CN111864080A - Two-dimensional organic-inorganic hybrid perovskite crystal photoelectric detector and preparation method thereof - Google Patents
Two-dimensional organic-inorganic hybrid perovskite crystal photoelectric detector and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a two-dimensional organic-inorganic hybrid perovskite crystal photoelectric detector and a preparation method thereof. The photoelectric detector comprises a substrate, a two-dimensional organic-inorganic hybrid perovskite layer and an electrode layer from bottom to top in sequence; the electrode layer is divided into an anode metal electrode and a cathode metal electrode which are interdigital electrodes. The photosensitive material is based on two-dimensional organic-inorganic hybrid perovskite crystals on a mica substrate, has the characteristics of high luminous efficiency, high carrier mobility and the like, and can be used as a transmission layer of electrons and holes in a device, so that the photoelectric detector device is simple in preparation process, low in cost, light, convenient and high in sensitivity.
Description
Technical Field
The invention belongs to the technical field of photoelectric detection, and particularly relates to a novel two-dimensional organic-inorganic hybrid perovskite photoelectric detector and a preparation method thereof.
Background
The photoelectric detector can convert incident photons into electrons which can be collected by the electrode, and due to the difference of photosensitive materials and device structures, the photoelectric response rate, the photoelectric response speed and the response wave band obtained by the detector are greatly different. The photoelectric detectors with different performances can be widely applied to different fields such as environment monitoring, night vision systems, image sensing and the like. The existing photoelectric detector based on semiconductor materials such as inorganic silicon, indium gallium arsenide and the like has good performances in the aspects of response speed, sensitivity and stability, but also has the defects of complex preparation process and high cost.
The hybrid perovskite material has very excellent photoelectric characteristics, such as: wide absorption spectrum from ultraviolet to infrared band, adjustable optical band gap, high external quantum efficiency, high absorption coefficient, high carrier mobility, and relative balance of electron and hole transport properties, etc., thus leading to rapid development in the field of photoelectricity (science, 49(2015), 1518-. The highest certification efficiency of the current hybrid perovskite-based solar cell is 23.3%, the index is very close to that of a commercial silicon-based solar cell, and the manufacturing cost of the hybrid perovskite solar cell is only one third of that of the silicon-based solar cell. These properties indicate that hybrid perovskites can be developed as important materials for the fabrication of low cost, high performance photodetectors. When the thickness of the hybrid perovskite is reduced to an atomic scale, electrons confined in the two-dimensional material are strongly subjected to quantum confinement, and the hybrid perovskite shows unique physical properties such as optics, electricity, mechanics and the like. The two-dimensional hybrid perovskite crystal can make up the defect of low photoelectric efficiency of the traditional two-dimensional material. No matter the semi-metal material is graphene or semiconductor material is molybdenum disulfide and the like, the photoelectric performance of a two-dimensional material in the conventional two-dimensional material sample library can be comparable with that of a hybrid perovskite crystal. However, the current photoelectric detector of the all-inorganic hybrid perovskite cannot simultaneously realize high sensitivity and quick response.
Therefore, aiming at the problems of low photoelectric efficiency, complex preparation process, high cost and the like of the traditional two-dimensional material, a photosensitive material with excellent photoelectric property needs to be explored, and a photoelectric detector with low manufacturing cost and high efficiency is designed to have better application prospect.
Disclosure of Invention
The invention aims to provide a two-dimensional organic-inorganic hybrid perovskite crystal photoelectric detector which can be simply prepared aiming at the defects in the prior art. Compared with the prior two-dimensional material photoelectric detector, the photosensitive material in the invention is based on two-dimensional organic-inorganic hybrid perovskite crystal on a mica substrate, has the characteristics of high luminous efficiency, high carrier mobility and the like, and can be used as a transmission layer of electrons and holes in the device, so that the photoelectric detector has the advantages of simple preparation process, low cost, convenience in urination and high sensitivity.
The technical scheme of the invention is as follows:
a two-dimensional organic-inorganic hybrid perovskite crystal photoelectric detector comprises a substrate, a two-dimensional organic-inorganic hybrid perovskite layer and an electrode layer from bottom to top in sequence;
the electrode layers are respectively an anode metal electrode and a cathode metal electrode which are interdigital electrodes; on the two-dimensional organic-inorganic hybrid perovskite layer, the interdigital of the anode metal electrode and the cathode metal electrode are distributed at intervals; the distance between adjacent interdigital is 50-100 microns;
wherein the anode metal electrode and the cathode metal electrode are palladium, gold, platinum, silver, copper or aluminum, and the anode metal electrode and the cathode metal electrode are the same or different;
the distance between the anode metal electrode and the cathode metal electrode is 100-600 microns; the thickness is 80-100 nm.
The width of the two-dimensional organic-inorganic hybrid perovskite crystal layer is 200-800 microns, and the thickness of the two-dimensional organic-inorganic hybrid perovskite crystal layer is 10-1000 nm.
The substrate can be a silicon-silicon dioxide substrate, a quartz substrate, a mica sheet or ITO glass.
The preparation method of the two-dimensional organic-inorganic hybrid perovskite crystal photoelectric detector comprises the following steps:
1) preparing a saturated organic-inorganic hybrid perovskite precursor solution;
organic halogen acid salt, PbX2Mixing (X ═ Cl, Br and I), adding gamma-butyrolactone (GBL), magnetically stirring at 35-45 ℃ for 20-40 minutes, filtering, pouring the obtained filtrate into a container, sealing, standing at 90-110 ℃ for 2-3 hours, and removing precipitated crystal grains to obtain a precursor solution of the organic-inorganic hybrid perovskite crystal;
wherein, the mol ratio is that the organic hydrogen halide salt: PbX21: 0.8-1.2; adding 4-6 ml of gamma-butyrolactone into each millimole of organic halogen acid salt;
2) extracting the precursor solution of the organic-inorganic hybrid perovskite crystal in the step 1) by using a micropipettor, dropwise adding the precursor solution on a substrate, putting the substrate into a spin coater, and spin-coating for 10-30 seconds, wherein 50-150 microliters of the organic-inorganic hybrid perovskite crystal solution is dropwise added on a 100-square-millimeter substrate; the glue homogenizing speed is 500-1000 r/min;
3) placing the growing device in the step 2) in an inert gas environment, and preserving heat for 8-10 hours at 40-60 ℃ to obtain a two-dimensional organic-inorganic hybrid perovskite crystal layer;
4) evaporating metal electrodes on the surface of the two-dimensional organic-inorganic hybrid perovskite crystal obtained in the step 3) to obtain a two-dimensional organic-inorganic hybrid perovskite photoelectric detector;
the crystal equipment in the step 3) is an atmosphere furnace, a hot plate in a glove box or a tube furnace.
The method comprises the step 1) of adding a surface modifier into a precursor solution of the organic-inorganic hybrid perovskite crystal, wherein the surface modifier is oleic acid or oleamide, and the adding amount of the surface modifier is 5-35% of the volume ratio of the perovskite growth solution.
The inert gas is nitrogen or argon.
The invention also discloses an electron and hole transport layer formed by the two-dimensional hybrid perovskite crystal grown on the mica substrate, and the film is uniform, compact and free of holes, so that the dark current of the device is reduced, and the detection rate of the device is improved.
The two-dimensional organic-inorganic hybrid perovskite crystal photoelectric detector prepared by the preparation method disclosed by the invention belongs to the protection scope of the invention.
The preparation method of the invention, which is used as an electron and hole transport layer together with two-dimensional organic-inorganic hybrid perovskite crystals, belongs to the protection scope of the invention.
The invention has the beneficial effects that:
the preparation method of the invention is to evaporate different types of metal electrodes on the two-dimensional organic-inorganic hybrid perovskite crystal, thereby obtaining the photoelectric detector with excellent performance. The two-dimensional organic-inorganic hybrid perovskite crystal grown on the mica substrate is applied to the photoelectric detector for the first time, and a novel photoelectric detector device is provided; secondly, by selecting different metal electrodes, the contact type between the metal and the semiconductor can be flexibly changed, so that the optical and electrical characteristics of the device are changed, and a new idea is provided for designing different types of photoelectric detectors; finally, the two-dimensional organic-inorganic hybrid perovskite photoelectric detector is simple in preparation process, extremely low in cost, light, convenient, flexible and high in detection rate.
The invention provides a two-dimensional organic-inorganic hybrid perovskite crystal photoelectric detector which can be simply prepared. Compared with the traditional photoelectric detector, the photosensitive material in the invention is a two-dimensional organic-inorganic hybrid perovskite crystal based on a mica substrate, the crystal is a single crystal material, the internal defect density is small, the photosensitive material not only has the characteristics of high photoresponse efficiency, high response speed and the like, but also can be used as a transmission layer of electrons and holes in a device, and therefore, the preparation of the photoelectric detector inherits the characteristics of simple process, low cost, lightness, convenience and the like of the prior generation photoelectric detector. Most of the commercial available photodetector substrate materials currently use P-doped single crystal silicon material to have an optical response power density of 10 over a spectrum of about 500 nm-3mW/cm2Compared with the traditional material, the two-dimensional organic-inorganic hybrid perovskite single crystal has higher optical power response density (10)-2～10- 1mW/cm2) And the on-off ratio of the device is as high as 104This means that the size of the blue-violet light band photodetector using the two-dimensional organic-inorganic hybrid perovskite single crystal as the base material can be made smaller and more sensitive. In the invention, the response rate of the two-dimensional organic-inorganic hybrid perovskite photoelectric detector is preferably 937A/W, which is higher than that of other hybrid perovskite photoelectric detectors. In the invention, the response time of the two-dimensional organic-inorganic hybrid perovskite photoelectric detector is 0.08-0.1 s; the two-dimensional organic and inorganicThe recovery time of the hybrid perovskite photoelectric detector is 0.08-0.1 s.
Drawings
FIG. 1 is a schematic diagram of a two-dimensional organic-inorganic hybrid perovskite crystal photodetector device of the present invention;
FIG. 2 is a diagram of a two-dimensional organic-inorganic hybrid perovskite crystal photoelectric detector device plated with a metal electrode;
FIG. 3 is a diagram of a mask plate;
FIG. 4 is a thickness diagram of a two-dimensional organic-inorganic hybrid perovskite crystal;
FIG. 5-1 is a characteristic curve diagram of photocurrent and voltage of a two-dimensional organic-inorganic hybrid perovskite crystal photoelectric detector plated with Au electrodes under different optical densities;
FIG. 5-2 is a characteristic curve diagram of photocurrent and voltage of a two-dimensional organic-inorganic hybrid perovskite crystal photoelectric detector plated with a Cu electrode under different optical densities;
5-3 are graphs of characteristics of photocurrent and voltage of two-dimensional organic-inorganic hybrid perovskite crystal photoelectric detectors plated with Ag electrodes under different optical densities;
5-4 are graphs of characteristics of photocurrent and voltage of two-dimensional organic-inorganic hybrid perovskite crystal photoelectric detectors plated with Au-Ag electrodes under different optical densities;
FIG. 6 is a graph showing the relationship between incident light power and responsivity of a two-dimensional organic-inorganic hybrid perovskite crystal photodetector;
FIG. 7-1 is a time-current diagram of a two-dimensional organic-inorganic hybrid perovskite crystal photodetector with Au-plated electrodes at different optical densities;
FIG. 7-2 is a time-current diagram of a two-dimensional organic-inorganic hybrid perovskite crystal photodetector plated with a Cu electrode at different optical densities;
7-3 are time-current diagrams of two-dimensional organic-inorganic hybrid perovskite crystal photodetectors coated with Ag electrodes at different optical densities;
7-4 are time-current diagrams of two-dimensional organic-inorganic hybrid perovskite crystal photoelectric detectors plated with Au-Ag electrodes under different optical densities.
Detailed Description
The following describes embodiments of the present invention in further detail with reference to the examples and the accompanying drawings. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
Example 1
A preparation method and steps of two-dimensional organic-inorganic hybrid perovskite crystal.
Step 1) all purchased chemical reagents were of analytical purity. Adding 7ml of methylamine solution into a beaker filled with magnetons, placing the beaker into an ice-water bath, slowly adding 10.6ml of hydriodic acid solution, stirring the mixture on a heating plate at 35 ℃ for 30min, filtering the mixture into a new beaker by using quick filter paper, adding 5.9ml of absolute ethyl alcohol into the new beaker to react for 2 to 3 hours in the ice-water bath environment, placing the new beaker on the heating plate in a glove box to react for 10 to 12 hours at the evaporation temperature of 40 to 60 ℃, obtaining a coarse product after evaporation and crystallization, washing the coarse product by using ethyl ether, and drying the coarse product in a vacuum drying oven at 60 ℃ for one night to obtain a pure white product, namely, the methylamine hydriodide (CH)3NH3I)。
The chemical reagents used in step 2) are all analytically pure products of the Aladdin company. Weighing 0.759g (5mmol) methylamine hydroiodide and 2.305g (5mmol) lead iodide, placing into a beaker with magnetons, adding 5ml gamma-butyrolactone (GBL), stirring for 30min on a heating plate at 40 deg.C to obtain clear yellow solution, filtering with quick filter paper to the beaker with a seal, placing on a hot plate in a glove box, heating at 100 deg.C for 2 hr to find black crystal grains, turning off the hot plate, taking out crystal grains, and collecting saturated solution of organic-inorganic hybrid CH3NH3PbI3A precursor liquid for the crystal. And then diluting the obtained 5ml of precursor growth liquid with 20ml of gamma-butyrolactone, and taking the diluted precursor growth liquid and oleic acid according to the volume ratio of 3: 1 (i.e. 8.33 ml of oleic acid) were mixed with each other and stored sealed, with oleic acid acting as a surface modifier.
Example 2 (two-dimensional CH with both anode and cathode of Au metal electrode3NH3PbI3Preparation of crystal photoelectric detector
A method for preparing a two-dimensional organic-inorganic hybrid perovskite crystal photoelectric detector and steps thereof.
Step 1) using a mica sheet as a substrate for crystal growth. A micropipette was used to transfer about 100. mu.L of the solution to 10X 0.2mm mica chips, which were placed in a spin coater at 800 rpm for 15 seconds.
And 2) placing the sample after glue homogenizing in a nitrogen environment, and preserving heat for 8 hours at 40 ℃ to obtain the two-dimensional organic-inorganic hybrid perovskite crystal.
Step 3) adding oleic acid to ensure that a large number of oily acid drops are formed on the surface of the sample, immersing the sample into cyclohexane for cleaning, and flushing the cyclohexane on the surface of the sample by using nitrogen to wash off the oleic acid to obtain the two-dimensional organic-inorganic hybrid perovskite CH with clean surface and thin thickness3NH3PbI3A crystal; and then the sample is placed in a glove box for storage, so that the sample is prevented from being decomposed due to high water oxygen content, the stability is prevented from being reduced, and the efficiency of a detector device is reduced.
And 4) performing ultrasonic treatment on the designed mask plate for 30 minutes by using acetone and absolute ethyl alcohol respectively, pouring the mask plate into deionized water at 35 ℃ for ultrasonic treatment for 20 minutes, blow-drying the mask plate by using a nitrogen gun, and storing the mask plate in a glove box to prepare for preventing a thin film material sample from being polluted and evaporating a regular electrode.
And 5) bonding a mask plate on a glass slide with the size of 3cm multiplied by 5cm, simultaneously bonding two-dimensional hybrid perovskite crystals on a mica substrate on the glass slide with the size of 5cm multiplied by 5cm, aligning the mask plate on the two-dimensional hybrid perovskite crystals to be tested by means of a three-dimensional adjusting frame, and tightly combining the two crystals under the action of an adhesive tape so as to enable the metal-hybrid perovskite semiconductor-metal to be orderly arranged. The mask is specifically XCZ-2357J-A1J, available from Shanghai microcrystalline equipment manufacturing company, and is described in the following examples.
And 6) evaporating a gold film with the thickness of 80nm by using a vacuum coating machine after the sample is shielded by the mask plate to respectively serve as the anode and the cathode of the photoelectric detector. The structure of the resulting photodetector device is shown in fig. 2.
FIG. 1 is a schematic diagram of a two-dimensional organic-inorganic hybrid perovskite crystal photoelectric detector designed by the invention, which comprises a mica sheet, a two-dimensional organic-inorganic hybrid perovskite crystal layer and a metal electrode layer from bottom to top in sequence;
FIG. 2 is a diagram showing a two-dimensional organic-inorganic hybrid perovskite crystal photodetector of the present invention, from which it can be seen that anode and cathode metal electrodes distributed in interdigital form are uniformly laid on the two-dimensional organic-inorganic hybrid perovskite crystal;
FIG. 3 is a picture of a mask showing a real object of the present invention, wherein it can be seen from the picture that the mask is designed to be a square of 1.2cm by 1.2cm in appearance, and is designed to be hollow in the middle, the index of the fingers is 15, the inter-finger distance is 30 μm, the width of the fingers is 30 μm, the length of the fingers is 80 μm, and the width of the two sides is 150 μm;
FIG. 4 shows two-dimensional CH grown on the surface of mica sheet3NH3PbI3Thickness of the crystal measured data, the thickness of the crystal was about 100 nm.
Example 3 (two-dimensional CH with both anode and cathode Cu metal electrodes3NH3PbI3Preparation of crystal photoelectric detector
A method for preparing a two-dimensional organic-inorganic hybrid perovskite crystal photoelectric detector and steps thereof.
Step 1) using a mica sheet as a substrate for crystal growth. A micropipette was used to transfer about 100. mu.L of the solution to 10X 0.2mm mica chips, which were placed in a spin coater at 800 rpm for 15 seconds.
And 2) placing the sample after glue homogenizing in a nitrogen environment, and preserving the heat for 8 hours at 40 ℃ to obtain the two-dimensional organic-inorganic hybrid perovskite crystal with thin thickness.
Step 3) adding oleic acid to ensure that a large number of oily acid drops are formed on the surface of the sample, immersing the sample into cyclohexane for cleaning, and flushing the cyclohexane on the surface of the sample by using nitrogen to wash off the oleic acid to obtain the two-dimensional organic-inorganic hybrid perovskite CH with a clean surface and a thickness of about 100nm3NH3PbI3A crystal; and then the sample is placed in a glove box for storage, so that the sample is prevented from being decomposed due to high water oxygen content, the stability is prevented from being reduced, and the efficiency of a detector device is reduced.
And 4) performing ultrasonic treatment on the designed mask plate for 30 minutes by using acetone and absolute ethyl alcohol respectively, pouring the mask plate into deionized water at 35 ℃ for ultrasonic treatment for 20 minutes, blow-drying the mask plate by using a nitrogen gun, and storing the mask plate in a glove box to prepare for preventing a thin film material sample from being polluted and evaporating a regular electrode.
And 5) bonding a mask plate on a glass slide with the size of 3cm multiplied by 5cm, simultaneously bonding two-dimensional hybrid perovskite crystals on a mica substrate on the glass slide with the size of 5cm multiplied by 5cm, aligning the mask plate on the two-dimensional hybrid perovskite crystals to be tested by means of a three-dimensional adjusting frame, and tightly combining the two crystals under the action of an adhesive tape so as to enable the metal-hybrid perovskite semiconductor-metal to be orderly arranged.
And 6) evaporating a copper film with the thickness of 80nm by using a vacuum coating machine after the sample is shielded by the mask plate to respectively serve as an anode and a cathode of the photoelectric detector. The structure of the resulting photodetector device is shown in fig. 2.
Example 4 (two-dimensional CH with both anode and cathode of Ag Metal electrode3NH3PbI3Preparation of crystal photoelectric detector
A method for preparing a two-dimensional organic-inorganic hybrid perovskite crystal photoelectric detector and steps thereof.
Step 1) using a mica sheet as a substrate for crystal growth. A micropipette was used to transfer about 100. mu.L of the solution to 10X 0.2mm mica chips, which were placed in a spin coater at 800 rpm for 15 seconds.
And 2) placing the sample after glue homogenizing in a nitrogen environment, and preserving the heat for 8 hours at 40 ℃ to obtain the two-dimensional organic-inorganic hybrid perovskite crystal with thin thickness.
Step 3) adding oleic acid to enable the surface of the sample to have a large number of oleic acid drops, immersing the sample into cyclohexane for cleaning, and flushing the cyclohexane on the surface of the sample with nitrogen to wash away the oleic acid to obtainTwo-dimensional organic-inorganic hybrid perovskite CH with clean surface and thickness of about 100nm3NH3PbI3A crystal; and then the sample is placed in a glove box for storage, so that the sample is prevented from being decomposed due to high water oxygen content, the stability is prevented from being reduced, and the efficiency of a detector device is reduced.
And 4) performing ultrasonic treatment on the designed mask plate for 30 minutes by using acetone and absolute ethyl alcohol respectively, pouring the mask plate into deionized water at 35 ℃ for ultrasonic treatment for 20 minutes, blow-drying the mask plate by using a nitrogen gun, and storing the mask plate in a glove box to prepare for preventing a thin film material sample from being polluted and evaporating a regular electrode.
And 5) bonding a mask plate on a glass slide with the size of 3cm multiplied by 5cm, simultaneously bonding two-dimensional hybrid perovskite crystals on a mica substrate on the glass slide with the size of 5cm multiplied by 5cm, aligning the mask plate on the two-dimensional hybrid perovskite crystals to be tested by means of a three-dimensional adjusting frame, and tightly combining the two crystals under the action of an adhesive tape so as to enable the metal-hybrid perovskite semiconductor-metal to be orderly arranged.
And 6) evaporating a silver film with the thickness of 80nm by using a vacuum coating machine after the sample is shielded by the mask plate to respectively serve as an anode and a cathode of the photoelectric detector. The structure of the resulting photodetector device is shown in fig. 2.
Example 5 (two-dimensional CH with Au and Ag Metal electrodes for the Anode and cathode, respectively)3NH3PbI3Preparation of crystal photoelectric detector
A method for preparing a two-dimensional organic-inorganic hybrid perovskite crystal photoelectric detector and steps thereof.
Step 1) using a mica sheet as a substrate for crystal growth. A micropipette was used to transfer about 100. mu.L of the solution to 10X 0.2mm mica chips, which were placed in a spin coater at 800 rpm for 15 seconds.
And 2) placing the sample after glue homogenizing in a nitrogen environment, and preserving the heat for 8 hours at 40 ℃ to obtain the two-dimensional organic-inorganic hybrid perovskite crystal with thin thickness.
Step 3) adding oleic acid to ensure that a large number of oleic acid drops exist on the surface of the sample, and soaking the sampleWashing in cyclohexane, flushing cyclohexane on the surface of the sample with nitrogen to wash off oleic acid to obtain two-dimensional organic-inorganic hybrid perovskite CH with clean surface and thickness of about 100nm3NH3PbI3A crystal; and then the sample is placed in a glove box for storage, so that the sample is prevented from being decomposed due to high water oxygen content, the stability is prevented from being reduced, and the efficiency of a detector device is reduced.
And 4) performing ultrasonic treatment on the designed mask plate for 30 minutes by using acetone and absolute ethyl alcohol respectively, pouring the mask plate into deionized water at 35 ℃ for ultrasonic treatment for 20 minutes, blow-drying the mask plate by using a nitrogen gun, and storing the mask plate in a glove box to prepare for preventing a thin film material sample from being polluted and evaporating a regular electrode.
And 5) bonding a mask plate on a glass slide with the size of 3cm multiplied by 5cm, simultaneously bonding two-dimensional hybrid perovskite crystals on a mica substrate on the glass slide with the size of 5cm multiplied by 5cm, aligning the mask plate on the two-dimensional hybrid perovskite crystals to be tested by means of a three-dimensional adjusting frame, and tightly combining the two crystals under the action of an adhesive tape so as to enable the metal-hybrid perovskite semiconductor-metal to be orderly arranged.
Step 6) after the sample is shielded by the mask plate, using an adhesive tape to shield half of the mask plate, and using a vacuum coating machine to evaporate a gold electrode with the thickness of 80nm as an anode of the photoelectric detector; and taking out the sample, taking down the adhesive tape, shielding the other half of the mask plate, and evaporating a silver electrode with the thickness of 80nm by using a vacuum film plating machine to be used as a cathode of the photoelectric detector. The resulting photodetector device structure is fabricated as shown in fig. 2.
Performance characterization 1: the two-dimensional organic-inorganic hybrid perovskite crystal photoelectric detection devices in example 2, example 3, example 4 and example 5 are subjected to voltage-current curve tests in a dark state and at different optical densities.
And carrying out voltage-current curve tests on the two-dimensional hybrid perovskite photoelectric detector plated with different metal electrodes under dark states and different optical densities. FIG. 5-1 shows two-dimensional CH with Au metal electrodes as the anode and cathode at different optical densities3NH3PbI3Response current-voltage characteristic of crystal photoelectric detectorThe figure shows that the photoresponse current value of the photoelectric detector is linearly increased along with the increase of the voltage and the optical density, and the dark current of the device is extremely low and can reach 10-12A, shows that with low carrier concentration, the on-off ratio of the device can be as high as 104(ii) a FIG. 5-2 shows two-dimensional CH with Cu metal electrodes as anode and cathode under illumination of specific excitation wavelength (520nm)3NH3PbI3The response current-voltage characteristic curve of the crystal photoelectric detector is obviously shown in the figure to be in an inverse S shape, the light response current value of the crystal photoelectric detector is increased along with the increase of voltage and optical density, and the dark current of the device is extremely low and can reach 10-12A, shows that with low carrier concentration, the on-off ratio of the device can be as high as 104(ii) a FIGS. 5-3 show two-dimensional CH with Ag metal electrodes for both anode and cathode under illumination of specific excitation wavelength (520nm)3NH3PbI3The response current-voltage characteristic curve of the crystal photoelectric detector is obvious from the figure, the curve is S-shaped, the light response current value is increased along with the increase of the voltage and the light density, and the dark current of the device is extremely low and can reach 10-12A, shows that with low carrier concentration, the on-off ratio of the device can be as high as 104(ii) a FIGS. 5-4 show two-dimensional CH with Au and Ag metal electrodes as anode and cathode, respectively, under illumination of specific excitation wavelength (520nm)3NH3PbI3The response current-voltage characteristic curve of the crystal photoelectric detector is obviously shown in the figure to be in an inverse S shape, the light response current value of the crystal photoelectric detector is increased along with the increase of voltage and optical density, and the dark current of the device is extremely low and can reach 10-12A, shows that with low carrier concentration, the on-off ratio of the device can be as high as 104. This indicates that changing the type of metal electrode provides the possibility to fabricate different photodetectors.
Performance characterization 2: responsivity tests under different light intensities were carried out on the two-dimensional organic-inorganic hybrid perovskite crystal photodetectors in example 2, example 3, example 4, and example 5, respectively.
And carrying out responsivity tests on the device under different light intensities under the bias voltage of 5V. FIG. 6 shows the responsivity curves of two-dimensional organic-inorganic hybrid perovskite crystal photodetectors plated with different metal electrodes under different light intensities under 5V bias. As can be seen from the figure, the responsivity of the device is increased along with the reduction of incident light power, and under the excitation wavelength of 520nm and the optical power of 0.03mW, the responsivity of the device can reach 937A/W at most, which is higher than the responsivity of other hybrid perovskite photodetectors.
Performance characterization 3: the two-dimensional organic-inorganic hybrid perovskite crystal photoelectric detection devices in example 2, example 3, example 4 and example 5 are subjected to time-current curve tests at different optical densities.
The devices were subjected to current testing under illumination of a specific wavelength (520nm) at 0V bias. FIG. 7-1 shows the current variation curve of the two-dimensional hybrid perovskite photodetector plated with Au electrode under different optical densities under 0V bias, and it can be seen that the current gradually increases with the increase of the optical density, and the highest current value can be stabilized at about 100 nA; fig. 7-2 shows the current variation curve of the Cu electrode-plated two-dimensional hybrid perovskite photodetector under different optical densities under a bias voltage of 0V, and it can be seen that the current gradually increases with the increase of the optical density, and the highest current value can be stabilized at about 120 nA; 7-3 show the current change curves of the two-dimensional hybrid perovskite photoelectric detector plated with the Ag electrode under different optical densities under the bias of 0V, and it can be seen that the current gradually increases along with the increase of the optical density, and the highest current value can be stabilized at about 23 nA; 7-4 show the current change curves of the two-dimensional hybrid perovskite photoelectric detector plated with the Au-Ag electrode under different optical densities under the bias of 0V, and it can be seen that the current gradually increases along with the increase of the optical density, and the highest current value can be stabilized at about 43 nA. It can be seen from the figure that under the illumination of a specific wavelength (520nm), the light response of each device has high repeatability and the response current to the light is relatively stable by changing the range of the optical density. And the response and recovery time of the photodetector is less than 0.100 s. As can be seen from the figure, the photodetectors of different metal electrodes have different values of the photocurrent, which illustrates that different types of metal-semiconductor contacts affect the electrical performance of the photodetectors.
The invention is not the best known technology.
Claims (8)
1. A two-dimensional organic-inorganic hybrid perovskite crystal photoelectric detector is characterized in that the photoelectric detector sequentially comprises a substrate, a two-dimensional organic-inorganic hybrid perovskite layer and an electrode layer from bottom to top;
wherein the anode metal electrode and the cathode metal electrode are palladium, gold, platinum, silver, copper or aluminum, and the anode metal electrode and the cathode metal electrode are the same or different;
the distance between the anode metal electrode and the cathode metal electrode is 100-600 microns; the thickness is 80-100 nm.
2. A two-dimensional organic-inorganic hybrid perovskite crystal photodetector as claimed in claim 1, wherein the width of said two-dimensional organic-inorganic hybrid perovskite crystal layer is 200-800 μm, and the thickness is 10-1000 nm.
3. A two-dimensional organic-inorganic hybrid perovskite crystal photodetector as claimed in claim 1, wherein the electrode layer is divided into an anode metal electrode and a cathode metal electrode which are both interdigital electrodes; on the two-dimensional organic-inorganic hybrid perovskite layer, anode metal electrodes and cathode metal electrodes are distributed at intervals in an interdigital manner; the spacing between adjacent fingers is 30 microns.
4. A two-dimensional organic-inorganic hybrid perovskite crystal photodetector as claimed in claim 1, wherein said substrate is selected from the group consisting of silicon-silica substrate, quartz substrate, mica sheet and ITO glass.
5. The method for preparing a two-dimensional organic-inorganic hybrid perovskite crystal photodetector as claimed in claim 1, characterized in that the method comprises the steps of:
1) preparing a saturated organic-inorganic hybrid perovskite precursor solution;
organic halogen acid salt, PbX2Mixing (X ═ Cl, Br and I), adding gamma-butyrolactone (GBL), magnetically stirring at 35-45 ℃ for 20-40 minutes, filtering, pouring the obtained filtrate into a container, and sealingClosing, standing for 2-3 h at 90-110 ℃, and removing precipitated crystal grains to obtain a precursor solution of the organic-inorganic hybrid perovskite crystal;
wherein, the mol ratio is that the organic hydrogen halide salt: PbX21: 0.8-1.2; adding 4-6 ml of gamma-butyrolactone into each millimole of organic halogen acid salt;
2) extracting the precursor solution of the organic-inorganic hybrid perovskite crystal in the step 1) by using a micropipette, dropwise adding the precursor solution on a mica substrate, putting the mica substrate into a spin coater, and spin-coating for 10-30 seconds, wherein 50-150 microliters of the organic-inorganic hybrid perovskite crystal solution is dropwise added on a 100-square-millimeter substrate; the glue homogenizing speed is 500-1000 r/min;
3) placing the growing device in the step 2) in an inert gas environment, and preserving heat for 8-10 hours at 40-60 ℃ to obtain a two-dimensional organic-inorganic hybrid perovskite crystal layer;
4) and (3) evaporating metal electrodes on the surface of the two-dimensional organic-inorganic hybrid perovskite crystal obtained in the step 3) to obtain the two-dimensional organic-inorganic hybrid perovskite photoelectric detector.
6. A preparation method of a two-dimensional organic-inorganic hybrid perovskite crystal photodetector as claimed in claim 5, characterized in that the crystal device in the step 3) is an atmosphere furnace, a hot plate in a glove box or a tube furnace.
7. The method for preparing a two-dimensional organic-inorganic hybrid perovskite crystal photodetector as claimed in claim 5, wherein the precursor solution of the organic-inorganic hybrid perovskite crystal in the step 1) is further added with a surface modifier, wherein the surface modifier is oleic acid or amine oleate, and the addition amount of the surface modifier is 5-35% of the volume ratio of the perovskite growth solution.
8. A method for preparing a two-dimensional organic-inorganic hybrid perovskite crystal photodetector as claimed in claim 5, wherein said inert gas is nitrogen or argon.
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| WO2023092727A1 (en) * | 2021-11-25 | 2023-06-01 | 中国科学院深圳先进技术研究院 | X-ray direct detector and method for preparing same |
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