CN111710750B - Deep ultraviolet photoelectric detector based on hexagonal boron nitride thick film and preparation method - Google Patents

Deep ultraviolet photoelectric detector based on hexagonal boron nitride thick film and preparation method Download PDF

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CN111710750B
CN111710750B CN202010588569.XA CN202010588569A CN111710750B CN 111710750 B CN111710750 B CN 111710750B CN 202010588569 A CN202010588569 A CN 202010588569A CN 111710750 B CN111710750 B CN 111710750B
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boron nitride
hexagonal boron
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殷红
李冬冬
高伟
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Jilin University
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Abstract

A deep ultraviolet photoelectric detector based on a hexagonal boron nitride thick film and a manufacturing method thereof comprise a substrate, an ultraviolet photosensitive layer and interdigital electrodes, wherein the ultraviolet photosensitive layer is a high-quality hexagonal boron nitride thick film and has good response to solar blind wave bands. The hexagonal boron nitride thick film has very excellent inherent performance, the purity of the hexagonal boron nitride thick film prepared by the ion beam sputtering deposition method is very high, and the hexagonal boron nitride thick film has the advantages of good stability, controllable thickness, no toxicity, no pollution and the like.

Description

Deep ultraviolet photoelectric detector based on hexagonal boron nitride thick film and preparation method
Technical Field
The invention belongs to the technical field of semiconductor photoelectric detectors, and particularly relates to a deep ultraviolet photoelectric detector based on a hexagonal boron nitride thick film and a preparation method thereof.
Background
The fields of military affairs, aviation, industry, environment, medicine, biology and the like have urgent need for deep ultraviolet photodetectors with excellent performance. The current common ultraviolet detector mainly comprises a silicon-based detector and a photomultiplier tube. The silicon-based detector is limited by the small forbidden band width (1.12 eV) of the material Si, and a filtering system with a complex structure and high price is required to be added when the silicon-based detector is used. Although some wide bandgap semiconductors such as SiC, alGaN, znMgO, etc. have the advantages of strong radiation resistance, room temperature operation, intrinsic visible solar blind, high thermal conductivity, high temperature resistance, high power, low electron hole mobility, high electron velocity under high field strength, etc., the performance of their photodetectors is still far lower than expected. For example, the forbidden band width of SiC is not adjustable (3.26 eV), and an ultraviolet filter is still required to realize deep ultraviolet photoelectric detection. While the forbidden band width of ZnMgO can be adjusted between 3.3 and 7.8eV by adjusting Mg component, structure segregation often occurs. AlGaN requires high Al composition to realize solar blind deep ultraviolet detection, but high crystal quality materials are difficult to realize at present.
The hexagonal boron nitride has a structural unit similar to graphene, has a super-wide forbidden band width, is aligned with a band gap, and has natural material performance for manufacturing a deep ultraviolet photoelectric detector. <xnotran> / (CN 5754 zxft 5754A; CN 3252 zxft 3252A; gao, M., meng, J., chen, Y., ye, S., wang, Y., ding, C., li, Y., yin, Z., zeng, X., you, J., jin, P., zhang, X., catalyst-free growth of two-dimensional hexagonal boron nitride few-layers on sapphire for deep ultraviolet photodetectors, journal of Materials Chemistry C, 3532 zxft 3532-15006.; lu, Y., wu, Z., xu, W., lin, S., znO quantum dot-doped graphene/h-BN/GaN-heterostructure ultraviolet photodetector with extremely highresponsivity, nanotechnology, 3425 zxft 3425.), , , / , . </xnotran> Therefore, the process and material quality cannot be well guaranteed. The performance of a few Deep ultraviolet photodetectors using hexagonal boron nitride films as ultraviolet photosensitive layer materials still cannot meet the requirements (CN 110649108a; doan, T.C., majety, S., grenadeier, S., li, J., lin, J.Y., jiang, H.X., simulation and characterization of solid-state thermal neutral Detectors based on hexagonal boron nitride insulators, nucleic Instruments and Methods in Physics Research Section A: accelters, spectrometers, detecors and Association Equipment,2014,748,84-90, wang, Y., meng, J., tian, Y., chen, Y., wang, G., yin, Z., jin, P., you, J., wu, J., zhang, X., deep ultrasound devices based on carbon-bonded two-dimensional hexanal boron nitride, ACS Appl Mater Interfaces,2020,12,27361-27367), mainly due to poor crystal quality, uneven thickness, poor doping efficiency of the material. Therefore, the crystal quality and thickness of the hexagonal boron nitride thick film are improved, the doping efficiency is improved by a proper means, the band gap width of the hexagonal boron nitride is effectively regulated and controlled, the high dislocation density is reduced or even eliminated, the dark current is reduced, the transmission rate of carriers is improved, and the method is a way for improving the deep ultraviolet photoelectric detection performance.
Disclosure of Invention
The invention aims to provide a deep ultraviolet photoelectric detector based on a hexagonal boron nitride thick film and a preparation method thereof, which can ensure that the device has high responsivity and response speed in a deep ultraviolet region, and meanwhile, in-situ doping is adopted, so that band gap regulation of an ultraviolet photosensitive layer material is realized, the doping efficiency is improved, the crystal quality is ensured, and the device performance is improved.
In order to achieve the above object, the present invention provides a deep ultraviolet photodetector based on a hexagonal boron nitride thick film, comprising:
(1) A substrate;
(2) The ultraviolet photosensitive layer is manufactured on the substrate and completely covers the substrate;
(3) And the interdigital electrode is manufactured on the deep ultraviolet photosensitive layer and covers part of the ultraviolet photosensitive layer.
The material of the substrate in the step (1) is polycrystalline or monocrystalline diamond, quartz glass, silicon or sapphire, and preferably is a silicon substrate.
The ultraviolet photosensitive layer in the step (2) is made of a hexagonal boron nitride thick film, and the thickness of the film is more than 40nm, preferably 500nm.
The ultraviolet photosensitive layer in the step (2) is a doped hexagonal boron nitride thick film, and the target doping impurities are carbon, aluminum, magnesium, sulfur or iron, preferably carbon.
The band gap width of the ultraviolet photosensitive layer in the step (2) is 1.8-6.0 eV, and preferably 2.5-3.5 eV.
The interdigital electrode manufactured in the step (3) is made of titanium, chromium, molybdenum, gold and silver, and is preferably a gold electrode; the finger width of the electrode is 3.2-3.6 μm, preferably 3.6 μm; the pitch is 5.6 to 6.4 μm, preferably 6.4 μm; the thickness is 80 to 120nm, preferably 100nm.
A preparation method of a deep ultraviolet photoelectric detector based on a hexagonal boron nitride thick film is characterized by comprising the following steps:
1) Providing a substrate;
2) Preparing a hexagonal boron nitride thick film or an in-situ doped hexagonal boron nitride thick film on the surface of the substrate by adopting a dual-ion beam sputtering deposition method;
3) And then preparing an interdigital electrode on the surface of the prepared hexagonal boron nitride thick film.
The preparation method of the deep ultraviolet photoelectric detector based on the hexagonal boron nitride thick film in the step 1) is characterized in that the substrate is made of polycrystalline or monocrystalline diamond, quartz glass, silicon or sapphire, and preferably is a silicon substrate.
And 2) introducing a gas source containing target doping impurities of carbon, aluminum, magnesium, sulfur or iron, preferably carbon, into the auxiliary ion source when the hexagonal boron nitride thick film is subjected to in-situ doping by adopting a dual-ion beam sputtering deposition method.
The interdigital electrode in the step 3) is made of titanium, chromium, molybdenum, gold or silver; the finger width of the electrode is 3.2-3.6 μm, preferably 3.6 μm; the pitch is 5.6 to 6.4 μm, preferably 6.4 μm; the thickness is 80 to 120nm, preferably 100nm.
The hexagonal boron nitride thick film ultraviolet photosensitive layer of the deep ultraviolet photoelectric detector based on the hexagonal boron nitride thick film has the advantages of high purity, low dislocation density, high carrier transmission rate and small dark current.
The invention provides a deep ultraviolet photoelectric detector based on a hexagonal boron nitride thick film with excellent performance, which has shorter cut-off wavelength and can have a very good response peak at 215nm when the voltage is increased to 15V. The high-voltage photoelectric detector can obtain good response at low voltage, and the selection of materials is widened for the deep ultraviolet photoelectric detector.
The invention has the following beneficial effects:
(1) According to the invention, the high-quality hexagonal boron nitride thick film is directly grown on various substrates by a double-ion beam sputtering deposition method, the structure and the growth quality of the hexagonal boron nitride thick film can be controlled by adjusting growth parameters, so that the high-quality large-area thick film is obtained, the dislocation density of the hexagonal boron nitride thick film is improved, the purity of the hexagonal boron nitride and other important deep ultraviolet photoelectric detector performance parameters are improved by the microstructure, the voltage for generating ultraviolet photoelectric response is reduced, and the voltage is reduced from 20V to 15V.
(2) The hexagonal boron nitride thick film prepared by the double-ion beam sputtering deposition method is used as a photosensitive layer material of the deep ultraviolet photoelectric detector, so that the ultraviolet detection range is widened, and the spectral responsivity in a specific area is enhanced. The method has the advantages of low cost, controllable technical process, convenient operation and easy industrial popularization.
(3) According to the invention, the band gap of the hexagonal boron nitride thick film is effectively regulated and controlled by means of in-situ doping, so that the doping efficiency is improved, the crystal quality of the material is ensured, and the improvement of the device performance is facilitated.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate an embodiment of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
fig. 1 is a schematic structural view of a deep ultraviolet photodetector according to the present invention;
FIG. 2 is a Scanning Electron Microscope (SEM) plan view of the UV-sensitive layer of the present invention;
fig. 3 is a plan view of an SEM of the interdigital electrode according to the present invention.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in detail below.
Referring to fig. 1, this embodiment specifically discloses a deep ultraviolet photodetector based on a hexagonal boron nitride thick film.
The deep ultraviolet photoelectric detector comprises an interdigital electrode 1, a hexagonal boron nitride thick film ultraviolet photosensitive layer 2, a silicon substrate 3 and a photoelectric detection device 4.
A hexagonal boron nitride thick film ultraviolet photosensitive layer 2 grows on a silicon substrate 3, the interdigital electrode 1 partially covers the hexagonal boron nitride thick film ultraviolet photosensitive layer 2, and the interdigital electrode 1 is connected with a photoelectric detection device 4 through a lead.
Preparing and cleaning a substrate: 1) Cutting an N-type silicon wafer (100) with a required size; 2) Placing the cut silicon wafer into boiling petroleum ether for 2min (the boiling point of the petroleum ether is 80-90 ℃), then ultrasonically cleaning the silicon wafer by using acetone, and then washing the silicon wafer by using deionized water; 3) Put into a mixture of boiling ammonia, hydrogen peroxide and deionized water for 2min (boiling point of mixture: 60 ℃), wherein the proportion of ammonia water, hydrogen peroxide and deionized water is 1; 4) Put into a mixture of boiling hydrochloric acid, hydrogen peroxide and deionized water for 2min (boiling point of the mixture: 90 ℃), the ratio of hydrochloric acid, hydrogen peroxide and deionized water being 1. Taking out and washing the product by deionized water; 5) Soaking in 10% hydrofluoric acid solution for 15s, taking out, and washing with deionized water. Introducing the cleaned substrate into ion beam deposition chamber, and pumping the ion beam deposition chamber to 9 × 10 at 500 deg.C -5 Pa or less; 2sccm argon gas is introduced; the auxiliary ion source is turned on, and the energy is 300eV. The substrate was etch cleaned for ten minutes using an argon ion beam generated by ion beam sputter deposition. An atomically clean surface is obtained.
Preparing an ultraviolet photosensitive layer: introducing a main ion source argon gas into the reactor by a double-ion-beam sputtering deposition method, wherein the argon gas is 6sccm; auxiliary ion sourceArgon gas is 2sccm; the auxiliary ion source nitrogen is 3sccm, and the working pressure is 3.4-3.6 multiplied by 10 -2 Pa; starting a double ion source, wherein the energy of a main ion source is 1500eV; the energy of the auxiliary ion source is 280eV; the acceleration voltage is 60eV; and moving the substrate to a working area, and sputtering for 8 hours to prepare the hexagonal boron nitride photosensitive layer. FIG. 2 is an SEM plan view of a hexagonal boron nitride photosensitive layer, and the thick film surface is compact, flat, uniform and free of falling-off phenomenon. The prepared hexagonal boron nitride thick film ultraviolet photosensitive layer is tightly adhered to the silicon substrate, and the thickness is 452nm. The FTIR spectrum and XRD spectrum prove that the film is a high-quality monocrystal hexagonal boron nitride thick film and has good crystallinity.
Preparing an interdigital electrode: placing the substrate with the hexagonal boron nitride ultraviolet photosensitive layer in a radio frequency magnetron sputtering instrument, placing a mask plate with interdigital electrode patterns according to the operation requirement, and then placing the mask plate at 1 × 10 -3 Sputtering gold atoms under Pa for 6min, wherein the thickness is 100nm; the size of the interdigital electrode pattern on the special mask is 1 × 1cm (fig. 3).
Connecting a sample with prepared interdigital electrodes to photoelectric detection devices on electrodes at two ends of the sample, and detecting the solar blind waveband performance of the detector; when the voltage is added to 15V, a photoelectric response signal clearly belonging to hexagonal boron nitride appears at 215 nm.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (3)

1. A preparation method of a deep ultraviolet photoelectric detector based on a hexagonal boron nitride thick film is characterized by comprising the following steps:
1) Providing a substrate;
2) Preparing a hexagonal boron nitride thick film or in-situ doping the hexagonal boron nitride thick film on the surface of the substrate by adopting a dual-ion beam sputtering deposition method to serve as an ultraviolet photosensitive layer;
3) Then preparing an interdigital electrode on the surface of the prepared hexagonal boron nitride thick film;
the thickness of the hexagonal boron nitride thick film is over 452 nm;
the band gap width of the hexagonal boron nitride ultraviolet photosensitive layer is 2.5-3.5 eV;
the deep ultraviolet photodetector has a short cut-off wavelength, and has a very good response peak at 215nm when the voltage is increased to 15V.
2. The method for preparing the deep ultraviolet photoelectric detector based on the hexagonal boron nitride thick film according to claim 1, wherein the substrate is made of polycrystalline or single-crystal diamond, quartz glass, silicon or sapphire.
3. The method for preparing a deep ultraviolet photodetector based on a hexagonal boron nitride thick film according to claim 1, wherein a gas source containing target doping impurities is introduced into the auxiliary ion source during in-situ doping of the hexagonal boron nitride thick film by using a dual ion beam sputter deposition method in the step 2).
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