CN110416333B - Ultraviolet photoelectric detector and preparation method thereof - Google Patents
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Abstract
The invention belongs to the technical field related to micro-nano manufacturing, and discloses an ultraviolet photoelectric detector and a preparation method thereof, wherein the preparation method comprises the following steps: (1) preparing an electrode layer on a silicon substrate with a silicon nitride insulating layer by adopting a photoetching alignment process and an evaporation coating process; (2) preparing an ultraviolet detection film on the electrode layer, wherein the ultraviolet detection film is Mn-doped CsPbBr3xCl3(1‑x)Ultraviolet detecting film formed by sequentially evaporating PbCl on the electrode layer2Layer, CsBr layer, CsCl layer and MnCl2Formed of a layer; wherein x is 0.05-0.1; (3) and preparing a packaging protective layer on the ultraviolet detection film in a dripping mode to package the ultraviolet detection film, thereby obtaining the ultraviolet photoelectric detector. The invention has the advantages of lower cost, easier obtaining, simpler preparation process, higher light absorption coefficient, faster carrier transmission and stronger applicability.
Description
Technical Field
The invention belongs to the technical field related to micro-nano manufacturing, and particularly relates to an ultraviolet photoelectric detector and a preparation method thereof.
Background
The photoelectric detector is an important component of a photoelectric system and has wide application in national defense safety and daily life. In recent years, ultraviolet band detection (10nm to 40nm) is another very important photoelectric detection technique besides laser detection and infrared detection. The ultraviolet radiation can be generated by cosmic space, flame, gas pollution molecules, corona of a power transmission line and the like, and the ultraviolet detection technology has important application value and wide application prospect in the fields of space technology, space early warning, communication, biological and civil detection and the like.
Conventional uv photodetectors are mainly classified into two main categories: the photoelectric emission ultraviolet detector adopts the working principle of external photoelectric effect, and the semiconductor ultraviolet detector mainly adopts the photoelectric effect or the photovoltaic effect. The traditional photoemission ultraviolet detector, such as a photoemission ultraviolet detector based on a cesium telluride (Cs2Te) and rubidium telluride (Rb2Te) photocathode, is technically mature, but has the disadvantages of low detection sensitivity, low photoelectric conversion efficiency, incapability of realizing true solar blindness, difficult production and the like in practical application. With the maturity of semiconductor materials and large-scale integrated circuit technology, wide bandgap semiconductor ultraviolet detectors such as GaN-based, SiC-based and ZnO-based have developed rapidly in recent years, and they have small volume, low power consumption, low cost, easily adjustable bandgap and wide application, but the devices still have the defects of low detection sensitivity, large dark current, thick material shortage (Ga), complex preparation process and the like. Therefore, the development of a new ultraviolet photosensitive film with high quality and wide forbidden band has great significance for the development of an ultraviolet detector.
The perovskite material has the excellent characteristics of high light absorption coefficient, high charge mobility, small dielectric constant, few internal defects, low surface recombination rate and the like, can show quick light response characteristics (subtle and even nanosecond scale) when being illuminated, and is an ideal component of a high-speed and high-sensitivity photoelectric detector. At present, the reported perovskite photodetectors have more advantages than the traditional photodetectors based on inorganic semiconductor materials such as Si, InGaAs, GaN and the like in the aspects of sensitivity, dynamic range, response speed and the like, and are obviously superior to novel photoelectric sensors such as organic photodetectors, quantum dot photodetectors and the like. In addition, the perovskite photoelectric detector is intersected with other types of detectors, and has the great advantages of good weak light responsivity, simple preparation process, low production cost, low requirement on production equipment and the like, so that the perovskite photoelectric detector has a very wide application prospect in the field of photoelectric detection. In order to realize high-precision ultraviolet detection and simultaneously reduce noise interference of visible light wave bands, the ultraviolet detection film needs to be provided withWider band gap, and traditional organic-inorganic hybrid perovskite MAPbI3The optical forbidden band is only 1.53eV, the visible light with the wave band of 400-810 nm has large response, and the ultraviolet light with the wavelength less than 400nm has small response, so the optical forbidden band is obviously not suitable for ultraviolet detection. All-inorganic CsPbX3The (X ═ Br, Cl) perovskite has wider optical forbidden band, higher stability and lower material cost than organic-inorganic hybrid perovskites, the highest forbidden band is 2.85eV, the lower limit of absorption wavelength is lower than 410nm (equivalent to SiC material which is widely applied in the field of ultraviolet detection), the perovskite has almost no response to visible light wave band, and has excellent absorption rate and response speed to ultraviolet wave band light, so the perovskite is an ideal ultraviolet detection material.
Full-inorganic wide bandgap CsPbX3The perovskite material brings a new opportunity for the development of ultraviolet light detection technology, but most of the traditional perovskite nanocrystalline thin films are prepared based on a solution method, and CsPbX exists3The material synthesis is difficult (such as quantum dot synthesis), and the prepared CsPbX3The film has the problems of high deep defect state (such as more Cl vacancies), poor film forming property (such as low continuity, small grain size and high grain boundary density) and the like, the defects can obviously reduce the carrier mobility and the optical response speed, and the solution method process is not beneficial to large-area CsPbX3The deposition of perovskite thin films limits the preparation of large-area ultraviolet detectors. Accordingly, there is a need in the art to develop a better quality uv photodetector and a method for manufacturing the same.
Disclosure of Invention
Aiming at the defects or improvement requirements of the prior art, the invention provides the ultraviolet photoelectric detector and the preparation method thereof, and the ultraviolet photoelectric detector with better quality and the preparation method thereof are researched and designed based on the working characteristics of the prior ultraviolet photoelectric detector. The preparation method adopts a multi-step evaporation process to prepare Mn-doped CsPbBr3xCl3(1-x)The ultraviolet detection film can realize the fine adjustment of the optical forbidden band by fine adjusting the element proportion of Cl and Br, simultaneously improve the transmission rate of current carriers and reduce the defect state density of the film, improve the grain size and the shape of the film, and is favorable for improving the filmThe photoelectric property is improved. In addition, Mn doping can further reduce CsPbBr3xCl3(1-x)The intrinsic defects of the nanocrystalline improve the conductivity and the carrier mobility of the film, reduce the unfavorable non-radiative recombination loss and improve the sensitivity and the response rate of the ultraviolet photoelectric detector.
To achieve the above object, according to one aspect of the present invention, there is provided a method of manufacturing an ultraviolet photodetector, the method comprising the steps of:
(1) preparing an electrode layer on a silicon substrate with a silicon nitride insulating layer by adopting a photoetching alignment process and an evaporation coating process;
(2) preparing an ultraviolet detection film on the electrode layer, wherein the ultraviolet detection film is Mn-doped CsPbBr3xCl3(1-x)Ultraviolet detecting film formed by sequentially evaporating PbCl on the electrode layer2Layer, CsBr layer, CsCl layer and MnCl2Formed of a layer; wherein x is 0.05-0.1;
(3) and preparing a packaging protective layer on the ultraviolet detection film in a dripping mode to package the ultraviolet detection film, thereby obtaining the ultraviolet photoelectric detector.
Furthermore, the electrodes of the electrode layer are regularly arranged, and the distance between the electrodes is 10-40 μm.
Further, the evaporation rate used in step (2) is
Further, in the step (2), the ultraviolet detection film is annealed for 15min at the temperature of 250-350 ℃.
Further, in the step (3), the packaging protective layer is heated for 15min to 20min at the temperature of 80 ℃ to 100 ℃ for drying.
According to another aspect of the present invention, there is provided an ultraviolet photodetector manufactured by the method for manufacturing an ultraviolet photodetector as described above.
Further, the ultraviolet photoelectric detector comprises a nitrideThe ultraviolet detector comprises a silicon substrate of a silicon insulating layer, an electrode layer formed on the silicon substrate, an ultraviolet detection film formed on the electrode layer and a packaging protection layer formed on the ultraviolet detection film; the ultraviolet detection film comprises PbCl which are arranged in sequence2Layer, CsBr layer, CsCl layer and MnCl2And (3) a layer.
Further, the PbCl2The thickness of the layer is 150nm to 200 nm; the MnCl2The thickness of the layer is 10nm to 15 nm.
Further, the thickness of the electrode layer is 80nm to 100 nm.
Further, the packaging protective layer is a PDMS layer; the forbidden band of the ultraviolet detection film is 2.85 eV.
Generally, compared with the prior art, the ultraviolet photoelectric detector and the manufacturing method thereof provided by the invention have the following beneficial effects:
1. the ultraviolet detection film is formed by sequentially evaporating PbCl on the electrode layer2Layer, CsBr layer, CsCl layer and MnCl2Formed as layers, i.e. by successive evaporation of PbCl2Preparation of CsPbBr from layer, CsBr layer and CsCl layer3xCl3(1-x)Perovskite nanocrystals; by adjusting CsBr layer, CsCl layer and PbCl2The thickness proportion of the layers can realize the accurate control of the components of the film, and the adoption of Br and Cl double-halogen inorganic perovskite can effectively improve the energy level structure of the film and reduce the defect state density of the film; in addition, compared with the traditional solution method, the CsPbBr prepared by the process3xCl3(1-x)The film has the advantages of high coverage rate, large grain size, few crystal boundaries, few defects, strong light absorption capacity, longer carrier diffusion distance and better optical and electrical properties.
2. The ultraviolet detection film is Mn-doped CsPbBr3xCl3(1-x)Compared with a photoelectric emission ultraviolet detector and a semiconductor ultraviolet detector, the perovskite photoelectric detector has the advantages of lower raw material cost, easier obtaining, simpler preparation process, higher light absorption coefficient, faster carrier transmission, higher detection sensitivity, smaller dark current and the like, and is a novel ultraviolet detection filmAn ideal component of the outer photodetector; meanwhile, compared with an organic-inorganic hybrid perovskite detection core material widely applied to a perovskite photoelectric detector, the all-inorganic CsPbBr is3xCl3(1-x)Compared with organic and inorganic hybrid perovskite, the perovskite nanocrystal has wider optical forbidden band, higher stability and lower material cost, the highest forbidden band is 2.85eV, the lower limit of absorption wavelength is lower than 410nm, the perovskite nanocrystal has almost no response to visible light wave band, and has excellent absorption rate and response speed to ultraviolet wave band light, thereby greatly reducing the interference of the visible light wave band to ultraviolet detection, and being an ideal ultraviolet detection material.
3. For CsPbBr3xCl3(1-x)The nanocrystalline is doped with Mn, so that CsPbBr can be effectively reduced3xCl3(1-x)The intrinsic defects of the nanocrystalline improve the conductivity and the carrier mobility of the film, reduce dark current and unfavorable non-radiative recombination loss, and improve the sensitivity and the response rate of the ultraviolet photoelectric detector.
4. The PDMS with low price, high stability and high hydrophobicity is used as a packaging layer material, and is prepared by a drop coating mode, the raw materials are easy to obtain, the process is simple, the operation is easy, the working stability of the ultraviolet detector is improved, the production cost is reduced, and the large-scale commercial production of the detector is facilitated.
Drawings
Fig. 1 is a schematic flow chart of a method for manufacturing an ultraviolet photodetector according to a preferred embodiment of the present invention;
fig. 2 is a schematic structural diagram of the ultraviolet photodetector provided by the present invention.
The same reference numbers will be used throughout the drawings to refer to the same or like elements or structures, wherein: 1-silicon substrate with silicon nitride insulating layer, 2-electrode layer, 3-ultraviolet detecting film, 4-packaging protective layer.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
Referring to fig. 1, a method for manufacturing an ultraviolet photodetector according to a preferred embodiment of the present invention mainly includes the following steps:
step one, providing a silicon substrate with a silicon nitride insulating layer, and cleaning the silicon substrate.
Specifically, providing a silicon substrate with a silicon nitride insulating layer, and ultrasonically cleaning the silicon substrate for 15-20 minutes by using a detergent, acetone, ethanol and deionized water respectively; and then, blowing the silicon substrate to dry by adopting nitrogen airflow, and then carrying out ultraviolet ozone treatment on the silicon substrate for 15-30 minutes.
And step two, preparing an electrode layer on the silicon substrate by adopting a photoetching alignment process and an evaporation coating process.
Specifically, an electrode layer is prepared on the silicon substrate by adopting a photoetching alignment process and an evaporation coating process, electrodes of the electrode layer are regularly arranged, and the interval between the electrodes is 10-40 mu m; the thickness of the electrode layer is 80 nm-100 nm.
Preparing an ultraviolet detection film on the electrode layer, wherein the ultraviolet detection film is Mn-doped CsPbBr3xCl3(1-x)Ultraviolet detecting film formed by sequentially evaporating PbCl on the electrode layer2Layer, CsBr layer, CsCl layer and MnCl2A layer is formed.
Specifically, an ultraviolet detection film is prepared on the electrode layer, and the ultraviolet detection film is Mn-doped CsPbBr3xCl3(1-x)The film is detected by ultraviolet light. The ultraviolet detection film is prepared by multi-step evaporation of PbCl2Layer, CsBr layer, CsCl layer and MnCl2The layer is prepared by the whole preparation process under the pressure of less than 1 × 10-3Pa in a high vacuum chamber.
In this embodiment, first, 150nm to 200nm thick PbCl is deposited on the electrode layer2A precursor, sequentially evaporating a CsBr layer, a CsCl layer and PbCl2Layer, wherein CsBr layer, CsCl layer and PbCl are changed2Varying the thickness ratio of CsPbBr3xCl3(1-x)The components of the nanocrystalline are controlled, wherein x is controlled to be 0.05-0.1, and the evaporation rate of each layer is controlled to be 0.05-0.1
Then, MnCl with a thickness of 10nm to 15nm is prepared on the CsCl layer by evaporation2Layer pair CsPbBr3xCl3(1-x)The nanocrystalline film is doped with Mn, and the evaporation rate of the film is
Finally, annealing for 15min at 250-350 ℃ to promote Mn doping CsPbBr3xCl3(1-x)The crystallization of (4).
And fourthly, preparing a packaging protective layer on the ultraviolet detection film in a dripping mode to package the ultraviolet detection film, so as to obtain the ultraviolet photoelectric detector.
Specifically, a packaging protective layer is prepared on the ultraviolet detection film in a dripping mode, and then the ultraviolet detection film is heated for 15-20 min at the temperature of 80-100 ℃ for drying. To this end, Mn-based doping of CsPbBr was accomplished3xCl3(1-x)And (3) preparing the ultraviolet photoelectric detector of the nanocrystalline film. In this embodiment, the encapsulation protection layer is a PDMS layer with low cost, good compactness, high stability and high hydrophobicity.
Referring to fig. 2, the present invention further provides an ultraviolet photodetector, wherein the ultraviolet photodetector is manufactured by the above-mentioned method for manufacturing an ultraviolet photodetector. The ultraviolet photoelectric detector comprises a silicon substrate 1 with a silicon nitride insulating layer, an electrode layer 2 formed on the silicon substrate 1, an ultraviolet detection film 3 formed on the electrode layer 2 and a packaging protection layer 4 formed on the ultraviolet detection film, wherein the ultraviolet detection film 3 is packaged by the packaging protection layer 4, the electrode layer 2 and the silicon substrate 1. In this embodiment, the ultraviolet detection film 3 is Mn-doped CsPbBr3xCl3(1-x)The perovskite nanocrystalline thin film, x is 0.05-0.1; the ultraviolet rayThe detection film has the highest forbidden band of 2.85eV, the lower limit of absorption wavelength of less than 410nm (equivalent to that of a SiC material widely applied in the field of ultraviolet detection), almost no response to a visible light waveband, excellent absorption rate and response speed to an ultraviolet light waveband, greatly reduced interference of the visible light waveband on ultraviolet detection, and is an ideal ultraviolet detection material.
Example 1
The method for manufacturing the ultraviolet photoelectric detector provided by the first embodiment of the invention mainly comprises the following steps:
s1, providing a silicon substrate with a silicon nitride insulating layer, and cleaning the silicon substrate.
Specifically, a silicon substrate with a silicon nitride insulating layer is provided, and the silicon substrate is subjected to ultrasonic cleaning for 15 minutes by respectively using a detergent, acetone, ethanol and deionized water; then, the silicon substrate is dried by adopting nitrogen airflow, and then the silicon substrate is subjected to ultraviolet ozone treatment for 15 minutes.
And S2, preparing an electrode layer on the silicon substrate by adopting a photoetching alignment process and an evaporation coating process.
Specifically, an electrode layer is prepared on the silicon substrate by adopting a photoetching alignment process and an evaporation coating process, electrodes of the electrode layer are regularly arranged, and the interval between the electrodes is 10 microns; the thickness of the electrode layer is between 85 nm.
S3, preparing an ultraviolet detection film on the electrode layer, wherein the ultraviolet detection film is Mn-doped CsPbBr3xCl3(1-x)Ultraviolet detecting film formed by sequentially evaporating PbCl on the electrode layer2Layer, CsBr layer, CsCl layer and MnCl2A layer is formed.
Specifically, an ultraviolet detection film is prepared on the electrode layer, and the ultraviolet detection film is Mn-doped CsPbBr3xCl3(1-x)The film is detected by ultraviolet light. The ultraviolet detection film is prepared by multi-step evaporation of PbCl2Layer, CsBr layer, CsCl layer and MnCl2The layer is prepared by the whole preparation process under the pressure of less than 1 × 10-3Pa in a high vacuum chamber.
This embodimentIn the formula, first, PbCl with a thickness of 180nm is vapor-deposited on the electrode layer2A precursor, sequentially evaporating a CsBr layer, a CsCl layer and PbCl2Layer, wherein CsBr layer, CsCl layer and PbCl are changed2Varying the thickness ratio of CsPbBr3xCl3(1-x)The components of the nanocrystalline are controlled, wherein x is controlled to be 0.05-0.1, and the evaporation rate of each layer is controlled to be 0.05-0.1
Then, 10nm thick MnCl was prepared on the CsCl layer by evaporation2Layer pair CsPbBr3xCl3(1-x)The nanocrystalline film is doped with Mn, and the evaporation rate of the film is
Finally, annealing at 300 ℃ for 15min to promote Mn doping CsPbBr3xCl3(1-x)The crystallization of (4).
S4, preparing a packaging protective layer on the ultraviolet detection film in a dripping mode to package the ultraviolet detection film, and thus obtaining the ultraviolet photoelectric detector.
Specifically, a packaging protective layer is prepared on the ultraviolet detection film in a dripping mode, and then the ultraviolet detection film is heated for 18min at 85 ℃ for drying. To this end, Mn-based doping of CsPbBr was accomplished3xCl3(1-x)And (3) preparing the ultraviolet photoelectric detector of the nanocrystalline film. In this embodiment, the encapsulation protection layer is a PDMS layer with low cost, good compactness, high stability and high hydrophobicity.
Example 2
The method for manufacturing the ultraviolet photodetector provided by the second embodiment of the invention mainly comprises the following steps:
and B1, providing a silicon substrate with a silicon nitride insulating layer, and cleaning the silicon substrate.
Specifically, a silicon substrate with a silicon nitride insulating layer is provided, and the silicon substrate is subjected to ultrasonic cleaning for 20 minutes by respectively using a detergent, acetone, ethanol and deionized water; then, the silicon substrate is dried by adopting nitrogen airflow, and then the silicon substrate is subjected to ultraviolet ozone treatment for 30 minutes.
And B2, preparing an electrode layer on the silicon substrate by adopting a photoetching alignment process and an evaporation coating process.
Specifically, an electrode layer is prepared on the silicon substrate by adopting a photoetching alignment process and an evaporation coating process, electrodes of the electrode layer are regularly arranged, and the interval between the electrodes is 40 mu m; the thickness of the electrode layer is between 90 nm.
B3, preparing an ultraviolet detection film on the electrode layer, wherein the ultraviolet detection film is Mn-doped CsPbBr3xCl3(1-x)Ultraviolet detecting film formed by sequentially evaporating PbCl on the electrode layer2Layer, CsBr layer, CsCl layer and MnCl2A layer is formed.
Specifically, an ultraviolet detection film is prepared on the electrode layer, and the ultraviolet detection film is Mn-doped CsPbBr3xCl3(1-x)The film is detected by ultraviolet light. The ultraviolet detection film is prepared by multi-step evaporation of PbCl2Layer, CsBr layer, CsCl layer and MnCl2The layer is prepared by the whole preparation process under the pressure of less than 1 × 10-3Pa in a high vacuum chamber.
In this embodiment, first, PbCl having a thickness of 160nm is deposited on the electrode layer2A precursor, sequentially evaporating a CsBr layer, a CsCl layer and PbCl2Layer, wherein CsBr layer, CsCl layer and PbCl are changed2Varying the thickness ratio of CsPbBr3xCl3(1-x)The components of the nanocrystalline are controlled, wherein x is controlled to be 0.05-0.1, and the evaporation rate of each layer is controlled to be 0.05-0.1
Then, MnCl was prepared to a thickness of 15nm on the CsCl layer by evaporation2Layer pair CsPbBr3xCl3(1-x)The nanocrystalline film is doped with Mn, and the evaporation rate of the film is
Finally, annealing at 280 ℃ for 15min to promote Mn doping CsPbBr3xCl3(1-x)The crystallization of (4).
B4, preparing a packaging protective layer on the ultraviolet detection film by adopting a dripping coating mode to package the ultraviolet detection film, thereby obtaining the ultraviolet photoelectric detector.
Specifically, a packaging protective layer is prepared on the ultraviolet detection film in a dripping mode, and then the ultraviolet detection film is heated for 18min at 90 ℃ for drying. To this end, Mn-based doping of CsPbBr was accomplished3xCl3(1-x)And (3) preparing the ultraviolet photoelectric detector of the nanocrystalline film. In this embodiment, the encapsulation protection layer is a PDMS layer with low cost, good compactness, high stability and high hydrophobicity.
Example 3
The method for manufacturing the ultraviolet photodetector provided by the third embodiment of the invention mainly comprises the following steps:
t1, providing a silicon substrate with a silicon nitride insulating layer, and cleaning the silicon substrate.
Specifically, a silicon substrate with a silicon nitride insulating layer is provided, and the silicon substrate is subjected to ultrasonic cleaning for 18 minutes by respectively using a detergent, acetone, ethanol and deionized water; then, the silicon substrate is dried by adopting nitrogen airflow, and then the silicon substrate is subjected to ultraviolet ozone treatment for 22 minutes.
And T2, preparing an electrode layer on the silicon substrate by adopting a photoetching alignment process and an evaporation coating process.
Specifically, an electrode layer is prepared on the silicon substrate by adopting a photoetching alignment process and an evaporation coating process, electrodes of the electrode layer are regularly arranged, and the interval between the electrodes is 20 microns; the thickness of the electrode layer is between 80 nm.
T3, preparing an ultraviolet detection film on the electrode layer, wherein the ultraviolet detection film is Mn-doped CsPbBr3xCl3(1-x)Ultraviolet detecting film formed by sequentially evaporating PbCl on the electrode layer2Layer, CsBr layer, CsCl layer and MnCl2A layer is formed.
Specifically, an ultraviolet detection film is prepared on the electrode layer, and the ultraviolet detection film is Mn-doped CsPbBr3xCl3(1-x)The film is detected by ultraviolet light. The ultraviolet detecting film isBy multi-step evaporation of PbCl2Layer, CsBr layer, CsCl layer and MnCl2The layer is prepared by the whole preparation process under the pressure of less than 1 × 10-3Pa in a high vacuum chamber.
In this embodiment, first, 150nm thick PbCl is deposited on the electrode layer2A precursor, sequentially evaporating a CsBr layer, a CsCl layer and PbCl2Layer, wherein CsBr layer, CsCl layer and PbCl are changed2Varying the thickness ratio of CsPbBr3xCl3(1-x)The components of the nanocrystalline are controlled, wherein x is controlled to be 0.05-0.1, and the evaporation rate of each layer is controlled to be 0.05-0.1
Then, 12nm thick MnCl was prepared on the CsCl layer by evaporation2Layer pair CsPbBr3xCl3(1-x)The nanocrystalline film is doped with Mn, and the evaporation rate of the film is
Finally, annealing at 250 ℃ for 15min to promote Mn doping CsPbBr3xCl3(1-x)The crystallization of (4).
And T4, preparing a packaging protective layer on the ultraviolet detection film in a dripping coating mode to package the ultraviolet detection film, thereby obtaining the ultraviolet photoelectric detector.
Specifically, a packaging protective layer is prepared on the ultraviolet detection film in a dripping mode, and then the ultraviolet detection film is heated for 20min at 100 ℃ for drying. To this end, Mn-based doping of CsPbBr was accomplished3xCl3(1-x)And (3) preparing the ultraviolet photoelectric detector of the nanocrystalline film. In this embodiment, the encapsulation protection layer is a PDMS layer with low cost, good compactness, high stability and high hydrophobicity.
Example 4
The method for manufacturing the ultraviolet photodetector provided by the fourth embodiment of the present invention mainly includes the following steps:
h1, providing a silicon substrate with a silicon nitride insulating layer, and cleaning the silicon substrate.
Specifically, a silicon substrate with a silicon nitride insulating layer is provided, and the silicon substrate is subjected to ultrasonic cleaning for 19 minutes by respectively using a detergent, acetone, ethanol and deionized water; then, the silicon substrate is dried by adopting nitrogen airflow, and then the silicon substrate is subjected to ultraviolet ozone treatment for 25 minutes.
H2, preparing an electrode layer on the silicon substrate by adopting a photoetching alignment process and an evaporation coating process.
Specifically, an electrode layer is prepared on the silicon substrate by adopting a photoetching alignment process and an evaporation coating process, electrodes of the electrode layer are regularly arranged, and the interval between the electrodes is 30 microns; the thickness of the electrode layer is between 100 nm.
H3, preparing an ultraviolet detection film on the electrode layer, wherein the ultraviolet detection film is Mn-doped CsPbBr3xCl3(1-x)Ultraviolet detecting film formed by sequentially evaporating PbCl on the electrode layer2Layer, CsBr layer, CsCl layer and MnCl2A layer is formed.
Specifically, an ultraviolet detection film is prepared on the electrode layer, and the ultraviolet detection film is Mn-doped CsPbBr3xCl3(1-x)The film is detected by ultraviolet light. The ultraviolet detection film is prepared by multi-step evaporation of PbCl2Layer, CsBr layer, CsCl layer and MnCl2The layer is prepared by the whole preparation process under the pressure of less than 1 × 10-3Pa in a high vacuum chamber.
In this embodiment, first, 200nm thick PbCl is deposited on the electrode layer2A precursor, sequentially evaporating a CsBr layer, a CsCl layer and PbCl2Layer, wherein CsBr layer, CsCl layer and PbCl are changed2Varying the thickness ratio of CsPbBr3xCl3(1-x)The components of the nanocrystalline are controlled, wherein x is controlled to be 0.05-0.1, and the evaporation rate of each layer is controlled to be 0.05-0.1
Then, 13nm thick MnCl was prepared on the CsCl layer by evaporation2Layer pair CsPbBr3xCl3(1-x)The nanocrystalline film is doped with Mn, and the evaporation rate of the film is
Finally, annealing at 250 ℃ for 15min to promote Mn doping CsPbBr3xCl3(1-x)The crystallization of (4).
H4, preparing a packaging protective layer on the ultraviolet detection film in a dripping mode to package the ultraviolet detection film, and thus obtaining the ultraviolet photoelectric detector.
Specifically, a packaging protective layer is prepared on the ultraviolet detection film in a dripping mode, and then the ultraviolet detection film is heated for 15min at 80 ℃ for drying. To this end, Mn-based doping of CsPbBr was accomplished3xCl3(1-x)And (3) preparing the ultraviolet photoelectric detector of the nanocrystalline film. In this embodiment, the encapsulation protection layer is a PDMS layer with low cost, good compactness, high stability and high hydrophobicity.
The invention provides an ultraviolet photoelectric detector and a preparation method thereof, wherein the preparation method adopts a multi-step evaporation method to prepare an all-inorganic ultraviolet detection film, and the ultraviolet detection film is Mn-doped CsPbBr3xCl3(1-x)The ultraviolet detection film has the advantages of lower and more accessible raw material cost, simpler preparation process, higher light absorption coefficient, faster carrier transmission, higher detection sensitivity, smaller dark current and the like, and is an ideal component of a novel ultraviolet detector.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (9)
1. A preparation method of an ultraviolet photoelectric detector is characterized by comprising the following steps:
(1) preparing an electrode layer on a silicon substrate with a silicon nitride insulating layer by adopting a photoetching alignment process and an evaporation coating process;
(2) preparing an ultraviolet detection film on the electrode layer, wherein the ultraviolet detection film is Mn-doped CsPbBr3xCl3(1-x)Ultraviolet detecting film formed by sequentially evaporating PbCl on the electrode layer2Layer, CsBr layer, CsCl layer and MnCl2Formed of a layer; wherein x is 0.05-0.1;
(3) and preparing a packaging protective layer on the ultraviolet detection film in a dripping mode to package the ultraviolet detection film, thereby obtaining the ultraviolet photoelectric detector.
2. The method of manufacturing an ultraviolet photodetector as claimed in claim 1, wherein: the electrodes of the electrode layer are regularly arranged, and the distance between the electrodes is 10-40 mu m.
3. The method of manufacturing an ultraviolet photodetector as claimed in claim 1, wherein: in the step (2), the CsBr layer, the CsCl layer and the PbCl layer2The evaporation rates of the layers are all
4. The method of manufacturing an ultraviolet photodetector as claimed in claim 1, wherein: in the step (2), the ultraviolet detection film is annealed for 15min at the temperature of 250-350 ℃.
5. The method for producing an ultraviolet photodetector as claimed in any one of claims 1 to 4, wherein: in the step (3), the packaging protective layer is heated for 15min to 20min at the temperature of 80 ℃ to 100 ℃ for drying.
6. An ultraviolet photodetector, characterized by: the ultraviolet photodetector is manufactured by the method for manufacturing the ultraviolet photodetector as claimed in any one of claims 1 to 5.
7. The ultraviolet photodetector of claim 6, wherein: the PbCl2The thickness of the layer is 150nm to 200 nm; the MnCl2The thickness of the layer is 10nm～15nm。
8. The ultraviolet photodetector of claim 6, wherein: the thickness of the electrode layer is 80 nm-100 nm.
9. The ultraviolet photodetector of claim 6, wherein: the packaging protective layer is a PDMS layer; the forbidden band of the ultraviolet detection film is 2.85 eV.
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