CN113964232A - Preparation method of bismuth-doped perovskite ultraviolet detector - Google Patents
Preparation method of bismuth-doped perovskite ultraviolet detector Download PDFInfo
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- CN113964232A CN113964232A CN202110499367.2A CN202110499367A CN113964232A CN 113964232 A CN113964232 A CN 113964232A CN 202110499367 A CN202110499367 A CN 202110499367A CN 113964232 A CN113964232 A CN 113964232A
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- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
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Abstract
The ultraviolet detector is an emerging detection technology, and is a sensor for converting an electromagnetic radiation signal into an easily-accepted signal. Ultraviolet light has extremely important influence on human production and life, has wide application in a plurality of fields and develops very rapidly. The ultraviolet detector is generally based on a wide-bandgap inorganic semiconductor, but the inorganic semiconductor is brittle and difficult to purify, so that the manufacturing cost of the ultraviolet detector is high and the manufacturing process is complicated. The invention aims to provide a photoelectric device for realizing highly sensitive detection on ultraviolet light of 10-400 nm, and solves the problems of high manufacturing cost, complex manufacturing process and the like of the conventional ultraviolet detector. The ultraviolet detector comprises three parts which are respectively as follows: a substrate layer ITO conductive glass substrate, a perovskite nanocrystalline film and a metal electrode layer. Wherein the calcium and the titaniumThe mineral nanocrystalline film is ABX3Is a matrix material.
Description
Technical Field
The invention relates to the technical field of photoelectric devices, in particular to a preparation method of a bismuth-doped perovskite ultraviolet detector.
Background
Although ultraviolet (10-400 nm) radiation only accounts for a small proportion of solar radiation, the ultraviolet radiation has extremely important influence on the production and life of human beings. As a new detection technology, the ultraviolet detector attracts the attention of many scientific researchers. At present, the ultraviolet detector has wide application fields, such as flame detection, optical communication, missile detection and the like. In recent years, semiconductor photoelectric devices are rapidly developed, and ultraviolet detectors are generally based on wide-bandgap inorganic semiconductors, but the inorganic semiconductors are brittle and difficult to purify, so that the manufacturing cost of the ultraviolet detectors is high, and the manufacturing process is complex. In order to solve these problems, it is feasible to improve the detector by doping.
At present, the sensitivity, the response speed and other aspects of most ultraviolet detectors need to be improved, and meanwhile, the absorption efficiency of incident photons in the detectors cannot reach a theoretical value due to the unavoidable surface reflection phenomenon, so that the current task is to solve the photoelectric performance problems of the ultraviolet detectors, such as the photoresponse rate, the quantum efficiency and the like. The perovskite material has the characteristics of small trap density, low intrinsic carrier concentration, few crystal boundaries and the like, and has great advantages in the aspect of high-performance and stable photoelectron detection devices. Among the many perovskite materials, bismuth-doped perovskites are considered an ideal material for ultraviolet detectors. The invention aims to prepare the ultraviolet detector by using a bismuth-doped perovskite method, and the method can greatly improve the stability of the ultraviolet detector, reduce the cost and the pollution to the environment and is beneficial to popularization and application based on the prior art.
Disclosure of Invention
The invention aims to provide a photoelectric device for realizing highly sensitive detection on ultraviolet light of 10-400 nm, and solves the problems of high manufacturing cost, complex manufacturing process and the like of the conventional ultraviolet detector. The ultraviolet detector comprises three parts which are respectively as follows: a substrate layer ITO conductive glass substrate, a perovskite nanocrystalline film and a metal electrode layer. Wherein the perovskite nanocrystalThe film is ABX3Is a matrix material. The technical scheme for realizing the invention is as follows:
and (3) carrying out liquid detergent, absolute ethyl alcohol, ultrasonic cleaning and UV ultraviolet cleaning on the ITO conductive glass substrate to obtain a clean substrate layer. And placing the substrate layer on a spin coater, and dropwise adding the previously prepared perovskite precursor liquid right above the substrate layer for spin coating. And annealing treatment is carried out on the heating plate after the spin coating is finished. And then a gold motor layer is vapor-plated on the perovskite nano film by a vacuum coating technology.
The perovskite nano film adopted by the invention is CsPb0.96Bi0.04I2Br, wherein the absorption of ultraviolet light can be realized through the doping of Pb and Bi, and the conversion effect on the perovskite nanocrystalline film can be obviously improved.
Compared with the prior art, the invention has the advantages that:
1. the process and the structure of the invention are relatively simple, and the bismuth-doped perovskite ultraviolet detector has higher response speed.
2. The invention can reduce the pollution to the environment by replacing lead element with partial bismuth element, and is beneficial to popularization and application.
3. The invention can enhance the stability of the ultraviolet detector by replacing lead element with partial bismuth element.
Detailed description of the preferred embodiments
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail below. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The ultraviolet photoelectric detector provided by the embodiment of the invention comprises: a substrate layer 1; a perovskite nanocrystalline thin film 2 covering the substrate layer 1; and an electrode layer 3 covering the perovskite nanocrystalline thin film 2. Wherein the perovskite nanocrystalline film is ABX3The perovskite nanocrystal is used as a matrix material.
In an exemplary embodiment of the invention, the substrate layer 1 is a glass substrate layer
In an embodiment of the invention, the perovskite nanocrystalline thin film 2, ABX3The A site in the perovskite nanocrystal is Cs+And the B site is Pb0.96Bi0.04X is I2Br, wherein the absorption of ultraviolet light can be realized through the doping of Pb and Bi on the B site, and the conversion effect on the perovskite nanocrystalline film can be obviously improved.
In an embodiment of the invention, the electrode 3 is a gold electrode.
The embodiment of the invention also provides a preparation method of the ultraviolet photoelectric detector, which comprises the following steps:
the method comprises the following steps of taking an ITO conductive glass sheet, cleaning a substrate layer, wherein the steps are totally divided into four steps, firstly, cleaning with a cleaning agent to remove bulk impurities, secondly, cleaning again with deionized water and absolute ethyl alcohol to remove other impurities, thirdly, ultrasonically cleaning for 25 minutes through acetone to remove stubborn impurities, and fourthly, carrying out ultraviolet ozone cleaning through UV ultraviolet cleaning equipment to treat for 15 minutes to ensure the cleanness of the substrate.
The perovskite precursor liquid of the invention is obtained by the following steps:
firstly, preparing a perovskite precursor solvent, wherein the perovskite precursor solvent is prepared by the volume ratio of DMSO: DMF =1:4 is used for preparing perovskite precursor solvent, solute is prepared in the second step, CsI, PbBr2 and BiI are added3Preparing the above solutes at a certain ratio, mixing the solvent with the solutes, heating and stirring at 70 deg.C for 12 hr in a magnetic heating stirrer to dissolve them sufficiently to obtain CsPb with concentration of 1.65mol/L0.96Bi0.04I2Br perovskite precursor solution.
The perovskite nanocrystalline thin film can be prepared by the following steps:
in the first step, the ITO conductive glass substrate which is clean in the early stage is placed in the middle of a spin coater, so that the solution is uniformly covered when the ITO conductive glass substrate rotates. And secondly, dropwise adding 200 mu L of perovskite precursor solution prepared in the early stage right above a spin coater, and quickly pressing a switch at 3500rpm to spin the perovskite precursor solution for 25 s. And thirdly, dripping a few drops of toluene quickly about 8s under the state of the second step. And fourthly, after the spin coater is stopped, taking down the substrate, and simultaneously, putting the spin-coated substrate on a heating plate to anneal for 10min at 100 ℃.
The metal electrode layer of the present invention can be obtained by the steps of:
a layer of gold electrode with the thickness of about 100 nanometers is evaporated on the perovskite nanocrystalline thin film by adopting a high-resistance evaporation apparatus and an evaporation method in a vacuum environment. The detailed process is as follows: placing gold particles in a high-resistance ferry instrument, covering a mask plate above the gold particles, and simultaneously vacuumizing a reaction chamber until the air pressure is lower than 5 x 10-5pa, raising the evaporation current to completely melt the gold particles, wherein the purpose of the process is to remove impurities in the gold particles, after the gold particles are completely melted, rotating the mask plate to enable the mask plate to be opposite to the substrate, and controlling the evaporation time to be about 1.5 h.
The attached drawings of the specification:
FIG. 1 uses a bench-top scanning electron microscope JCM-7000 to observe the surface topography.
Fig. 2 shows a structure of the ultraviolet detector.
FIG. 3 spectral sensitivity test.
FIG. 4 shows the recording of the photocurrent signal of the infrared photodetector produced by the method of the present invention using a solarcelscan 100 photoelectric converter under the irradiation of a continuous 400nm light source at room temperature.
Fig. 5 shows that the current intensity can be obtained at different laser luminous power densities, and finally, the responsivity and the sensitivity of the ultraviolet detector manufactured and implemented by the invention are calculated through formulas.
Claims (10)
1. An ultraviolet photodetector includes: ITO substrate layer, perovskite nanocrystalline film, electrode layer.
2. The perovskite nanocrystalline thin film adopts ABX3 Is a matrix material.
3. The ultraviolet photodetector of claim 1, wherein the ABX is3Sodium perovskiteA of the rice crystal is Cs+。
4. The ultraviolet photodetector of claim 1, wherein the ABX is3B of the perovskite nanocrystal is Pb0.96Bi0.04。
5. The ultraviolet photodetector of claim 1, wherein the ABX is3X of the perovskite nanocrystal is Br-、I-And (4) mixing.
6. The uv photodetector of claim 1, wherein gold electrodes are used.
7. The UV photodetector as claimed in claims 1 to 4, which is prepared by cleaning a substrate layer, dripping a prepared perovskite precursor solution on the substrate layer before spin coating, preparing a perovskite nanocrystalline thin film by using a spin coating method, and plating a gold electrode by using an evaporation technique.
8. The UV photodetector of claims 1-4, wherein the solvent of the perovskite precursor solution is a mixture of DMF and DMSO in a volume ratio of 4:1, and CsI, PbBr2, BiI are used3As a solute.
9. The method of any one of claims 1-7, comprising the steps of:
and (3) taking the conductive glass sheet, carrying out ultrasonic cleaning on the conductive glass sheet by using a detergent, deionized water, absolute ethyl alcohol and acetone in sequence, and then carrying out ultraviolet ozone cleaning to keep the conductive glass sheet clean and dry.
10. Adding DMF and DMSO according to the volume ratio of 4:1 to prepare a perovskite precursor solvent, and adding CsI and PbBr according to a certain proportion2、BiI3And 1.65mol/L of perovskite precursor solution is obtained by oscillating heating configuration for standby.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109411554A (en) * | 2018-09-10 | 2019-03-01 | 暨南大学 | A kind of miscellaneous inorganic perovskite thin film of cation-anion co-doping and the preparation method and application thereof |
| CN110165000A (en) * | 2019-07-10 | 2019-08-23 | 合肥工业大学 | A kind of deep ultraviolet light electric explorer and preparation method thereof based on the unleaded perovskite caesium copper iodine microcrystalline film in broad stopband |
| CN111403605A (en) * | 2020-03-19 | 2020-07-10 | 华中科技大学 | Self-powered perovskite photoelectric detector and preparation method thereof |
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2021
- 2021-05-08 CN CN202110499367.2A patent/CN113964232A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109411554A (en) * | 2018-09-10 | 2019-03-01 | 暨南大学 | A kind of miscellaneous inorganic perovskite thin film of cation-anion co-doping and the preparation method and application thereof |
| CN110165000A (en) * | 2019-07-10 | 2019-08-23 | 合肥工业大学 | A kind of deep ultraviolet light electric explorer and preparation method thereof based on the unleaded perovskite caesium copper iodine microcrystalline film in broad stopband |
| CN111403605A (en) * | 2020-03-19 | 2020-07-10 | 华中科技大学 | Self-powered perovskite photoelectric detector and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| YANQIANG HU: "Bismuth Incorporation Stabilized α‑CsPbI3 for Fully Inorganic Perovskite Solar Cells", ACS ENERGY LETTERS * |
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