n-i structure prepared in the embodiment 5-6 also has lower dark current, and in addition, the i-type perovskite functional layer adopts CsPbI3The perovskite material has relatively poor phase state stability, and is easy to convert from an alpha phase to a delta phase, so that the detection sensitivity of the device is reduced. The n-i structure perovskite-based X-ray detector provided by the embodiment of the application has the advantages that the detection sensitivity of the device is improved and the dark current of the device is effectively inhibited through the synergistic cooperation effect of the i perovskite active layer and the n type perovskite functional layer. The X-ray detector of comparative example 1 is a device formed by directly arranging electrodes on two sides of the perovskite active layer, and has large dark current up to 463nA/cm2. Compared with the amorphous selenium-based X-ray detector of Canada analog company in comparative example 2, the detection sensitivity of the device is low and is only 20 mu C Gyair -1cm-2。
The above description is only exemplary of the present application and should not be taken as limiting the present application, as any modification, equivalent replacement, or improvement made within the spirit and principle of the present application should be included in the protection scope of the present application.

Claims (10)

1. The n-i structure perovskite-based X-ray detector is characterized by comprising an n-type perovskite functional layer and an i-type perovskite active layer which are laminated and attached; the n-type perovskite functional layer contains APbBr3A perovskite material, wherein the i-type perovskite active layer contains A' PbI3A perovskite material, wherein a and a' are each independently selected from alkali metal ions or organic ammonium ions.
2. The n-i structured perovskite-based X-ray detector according to claim 1, wherein the organic ammonium ions comprise: CH (CH)3NH3 +、CH2(NH3)2 +At least one of;
and/or, the alkali metal ions comprise: cs+、Rb+At least one of (1).
3. The n-i structured perovskite-based X-ray detector of claim 2, wherein a and a' are each independently selected from the group consisting of: CH (CH)3NH3 +、CH2(NH3)2 +、Cs+Or Cs+And Rb+。
4. The n-i structure perovskite-based X-ray detector according to any one of claims 1 to 3, wherein the thickness of the n-type perovskite functional layer is 15 to 25 μm;
and/or the thickness of the i-type perovskite active layer is 100-1000 mu m.
5. A method for preparing a perovskite-based X-ray detector with an n-i structure is characterized by comprising the following steps:
obtaining a conductive substrate, and preparing a first functional layer on the surface of the conductive substrate;
preparing a second functional layer on the surface of the first functional layer, which is far away from the conductive substrate;
preparing a back electrode on the surface of the second functional layer, which is far away from the first functional layer, so as to obtain the perovskite-based X-ray detector with the n-i structure;
the first functional layer and the second functional layer are different and are respectively an n-type perovskite functional layer or an i-type perovskite active layer, and the n-type perovskite functional layer contains APbBr3A perovskite material, wherein the i-type perovskite active layer contains A' PbI3A perovskite material, wherein a and a' are each independently selected from alkali metal ions or organic ammonium ions.
6. The method of manufacturing an n-i structure perovskite-based X-ray detector as claimed in claim 5, wherein the first functional layer is the n-type perovskite functional layer, and the step of manufacturing the n-type perovskite functional layer comprises: mixing ammonium bromide salt or alkali metal bromide salt with lead bromide, a surfactant and a first organic reagent to obtain a first perovskite solution;
and depositing the first perovskite solution on the surface of the conductive substrate, and carrying out primary drying annealing to form the n-type perovskite functional layer.
7. The method of manufacturing an n-i structured perovskite-based X-ray detector according to claim 6, wherein the second functional layer is the i-type perovskite functional layer, and the step of manufacturing the i-type perovskite functional layer comprises: mixing and processing ammonium iodide salt or alkali iodide salt, lead iodide, a conductive polymer adhesive and a second organic reagent to obtain second perovskite slurry;
and depositing the second perovskite slurry on the surface of the first functional layer, and carrying out secondary drying annealing to form the i-type perovskite functional layer.
8. The method for producing an n-i-structured perovskite-based X-ray detector according to claim 7, wherein the ratio of the molar amount of the ammonium bromide salt or the alkali metal bromide salt to the molar amount of the lead bromide in the first perovskite solution is 1: (1-1.2);
and/or, in the first perovskite solution, the mass ratio of the total mass of the ammonium bromide salt, the alkali metal bromide salt and the lead bromide to the mass of the surfactant and the first organic reagent is 100: (0.5-1.5): (50-75);
and/or the surfactant is selected from quaternary ammonium salt surfactants;
and/or, the first organic solvent comprises: at least one of N, N-dimethylformamide, N-methylpyrrolidone and dimethyl sulfoxide;
and/or, in the second perovskite slurry, the ratio of the molar amount of the ammonium iodide salt or the alkali metal iodide salt to the molar amount of the lead iodide is 1: (1-1.10);
and/or in the second perovskite slurry, the mass ratio of the total mass of the ammonium iodide salt, the alkali metal iodide salt and the lead iodide to the mass of the conductive polymer binder and the second organic reagent is 100: (0.5-2.5): (35-50);
and/or, the conductive polymer binder is selected from: at least one of polythiophene, poly [ bis (4-phenyl) (2,4, 6-trimethylphenyl) amine ], poly [ bis (4-phenyl) (4-butylphenyl) amine ], and poly (p-phenylene vinylene);
and/or, the second organic solvent comprises: at least one of chlorobenzene, toluene, dimethyl sulfoxide and ethylene glycol.
9. The method of manufacturing an n-i structured perovskite-based X-ray detector according to claim 8, wherein the step of depositing the first perovskite solution on the surface of the conductive substrate comprises: spin-coating the first perovskite solution on the surface of the conductive substrate under the condition that the spin-coating revolution number is 5000-7000 rmp/s;
or coating the first perovskite solution on the surface of the conductive substrate under the conditions that the coating speed is 10-15 mm/s and the height of a scraper is 30-50 mu m;
and/or the conditions of the first drying annealing comprise: drying for 6-8 hours at the temperature of 20-40 ℃, and then annealing for 25-30 minutes at the temperature of 90-100 ℃;
and/or the step of depositing the second perovskite slurry on the surface of the first functional layer comprises: under the conditions that the scraping speed is 10-15 mm/s and the height of a scraper is 100-1500 mu m, scraping the second perovskite slurry on the surface of the first functional layer;
and/or the conditions of the second drying annealing comprise: drying the mixture for 12 to 14 hours at the temperature of 20 to 40 ℃, and then annealing the dried mixture for 45 to 60 minutes at the temperature of 90 to 100 ℃.
10. The method of manufacturing an n-i structured perovskite-based X-ray detector according to claim 9, wherein the step of manufacturing the back electrode comprises: at vacuum degree of not less than 10-6mbar, evaporation rate of
Figure FDA0003198328600000031
Under the condition that the evaporation time is 100-150 s, evaporating and depositing a metal electrode on the surface of the second functional layer, which is far away from the first functional layer;
and/or, the surfactant comprises: at least one of cetyl trimethyl ammonium bromide, cetyl trimethyl ammonium chloride and didodecyl dimethyl ammonium bromide;
and/or the first organic solvent is (3-5) in volume ratio: 1 of a mixed solvent of N, N-dimethylformamide and N-methylpyrrolidone;
and/or the second organic solvent is a mixture of 1: (0.33-2) a mixed solvent of ethylene glycol and chlorobenzene.
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