CN112420397A - Polarity inversion type wavelength-distinguishable photodetector based on gallium nitride and preparation method thereof - Google Patents
Polarity inversion type wavelength-distinguishable photodetector based on gallium nitride and preparation method thereof Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/205—Light-sensitive devices comprising a semiconductor electrode comprising AIII-BV compounds with or without impurities, e.g. doping materials
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01J—MEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
- G01J1/00—Photometry, e.g. photographic exposure meter
- G01J1/42—Photometry, e.g. photographic exposure meter using electric radiation detectors
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Microelectronics & Electronic Packaging (AREA)
- Light Receiving Elements (AREA)
Abstract
The invention discloses a photoelectrochemical photodetector which comprises a photoelectrode, a substrate and a heterojunction nanostructure formed on the surface of the substrate and based on gallium nitride (GaN) materials, wherein the heterojunction nanostructure is vertical to the substrate. The invention also discloses a preparation method of the photoelectrochemical photodetector based on the GaN-based material. According to the photoelectrochemical photodetector based on the GaN-based heterojunction nanostructure, the response current is a positive current under the illumination of the specific wavelength, and the response current is a negative current under the illumination of other wavelengths except the specific wavelength (namely, the polarities of photocurrents generated by the illumination of different wavelengths are different), so that the essential defects of the traditional photodetector are overcome on the working principle, and the detection, the differentiation and the light intensity measurement of the optical signals with different wavelengths are realized.
Description
Technical Field
The invention relates to the technical field of photoelectrochemical photodetectors, in particular to a polarity-reversal wavelength-distinguishable photodetector based on a gallium nitride (GaN) -based nanostructure and a preparation method thereof.
Background
Photodetectors, i.e., devices that capture and convert optical signals into electrical signals, are widely used in the fields of imaging, communication, sensing, computing, and emerging wearable devices. The photoelectric detector has wide application in various fields of military and national economy. The infrared radiation sensor is mainly used for ray measurement and detection, industrial automatic control, photometric measurement and the like in visible light or near infrared wave bands; the infrared band is mainly used for missile guidance, infrared thermal imaging, infrared remote sensing and the like; the ultraviolet band is mainly used for flame detection, missile alarm, ozone monitoring, non-line-of-sight optical communication and the like.
Most of the existing photo-detectors are based on a simple Metal-Semiconductor-Metal (MSM) structure, and an external bias is required to achieve the optimal detection performance during operation of the photo-detector, so that not only is power consumed, but also the responsivity and the response speed need to be improved. For conventional solid-state photodetectors, there is also one of the most essential drawbacks: it is very difficult to distinguish the wavelength of the detected light, specifically, the conventional photo-detector can only detect photons with energy larger than the forbidden bandwidth of the photo-detector: for example, a uv detector should be theoretically designed to respond only to uv light and not to visible light. A theoretical "resolved wavelength" is achieved, i.e. a response only to the wavelength of interest. However, since there must be crystal defects in the semiconductor material, any photodetector will respond to photons with energy greater than its forbidden bandwidth, as well as photons with energy less than its forbidden bandwidth. In practical applications, for example, an ultraviolet light detector, when the detector detects a small light signal, one cannot strictly judge whether the light signal is ultraviolet light. It may be either a "uv signal" for low intensity uv light or a "visible signal" for high intensity visible light. Therefore, the conventional photo-detector can only improve the photo-detection selection ratio as much as possible, namely, continuously reduce the defect energy level transition and control the visible light response to a certain extent for normal use of photo-detection. This strategy does not solve the essential problems in the field of photodetectors: how to achieve true "wavelength resolution". Accordingly. Achieving light detection of spectral characteristics with a single absorbing material having a particular band gap is highly challenging.
Although the photoelectrochemical light detector has great technical advantages compared with the traditional light detector, the photoelectrochemical light detector is still in the starting stage, and the existing photoelectrochemical light detector is similar to a solid-state light detector in actual operation and has the problem that the detection wavelength is difficult to distinguish. Therefore, a need exists for a photoelectrochemical photodetector that effectively distinguishes between the wavelengths of light detected.
Disclosure of Invention
In view of the above, the present invention is directed to a GaN-based nanostructure-based polarization-reversed wavelength-resolved photodetector and a method for fabricating the same, so as to solve at least one of the above problems.
To achieve the above object, as an aspect of the present invention, there is provided a photoelectrochemical photodetector including a photoelectrode
Comprises a conductive substrate and a plurality of conductive layers,
further comprising heterojunction nanostructures formed on the surface of the substrate,
the heterojunction nanostructure is perpendicular to the substrate.
Wherein the heterojunction comprises two gallium nitride (GaN) -based semiconductor materials with different forbidden band widths, including AlxGa1-xN，InxGa1-xN，InyAlxGa1-x-yN，BxAlyGa1-x-yN，BxInyGa1-x-yAnd the heterojunction comprises a N material, wherein x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, and the heterojunction comprises a p-N junction, an N-p junction, a p-i-N junction and a tunneling junction structure which is added correspondingly, wherein the p-N junction, the N-p junction and the p-i-N junction are formed after N-type doping or p-type doping is carried out on the GaN.
Wherein the heterojunction nanostructure comprises a nanowire structure, a nanorod structure or a nanopore structure, so as to achieve the purpose of contacting all parts of the nanostructure with a solution.
The conductive substrate is a conductive semiconductor material-based substrate and comprises a conductive silicon substrate and a solid metal substrate comprising a metal molybdenum substrate.
Wherein the photoelectrochemical photodetector further comprises:
an electrolyte solution in contact with the photoelectrode, and
a reference electrode and a counter electrode in contact with the electrolyte solution,
the distance between the reference electrode and the counter electrode and between the reference electrode and the photoelectrode is more than or equal to 0.01 mm;
the reference electrode, the counter electrode and the photoelectrode are respectively connected with an electrochemical workstation with a current monitoring function.
Wherein the content of the first and second substances,
the electrolyte solution comprises an acidic or neutral electrolyte solution, the neutral electrolyte solution is sodium sulfate and a phosphate buffer solution, the acidic electrolyte solution comprises hydrobromic acid, sulfuric acid, hydrochloric acid and perchloric acid, and the concentration of the electrolyte solution is 0.01-5 mol/L;
the reference electrode is a silver/silver chloride (Ag/AgCl) electrode;
the counter electrode includes a platinum (Pt) electrode, a carbon (C) electrode.
As another aspect of the present invention, there is provided a method for manufacturing a photoelectrochemical photodetector, comprising the steps of:
selecting a corresponding band gap according to actual detection requirements;
calculating according to the corresponding band gap to obtain a nanostructure with proper atomic ratios of B, In, Al, Ga and N, growing and synthesizing a GaN-based material In epitaxial equipment according to the ratios, and correspondingly doping (N-type doping or p-type doping) the designed nanostructure to prepare a heterojunction nanostructure;
correspondingly packaging the whole substrate with the heterojunction nano structure on the surface of the conductive substrate to prepare a photoelectrode;
and building a photoelectrochemical photodetector.
Wherein, the step of preparing the heterojunction nano structure needs to ensure that all parts of the heterojunction are fully contacted with the electrolyte solution.
Wherein the heterojunction nanostructure obtained by molecular beam epitaxy and organic chemical vapor deposition growth on the conductive substrate can be replaced by directly transferring the heterojunction nanostructure onto the conductive substrate.
Based on the technical scheme, compared with the prior art, the polarity inversion type wavelength-resolved photodetector based on the GaN-based nanostructure and the preparation method thereof have at least one or part of the following beneficial effects:
(1) according to the photoelectrochemical photodetector based on the heterojunction nanostructure, the response current is a positive current under the illumination of a certain wavelength, and the response current is a negative current under the illumination of another wavelength (namely, the polarities of the photocurrents generated by the illumination of different wavelengths are different), so that the essential defects of the traditional photodetector are avoided on the working principle, and the detection, the differentiation and the light intensity measurement of the optical signals of different wavelengths are realized.
(2) The function of the semiconductor p-n junction is expanded. The traditional p-n junction is only conducted in a single direction, and the solid-state light detector based on the traditional p-n junction cannot realize current opposite sign under the condition of different detection wavelengths.
(3) The functions which cannot be realized by a plane p-n heterojunction structure are realized by the p-n heterojunction nano structure. If it is of planar structure, i.e. p-type Al0.4Ga0.6N is grown on the N-GaN in a covering mode, and the N-GaN is not in contact with the electrolyte solution, so that the oxidation reaction cannot occur, and the working mode cannot be realized.
(4) Compared with the existing photodetector, the photoelectrochemical photodetector provided by the invention has the advantages of strong detection signal (the photocurrent is higher than that of the existing photodetector by several orders of magnitude), good repeatability (a clear working mechanism), good universality (almost suitable for any semiconductor system) and low cost.
Drawings
FIG. 1 is a schematic flow chart of a method for manufacturing a photoelectrochemical photodetector capable of effectively distinguishing a photodetection wavelength according to an embodiment of the present invention;
FIG. 2 shows the wavelength of light and Al corresponding to different kinds of lightxGa1-xN，lnxGa1-xThe trend of the energy band of the N material changing along with the components;
FIG. 3 is a schematic diagram of a nanowire structure according to an embodiment of the present invention;
FIG. 4 is a schematic diagram of a photoelectrode prepared according to an embodiment of the present invention;
FIG. 5 is a schematic diagram of a built photoelectrochemical photodetector provided by an embodiment of the present invention;
fig. 6 is a schematic diagram illustrating an operation principle of the photoelectrochemical photodetector according to the embodiment of the present invention.
Detailed Description
The invention aims to break through the essential defects brought by the traditional solid-state optical detector principle and realize the effective differentiation of the optical detection wavelength.
Because a crystal defect is inevitably present in a semiconductor, any photodetector responds to photons with a forbidden bandwidth smaller than the forbidden bandwidth of the photodetector (for example, the response current of the ultraviolet photodetector to ultraviolet light in actual operation is 10A, and the response to visible light is possibly 1A due to the energy level transition of the semiconductor defect, and the ratio of the two currents reflects the performance of the photodetector: the photodetection selectivity ratio.
In practical applications, when the detector detects a 1A light signal, it is strictly impossible for people to determine whether the light signal is ultraviolet light, and the light signal may be an ultraviolet light signal of ultraviolet light with small light intensity or a visible light signal of visible light with large light intensity. Therefore, the conventional photodetector can only improve the light detection selection ratio as much as possible, continuously reduce the defect energy level transition, and control the visible light response to be below a certain degree for normal use. The essential problems of the device are not solved.
The novel photoelectrochemical photodetector provided by the invention successfully solves the problems: for example, the response current for ultraviolet light is 10A, and the response current for visible light is-5A.
1. The light intensity of ultraviolet light and visible light is detected simultaneously;
2. for an unknown optical signal, the true wavelength of the light can be judged through the sign of the response current, the problem of the traditional optical detector can not exist, and the true wavelength resolution is realized.
The design idea is as follows: the long wavelength photon illumination current is a positive current, the short wavelength photon illumination current is a negative current, and the light wavelength is split through different areas of current polarity. For example: for conventional solid-state solar blind (short wavelength) detectors, there is always a small non-solar blind (long wavelength) current, and the current is of the same polarity as the short wavelength current. In the actual detection process, when a small current is detected, it cannot be determined whether the small current signal is caused by a small dose of short-wavelength light or a large dose of long-wavelength light. Thus, the present invention takes advantage of the intrinsic advantage of a photoelectrochemical photodetector (PEC PD) that the detection current of the PEC PD represents the number of photogenerated carriers that participate in the redox reaction. The positive current detected by the electrochemical workstation represents the number of photogenerated holes participating in the oxidation reaction at the working electrode, whereas the negative current detected represents the amount of photogenerated electrons undergoing the reduction reaction at the working electrode. Specifically, the PEC PD is controlled to perform a reduction reaction under short-wavelength light irradiation and a reduction reaction under long-wavelength light irradiation, so that current polarity inversion is realized in a physical and chemical combination mode, and wavelength discrimination is realized.
Unlike traditional solid-state photodetectors, photoelectrochemical photodetectors involve physical and chemical processes that are beneficial in developing new devices and mechanisms for semiconductors. In particular, for solid-state photodetectors, the photocurrent thereof only involves photoelectric conversion processes in the semiconductor physics, representing only the quantity of photogenerated carriers flowing through the detector. Whereas the detection current of the PEC PD represents the number of photogenerated carriers participating in the redox reaction. The positive current detected by the electrochemical workstation represents the number of photogenerated holes participating in the oxidation reaction at the working electrode, whereas the negative current detected represents the amount of photogenerated electrons undergoing the reduction reaction at the working electrode. Based on this, the invention provides a novel optical detector structure which can effectively distinguish light intensity and wavelength and respond to different light wavelength with different current signs: photoelectrochemical photodetectors based on p-n heterojunction nanowires. Specifically, the response current of the detector is positive current under certain wavelength illumination, and the response current is negative current under the other wavelength illumination, so that the essential defects of the traditional optical detector are overcome on the working principle, and the detection, the differentiation and the polarity inversion (the current is changed from negative to positive) of optical signals with different wavelengths are realized.
Specifically, the invention discloses a photoelectrochemical photodetector which comprises a photoelectrode, wherein the photoelectrode comprises a conductive substrate and a heterojunction nanostructure formed on the surface of the substrate, and the heterojunction nanostructure is vertical to the substrate.
The photoelectrode referred to in the present invention may be a photocathode or a photoanode, and may be specifically distinguished by its doping component, corresponding to a reduction reaction or an oxidation reaction in the present invention.
As an alternative embodiment, the heterojunction comprises two semiconductor materials with different forbidden band widths, including AlxGa1-xN，InxGa1-xN，InyAlxGa1-x-yN，BxAlyGa1-x-yN，BxInyGa1-x-yN (where 0 ≦ x ≦ 1, 0 ≦ y ≦ 1), including but not limited to p-N junctions, N-p junctions, p-i-N junctions, tunneling junctions, and the like, semiconductor materials including but not limited to gallium arsenide, indium phosphide, or all the three or five compound semiconductors of their ternary/quaternary compounds, or other titanium dioxide (TiO)2) Gallium oxide (Ga)2O3)，GaN/Ga2O3And the like.
As an alternative embodiment, the heterojunction nanostructure includes, but is not limited to, a nanowire structure, a nanorod structure, a nanopore structure, or the like.
As an alternative embodiment, the substrate comprises a conductive substrate to ensure that the nanostructures are electrically conductive in contact with the conductive substrate.
As an alternative embodiment, the photoelectrochemical photodetector further comprises:
an electrolyte solution in contact with the photoelectrode, and
a reference electrode and a counter electrode in contact with the electrolyte solution,
the distance between the reference electrode and the counter electrode and between the reference electrode and the photoelectrode is more than or equal to 0.01 mm;
the reference electrode, the counter electrode and the photoelectrode are respectively connected with an electrochemical workstation with a current monitoring function.
The invention also discloses a preparation method of the photoelectrochemical photodetector, which is applied to the preparation of the photodetector and comprises the following steps:
selecting a semiconductor corresponding to the band gap according to the actual detection requirement;
respectively doping the selected semiconductors to prepare heterojunction nano structures, and correspondingly packaging to prepare photoelectrodes;
or transferring the heterojunction nano structure to a conductive substrate, and carrying out corresponding packaging to prepare a photoelectrode;
and building a photoelectrochemical photodetector.
As an alternative, the step of fabricating the heterojunction nanostructure is performed in such a way that all parts of the heterojunction are in sufficient contact with the electrolyte solution.
As an alternative embodiment, the heterojunction nanostructure is grown directly on a conductive substrate.
The invention is unique in that it combines physical and chemical processes, specifically:
1. the function that the traditional solid-state light detector can not realize is realized, and the polarity of the current is reversed due to different detection wavelengths (namely, for a certain specific wavelength, the photocurrent is a positive sign, and for another wavelength, the photocurrent is a negative sign);
2. the function of the p-n junction is expanded (the traditional p-n junction is only conducted in a single direction, and the current opposite sign of the solid-state light detector based on the traditional p-n junction can not be realized under the condition of different detection wavelengths);
3. the function which cannot be realized by a plane p-n heterojunction structure is realized by the p-n heterojunction nanowire structure (if the structure is a plane structure, namely p-type Al0.4Ga0.6N blanket grows on N-GaN, and this mode of operation cannot be achieved because N-GaN is not in contact with the electrolyte solution and cannot undergo oxidation reaction).
In order that the objects, technical solutions and advantages of the present invention will become more apparent, the present invention will be further described in detail with reference to the accompanying drawings in conjunction with the following specific embodiments.
FIG. 1 is a schematic flow chart of a method for manufacturing a photoelectrochemical photodetector capable of effectively distinguishing the wavelengths of light detected; the method comprises the following steps:
1. selecting corresponding GaN material components according to detection requirements
As shown in fig. 2 for AlxGa1-xN/InxGa1-xN, the band gap of which is graded with the doping composition, following the empirical formula:
AlxGa1-xN：Eg＝3.42eV+x*2.86eV-x(1-x)*1.0eV
InxGa1-xN：Eg＝3.42eV-x*2.65eV-x(1-x)*2.4eV
therefore, the band gap can be accurately regulated and controlled only by controlling the proportion of Al and In components when the nanowires grow, and light absorption corresponding to infrared light, visible light and ultraviolet light is realized. Selecting proper Al according to the practical application scene of the optical detectorxGa1- xN，InxGa1-xN，InyAlxGa1-x-yN，BxAlyGa1-x-yN，BxInyGa1-x-yAnd N (wherein x is more than or equal to 0 and less than or equal to 1, and y is more than or equal to 0 and less than or equal to 1) material component.
In the present example, Al is selected according to actual detection requirements0.4Ga0.6The N component is used as a 280nm light absorption layer, and the GaN is used as a 360nm light absorption layer.
2. High-quality nanowires are epitaxially grown in situ on a conductive substrate silicon (Si) wafer through Molecular Beam Epitaxy (MBE), n-type GaN with a certain length is grown first by controlling the growth conditions of the MBE, and p-type AlGaN with a certain length is grown again (the same orientation is ensured, and the problems of current offset and the like caused by different orientations are avoided), as shown in FIG. 3.
3. The photoelectrode is prepared on a semiconductor conductive substrate such as a Si substrate, and because the semiconductor conductive substrate Si is directly contacted with a metal wire, a Schottky barrier is formed, which is not beneficial to current conduction, and an electrode with ohmic contact characteristic needs to be prepared. Firstly, the back surface of the Si substrate (the surface on which the nano wire does not grow) is scraped by a diamond knife to remove the naturally grown SiO2And coating the layer with liquid GaIn alloy to form good conductive contact. If the conducting metal is used as the substrate, the liquid GaIn alloy is directly coated on the side of the conducting metal substrate without the growing nano-wires. Then, Ag paste is coated on the Cu strips and is compacted with the surface of the Si substrate coated with GaIn alloy, and finally, the electrodes are encapsulated with epoxy resin, leaving only the growth surface of the nanowires exposed, as shown in fig. 4.
4. A photoelectrochemical photodetector was constructed as shown in fig. 5. The electrolyte solution is added into a light-transmitting container, and the invention uses 0.5 mol per liter of sulfuric acid (H)2SO4) Taking an aqueous solution as an example, placing the nanowire electrode, a reference electrode (a silver/silver chloride (Ag/AgCl) reference electrode is selected in the invention), a counter electrode (a Pt mesh electrode is selected in the invention) in the solution, connecting a conductive end with an electrochemical workstation, setting test parameters of the electrochemical workstation through a computer, and completing the construction of the device.
The mode of operation of the present invention is described below.
The operation principle of the device will be described with 254nm (UVC band light) and 365nm (UVA band light) as examples.
As shown in fig. 6, when 365nm light irradiates the photoelectrode, only the material with a band gap smaller than the photon energy can be excited to generate photo-generated electron-hole pairs, as known from semiconductor physics. I.e. n-GaN-only absorption, p-Al0.4Ga0.6N does not absorb light, and only N-GaN generates photogenerated carriers. Because n-GaN can be bent upward in aqueous solution, photo-generated holes tend to migrate to the semiconductor/solution interface, oxidation occurs, and electrons tend to flow through an external circuit to the counter electrode, at which time the photo-response signal appears as a positive photocurrent.
When the photoelectrode is irradiated by 254nm light, n-GaN and p-Al0.4Ga0.6N is simultaneously absorbed. Due to n-GaN/p-Al0.4Ga0.6The N heterojunction space charge region has small width, and N-GaN is stimulated to generate photogenerated electrons and p-Al0.4Ga0.6The generated photo-generated holes generated by the N excitation are easy to generate tunneling recombination. Due to p-Al0.4Ga0.6N can be bent upward in aqueous solution, p-Al0.4Ga0.6N photo-generated electrons tend to migrate to the semiconductor/solution interface, generatingThe original reaction, while the n-GaN photoproduction holes tend to flow through the external circuit, showing a negative photocurrent.
In addition, the present invention may adopt the following schemes instead of the technical means of the above-described schemes.
1. Other compound semiconductor systems (such as gallium arsenide, indium phosphide, gallium phosphide GaP, GaAs, InP, etc.) can also be selected to realize the function;
2. a bandgap non-adjustable semiconductor heterojunction (i.e. a certain n-type semiconductor is selected and combined with a p-type semiconductor to form a nano structure, and the function is hopefully realized);
3. changing different semiconductor band combinations (e.g., n-p junctions);
4. different nanostructures (e.g., nanopores, nanopillars, nanoplatelets, etc.) are replaced.
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 (9)
1. A photoelectrochemical photodetector, comprising a photoelectrode, wherein said photoelectrode
Comprises a conductive substrate and a plurality of conductive layers,
further comprising heterojunction nanostructures based on gallium nitride material grown on the substrate surface,
the heterojunction nanostructure is perpendicular to the substrate.
2. The photodetector of claim 1, wherein the heterojunction comprises two gallium nitride based semiconductor materials of different forbidden band widths, including AlxGa1-xN，InxGa1-xN，InyAlxGa1-x-yN，BxAlyGa1-x-yN，BxInyGa1-x-yAnd the heterojunction comprises a N material, wherein x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, and the heterojunction comprises a p-N junction, an N-p junction, a p-i-N junction and a tunneling junction structure which is added correspondingly, wherein the p-N junction, the N-p junction and the p-i-N junction are formed after N-type doping or p-type doping is carried out on the GaN.
3. The photodetector of claim 1, wherein the heterojunction nanostructure comprises a nanowire structure, a nanorod structure, or a nanopore structure, such that all portions of the nanostructure are in contact with the solution.
4. The photodetector of claim 1, wherein the conductive substrate is a conductive semiconductor material based substrate comprising a conductive silicon substrate and the solid state metal substrate comprises a metallic molybdenum substrate.
5. The photo-detector of claim 1, wherein the photo-electrochemical photo-detector further comprises:
an electrolyte solution in contact with the photoelectrode, and
a reference electrode and a counter electrode in contact with the electrolyte solution,
the distance between the reference electrode and the counter electrode and between the reference electrode and the photoelectrode is more than or equal to 0.01 mm;
the reference electrode, the counter electrode and the photoelectrode are respectively connected with an electrochemical workstation with a current monitoring function.
6. The light detector of claim 5,
the electrolyte solution comprises an acidic or neutral electrolyte solution, the neutral electrolyte solution is sodium sulfate and a phosphate buffer solution, the acidic electrolyte solution comprises hydrobromic acid, sulfuric acid, hydrochloric acid and perchloric acid, and the concentration of the electrolyte solution is 0.01-5 mol/L;
the reference electrode is a silver/silver chloride (Ag/AgCl) electrode;
the counter electrode includes a platinum (Pt) electrode, a carbon (C) electrode.
7. A method of manufacturing a photo-electrochemical photo-detector for use in manufacturing a photo-detector according to any one of claims 1 to 6, comprising the steps of:
selecting a corresponding band gap according to actual detection requirements;
calculating according to the corresponding band gap to obtain proper B, In, Al, Ga and N atomic ratio, growing the GaN-based material In the epitaxial equipment according to the proportion, and carrying out corresponding N-type or p-type doping on the designed area to prepare AlxGa1-xN，InxGa1-xN，InyAlxGa1-x-yN，BxAlyGa1-x-yN，BxInyGa1-x-yN, wherein x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, and the heterojunction nanostructure;
correspondingly packaging the heterojunction nano structure grown on the conductive substrate to prepare a photoelectrode;
and building a photoelectrochemical photodetector.
8. The method of claim 7, wherein the step of forming the heterojunction nanostructure comprises ensuring that all portions of the heterojunction are in sufficient contact with the electrolyte solution.
9. A method of manufacturing as claimed in claim 7 wherein the scheme of growing the heterojunction nanostructure by molecular beam epitaxy and organic chemical vapor deposition on top of a conductive substrate can be replaced by directly transferring the heterojunction nanostructure onto the conductive substrate.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010062644A2 (en) * | 2008-10-28 | 2010-06-03 | The Regents Of The University Of California | Vertical group iii-v nanowires on si, heterostructures, flexible arrays and fabrication |
| CN102376817A (en) * | 2010-08-11 | 2012-03-14 | 王浩 | Method for preparing semiconductor photoelectric device |
| CN106057954A (en) * | 2016-06-23 | 2016-10-26 | 西南交通大学 | Lead iodide photo-detector with double-optical-band function |
| CN109473489A (en) * | 2018-10-18 | 2019-03-15 | 北京镓族科技有限公司 | A kind of self-powered photodetector for distinguishing ultraviolet band |
| CN111640768A (en) * | 2020-05-09 | 2020-09-08 | 北京科技大学 | Vertical double-heterojunction optical detector area array and manufacturing method thereof |
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| US7307291B2 (en) * | 2005-01-22 | 2007-12-11 | Formosa Epitaxy Incorporation | Gallium-nitride based ultraviolet photo detector |
| EP1748494B1 (en) * | 2005-07-29 | 2008-04-09 | Interuniversitair Microelektronica Centrum | Wavelength-sensitive detector with elongate nanostructures |
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| CN109103282B (en) * | 2018-08-29 | 2020-12-29 | 北京镓族科技有限公司 | Photoelectrochemical solar blind ultraviolet detector based on gallium oxide nano-pillar array |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010062644A2 (en) * | 2008-10-28 | 2010-06-03 | The Regents Of The University Of California | Vertical group iii-v nanowires on si, heterostructures, flexible arrays and fabrication |
| CN102376817A (en) * | 2010-08-11 | 2012-03-14 | 王浩 | Method for preparing semiconductor photoelectric device |
| CN106057954A (en) * | 2016-06-23 | 2016-10-26 | 西南交通大学 | Lead iodide photo-detector with double-optical-band function |
| CN109473489A (en) * | 2018-10-18 | 2019-03-15 | 北京镓族科技有限公司 | A kind of self-powered photodetector for distinguishing ultraviolet band |
| CN111640768A (en) * | 2020-05-09 | 2020-09-08 | 北京科技大学 | Vertical double-heterojunction optical detector area array and manufacturing method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114551629A (en) * | 2022-04-26 | 2022-05-27 | 北京邮电大学 | Ultraviolet-visible light waveband distinguishable photoelectric detector and preparation method thereof |
| CN114551629B (en) * | 2022-04-26 | 2022-09-16 | 北京邮电大学 | Ultraviolet-visible light waveband distinguishable photoelectric detector and preparation method thereof |
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